Surface Science Reports 63 (2008) 515–582

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Surface Science Reports

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TiO2 photocatalysis and related surface phenomena

Akira Fujishima a,∗ , Xintong Zhang b , Donald A. Tryk c
a
Kanagawa Academy of Science and Technology, 3-2-1 Sakado, Takatsu-ku, Kawasaki-shi, Kanagawa 213-0012, Japan
b
Center for Advanced Optoelectronic Functional Materials Research, Northeast Normal University, 5268 Renmin Street, Changchun 130024, China
c
Fuel Cell Nanomaterials Center, University of Yamanashi, Takeda 4-3-11, Koufu, Yamanashi 400-8510, Japan

article info a b s t r a c t

Article history: The field of photocatalysis can be traced back more than 80 years to early observations of the chalking of
Accepted 1 October 2008 titania-based paints and to studies of the darkening of metal oxides in contact with organic compounds
editor: Y. Murata in sunlight. During the past 20 years, it has become an extremely well researched field due to practical
interest in air and water remediation, self-cleaning surfaces, and self-sterilizing surfaces. During the same
Keywords: period, there has also been a strong effort to use photocatalysis for light-assisted production of hydrogen.
Titanium dioxide
The fundamental aspects of photocatalysis on the most studied photocatalyst, titania, are still being
Titania
TiO2
actively researched and have recently become quite well understood. The mechanisms by which certain
Self-cleaning surfaces types of organic compounds are decomposed completely to carbon dioxide and water, for example,
Superhydrophilic effect have been delineated. However, certain aspects, such as the photo-induced wetting phenomenon,
Anion doping remain controversial, with some groups maintaining that the effect is a simple one in which organic
Water splitting contaminants are decomposed, while other groups maintain that there are additional effects in which
Environmental cleaning the intrinsic surface properties are modified by light. During the past several years, powerful tools such
as surface spectroscopic techniques and scanning probe techniques performed on single crystals in ultra-
high vacuum, and ultrafast pulsed laser spectroscopic techniques have been brought to bear on these
problems, and new insights have become possible. Quantum chemical calculations have also provided
new insights. New materials have recently been developed based on titania, and the sensitivity to visible
light has improved. The new information available is staggering, but we hope to offer an overview of
some of the recent highlights, as well as to review some of the origins and indicate some possible new
directions.
© 2008 Elsevier B.V. All rights reserved.

Contents

1. Introduction........................................................................................................................................................................................................................516
2. Historical overview ............................................................................................................................................................................................................516
3. Properties of TiO2 materials ..............................................................................................................................................................................................519
3.1. Crystal structures ...................................................................................................................................................................................................519
3.2. Electronic properties .............................................................................................................................................................................................520
3.3. Surface structure studies.......................................................................................................................................................................................523
3.4. Surface chemical studies: Interactions with water .............................................................................................................................................523
3.5. Surface chemical studies: Interactions with dioxygen and other species .........................................................................................................527
3.6. Bulk chemistry—Hydrogen....................................................................................................................................................................................527
3.7. Electrochemical properties ...................................................................................................................................................................................529
3.8. Photoelectrochemical properties..........................................................................................................................................................................534
4. Fundamentals of photocatalysis........................................................................................................................................................................................534
4.1. Mechanisms of photocatalysis ..............................................................................................................................................................................534
4.1.1. Photoelectrochemical basis of photocatalysis ......................................................................................................................................534
4.1.2. Time scales ..............................................................................................................................................................................................538
4.1.3. Trapping of electrons and holes.............................................................................................................................................................541

∗ Corresponding author. Tel.: +81 (0)44 819 2020; fax: +81 (0)44 819 2038.
E-mail address: fujishima@newkast.or.jp (A. Fujishima).

0167-5729/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfrep.2008.10.001
516 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

4.1.4. Oxidizing species at the TiO2 surface ....................................................................................................................................................542

4.1.5. Role of molecular oxygen .......................................................................................................................................................................545
4.1.6. Effect of crystal face................................................................................................................................................................................547
4.1.7. Remote photocatalysis ...........................................................................................................................................................................549
4.2. Photocatalytic reactions ........................................................................................................................................................................................551
4.2.1. Decomposition of gaseous pollutants ...................................................................................................................................................551
4.2.2. Decomposition of aqueous pollutants...................................................................................................................................................552
4.2.3. Decomposition of liquid and solid films ...............................................................................................................................................553
4.2.4. Photocatalytic sterilization ....................................................................................................................................................................553
4.3. Visible-light-induced photocatalysis....................................................................................................................................................................555
4.3.1. Non-metal doping...................................................................................................................................................................................555
4.3.2. Origin of visible light photoactivity.......................................................................................................................................................556
4.3.3. Activity and stability of N-doped TiO2 photocatalysts .........................................................................................................................558
5. Fundamentals of the photo-induced hydrophilic (PIH) effect ........................................................................................................................................560
5.1. Overview ................................................................................................................................................................................................................560
5.2. Mechanisms of the PIH effect................................................................................................................................................................................562
5.2.1. Decomposition of organic films .............................................................................................................................................................562
5.2.2. Reductive mechanism ............................................................................................................................................................................563
5.2.3. Oxidative mechanism.............................................................................................................................................................................563
5.2.4. Combined redox mechanism .................................................................................................................................................................563
5.2.5. Visible-light-induced PIH effect.............................................................................................................................................................564
6. Brief review of applications...............................................................................................................................................................................................565
6.1. Self-cleaning surfaces ............................................................................................................................................................................................565
6.2. Water purification .................................................................................................................................................................................................567
6.3. Air purification .......................................................................................................................................................................................................568
6.4. Self-sterilizing surfaces .........................................................................................................................................................................................569
6.5. Anti-fogging surfaces.............................................................................................................................................................................................570
6.6. Heat transfer and heat dissipation........................................................................................................................................................................571
6.7. Anticorrosion applications ....................................................................................................................................................................................571
6.8. Environmentally friendly surface treatment .......................................................................................................................................................572
6.9. Photocatalytic lithography ....................................................................................................................................................................................572
6.10. Photochromism......................................................................................................................................................................................................574
6.11. Microchemical systems .........................................................................................................................................................................................574
7. Summary ............................................................................................................................................................................................................................575
Appendix. TiO2 film preparation methods ..................................................................................................................................................................576
References...........................................................................................................................................................................................................................576

1. Introduction have tried to put together an overview of some of the more

Photocatalysis is generally thought of as the catalysis of a
photochemical reaction at a solid surface, usually a semiconductor
[1–16]. This simple definition, while correct and useful, however,
conceals the fact that there must be at least two reactions occurring
simultaneously, the first involving oxidation, from photogenerated
holes, and the second involving reduction, from photogenerated
electrons. Both processes must be balanced precisely in order for
the photocatalyst itself not to undergo change, which is, after all,
one of the basic requirements for a catalyst.
It will be seen in this review of the fundamentals and selected
applications of photocatalysis, principally on titanium dioxide,
that there is a host of possible photochemical, chemical and
electrochemical reactions that can occur on the photocatalyst
surface. The types of reactions occurring, their extent and their
rates depend upon a host of factors that are still in the process
of being unraveled. Furthermore, there can indeed be changes
that occur, involving the surface and bulk structure and even
decomposition of the photocatalyst, a fact that appears to stretch
the definition of the term.
This topic started its early history as mostly a nuisance involving
the chalking of titania-based paints [17,18] and then gradually
transformed into a highly useful approach to the remediation of
water and air and then into an approach to maintain surfaces clean
and sterile. Along the way, it has also transformed into an approach
to photolytically split water into hydrogen and oxygen [19–21]
and also an approach to perform selective oxidation reactions in
organic chemistry [22].
Clearly, with so many varied aspects, photocatalysis is nearly
impossible to review comprehensively. In the present review, we
fundamental aspects, which are in their own right extremely
scientifically interesting and which also need to be better
understood in order to make significant progress with applications.
The review will be divided into several sections: 2. Historical
overview; 3. Properties of TiO2 materials; 4. Fundamentals of
photocatalysis; 5. Fundamentals of the photo-induced hydrophilic
effect; 6. Brief review of applications; 7. Summary, and Appendix
(film preparation methods).
2. Historical overview
We will give a brief overview of the early history of
photocatalysis, which will be based just on papers that we have
been able to access, which means that we will almost certainly
be ignoring some important papers. The earliest work that we
have been able to find is that of Renz, at the University of Lugano
(Switzerland), who reported in 1921 [17] that titania is partially
reduced during illumination with sunlight in the presence of an
organic compound such as glycerol, the oxide turning from white
to a dark color, such as grey, blue or even black; he also found
similar phenomena with CeO2 , Nb2 O5 and Ta2 O5 . For TiO2 , the
reaction proposed was:
TiO2 + light → Ti2 O3 or TiO. (2.1)
Baur and Perret, at the Swiss Federal Institute of Technology, were
the first to report, in 1924, the photocatalytic deposition of a silver
salt on zinc oxide to produce metallic silver [23]. Even at this
early date, the authors suspected that both oxidation and reduction
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
were occurring simultaneously. The reaction pathway proposed
was this:
ZnO + hν → h+ + e−
1 1
h+ + OH− → O2 + H2 O
4 2
e− + Ag+ → Ag0 .
Three years later, Baur and Neuweiler proposed simultaneous
oxidation and reduction to explain the production of hydrogen
peroxide on zinc oxide [24].
2h+ + CH2 O + 2OH− → CO + 2H2 O
2e + 2H + O2 → H2 O2 .
− +
It was not until many years later that this was absolutely
confirmed, however. In 1932, Renz reported the photocatalytic
reduction of silver nitrate to metallic silver and gold chloride to
metallic gold on a number of illuminated oxides, including TiO2 and
Nb2 O5 , [25] and discussed the results in terms of the Baur redox
mechanism.
It has been recognized for quite a long time that titania-based
exterior paints tend to undergo ‘‘chalking’’ in strong sunlight.
This means that a non-adherent, white powdery substance tends
to form on the surface, similar to the chalk on a blackboard.
This effect was recognized to result from the actual removal of
part of the organic component of the paint, leaving the titania
itself exposed. With this background, Goodeve and Kitchener, at
University College, London, carried out an excellent study on the
photocatalytic decomposition of a dye on titania powder in air in
1938, including absorption spectra and determination of quantum
yields (Fig. 2.1) [26]. These authors proposed that titania acts as a
catalyst to accelerate the photochemical oxidation and also studied
a number of other oxides and speculated on the precise mechanism
[27]. In 1949, Jacobsen, at the National Lead Company (USA), also
attempted to explain the paint chalking phenomenon in terms of
a redox mechanism. He found a correlation between the tendency
of a number of different titania powders to undergo photo-induced
reduction in the presence of organic compounds to their chalking
tendency [18]. The photo-induced reduction was measured as a
loss of reflectivity, due to the discoloration of the powder upon
reduction, presumably to various oxygen-deficient forms, all the
way to Ti2 O3 . The author proposed a cyclic redox process in which
the titania was reduced while the organic paint components were
oxidized, followed by re-oxidation of the titania by oxygen from
the air. The changes experienced by the titania were recognized to
be completely reversible, while those experienced by the organic
paint were recognized to be irreversible, leading to the formation
of water-soluble organic acids and CO2 . Even though Jacobsen was
apparently unaware of the work of Baur on the redox mechanism,
he referred to the 1921 paper of Renz on the photo-reduction of
metal oxides and proposed the same basic mechanism that had
been proposed by Baur; thus, a foundation was laid for later work
on the redox mechanism.
During the 1950s, the development of photocatalysis shifted to
zinc oxide. In 1953, two studies appeared in which the puzzling
phenomenon of hydrogen peroxide production on zinc oxide
illuminated with UV light was studied [28,29], followed by a series
of follow-up studies in ensuing years [30–34]. In these studies, the
overall reactions and mechanisms were completely clarified, and
it became apparent that an organic compound was oxidized while
atmospheric oxygen was reduced. Even in the earliest study, an
overall reaction with phenol to produce catechol was proposed,
and the involvement of radical species such as the hydroxyl radical
(•OH) was also speculated upon [28]. Thus, the original proposal
517
(2.2)
(2.3)
(2.4)
(2.5)
(2.6)
Fig. 2.1. Original data of Goodeve and Kitchener showing the photocatalytic
decomposition of a dye (‘‘chlorazol sky blue)’’ adsorbed on anatase powder under
UV illumination at 365 nm [26].
© 1938, Royal Society of Chemistry.
of Baur and Neuweiler was finally confirmed, with the overall
reaction:
RHOH + H2 O + O2 → H2 O2 + R(OH)2 . (2.7)
Markham, first at the Catholic University of America and later
at St. Joseph’s College (USA), continued to study photocatalytic
reactions on ZnO, and her papers constitute an impressive, yet
underappreciated, body of work [28,30,31,35–39]. This work
culminated in a highly intriguing study in which Markham and
co-worker Upreti constructed and studied a number of different
types of photo-assisted fuel cells, using illuminated ZnO as the
photo-anode with formamide or several alcohols as the organic
substrates [39]. At the dark cathode (platinum), several different
redox mediators were examined, with atmospheric oxygen
ultimately being the electron acceptor. The authors may have been
discouraged by the inevitable problem of ZnO photocorrosion,
which prevented this system from reaching practical application.
It was not until years later that the same basic ideas were re-
examined with TiO2 . Unfortunately, Markham and Laidler, in their
initial study in 1953, examined TiO2 but subsequently abandoned
it, since it did not produce measurable amounts of hydrogen
peroxide [28].
It is also interesting to note that Stephens et al. (Wayne
State University), in their study in 1955 of hydrogen peroxide
production on a large assortment of illuminated semiconductors,
but, unfortunately, not TiO2 , remarked that ‘‘zinc oxide and the
other catalytic solids should not be abandoned as devices for
capturing solar energy in a form capable of transfer to some
chemical system’’ [32]. These authors found that CdS was the most
active photocatalyst, exceeding ZnO in activity.
In a study reported in 1956 in Nature, Hindson and Kelly
(Defense Standards Laboratory) reported on the effects of various
rot-inhibitors on tent fabrics for use in Australia. They examined
the effects of fabric strength after one year of exposure to sunlight.
They stated: ‘‘The effect of anatase is startling. Fabrics containing
3% of this pigment lost 90% in strength’’.
In 1958, Kennedy et al., at the University of Edinburgh, studied
the photo-adsorption of O2 on TiO2 in order to try to more fully
understand the photocatalytic process [40]. They concluded that
electrons were transferred to O2 as a result of photoexcitation, and
the resulting reduced form of O2 adsorbed on the TiO2 surface.
These authors found a correlation between the ability of the TiO2
sample to photocatalytically decompose chlorazol sky blue (the
same dye used earlier by Goodeve and Kitchener) and the ability
518 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
to photo-adsorb O2 . This phenomenon is certainly important for
photocatalysis and will be commented upon later.
During this period, researchers in Russia were active. Photo-
adsorption of O2 on illuminated ZnO was studied by Terenin and
Solonitzin at the University of Leningrad (now University of St.
Petersburg) [41]. In a very interesting early work, Filimonov, at
the same institution, compared the photocatalytic oxidation of
isopropanol to acetone on ZnO and TiO2 [42] and concluded that
the mechanism on TiO2 involved an overall reduction of O2 to H2 O,
while the reduction of O2 on ZnO only went as far as H2 O2 . On TiO2 ,
the surface reactions were proposed to be:
TiO∗2 + (CH3 )2 CHOH → (CH3 )2 CO + TiO + H2 O
1
TiO + O2 → TiO2 .
2
Thus, this mechanism is a more detailed version of the Baur cyclic
mechanism. It involves the removal of a surface lattice oxygen
atom, which would be a kind of reduction process. This mechanism
will be discussed later also, in Section 3.3.
In Japan, at the Kyoto Institute of Technology, an early study
(1964) by Kato and Mashio also found that various types of
titania powders had different photocatalytic activities, specifically
to oxidize hydrocarbons and alcohols, simultaneously producing
hydrogen peroxide [43]. Interestingly, these authors found that
anatase powders were more active than the rutile ones.
In further work at the University of Edinburgh, McLintock and
Ritchie, using gas-phase adsorption measurements, studied the
photocatalytic oxidation of ethylene and propylene at TiO2 [44].
This study is one of the first that we have found that shows that
it is possible to oxidize organic compounds completely to CO2 and
H2 O:
C2 H4 + 3O2 → 2CO2 + 2H2 O. (2.10)
The mechanism was proposed to involve the production of
superoxide from oxygen:
2 .
O2 + e− → O•− (2.11)
Markham et al. had already proposed this reaction to take place
on illuminated ZnO [31]. Work on similar photo-reactions has
continued into more recent years [45].
In an important study for the relationship between photoelec-
trochemistry and photocatalysis, which we will come back to later,
in Section 3.2, Lohmann, at the Cyanamid European Research Insti-
tute, in 1966 published a highly detailed study of the photoelectro-
chemical (PEC) behavior of ZnO, both in the presence and absence
of redox couples, including ferro/ferricyanide and methylene blue
[46]. He clearly showed that the overall current at the ZnO elec-
trode under illumination is the sum of anodic and cathodic cur-
rents, the anodic current being a combination of the dissolution of
the ZnO itself and the oxidation of any redox species present. The
cathodic process was the reduction of O2 to H2 O2 . This same ap-
proach had been introduced in 1938 by Wagner and Traud, at the
Technical University of Darmstadt, to help explain the corrosion of
metals, coupled with either hydrogen evolution or oxygen reduc-
tion [47,48].
Another PEC study that we will mention in this overview is that
of Morrison and Freund, of the Stanford Research Institute, who
also studied ZnO [49]. These authors also demonstrated in detail
the various situations that arise in the presence and absence of
redox couples. They also showed that oxidation products of some
organic compounds are different in the case of the PEC electrode
poised at the open circuit potential, i.e., with both oxidation and
reduction currents balanced, compared to the case of a purely
electrochemical oxidation. This difference was proposed to be due
to the presence of cathodically generated superoxide. This is one of
(2.8)
(2.9)
Fig. 2.2. Photocurrent vs. potential for illuminated rutile single crystal. SCE refers
to the saturated calomel electrode, which is 0.241 V vs. the standard hydrogen
electrode (SHE) (taken from Fujishima et al. [214]).
© 1971, Chemical Society of Japan.
the key points in understanding photocatalysis, and we will return
to it later.
During the late 1960s, one of the present authors, at the
University of Tokyo, began to study the photoelectrochemistry of
titania and found that oxygen gas was evolved at potentials very
much shifted from the thermodynamic expectation, for example,
with an onset of ca. −0.25 V vs. the standard hydrogen electrode
(SHE), compared to the standard potential of +0.95 V in pH 4.7
aqueous buffer (Fig. 2.2) [50,51]. At first, there was skepticism of
this result, but then it slowly became accepted. One reason that
this result was difficult to understand is that the photoexcitation
process converts the photon energy to chemical energy with little
loss, and thus the photogenerated hole has a very high reactivity, so
that it can react directly with either water or quite robust organic
and inorganic compounds. Subsequently, a number of studies were
carried out in which the photoelectrochemical oxidation process
on TiO2 was examined for the competitive oxidation of water
to O2 with the oxidation of a variety of inorganic and organic
substrates [52,53]. Both types of reactions, of course, involve the
use of light energy to get over an energy barrier, either an overall
uphill process, as in the case of O2 evolution, or an overall downhill
process, as in the case of organic oxidations.
With the report of the ability to simultaneously generate hydro-
gen gas in 1972 (see Fig. 2.3) [19], the PEC field started to receive
much wider attention, due to its implications for solar energy con-
version [54,55]. From this point, also, photoelectrochemistry be-
came closely associated with photocatalysis. We shall return to this
topic later, in Section 3.2, and more carefully describe the detailed
relationships.
In this overview, we briefly mention some of the early work
of Bard and co-workers at the University of Texas. Frank and Bard
were the first ones to propose that illuminated TiO2 could be used
for the purification of water via the photocatalytic decomposition
of pollutants [56,57]. They suggested that cyanide and sulfite could
be photocatalytically oxidized to cyanate and sulfate, respectively.
In one of these studies, they found that photocatalytic oxidations
could also occur at other illuminated semiconductors, such as
ZnO, CdS, Fe2 O3 and WO3 . The most active semiconductor was
found to be ZnO [57]. These authors expanded this study to a
long list of inorganic and organic species [58] and speculated that
photocatalysis could be a useful approach to both environmental
cleanup and photo-assisted organic synthesis. The Bard group
also suggested that each small illuminated semiconductor particle
could be considered as a PEC cell, with both photo-assisted
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 2.3. Photoelectrochemical cell used in the photolysis of water [19].
© 1972, Nature Publishing Group.
oxidation and dark reduction reactions taking place [59]. The Bard
group also proposed photocatalysis as a way to remove toxic
metals from wastewater [60].
For a period of several years, the photocatalysis area continued
to expand as a technology for both the selective oxidation of
organic compounds [22] and the unselective oxidation of organic
compounds for purposes of water purification [1,2,61–64] and,
to some extent, also air purification [65–69]. There have also
been reviews and listings of references of work on both air
and water purification [4,70–72]. For these technologies, it is
typically necessary to use powerful ultraviolet (UV) light sources.
For passive purification, without special light sources, it became
apparent in the early 1990s that the amount of light present in
either natural sunlight or artificial light was insufficient to process
large amounts of organic compounds. Therefore, attention was
turned to applications in which a relatively small number of UV
photons could be used to carry out reactions at the TiO2 surface,
for example, to decompose thin organic films on solid surfaces or
to kill bacteria on surfaces [5,6,73–76]. Thus, the focus turned from
water purification to passive, self-cleaning, self-sterilizing solid
surfaces, which, with sometimes only slight modification, could
also be used to purify air. For these types of applications, it was
necessary to develop ways to coat various materials with TiO2
films. Such applications included the self-cleaning glass cover for
highway tunnel lamps, as well as a number of others, which have
been reviewed previously and which will also be reviewed briefly
later in this article.
The large number of applications has also generated a renewed
scientific interest in photocatalysis, and indeed on photo-assisted
reactions on semiconducting metal oxides in general. One of the
ways that we have tracked this activity is by looking at the
number of citations of the 1972 Nature paper on water photolysis
(Fig. 2.4(a)). This number of yearly citations has been climbing
steadily over the past ten years or so and of course is correlated
with the number of publications appearing on photocatalysis
(Fig. 2.4(b)).
519
Fig. 2.4. (a) Citations per year of the 1972 Nature paper: ‘‘Electrochemical
photolysis of water at a semiconductor electrode’’ [19]; (b) Numbers of research
articles appearing on photocatalysis per year: search results in the period of
1972–2007 with the ‘‘Web of Science’’ (a) by the keyword ‘‘photocataly∗ ’’ (blue bars)
and (b) the keywords ‘‘TiO2 AND photocataly*’’ (green bars). (For interpretation
of the references to colour in this figure legend, the reader is referred to the web
version of this article.)
3. Properties of TiO2 materials
3.1. Crystal structures
As often described, there are three main types of TiO2
structures: rutile, anatase and brookite. The size dependence of
the stability of various TiO2 phases has recently been reported
[77,78]. Rutile is the most stable phase for particles above 35 nm
in size [77]. Anatase is the most stable phase for nanoparticles
below 11 nm. Brookite has been found to be the most stable
for nanoparticles in the 11–35 nm range, although the Grätzel
group finds that anatase is the only phase obtained for their
nanocrystalline samples [79,80]. These have different activities
for photocatalytic reactions, as summarized later, but the precise
reasons for differing activities have not been elucidated in detail.
Since most practical work has been carried out with either rutile
or anatase, we will focus more attention on these.
Rutile has three main crystal faces, two that are quite low
in energy and are thus considered to be important for practical
polycrystalline or powder materials [81]. These are: (110) and
(100) (Fig. 3.1a, b). The most thermally stable is (110), and
therefore it has been the most studied. It has rows of bridging
oxygens (connected to just two Ti atoms). The corresponding Ti
atoms are 6-coordinate. In contrast, there are rows of 5-coordinate
Ti atoms running parallel to the rows of bridging oxygens and
alternating with these. As discussed later, the exposed Ti atoms
are low in electron density (Lewis acid sites). The (100) (Fig. 3.1b)
surface also has alternating rows of bridging oxygens and 5-
coordinate Ti atoms, but these exist in a different geometric
520 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 3.1. Schematic representations of selected low-index faces of rutile: (a) (110); (b) (100); and (C) (001).
relationship with each other. The (001) face (Fig. 3.1c) is thermally
less stable, restructuring above 475 ◦ C [81]. There are double rows
of bridging oxygens alternating with single rows of exposed Ti
atoms, which are of the equatorial type rather than the axial type.
Anatase has two low energy surfaces, (101) and (001)
(Fig. 3.2a, b), which are common for natural crystals [80,82].
The (101) surface, which is the most prevalent face for anatase
nanocrystals [79], is corrugated, also with alternating rows of
5-coordinate Ti atoms and bridging oxygen, which are at the
edges of the corrugations. The (001) (Fig. 3.2b) surface is rather
flat but can undergo a (1 × 4) reconstruction [82,83]. The (100)
surface is less common on typical nanocrystals but is observed
on rod-like anatase grown hydrothermally under basic conditions
(Fig. 3.2c) [80]. This surface has double rows of 5-coordinate Ti
atoms alternating with double rows of bridging oxygens. It can
undergo a (1 × 2) reconstruction [84].
Recently, the brookite phase, which is rarer and more difficult
to prepare, has also been studied as a photocatalyst (see later). The
order of stability of the crystal faces is (010) < (110) < (100)
(Fig. 3.3) [85].
Recently also, the discovery of high-pressure phases of TiO2
was made [86]. These are expected to have smaller band-
gaps but similar chemical characteristics [87]. Their existence
was theoretically predicted and then experimentally proven;
specifically, a form of TiO2 with the cotunnite structure was
prepared at high temperature and pressure and then quenched in
liquid nitrogen. It is the hardest known oxide.
There are actually quite a variety of different structures for
compounds with compositions close to TiO2 , including those with
excess titanium, such as the Magneli phases, Tn O2n−1 , where n
can range from 4 up to about 12 and the titanium oxide layered
compounds, in which there can be as much as several percent
excess oxygen. The oxygen-deficient Magneli phases, which also
exist for V, Nb, Mo, Re and W, have been known for many years
[88–91]. In these compounds, oxygen vacancies are ordered and
lead to the slippage of crystallographic planes with respect to
each other; this leads to formation of planes in which, instead of
corner or edge-shared TiO6 octahedra, there are now face-shared
octahedra. Fig. 3.4 shows a schematic diagram of this situation. The
corresponding Ti atoms are then unusually close and can interact
electronically [92]. It has been found recently that laser ablation of
a TiO2 rutile target can produce Magneli-phase nanoparticles [93].
There are also quite a number of layered titanate compounds
in which there is an apparent excess of oxygen. For example, the
layered protonic titanate Hx Ti−2 x/4x/4 O4 • H2 O has been prepared
and exfoliated into single sheets, termed ‘‘titania nanosheets’’.
Fig. 3.5 shows (a) a diagram of the layered structure and (b) TEM
and AFM images of single sheets.
3.2. Electronic properties
It was reported in 1942 by Earle that rutile and anatase TiO2
in the form of powders are n-type semiconductors and that
the conductivity decreases with increasing O2 partial pressure at
temperatures above 600 ◦ C [94]. The effect of O2 was explained on
the basis of an equilibrium involving thermal release of O2 from the
lattice. We recognize today that this leads to the creation of Ti3+
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 3.2. Schematic representations of selected low-index faces of anatase: (a) (101); (b) (100); and (C) (001).
sites, which are responsible for the electronic conductivity. The
activation energy for the electronic conductivity was found to be
1.75 eV for unsintered rutile powder and 1.7 eV for sintered rutile
powder. No evidence for ionic conduction was found. Cronemeyer
and Gilleo reported in 1951 that rutile single crystals exhibit
a band-gap energy of 3.05 eV [95]. Absorption spectra were
reported for both normal and slightly reduced crystals. For the
latter, the blue color was based on a very broad absorption that
peaked at 1.8 µm. In the following year, Cronemeyer published
a very extensive study of the electronic properties of single
crystal rutile in which the preliminary findings were substantiated
[96]. Detailed photoconductivity measurements were made. Dark
conductivity and photoconductivity measurements were also
made on a slightly reduced sample (reduction in H2 at 600 ◦ C).
Interestingly, there was found to be a marked hysteresis in the dark
conductivity when the sample was raised from room temperature
to 250 ◦ C and then cooled back to room temperature. After cooling
with a high applied electric field, the blue color was found to be
concentrated at the negative electrode; the author ascribed this to
movement of oxygen vacancies, but this is not confirmed. It is also
521
possible that the migration involved interstitial hydrogen. This is
an ambiguity that has persisted for many years.
Strong reduction of various types of samples was examined,
at various temperatures between 300 and 1150 ◦ C. The strong
reduction turns the samples blue–black. The activation energy
for electronic conduction had already been reported to be
0.07 eV at room temperature, to produce a conductivity of ca.
1 −1 cm−1 . The conductivities were found to increase with
increasing reduction time. A ceramic sheet sample heated in
hydrogen at 800 ◦ C was found to experience a weight loss of
0.1%, corresponding to a release of oxygen that would provide
3 × 1020 electrons cm−3 . Hall effect measurements showed a close
agreement between the numbers of carriers and those calculated
on the basis of the weight loss, indicating that all of the electrons
were electrically active.
Breckenridge and Hosler also published extensive work on the
electrical properties of rutile [97]. The effective electron mass was
found to be anomalously large, 30–100 times greater than that of
the free electron. These authors presented convincing arguments
that the source of electronic conductivity in rutile is Ti3+ , which
522 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 3.3. Schematic representation of the brookite structure (taken from Beltran
et al. [85]).
© 2006, American Chemical Society.
Fig. 3.4. Schematic representation of the crystallographic shear process to form
Magneli phases from rutile (taken from Marezio et al. [632]).
© 2000, Elsevier Science.
results from the loss of oxygen, which produces oxygen vacancies
Ov . It was proposed that these vacancies (valence +2) can have
0, 1 or 2 electrons associated with them, with distinct energies,
Fig. 3.5. Layered lepidocrocite-like protonic titanate: (a) schematic representation;
(b) AFM image (taken from Shibata et al. [633] and Sasaki [634], respectively).
© 2007, Royal Society of Chemistry; 2007, Ceramic Society of Japan.
the neutral (fully reduced) vacancy being the lowest, followed
by the singly reduced and finally the unreduced vacancy. The
observed optical absorption edge was proposed to correspond to
the transition between the valence band (based on O2− ) to the
neutral oxygen vacancy, which was considered to be a narrow
impurity band, with a high effective electron mass. The band at 3.67
eV above the valence band was proposed to be due to Ti4+ . The
observed temperature and oxygen partial pressure dependences
were fully explained by the equilibrium:
1
O2 − = O2 + O2v+ + 2e− . (3.1)
2
The electronic properties of rutile and anatase thin films were
studied by Tang et al. [98]. There were large differences in the
electronic conductivities of the two types of films after reduction
by heating in vacuum at either 400 or 450 ◦ C. The anatase films
became essentially metallic, with no change in conductivity with
temperature. The rutile films, in contrast, retained measurable
activation energies, 0.076 eV for 400 ◦ C and 0.06 eV for 450 ◦ C. The
difference in behavior was considered to be due to the following
properties for rutile: the average static dielectric constant of ca.
100, the effective electron mass of 20 m0 , and the donor state radius
of ca. 2.6 Å. Since the latter is similar to the distance between Ti4+
sites, there is little overlap between donor wave functions. Anatase
has the following properties: static dielectric coefficient of ca. 30,
and reduced effective mass of ca. 1 m0 , based on an estimated
donor state radius of ca. 15 Å. Based on optical absorption spectra,
the band-gap energies were estimated to be 3.0 eV for rutile and 3.2
eV for anatase. Forro et al. reported on the electronic properties of
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
high purity anatase single crystals and found an activation energy
for electronic conduction of 0.004 eV [99].
Recently, Hendry et al. pointed out the problem that the exact
nature of electron transport had not been solved, given the very
wide range of values of Hall mobilities (0.01–10 cm2 V−1 s−1 )
and polaron (electron + accompanying lattice distortion) effective
masses (8me –190me , where me is the free electron mass) [100].
Part of the problem might involve the presence or absence
of dopants, which were found to decrease the mobility. These
workers, using THz spectroscopy with undoped rutile single
crystals, based on Feynman’s analysis [101], found intermediate
size polarons and a mobility of ∼1 cm2 V−1 s−1 . Thus, they
concluded that, in TiO2 films such as those used in dye-sensitized
nanocrystalline solar cells, the main limiting factor might be
interparticle contacts. However, this assumes a zero dopant level,
which is unrealistic. Clearly, even now, further work needs to be
done to clarify this basic issue.
Other recent studies have also focused on the electronic
properties from the standpoint of the dye-sensitized solar cell
application (see, e.g., work of Aduda et al. [102]). For example, the
effect of the morphology of porous titania films on the electron
drift mobility was studied. Other studies have been focused on
the gas-sensing properties, e.g., for hydrogen gas [103–105]. In
nanostructured form, titania has very high sensitivity for H2 ,
increasing greatly in electronic conductivity in the presence of
low concentrations, for example, an increase of three orders
of magnitude upon introduction of 1000 ppm H2 [103]. The
mechanism proposed for the increased conductivity was thought
to involve the adsorption of hydrogen on the titania surface,
rather than incorporation into the bulk. The platinum electrodes
that were used to contact the surface in this study were also
possibly involved, acting to dissociate the H2 molecule, so that H
atoms could be produced and adsorbed more easily. The subject of
hydrogen interactions with titania has been well studied and will
be treated in more detail in Section 3.5.
3.3. Surface structure studies
It is quite difficult to separate work that has been carried out
on the surface structure of titania from work that has been carried
out on surface science in general and also on surface chemistry. The
latter two subjects will be taken up in the two sections that follow.
In this section, we will briefly treat the stoichiometric rutile and
anatase surfaces. A detailed treatment has been given as part of
Diebold’s extensive review on the surface science [106].
Diebold shows how rutile can be cleaved to produce the
commonly shown (110) surface, which is the most stable rutile
surface (see Fig. 3.6). Ramamoorthy et al. carried out theoretical
calculations on the rutile structure and found the (110) surface
to be the most stable, based on the fact that it has the least
dangling bonds [81]. The structure shown in Fig. 3.1a is that of
the unrelaxed bulk and is rather flat, but these authors predicted
that this structure should pucker slightly upon relaxation, with the
five-fold-coordinated Ti atoms depressed by 0.32 a.u. (0.169 Å),
and the bridging oxygens also depressed, by 0.15 a.u. (0.079 Å).
Vogtenhuber et al., using similar calculations, found that the five-
fold Ti atoms were depressed by 0.180 Å, the bridging O atoms
by 0.156, the planar O atoms by 0.115 Å and the six-fold Ti atoms
by 0.049 Å [107]. An experimental study that made use of surface
X-ray diffraction found that the five-coordinate Ti was depressed
by 0.16 Å, while the six-coordinate Ti was pushed out by 0.12 Å,
and the bridging O was depressed by 0.27 Å. A total of seven
theoretical studies were compared with the experimental surface
X-ray diffraction results in the review of Diebold [106]. Most of
these studies have agreed on the depression of the five-coordinate
Ti, on the pushing out of the six-coordinate Ti and the depression
523
Fig. 3.6. Schematic diagram of the cleavage of rutile along the (110) plane (taken
from Diebold [106]).
© 2003, Elsevier Science.
of the bridging O. However, a more recent experimental study that
used LEED found that the bridging O is pushed out by 0.12 Å, in
contrast to the earlier experimental study [108]. New theoretical
calculations were mostly in agreement with the LEED study, except
that the bridging O position was almost unchanged from the
unrelaxed structure [109].
The titania surface may undergo significant structural changes
when it is exposed to water. Onishi and co-workers have shown
that single crystal rutile surfaces that have been prepared by
standard methods used for UHV can actually erode and roughen
when exposed to an aqueous electrolyte [110]. Subsequently,
Nakato and co-workers reported on a method by which atomically
flat single crystal surfaces could be prepared that were stable in
aqueous electrolyte [111]; this method involved etching in 20% HF,
followed by air-annealing at 600 ◦ C.
The X-ray crystal truncation rod (CTR) technique has been
used by Zhang et al. to examine the rutile (110) surface in the
presence of pure water and of 1 molal RbOH aqueous solution
[112]. Interestingly, the five-coordinate Ti, which had been found
to be significantly depressed in UHV, was found to be depressed
to a much smaller degree in pure water (0.051 Å) and only slightly
depressed in 1 m Rb+ . This is because the terminal position, which
is empty in UHV, is occupied by a water molecule in aqueous
solution and by a hydroxide ion in the alkaline Rb+ solution. The
six-coordinate Ti, which had been found to be pushed out in UHV,
was found to be depressed to a small degree (0.002 Å in water and
0.019 in Rb+ solution). The bridging O, which had been previously
been observed to be depressed in the X-ray study and pushed out
in the LEED study, was found to be pushed out, by 0.004 Å in water
and 0.010 in Rb+ solution. All of the displacements were smaller
than those found in vacuum, which the authors propose to be due
the fact that either water molecules or Rb+ ions occupy positions
that would be occupied in the bulk lattice. Further conclusions
from this study will be discussed in Section 3.4, in which we treat
interactions of titania with water.
Other predictions from the Ramamoorthy work were in regard
to the relative stabilities of the other rutile single crystal surfaces.
The order of stability was found to be (110) > (100) >
(011) > (001). This calculation is strictly only valid for 0 K and
is for vacuum. Based on the results of the X-ray CTR study for
aqueous solution, this ordering might be modified slightly, since
the stabilities are based in part on the presence of dangling bonds,
which would of course not be present any longer in the presence
of water.
3.4. Surface chemical studies: Interactions with water
The interactions of titania surfaces with water have been stud-
ied extensively and have been reviewed [106,113]. The earlier
work involved conventional surface science methods. The studies
524 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

Fig. 3.7. High-resolution electron energy loss spectra of rutile (110) at various
dosages of water, starting from the clean surface at bottom (taken from Henderson
et al. [114]).
© 1996, Elsevier Science.

reported during the past five years on this subject have involved
both theoretical and experimental studies, the latter including a
large number of scanning tunneling microscopy studies. The inter-
actions with water are important to understand, because water,
either liquid or vapor, is almost always present in photocatalytic
reactions. These interactions are especially important for the later
discussion of the photo-induced hydrophilic effect.
Much of the work that has appeared over the past decade has
been targeted at the question of whether water is adsorbed molec-
ularly or dissociatively. Going back to one of the pioneering works
on this subject, Henderson reported a high-resolution electron en-
ergy loss spectroscopy (HREELS)-temperature-programmed des-
orption (TPD) study that concluded that the adsorption of water
on rutile (110) is molecular on the stoichiometric surface and dis-
sociative on the reduced surface, which is conventionally produced
by heat treatment, presumably forming oxygen defects [114]. The
progression of HREELS spectra as a function of water coverage is
shown in Fig. 3.7. In the background spectrum at the bottom, there
is a very small peak at 3690 cm−1 . This is due to the O–H stretch
for OH groups that are not hydrogen-bonded, often called ‘‘iso-
lated’’ OH groups. This vibrational frequency is close to that for
OH groups that stick out from the surface of liquid water, without
being hydrogen-bonded to any neighbors, as observed with sum-
frequency generation (SFG) spectroscopy [115]. At higher cover-
ages, the peaks that appear are shifted to lower wavenumbers,
indicating hydrogen bonding. There is no longer any evidence of
the high wavenumber peak, except at the highest coverage. There
is also a peak that appears at 1605 cm−1 , which is due to the H–O–H
bending mode of liquid water. Thus, it is certain that there are wa-
ter molecules adsorbed. However, it is not certain whether there
are also dissociated water molecules present that are hydrogen
bonded to neighboring water molecules or to bridging oxygens.
There is not much doubt that water dissociates at oxygen
vacancies that are produced by heating in vacuum [113]. The
Fig. 3.8. Schematic diagram of a mixed molecular water-dissociated water
monolayer on the rutile (110) surface (taken from Lindan [127]).
© 2003, American Institute of Physics.
main question is whether or not this is true for the non-reduced,
stoichiometric surface. Theoretical studies have been divided into
those that predict molecular adsorption [116–122], those that
predict dissociative adsorption [123–129], and those that also find
stability for mixed molecular-dissociative adsorption [122,125–
127]. This is a particularly difficult problem, since the energy
differences are rather small. One of the studies that has predicted
dissociative adsorption also predicts a mixed layer of molecular
and dissociated water at higher coverages [127]. Fig. 3.8 is a
schematic diagram taken from this paper that shows how the
mixed monolayer is arranged; the two structures both include
hydrogen bonding between a water molecule adsorbed at a five-
coordinate Ti site and an OH group adsorbed at an adjacent 5-
coordinate Ti site. There is also a weak interaction of the water
molecule with the bridging oxygen. For reference, the diagrams
for purely dissociative and purely molecular adsorption are shown.
Zhang and Lindan have also calculated a theoretical vibrational
spectrum, which we show along with one of the HREELS spectra
from Henderson’s work (Fig. 3.9). Even though the simulated
spectrum is significantly shifted upward in wavenumber, the two
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 3.9. (a) A HREELS spectrum for water adsorbed on rutile (111), taken from
Henderson [114]; (b), (c) and (d) show simulated vibrational spectra for the various
types of submonolayers and monolayers studied by Zhang and Lindan [127].
© 2003, American Institute of Physics.
peaks have an appearance that is similar to the experimental
spectrum. The strong peak at high wavenumber is due to an almost
completely non-hydrogen-bonded OH, presumably the terminal
hydroxyl group, and the weaker, lower wavenumber peak is due to
the OH group of the water molecule that is bonded to the hydroxyl
group.
This type of double-peak structure is rather commonly
observed in experimental infrared spectra for both rutile and
anatase powders (Fig. 3.10). The quite sharp peak or peaks at
high wavenumber are due to isolated OH groups, and the broader,
lower wavenumber peak or peaks are due to hydrogen-bonded OH
groups. In all of the spectra shown, there is some fine structure.
Although not certain, this could be due to the existence of different
crystal faces, with slightly different geometries for adsorption.
Thus, it appears likely that, at least on powders, with coverages
on the order of a monolayer, there could be mixed monolayers.
Certainly, there is molecular water, and there must also be
hydroxyl groups, with the OH group pointing up, normal to the
surface, so that there is little opportunity for hydrogen bonding.
However, for powders, there are, of course, a variety of crystal
faces exposed, and distinct situations might be found on each. This
is expected from the work of Henderson in a comparison of the
(110) and (100) surfaces [130]. The latter was found to support
dissociative, while the former was found to support molecular
adsorption.
Direct evidence for molecular adsorption on stoichiometric
rutile (110) can also be found in STM work that has been targeted
at interactions of water with oxygen vacancies. This general topic
will be discussed next.
The background of the work on the interaction of water with
oxygen vacancies on rutile (110) has been given by Henderson
525
Fig. 3.10. A series of three sets of infrared spectra for (a) anatase [635] and (b) [636],
(c) [637]) rutile powders acquired at various temperatures and water coverages. In
(a), the water coverage decreases with spectrum number, and in (b) and (c), with
spectrum letter. In (b) and (c), the original spectra were obtained in the transmission
mode; all spectra have also been replotted with increasing wavenumber. In (b), the
main peaks are listed.
© 1988, Royal Society of Chemistry; 1987, American Chemical Society; 1971, Royal
Society of Chemistry.
[113]. One of the interesting aspects is that Ti3+ sites by themselves
do not have special reactivity; for example, such sites on rutile
(100) and on Ti2 O3 are not reactive. Only on the (110) surface are
they reactive.
The background of the STM work has also been discussed
in the thorough reviews of Henderson [113] and Diebold [106].
For example, the latter discusses the problems of distinguishing
between oxygen vacancies and hydroxyl groups that have been
produced as a result of a water molecule reacting with an
oxygen vacancy. A number of authors concluded that the medium-
brightness spots that they observed in STM between bright rows
were due to oxygen vacancies. Diebold et al. pointed out that there
appeared to be two types of defects that were observable on rutile
(110), which they termed ‘‘A’’ and ‘‘B’’ [131]. Between the rows
of 5-coordinate Ti atoms, which appear bright due to their high
electron density, there are darker rows that are due to the bridging
oxygens. The ‘‘A’’ type were observed to be significantly brighter
than the ‘‘B’’ type and were proposed to be oxygen vacancies. The
A defects were removed by scanning the tip at a voltage of +3 V,
while the B type remained. The A-type defects were also found
to be quite mobile. Suzuki et al. subsequently reported similar
images and also found that the brighter spots were removable with
a scan at +3 V [132]. These authors found that the spots were also
removable by electron-stimulated desorption. They were also able
to produce additional spots by dosing with atomic hydrogen. Thus,
they proposed that the bright spots were due to hydroxyl groups
formed by hydrogen adsorption on bridging oxygens. Brookes et al.
also carried out STM measurements on rutile (110) and found that,
526 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

Fig. 3.11. STM images of rutile (110) showing (a) oxygen vacancies and (b) bridging hydroxyl groups (taken from Wendt et al. [129]).
© 2005, Elsevier Science.

when they purposefully dosed the surface with water, it adsorbed

without dissociation at 150 K and then dissociated at 290 K.
Significantly, no terminal features were observed, i.e., there was
no evidence for oxygens or hydroxyls adsorbed on 5-coordinate Ti
sites, which would have resulted if the water had dissociated on the
stoichiometric surface. Features were only observed on the dark,
bridging oxygen rows. Thus, the authors concluded that the water
had dissociated at oxygen vacancies.
Schaub et al. carried out further work and found that there
were two types of ‘‘A’’ defects, a smaller type and a larger, brighter
one [117]. The latter was assigned to an oxygen vacancy and the
former to a hydroxyl group, based on theoretical calculations.
These authors continued to support the idea of water being
dissociatively adsorbed only at oxygen vacancies, in line with
their theoretical calculations. In further work from this group,
however, the assignments were modified [129]. In this work, it was
recognized that the surfaces that had been examined earlier were
mostly hydroxylated. Special care was taken to achieve extremely
low levels of background water, and thus it became clear that the
darker features were the actual oxygen vacancies and the medium- Fig. 3.12. STM images of rutile (110) showing the dissociation of a water molecule
bright features were individual hydroxyl groups that had been at an oxygen vacancy (taken from [133]).
formed via water dissociation (Fig. 3.11). © 2006, American Physical Society.
Subsequent work showed even more clearly how a water
molecule moves along a row of 5-coordinate Ti sites and then to move, whereas the one that is produced at an adjacent bridging
reacts with a vacancy, first producing a pair of hydroxyl groups oxygen due to the addition of a proton, is quite mobile. This result
on neighboring bridging oxygens [133]. A second water molecule appears to be consistent with the report of Wendt et al., in which
can then further catalyze the splitting of the hydroxyl pair in it was shown that proton can jump several rows away [133].
an energetic reaction that can result in one of the protons The implication is that the electrons associated with the original
jumping several rows away. The initial water-dissociation process vacancy are rather localized. All the theoretical results have not
is shown in Fig. 3.12. Both the dissociation and splitting processes been in agreement with this picture.
are also available as movies [134,135]. This paper also corrects The work just described on the interactions of water with
the assignments that had been given in work focused on the vacancies on rutile (110) has a more general implication, in
interaction of oxygen (O2 ) with oxygen defects [136]. addition to the obvious one. Some of the studies that have been
A paper by Bikondoa et al. appeared in early 2006 [137], carried out over the years that have discussed reactions of oxygen
apparently written without the knowledge of the one by Wendt vacancies may have been actually dealing with bridging hydroxyl
et al., which appeared in 2005 [129]; this paper also clearly showed groups. Henderson had already pointed out this effect in 1996
the whole situation regarding previously published assignments [114].
by the various groups. These authors can be credited with having We note also the work of Mezhenny et al., which was focused on
recognized, from the beginning, the fact that the bright spots the question of whether or not UV light produces oxygen vacancies
that were being observed by various groups were in fact due to on the rutile (110) surface [139]. This work showed little effect
hydroxyl groups, either single or double, that had been formed via of ordinary intensity levels of UV light, i.e., similar to those that
water reaction at oxygen vacancies. are present in sunlight, in producing oxygen vacancies on the
Additional work has recently appeared on the STM observation surface. It is likely that this work might have also suffered from
of the reaction of water molecules with oxygen vacancies. Zhang unrecognized background levels of water, since they report STM
et al. reported that the two bridging OH groups that are produced images that are characterized by the brighter spots that have been
from the reaction are actually not identical [138]. The one that is assigned by later workers to bridging hydroxyls. Nevertheless, if
produced at the site of the original oxygen vacancy is not observed oxygen vacancies had indeed been produced, there would have
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582 527

been an increase in the number of such hydroxyls, whereas

no increase was observed. This result is in contrast to earlier
results obtained with second harmonic generation and X-ray
photoelectron spectroscopy that concluded that large numbers of
defects were in fact produced and were reactive toward dioxygen
[140]. These issues will be discussed at greater length in the next
section and in Section 4, which deals with the photo-induced
hydrophilic effect.
Work on the interaction of water with titania surfaces has also
been carried out with other techniques. For example, anatase pow-
der was examined with gas-chromatography–mass spectrometry
(GC–MS) and quantum chemical calculations. Experimental evi-
dence was found for water dissociation, which was consistent with
the theoretical calculations; the latter showed that the adsorption
is molecular on the anatase (101) surface and dissociative on the
(001) surface.
The previously mentioned X-ray CTR study of Zhang et al.
provides rather clear evidence for molecular adsorption for pure
water on the stoichiometric rutile (110) surface and dissociative
adsorption in alkaline aqueous solution (pH 12) [112].

3.5. Surface chemical studies: Interactions with dioxygen and other

species

It was realized in 1998 that dioxygen does not only react with
oxygen vacancies (or possibly, as discussed above, bridging hy-
droxyls) to produce a near-stoichiometric surface at temperatures
above 600 K, but also, at temperatures below 600 K, it can leave be-
hind an oxygen atom adsorbed at a 5-coordinate Ti site [141]. This
realization led to doubts concerning previously published work
that had found dissociative water adsorption at rutile (110). It also
led to a reassessment of what had been an accepted procedure for
the preparation of high quality, clean surfaces. The scheme that
Epling et al. proposed to explain the interactions of O2 with oxygen
vacancies and subsequent reaction with water is shown in Fig. 3.13.
In the same paper, these authors also found evidence to support a
similar end product that resulted when water was present initially,
so that bridging hydroxyls had already been formed.
Henderson et al. reported later that O2 can adsorb at a reduced,
i.e., vacancy-containing, rutile (110) surface without dissociation
at temperatures below 150 K [142]. One of the more interesting
aspects was the observation that O2 can adsorb, probably as O•− 2 ,
at a ratio of up to three molecules per oxygen vacancy, which
necessarily means that it does not have to interact directly with
the vacancy but can reside on an adjacent cation site. Another
paper from the same group appeared more recently exploring the
reaction of O2 with bridging hydroxyl groups in more detail [143].
These authors conclude that the role played by O2 in photocatalysis
involves specifically this reaction. They also found, in agreement
with their earlier work, that a second monolayer of water blocks
the access of O2 to the bridging OH groups, effectively impeding the
electron transfer. On the basis of these results and other studies in
which superoxide was generated both on thermally reduced titania
and on UV-illuminated titania, the authors proposed that bridging
hydroxyls are a key intermediate in the photocatalytic process.
We agree with this proposal and also propose (see later) that such
bridging hydroxyls can be generated electrochemically.
The effect of gas-phase O2 on nanocrystalline titania films has
been studied in terms of the gas-sensing application [144]. It
was found that the film conductivity decreased in the presence
of O2 . This effect could also be related to the effect discussed
above but is more likely to involve the scavenging of bulk trapped
electrons, as discussed in the next section. The authors also
observed photo-induced adsorption of O2 , a phenomenon that had
been described by Kennedy et al. in 1958, as mentioned in the
historical overview [40].
Fig. 3.13. Schematic diagram of an O2 molecule reacting at an oxygen vacancy on
rutile (110) and dissociating, with further reaction with a water molecule (taken
from Epling et al. [141]).
© 1998, Elsevier Science.
We include here a brief mention of surface photochemical
reactions involving O2 . The work of Thompson and Yates has
employed the photodesorption of O2 as a means of monitoring
the arrival of photogenerated holes to the surface of a rutile single
crystal with exposed (110) face [145]. This process is essentially
the reverse of the photo-adsorption process just alluded to, which
requires a trapped electron, creating a partially or fully reduced
O2 , i.e., O•−
2 . The presence of methanol as a hole trapping agent
significantly decreased the photodesorption. In further work by the
same authors, they proposed a fractal rate law to fit the observed
kinetics of the reaction of trapped electrons with trapped holes
[146]. It was assumed that the electrons were associated with
oxygen vacancies, but this picture may be in some doubt, based on
the ability of trace water to convert these to bridging hydroxyls.
3.6. Bulk chemistry—Hydrogen
In this section, we briefly review the literature on the
bulk chemistry of titania. This subject is mostly limited to the
incorporation of elemental hydrogen. It also can include the
incorporation of lithium or sodium, but this is beyond the present
scope. The subject of hydrogen incorporation can also include
electrochemically-induced processes; these will be treated in the
next section. The characteristics of hydrogen as a bulk impurity
in titania are central to the understanding of its electrical,
electrochemical and photoelectrochemical behavior, which is, in
turn central to the understanding of the photocatalytic behavior.
An early paper on the optical and infrared absorption spectra
of rutile single crystals by Soffer showed evidence for the
incorporation of H, already present in the as-received crystal,
528 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 3.14. (a) H binding site within the rutile structure and (b) proposed diffusion path within the solid structure, along a c-channel (taken from Bates and Perkins [154]).
© 1979, American Physical Society.
and D, which was introduced by heating at 900 ◦ C in D2 ; these
were evidenced by the appearance of IR bands at 3277 (main)
and 3322 cm−1 due to an O–H stretch and at 2442 cm−1 for the
corresponding O–D stretch [147]. The author remarked that the
bands are unusually narrow for a solid-state O–H stretch and also
discussed the possibility of a hydrogen-bonding-related shift.
Prior to the work of Hill in 1968 [148], a number of different
studies had suggested that non-stoichiometry in rutile TiO2
was associated with increased electrical conductivity, but the
mechanism was not clear. It had also been suggested that hydrogen
acts as a dopant in rutile. In Hill’s work, heating rutile crystals
in hydrogen below 600 ◦ C led to increases in the bulk hydrogen
concentration, measured by IR. Heating above 650 ◦ C in vacuum
led to decreases in hydrogen concentration, coupled with oxygen
loss to produce water. This led to increased conductivity, probably
due to the formation of faults involving Magneli phases. For the
heated crystals, the electrical behavior was modeled involving
a series network of two parallel RC circuits, with one being
associated with an ‘‘exhaustion layer’’, i.e. either a depletion layer
or layer that is very low in carriers, as discussed in the next section.
Johnson et al. reported further detailed work on the optical and
infrared spectra for H and D incorporated in rutile single crystals
[149]. This paper referred to the earlier work of von Hippel et al.
that provided presumably more accurate values for the absorption
maxima: 3276 and 3317 cm−1 for O–H and 2435 and 2463 cm−1
for O–D. That paper had proposed that the peak splitting was due
to slightly differing O–Ti distances. Johnson et al., however, denied
this possibility due to the symmetry of the structure. H and D
doping was carried out by heating in an atmosphere of H2 O or
D2 O, plus O2 at 850 ◦ C, or in some cases, H2 or D2 below 550 ◦ C.
Conduction-band electrons produced a broad absorption band at
1.5 µm. This was remarked to not be due to conventional free
electron behavior, which should produce no peak. These authors
carried out a detailed analysis of the various possible binding
sites for H or D within the crystal. The same group reported the
use of the IR absorption band in the precise determination of H
and D concentrations in rutile [150]. DeFord and Johnson studied
the H/rutile system in detail from the viewpoint of theoretical
semiconductor and thermodynamic properties [151]. Later, they
made measurements of H and D diffusion using the isotope
exchange technique in order to avoid internal electric fields [152].
The diffusion was carried out simply by heating the samples in the
appropriate atmosphere (see above) for various times and then
measuring the H or D concentrations via the IR absorption. The
diffusion coefficients for H varied from ca. 3 × 10−8 cm2 s−1 at
350 ◦ C to ca. 1.7 × 10−6 cm2 s−1 at 700 ◦ C along the c-axis,
compared with 8 × 10−8 cm2 s−1 at 698 ◦ C along the a-axis. The
diffusion coefficient estimated for room temperature was 1.8 ×
10−13 cm2 s−1 , which was in reasonable agreement with the value
very roughly estimated by Chester and Bradhurst, in the range
10−11 –10−13 cm2 s−1 , based on electrochemical insertion.
Bates and Perkins measured the infrared frequencies for H, D
and T in rutile TiO2 and carried out a detailed structural analysis,
comparing the results with theory for anharmonic oscillators and
also with that of hydrogen bonding [153]. The agreement with the
latter was poor. Bates et al. later published a much more detailed
study, including a review of the literature up to 1979 [154]. They
carried out a detailed analysis of the mechanism of diffusion of H in
rutile. The binding site within the lattice for the proton is shown in
Fig. 3.14a, and the proposed path for diffusion in Fig. 3.14b. The
binding site was later confirmed by Klauer and Wöhlecke using
polarized Raman [155]. The understanding of this system achieved
in this work is excellent. It was concluded that the wavenumber
shift of the IR absorption was not due to hydrogen bonding, which
is consistent with the observed sharpness of the band. Instead, it
was proposed to be due to the electrostatic environment within
the lattice (however, see below). Further work was also published
on tritium diffusion [156].
Peacock and Robertson have carried out quantum chemical
calculations for H in a variety of oxides that are considered as
high dielectric constant oxide gate materials [157,158]. They find
that the H0 energy level lies above the conduction band in ZnO,
TiO2 and SrTiO3 , consistent with the fact that H is a shallow
donor in all the three. Work of Park et al. also confirmed these
results for rutile [159]. Koudriachova et al. have also carried out a
recent ab initio quantum chemical calculation on H incorporation
in rutile [160]. These authors sought to recheck the binding site,
due to the difficulty already mentioned, i.e., the O–H–O bond
distances were not consistent with established rules relating them
to vibrational frequencies. The new calculation found a distortion
in the cage surrounding the H atom such that the distances
became highly consistent with the correlation. They found that
the H atoms are most favorably located at ordered positions, as
shown in Fig. 3.15a. The lattice expands linearly with increasing
H incorporation (Fig. 3.15b).
It is also appropriate to mention here theoretical calculations
that were carried out on the surface adsorption of hydrogen as
H2 [161]. In that work, it was found that up to one monolayer is
adsorbed, with all of the bridging oxygens becoming hydroxylated
and the underlying Ti4+ ions being reduced to Ti3+ . We might note
that this type of surface could in principle be produced thermally
by removing half of the bridging oxygens, followed by exposure to
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 3.15. (a) Illustration of a high stability ordered arrangement of interstitial
hydrogen atoms in the rutile structure, with stoichiometry H1/4 TiO2 (taken from
Koudriachova et al. [160]). (b) Plot of lattice volume for various numbers of
interstitial H (open circles) and Li atoms (filled circles) (taken from Koudriachova
et al. [160]).
© 1994, American Physical Society.
water. It could also be produced in principle electrochemically (see
Section 3.7).
It has been found that titania nanotubes respond to the
presence of hydrogen in the gas phase, as already discussed in
the section on electronic properties. In that work, it was not
considered that hydrogen could actually be absorbed. However,
work of Lim et al. showed that for nanotubes that were prepared
hydrothermally, there was a reversible uptake of ca. 2% [162]. The
incorporation led to an increase in the IR absorption (3427 cm−1 ),
which is significantly higher than that for single crystal rutile. Only
75% of the uptake was reversible at room temperature with the
remaining 25% requiring temperatures up to 130 ◦ C to desorb.
A relatively detailed study has been carried out on small
rutile crystals by the use of optical and IR absorption and Raman
scattering [163]. The effect of neutron irradiation was also studied.
The incorporation of H in minerals is of interest to geologists,
because it affects the macroscopic properties and can be a way
by which water is incorporated in minerals that normally do not
absorb water.
529
Panayotov and Yates recently reported on experiments in
which they reduced titania pellet samples (Degussa P25) with
a source of H atoms [164]. They were able to observe the
broad, featureless background visible-IR spectrum expected for
conduction-band electrons. In addition, there were increases in
electronic conductivity. However, there was no discernable IR
absorption at ca. 3280 cm−1 for the internally bound O–H stretch
already discussed above. The activation energy for the diffusion of
H into the solid was estimated to be 0.09 eV.
3.7. Electrochemical properties
The intrinsic electrochemistry of TiO2 has been studied
continuously for a long period, since the first report of Boddy in
1968 on the oxygen evolution reaction [165]. This work made use
of single crystal rutile electrodes. Interestingly, this work contains
a figure in which the photocurrent vs. potential behavior is given,
one year prior to the reports of one of the present authors [50,166].
This will be discussed further, in the next section.
Many aspects of the behavior of TiO2 can be explained on the
basis of a semiconductor model, as already discussed. One of the
ways of characterizing a semiconductor is to measure its flat-band
potential electrochemically, for example, with capacitance. In our
original work reported in 1969, we described such measurements
and concluded that the flat-band potential EFB for rutile (001) is
pH-dependent, with a relationship similar to the following [167]:
TiO(O) + H+ + e− = TiO(OH) (3.2)
with the resulting Nernst relationship:
F
EFB = 0.00 + ln[H+ ] = −0.0591pH at 25 ◦ C. (3.3)
RT
This result has essentially been confirmed by subsequent workers,
with the value at pH 0 being +0.01 ± 0.05 V vs. SHE for rutile
(001) [169,171,175]. The pH dependence is typical of the behavior
of most oxide semiconductors and has generally been considered
to be due to a surface acid–base equilibrium for these oxides. The
value for anatase is more negative: −0.20 V vs. SHE [168].
There has been a certain amount of discussion devoted to the
question of exactly how the capacitance measurements should be
conducted and how the results should be interpreted, even for
single crystals. This discussion is interesting, because it displays
the convergence of an ideal, simple theoretical model with a real,
non-ideal complicated material. The model, already discussed,
involves an ideal semiconductor with a space charge region whose
thickness is dependent upon the potential difference between the
Fermi level, to which we can assign an electrochemical equivalent
EFL and the conduction-band-edge energy, again given on the
electrochemical scale, ECB . The energy difference ξ between ECB and
EFL deep within the bulk of the material is dependent upon the
carrier concentration. The space charge capacitance CSC based on
this simple model is given by
1 2(E − EFB )
= (3.4)
2
CSC εε0 eND
where ND is the bulk concentration of donors, with the conse-
quence that a plot (Mott–Schottky) of C −2 vs. potential yields the
carrier concentration from the slope and the flat-band potential
from the intercept with the potential axis. Many workers have
found that these plots are either non-linear or that the intercept
gives a result that is not reasonable, for example, more negative
than that given in Eq. (3.3). Such results have been explained in
various ways, including (1) non-uniform depth profile of carriers
and (2) deep trap levels. There appears to be some consensus on
the merits of the first explanation.
530 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 3.16. Mott–Schottky plots for a rutile (001) surface in pH 4.7 buffer: (a) raw
data for a more lightly doped sample (circles), with a solid line showing the fit
to Eq. (3.5) (including both space charge CSC and passive layer CPL contributions);
(b) calculated intrinsic CSC behavior, after removing the effect of CPL ; (c) raw data
for a more heavily doped sample (squares), with a solid line showing the fit to
Eq. (3.5); (d) calculated intrinsic CSC behavior, after removing the effect of CPL . SCE
refers to the saturated calomel electrode, which is 0.241 V vs. the standard hydrogen
electrode (SHE) (based on [167]).
A model that can explain the appearance of a steep slope near
the intercept and a shallower slope at more positive potentials
is that of a thin layer near the surface that has a lower carrier
concentration. This model is reasonable, because, as has been
reported often, the effect can arise as a result of oxidizing etching
treatments, which could remove electrons from such a surface
layer, especially if the treatment is conducted for a relatively
short time. In this case, the overall capacitance behaves as if
there is a smaller, potential-independent capacitance due to the
passive layer CPL , in series with the potential-dependent space
charge capacitance. The slope of the upper portion of the curve
is somewhat increased from that which is characteristic of the
carrier concentration in the bulk of the material, and the intercept
is shifted to the negative. The overall behavior is described by
1/2 
2(E − EFB ) 2(E − EFB )
   
1 1 1
= + + (3.5)
2
CTOT εε0 eND εε0 eND CPL 2
CPL
which is derived by substituting
1 1 1 capacitance, the slope should be 1.0, while, for a pure resistance,
= + (3.6)
CTOT CSC CPL
into Eq. (3.4). In our original paper, we reported curves with this
type of double slope (see Fig. 3.16) and made a mathematical
correction of this type in order to estimate the true flat-band
potential [167]. Our explanation at that time invoked a Helmholtz
layer capacitance, which was later correctly disputed by Dutoit
et al. [169]. Based on our nitric acid etching procedure used
in that work, however, it is quite reasonable to invoke the
passive layer model just described. DeGryse et al. also found fault
with the involvement of the Helmholtz layer and proposed an
inhomogeneous carrier concentration [170]. Tomkiewicz proposed
a model based on surface states with energies in the middle of
the band-gap [171]; this model was criticized by Ullman, who
proposed a surface passive layer [172].
It should be noted that this same model has been discussed by
Schoonman et al. [173], but the equation given in that paper was
different, in that the cross-term was not included, leading to the
erroneous result that the curve is simply raised but has the same
slope. If the Mott–Schottky behavior does not fit this simple model,
it is still possible that it can be fitted with a more complicated
model, in which the slope at any given point in the curve can
be related to the carrier concentration at a certain depth; thus a
complete concentration profile can be estimated [174].
Finklea has given an excellent summary of the practical
methods of obtaining linear Mott–Schottky plots with correct
intercepts [175]. The opposite situation can also arise if a surface
layer exists with a higher concentration of carriers compared to
the bulk. This leads to a shallow slope near the flat-band potential,
followed by a steeper slope at more positive potentials.
In certain cases, if the carrier concentration is sufficiently
high, the space charge capacitance can approach that of the
electrical double layer, and the Helmholtz capacitance must also
be considered.
It can be argued in general that the behavior of TiO2 is simply
not ideal, and, in each individual case, a full impedance treatment
is necessary to extract the space charge capacitance or even to
evaluate whether or not it exists. Similar situations also exist for
oxide films; the situation is particularly complicated for oxide films
grown on metals, for example, iron and zirconium [176].
For certain types of TiO2 electrodes, it may be doubtful that the
behavior can be strictly described with a semiconductor model.
For example, the Mott–Schottky plots may exhibit a significant
frequency dispersion, either with or without non-linearities. This
can signal the fact that a different type of model might be
more appropriate. In most cases, it is advisable to examine the
full impedance spectrum over a range of potentials in order
to determine whether or not the behavior does in fact follow
that expected for a semiconductor. One specific type of behavior
that has been observed is that of an electrochromic film, in
which all of the charge injected into the film is associated with
increased absorption of visible light (see Refs. [177–181] and later
discussion).
The electrochemical impedance spectral (EIS) behavior can
be quite powerful in elucidating the behavior of electroactive
materials, i.e., those that can undergo electron transfer reactions
within pores and even within the solid material itself. Nogami
examined the EIS behavior of several single crystal rutile samples
and obtained sets of straight lines, with varying slopes in Bode
amplitude (log |Z | vs. log frequency) plots [182]. He explained
this behavior on the basis of a disordered layer on the surface
of the single crystal. The Bode plots show straight lines for the
logarithm of the magnitude of the impedance (absolute value of the
complex impedance) vs. the logarithm of the frequency. At more
positive potentials, the slopes of the lines are close to 0.7, while,
at more negative potentials, the slopes are close to 0.5. For a pure
it should be 0.0. For intermediate cases, there are both resistance
and capacitance distributed through the material. The simplest
electrical case is that of the uniform semi-infinite transmission
line, in which there is a ‘‘ladder’’ of constant resistances and
capacitances (Ref. [183] and references therein). This type of
behavior has been shown to be followed by a porous medium
with cylindrical pores. A rate-limiting diffusion process in which an
electroactive species diffuses through a uniform medium behaves
electrically in the same way, and thus there is some ambiguity as to
which process is actually operating. In either case, the slope should
be 0.5, as observed by Nogami for more negative potentials.
For the general case, in which the slope of the Bode plot can
have an arbitrary value between 0.5 and 1, the same type of
RC ladder is also valid, and the physical picture is also similar
to that for the uniform network, but with pores that are non-
cylindrical. For example, Wang and Bates have shown that horn-
shaped pores can give rise to Bode slopes in this range [184]. Thus,
the results of Nogami could be explained by a situation in which
horn-shaped pores of larger diameter (lower roughness factor)
exist at higher potentials; at intermediate potentials, the diameters
become smaller (higher roughness factor); finally, at the most
negative potentials, the pores behave as if they are cylindrical and
longer than the penetration length of even the lowest frequencies
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 3.17. Electrochemical impedance spectrum for a nanocrystalline anatase film on a conductive support: (upper left) experimental results from Cao et al. [187]; (upper
right, lower right) simulated log of the impedance amplitude vs. log frequency and phase angle vs. log frequency, respectively.
© 1995, American Chemical Society.
measured. It should be noted that impedances with arbitrary
slopes are often referred to as constant phase elements, meaning
simply that the phase angle, which is 0◦ for a pure resistance, 90◦
for a pure capacitance and 45◦ for the uniform transmission line, is
constant but is not one of these standard ones. In any case, it seems
clear that Nogami’s conclusion, i.e., that the frequency dispersion of
the Mott–Schottky plots is due to the presence of a disordered layer
on the single crystal surface, might be valid. Frequency dispersion
is a result of the mixing of resistive (i.e., electronically conducting)
character with capacitive (i.e., ionically conducting) character.
Furthermore, his proposal that the behavior involves surface
states might also be valid. Wang also has shown that constant-
phase angles between 90◦ and 45◦ can be obtained if the
resistances and capacitances in the ladder are non-uniform,
e.g., with the resistance increasing and the capacitance decreasing
in a logarithmic manner [183]. Even a 45◦ angle can result with
a non-uniform situation. A non-linear gradient of resistance and
capacitance could well result if there is a similar gradient of
concentration of Ti3+ sites within the film. Cahan and Chen have
discussed such gradients in the passive oxide film on iron. They
have also pointed out that these gradients can naturally give rise
to linear log current vs. potential behavior (linear Tafel slope; see
below) that mimics that for rate-limiting electron transfer [185,
186].
Cao et al. have reported impedance results for a nanocrystalline
anatase TiO2 film at a single, intermediate potential (0.24 V vs. SHE)
[187]. In this case, the Bode plot exhibited three regions: capacitive
behavior at high frequency, diffusive behavior at intermediate fre-
quencies, and capacitive behavior at lower frequencies (Fig. 3.17).
This behavior can be simulated approximately by the equivalent
circuit shown, with the resulting Bode plot shown on the right.
Here, we have not attempted a perfect fit, which would have re-
quired the introduction of constant-phase elements to simulate
the non-ideal capacitive behavior, which results in phase angles
considerably below 90◦ . The similar shape of the calculated plot
531
compared to the experimental result shows that there is some va-
lidity for this model. The higher frequency capacitive behavior,
with a capacitance of ca. 10 µF cm−2 , is typical for the flat surface
of the film. The lower frequency capacitance (ca. 25 µF cm−2 ) is
proposed to involve a bulk reduction of Ti4+ to Ti3+ , as discussed
below. The diffusion-like process might involve either actual diffu-
sion in pores or combined gradients of resistance and capacitance,
or even a combination.
Muñoz et al. studied the impedance behavior of titania
nanotube arrays using EIS and also found behavior with similar
aspects [188]. The nanotubes were prepared via anodic oxidation
of Ti metal; the titania produced in this way is amorphous
and can be converted to anatase with heat treatment. The
impedance of both forms was measured. For the amorphous films
at intermediate potential (0.0 V vs. Hg/Hg2 SO4 ), there were two
capacitive regions, as in the work described above, with a transition
region at intermediate frequencies that could be attributed to a
Warburg impedance. At higher potential (+1.0 V), the impedance
was almost purely capacitive, and, at lower potential (−0.5 V),
it was capacitive at lower frequencies, with a relatively low
impedance (higher capacitance) and predominantly resistive at
higher frequencies. The capacitive components are discussed in
terms of a space charge capacitance due to the oxide film at the
base of the nanotubes, the film being in contact with the metal,
and a Helmholtz (double layer) capacitance of the pore walls.
Interestingly, for the annealed compact film, without nanotubes,
the impedance also exhibited two distinct capacitive regions, just
as found by Cao et al., with little dependence upon potential. In
contrast, after annealing, the spectra for the nanotube films were
almost entirely capacitive, with a single component.
This general behavior is similar to that for other oxides of
transition metals of the early transition series, e.g., MoO3 and
WO3 . Our own work with amorphous WO3 films clearly showed
frequency regions in which the behavior was more capacitive
and regions in which it was more diffusive [189,190]. There
532 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

even appeared to be two types of diffusion, which we attributed

to diffusion in pores and diffusion within particles. In recent
work on MoO3 films, impedance results also showed diffusive
behavior at intermediate frequencies and capacitive behavior at
lower frequencies; the latter was attributed to an electrochemical
reduction process [191]. With impedance, in which the potential
variation is usually only a few millivolts, an electrochemical
process can behave exactly like a capacitance and is often termed
as pseudocapacitance.
The use of impedance measurements can clearly yield much
information about TiO2 photocatalytic films. It is clear from a
comparison of the reported impedance results that more work
is needed in order to fully elucidate the physical significance.
Further studies could establish the relationships between the film
nanostructure and the electrochemical behavior.
The electrochemical behavior of TiO2 in the more negative
region has been studied by several groups with the more
commonly used cyclic voltammetric (CV) technique, on single
crystal rutile [192], single crystal anatase [168] and nanocrystalline
anatase [187,193]. In all cases, there is a distinctive feature that
involves a cathodic voltammetric peak (reduction reaction) as
the potential is swept negatively, followed by an anodic peak
Fig. 3.18. Compendium of Tafel plots for oxygen reduction at various types of TiO2
(anodic reaction) as the potential is swept back in the positive
electrodes, with curves at the left in alkaline solution (pH 13 or 14) and curves at the
direction. Similar voltammetric features have been obtained for right for acid solution (pH 0): (a) anodized Ti in 1 M NaOH (O2 ) [203]; (b) anodized
lithium ion-containing non-aqueous electrolytes and thus have Ti in 0.05 M H2 SO4 (O2 ) [203]; (c) rutile (001) in 1 M KOH (air) [192]; (d) rutile (001)
been attributed to the intercalation of lithium [194,195]: in 1 M NaOH (air) [204]; (e) anatase film in 0.1 M NaOH (O2 ) [206]; (f) rutile (001) in
0.1 M NaOH (O2 ) [206]; (g) anatase (001) in 0.1 M NaOH (O2 ) [206]; (h) rutile (001)
TiO2 + xLi+ + xe− → Lix TiO2 . (3.7) in 1 M NaOH (O2 ) [205]. In cases in which air was used (curves c and d), the curves
have been multiplied by a factor of 5 to make them more directly comparable with
The proton counterpart has the same form and has been argued to those in which pure O2 was used.
also involve intercalation (see below):
H0 = −8 to H− = +23, i.e., 31 log units of proton activity
TiO2 + xH+ + xe− → Hx TiO2 . (3.8) or pH. Quartz crystal microbalance (QCMB) measurements were
The latter reaction has been associated with the filling of electron also carried out from H0 = −6 to pH = 12. In fact, the QCMB
trap sites, with an elevation of the Fermi level. These changes can measurements were consistent with the mass corresponding to the
be followed spectroscopically, by an increase in the absorption of uptake of a proton, or to a deuteron in the case of D2 O solution. It
light in the wavelength region from 380 to 600 nm. However, there was argued that only intercalation (Eq. (3.8)), rather than surface
has been some controversy involved with this idea. Some workers protonation–deprotonation (Eq. (3.2)) can account for the variation
conclude that the coloring of TiO2 films occurs as a result of the of ECB with proton activity and mass changes.
filling of the conduction band, with the absorption of light exciting The electrochemical insertion of protons was used later by
electrons from lower to higher energy levels within the CB. This Pelouchova et al. as a means of controlling the doping level
is a more physical view, which has been advanced by Fitzmaurice of anatase single crystals and the electrochemical behavior of
and others [196–201]. Other workers have concluded that the the electrode in the presence of a redox couple, in this case,
coloring process does indeed involve reaction (3.8) and that the methylviologen [180]. Specifically, the electrochemical doping
absorption of light involves electronic transitions associated with increased the rate of electron transfer to the oxidized form of the
the Ti3+ ion. This is a more chemical view, which has been methylviologen. There have been no other results reported thus far
advanced by Meyer and co-workers [187]. It has been difficult for other redox couples, but similar results could be expected.
to conclude which is correct, because the absorption spectrum The behavior of the oxygen reduction reaction (ORR) on TiO2
includes aspects that can be explained in both ways. Specifically, electrodes as a dark reaction has been examined by several groups
if the electrons are not trapped at specific sites, the absorption over the past 30 years: Clechet et al. used an anodized Ti electrode
should exhibit a steadily increasing absorbance with increasing and made measurements in both acid and alkaline solutions [203];
wavelength, as was observed by Panayotov and Yates, as discussed Parkinson et al. [192], Kesselman et al. [204], Tafalla and Salvador
earlier [164]. This is because there are many, closely spaced energy [205], and Tsujiko et al. [206] all used rutile single crystal (001)
levels that are available, with the probability being larger to absorb electrodes, and Tsujiko et al. also made measurements with an
a smaller amount of energy. If, on the other hand, the electrons anatase (001) single crystal [206]. Most of these studies used
alkaline solution but also examined the behavior at other pH
are trapped at specific, relatively well-defined sites, there should
values. In Fig. 3.18, all curves except one (b) are shown for alkaline
be specific, widely spaced energy levels, which would lead to
solution, either pH 13 or 14, while curve b is for pH 0.
absorbance peaks. Cao et al. argue that, since there is a broad peak
Clechet measured oxygen reduction of anodized Ti in both
in the absorbance at ca. 1000 nm, which corresponds to a specific
acidic and basic solutions and found a large difference in the
absorption process for Ti3+ , the electrons are essentially trapped at
behavior [203] (Fig. 3.18, curves a and b). The most striking
these sites [187].
difference is the large difference in the slope. In basic solution, the
In situ reflectance measurements have been used by Lyon
inverse of the slope (known as the Tafel slope) is quite close to that
and Hupp to follow the variation of the conduction-band energy
expected for a one-electron transfer as the rate-determining step
ECB with pH over an extremely wide range for nanocrystalline
(rds), i.e.,
anatase films [202]. They used solutions with standard Hammett
acidity functions H0 and H− , from H0 = −10 to H− = +27. dE (ln 10)RT
These workers found that Nernstian behavior was observed from = = 0.1183 V decade-1 (3.9)
d log i α nF
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582 533

Table 3.1
Exchange current densities (log i0 , A cm−2 ) and Tafel slopes (V decade−1 ) for the reduction of O2 to O•−
2 at various types of TiO2 electrodes.

Electrode type log i0 , A cm−2 Slope, V dec−1 Reference

Anodized Ti in 1 M NaOH (O2 ) −5.2 0.12 Clechet et al. [203]

Anodized Ti in 0.05 M H2 SO4 (O2 ) −3.4 0.40 Clechet et al. [203]
Rutile (001) in 1 M KOH (air) −5.7 0.12 Parkinson et al. [192]; currents were multiplied by a factor of 5.
Rutile (001) in 1 M NaOH (air) −10.2 0.06 Kesselman et al. [204]; currents were multiplied by a factor of 5.
Anatase film in 0.1 M NaOH (O2 ) −5.2 0.12 Tsujiko et al. [206]
Rutile (001) in 0.1 M NaOH (O2 ) −9.3 0.12 Tsujiko et al. [206]
Anatase (001) in 0.1 M NaOH (O2 ) −8.0 0.06 Tsujiko et al. [206]
Rutile (001) in 1 M NaOH (O2 ) −8.4 0.10 Tafalla et al. [205]

where i is the current density in A cm−2 , E is the potential,

α is the transmission coefficient (usually 0.5), F is the Faraday
constant (96 485 C mol−1 ), R is the gas constant (8.314 J K−1 mol−1 ,
and T is the absolute temperature. This slope is consistent with
the rds being superoxide production (Eq. (2.11)). The standard
potential for this reaction has been reported as −0.284 V vs. SHE
[207], as shown at the bottom of the figure. In contrast, the slope
for acid solution is approximately 0.40 V decade−1 . There is no
simple interpretation for slopes larger than 0.118 V decade−1 ; one
possibility is that there is a thin passive surface layer, which would
lead to an effective transmission coefficient less than 0.5, in this
case, 0.148. Tsujiko et al. have discussed this dramatic difference in
behavior between acid and base and have concluded that, in basic
solution, there is an adsorption of O2 on the negatively charged
TiO2 surface [206], whereas adsorption does not take place in acid,
due to the protonation of the surface at pH lower than the potential
of zero charge.
Tafalla and Salvador proposed that the ORR on rutile takes place
with the involvement of surface states in a manner similar to
that proposed by Vandenmolden et al. for outer-sphere electron
transfer to various metal complexes [205]. The model states that
the first step is the relatively fast production of surface states,
assumed for the moment to be essentially Ti3+ in nature, in an Fig. 3.19. Comparison of Tafel plots for oxygen reduction on rutile (001) at various
electrochemical step, written here as an equilibrium: pH values: (a) pH 14 [204]; (b) pH 10.3 [204]; (c) pH 7.2 [204]; (d) pH 13 [206];
(e) pH 11.1 [206]; (f) pH 14 [205]; (g) pH 3 [205]. Curves a, b and c, measured in
air, were multiplied by 5 to make them more directly comparable with the other
Ti4+ + e− ↔ Ti3+ (3.10) curves, which were measured in pure O2 .
followed by a rate-determining step that is a purely chemical
reaction with oxygen: current densities, which are given in Table 3.1. Based on these
data, one is impressed by the wide variation in the results for
O2 + Ti3+ → O•−
2 + Ti
4+
. (3.11) similar surfaces (rutile (001)) on the one hand and the similarity
of the results for seemingly different surfaces, e.g., rutile (001) and
This model should result in a Tafel slope of 0.06 V decade−1 ,
anodized Ti.
however, not 0.12 V decade−1 , as observed experimentally. The
In comparing results for rutile (001) in various pH solutions
0.06 V decade−1 slope results from the fact that since the
from different groups, we see the variations even more graphically
electron transfer step is sufficiently fast to be considered to be in
(Fig. 3.19). Curves a, b and c show a regular positive shift in
equilibrium, its potential dependence is described by the Nernst
potential with decreasing pH [204], all with similar slopes, which
equation:
again can be approximately fitted to the standard 118 mV slope.
E = E0 − (RT /F )(ln([Ti3+ ]/[Ti4+ ])). (3.12) Curves f and g, from a different group (Tafalla and Salvador [205])
also show a positive shift in going from pH 14 to pH 3, but the
The fact that the electron transfer occurs at potentials that are as shift in comparing curve g for pH 3 with curve c for pH 7.2
much as 0.4 V positive of the flat-band potential is not consistent is unexpectedly small. The behavior obtained by Tsujiko et al.
with purely semiconducting behavior. Instead, it can be reasonably recently shows much different behavior: in going from pH 13 to pH
proposed that the electrode is sufficiently highly doped so that it 11.1, there is actually a negative potential shift. One must believe
behaves like a metal, and the band-edge energies become mobile that the surface preparation in the more recent work is superior,
or ‘‘unpinned’’. given the access to advanced surface characterization techniques.
However, curve b, for pH 0, follows a much shallower slope, This would explain the much lower absolute currents, presumably
approximately 400 mV decade−1 , i.e., an α value of ca. 0.15. For due to a nearly atomically smooth surface. The opposite trend in
the ORR in base, the first ET would involve the production of pH behavior is perplexing, however [206].
superoxide (Eq. (2.11)), which has a standard redox potential E 0 The explanation of the wide variation in electron transfer
of −0.284 V [207], indicated on the potential axis of the figure. The rates from titania electrodes to oxygen to produce superoxide
curves appear to show an onset in the region near this potential, (Eq. (2.11)) in alkaline solution may necessarily involve the bulk
while having no apparent correlation with the flat-band potential, electronic properties close to the surface. The doping level can
which is ca. −0.83 V vs. SHE (also indicated). The intercepts of the certainly vary over many orders of magnitude. From the pure
straight lines with 118 mV slopes with the E 0 yield the exchange semiconductor standpoint, Pleskov and Myamlin, among others,
534 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
have summarized this problem, concluding that the ET rate is
proportional to the density of electronic states and the electron
energy distribution function [208]. As we have seen, the doping
level can continue to increase above the point at which the
behavior is no longer like that of a semiconductor. In this regime,
characterized by the presence of surface states, one could expect
that the ET rate must also continue to rise.
3.8. Photoelectrochemical properties
Although the field of semiconductor photoelectrochemistry
was introduced to a large extent by workers at Bell Laboratories
as part of their work on semiconductor electrochemistry [165,
209–211], the field was developed to a very high level by the
work of Gerischer on materials such as Ge, GaAs, CdS and ZnO
[212]. Our early efforts were very much influenced by this work.
These semiconductors were fundamentally interesting, but the
possibilities for practical applications seemed limited due to
their susceptibility to photocorrosion. Our work [19,50,167,213,
214], showed that TiO2 is much less susceptible and could thus
be considered for applications such as solar energy conversion.
Interestingly, Boddy, as part of a study on anodic oxygen evolution,
had already just published a photocurrent vs. potential curve
(similar to Fig. 2.2) when our studies appeared, but the full
implications of the result were not recognized [165].
The photoelectrochemistry of TiO2 can be summarized by
referring to Fig. 3.20. It can be seen that the conduction-band
energy ECB of rutile is essentially coincident with the reversible
hydrogen potential at all pH values, whereas that for anatase is
more negative by 0.20 V. At lower pH values, the ECB for rutile
is also coincident with the reversible potential for O2 reduction
to hydroperoxyl radical HO2 •, but, at higher pH, ECB continues to
become more negative, while the potential for O2 reduction to
superoxide radical anion O•− 2 remains constant at −0.284 V [207].
This implies that this process should become more favorable in the
alkaline pH region, as already discussed in the previous section.
The fact that the ECB for anatase is sufficiently negative to reduce
O2 to O•−2 over a wide pH range is consistent with its higher
photocatalytic activity. The valence-band energies EVB for both
rutile and anatase lie at approximately the same potential, which is
−
sufficiently positive to produce free •OH radicals (lower pH) or O•
radicals (higher pH). However, it is only positive enough to oxidize
2-propanol to its radical cation, in principle, in the acidic pH region.
The EVB for both materials is more than sufficiently positive
to oxidize water, by approximately 1.8 V, at all pH values. The
potentials for water oxidation are also much less positive than
those for the reactions involved in photocatalysis, for example,
the production of •OH radicals and the direct hole-mediated
oxidation of organic compounds. Nevertheless, some of the same
reactions and intermediates may also be involved. Various workers
have studied the detailed mechanisms of oxygen photoevolution
reaction (OPER) on TiO2 [111,215–221]. The originally proposed
mechanism involved the reaction of photogenerated holes with
adsorbed hydroxyl groups (OH− ) to produce •OH radicals, which
then coupled to form H2 O2 , which was further oxidized to O2
[215,216]. In order to explain the photo-etching of TiO2 , Nakato
and co-workers have proposed alternative pathways involving the
reaction of photogenerated holes with bridging Ti–O–Ti moieties,
with breakage of the Ti–O bond [111,217–220] (see Section 4.1.4).
Recently, Neumann et al. have proposed a further modification
of this model [221]. Qu et al. have carried out quantum chemical
calculations related to these mechanisms; these workers found
large energy barriers to the diffusion of O-adatoms and thus
questioned whether O2 could be evolved as a result of the
recombination of O-adatoms [222].
Fig. 3.20. Energy bands on TiO2 as a function of pH. Note that the rutile CB line is
superimposed on the reversible hydrogen potential H+ /H2 at all pH.
The photoelectrochemical oxidation of organic compounds
has been studied extensively. In a recent example, Villareal
et al. studied the photoelectrochemistry of polycrystalline anatase
electrodes as a model system for photocatalysis and found that
it was possible to distinguish between direct hole-mediated
oxidation and •OH radical-mediated oxidation [223]. For example,
methanol, which is less strongly adsorbed, was found to be
oxidized via an •OH radical, while formic acid, which is more
strongly adsorbed, was oxidized directly.
4. Fundamentals of photocatalysis
4.1. Mechanisms of photocatalysis
4.1.1. Photoelectrochemical basis of photocatalysis
As described in the Historical Overview, it became recognized
by several researchers that photocatalysis is based on ‘‘back-to-
back’’ or short-circuited photoelectrochemical and electrochem-
ical reactions, involving electrogenerated electrons and holes. At
the most global level, these can be written:
hν → e− +
CB + hVB (4.1)
+
2H2 O + 4hVB → O2 + 4H +
(4.2)
O2 + 4H + 4eCB → 2H2 O.
+ −
(4.3)
Reactions (4.2) and (4.3) can be designated as the oxygen
photoevolution reaction (OPER) and the oxygen reduction reaction
(ORR), respectively. Of course, the latter can occur either, as
shown, on the titania surface itself or on a separate electrode.
These processes can be examined separately with standard
electrochemical methods and can provide an overall rationale for
the energetics, as seen in Fig. 4.1. The point at which the anodic and
cathodic (flipped up to view the crossing point) currents are equal
is a good indication of the local current that could be expected
under a given set of conditions. We first showed such crossing-
point diagrams in a paper by Inoue et al. to show the short-
circuit current for PEC cells [224]. The basic idea has been used
for many years to quantitatively analyze the energetics of local
electrochemical cells on corroding metals [47,48].
The set of results in Fig. 4.2, from Lewis and Hoffman and co-
workers [204] shows that, in 1 M NaOH, the crossing point for the
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.1. Energy band diagram showing a photoelectrochemical cell, at open circuit,
in which oxygen photoevolution is occurring at a rutile electrode and oxygen
reduction is occurring at a platinum electrode. This shows the maximum open
circuit potential that could be expected with a highly active catalyst.
Fig. 4.2. Current–potential curves for (a) oxygen photoevolution on a rutile single
crystal; (b) hydrogen evolution on the same rutile electrode, where the cathodic
current is flipped up to show the point at which it crosses curve A; (c) hydrogen
evolution on a roughened platinum electrode, cathodic current and flipped up to
show the crossing point; and (d) oxygen reduction on the roughened platinum
electrode, cathodic and [187] flipped up to show the crossing point (based on
Kesselman et al. [204]).
OPER on the illuminated rutile TiO2 single crystal surface with the
ORR also on TiO2 is at ca. 2 µA cm−2 , or ca. 25% of the maximum
photocurrent available (Fig. 4.2, curves +B and −B, the latter being
flipped up to show the crossing point). Interestingly, if we show
the hydrogen evolution reaction (HER) on a platinum electrode
(curve +C and −C), which is similar to a situation in which a TiO2
particle is platinized, but with no oxygen to reduce, the cross-over
is slightly higher, ca. 3 µA cm−2 , or ca. 37.5% of the maximum.
This situation is also essentially the same as that in a complete PEC
cell and is consistent with our original work on the photo-assisted
electrolysis of water; this was reported for the 1 M NaOH case in
1975 [55], as well as with measurements of the flat-band potential
[167,169,171].
If we now look at what happens when we couple the OPER on
rutile TiO2 with the ORR on platinum, i.e., similar to the situation
on the platinized TiO2 particle in the presence of dissolved oxygen,
we can see that the crossing point is now near the maximum
(ca. 7.5 µA cm−2 ). This idea was first proposed by Bard and co-
workers [225] and has prompted several groups of researchers,
principally Heller and Gerischer and co-workers [226], to enhance
535
the photocatalytic process by adding catalysts for the ORR, such as
Pt and Pd, to TiO2 . Kesselman et al. noted that the extension of their
work to the case of real photocatalysts was not a simple one, due
to differences, for example, between rutile and anatase [204]. This
is an important point, which will be taken up again later.
This picture can then be related directly to the energy-level
diagram, in which the Fermi levels for the photo-anode (reaction
(4.2)) and cathode (reaction (4.3)) are shown as being equal (at
the crossing point in Fig. 4.2), which they must be, in a short-
circuited PEC cell (Fig. 4.1). This is helpful in understanding the
energetics and demonstrates that the reactions are expected to
proceed spontaneously. Of course, we are ignoring the detailed
mechanisms at the moment and will return to these later.
Surprisingly, the photocurrent at a single crystal rutile electrode
(Fig. 4.2, curve A), which can be totally consumed in generating
O2 , is not significantly affected by the presence of an organic
compound, as shown by Izumi et al. [227] and again by Kesselman
et al. [204]. This is because the photocurrent is essentially
determined by the characteristics of the semiconductor. At
increasingly positive potentials (low Fermi levels), the band
bending becomes sufficient for the photogenerated electrons and
holes to be efficiently separated, while, at increasingly negative
potentials, the band bending continues to decrease to the flat-band
condition, and then, contrary to the expected behavior for an ideal
diode (Fig. 2.2, curve 1–3), in the absence of oxygen, there is a
gap of several tenths of a volt before cathodic current starts. For
the moment, we are also ignoring the fact that there is actually
some transient cathodic current as one sweeps the potential in the
negative direction [204], which could be due to the intercalation of
protons into the TiO2 structure (see later).
A series of papers were published in which a microelectrode
was placed at various distances above an illuminated anatase film,
which was deposited on an indium–tin oxide (ITO) substrate [228–
233]. Measurements that were carried out with the microelectrode
technique showed that, even when an anatase film is actively
oxidizing an electron donor (in this case, ferrocyanide) and even
while there is oxygen reduction occurring at a bare section of the
ITO substrate, there is still a quite significant reduction current
passing at the anatase surface (Fig. 4.3) [232].
At this point, it is possible to propose a tentative working
mechanism for photocatalysis in terms of the balancing of anodic
and cathodic reactions. The anodic reaction can be oxygen
evolution, hydroxyl radical production or organic oxidation. The
cathodic reaction can either be oxygen reduction, to superoxide,
hydrogen peroxide or water, or reduction of the titanium dioxide
itself, via hydrogen insertion, for example. On a polycrystalline
film, certain crystal faces may be favored as reduction sites. This
is not certain at the present stage of understanding. Nevertheless,
it is certain that the oxygen reduction consumes protons, thereby
making the adsorbed water alkaline, as long as there are some
cations present. We already know that the potentials at which
ORR proceeds are more negative in alkaline solution. Thus, the
reaction becomes progressively more difficult. However, there are
two mitigating factors: (1) the presence of CO2 in the atmosphere
and its absorption could buffer the pH; and (2) O2 reduction occurs
more easily in alkaline solution, i.e., larger changes in current per
unit potential change compared to acid, as already mentioned in
Section 3.8.
There are two other factors that could help in offsetting the
inhibiting effects of pH changes. First, the trapping of electrons
in restricted areas of the TiO2 surface and consequent increase
in the local electrical conductivity can lead to an increase in the
ability of that area to transfer electrons to solution phase species.
If the concentration of trapped electrons becomes high enough,
the local area can become like a metal. At that point, the fact that
the conduction band edge should shift to more negative potentials
536 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

Fig. 4.3. (a) Schematic diagrams of the microelectrode monitoring system, with the microelectode situated far from the surface (left) and close to the surface (right), where
it can sense the oxygen reduction reaction that is occurring in parallel with ferrocyanide oxidation; (b) current vs. time curves showing the current when the electrode is
105 µm from the electrode (left) and when it is 15 µm from the surface; the concentration of ferrocyanide is 5 mM; the microelectrode diameter is 15 µm; supporting
electrolyte, 0.1 M K2 SO4 ; UV light intensity, 8.5 mW cm−2 , electrode potential, +0.70 V vs. SCE (taken from Maeda [232]).
© 1999, American Chemical Society.

due to a pH effect becomes meaningless, and the electrons are not
required to pass over such an energy barrier (Fig. 4.4). At neutral
pH, the conduction band energy for anatase should be ca. −0.6 V
vs. SHE, and the Fermi level should be ca. −0.4 V vs. SHE. This is
just negative enough to reduce O2 to O•− 2 (E 0 = −0.284 V vs.
SHE) [207]. We also note here that, for rutile, the energetics are
not as favorable, i.e., the conduction-band energy would be ca.
−0.4 V and the Fermi level ca. −0.2 V, which is not quite negative
enough to reduce O2 , as discussed in Section 3.7. If the local area
in which the electrons are trapped is relatively small and the
remaining area, in which oxidation takes place is relatively large,
the anodic current density in this remaining area will be small. In
such a case, the pH change will be smaller than expected, i.e., the
conduction-band lowering due to acidification will be minimized,
and thus there may be minimal enhancement of the tendency to
accumulate electrons at the surface (see Fig. 4.5). Now, we have a
possible scenario in which the effect of the natural pH changes that
could occur in a weakly buffered solution is largely avoided, and
it becomes energetically possible to reduce oxygen to superoxide
in areas that cover a small fraction of the surface while oxidation
of organic molecules or other reactions (e.g., peroxide or oxygen
production) can occur in areas that cover a large fraction of the
surface.
This model is basically an extension or modification of that
of Gerischer and Heller [226,234–236], in which relatively small
areas of TiO2 particle surfaces are proposed to act as reducing
sites. The novel aspect of the present modification is that it
provides a specific mechanism by which small reducing centers
could develop, i.e., more or less randomly selected portions of
the TiO2 surface are proposed to provide starting points for
conductive regions to begin to develop within the bulk of the
particle or film. This can occur as a result of electrochemical
hydrogen insertion (Fig. 4.5). As illumination proceeds, and more
electrons are produced, the latter can be partially consumed in the
generation of such bulk conductive regions. The reason that such
structures would be spontaneously generated is that the electrons
would be transported to the surface more efficiently in a more
conductive region (‘‘wire’’). In other words, the first electron that
goes to the surface and produces an interstitial hydrogen atom
makes it more likely that a second electron might be directed to
the same area. The probability depends on the spatial distribution
of the electron density for this first bulk trapped electron. This
effect could explain why only relatively small surface regions
might exist. Furthermore, if the electrons are channeled in this
way, they not only avoid electrostatic repulsion, which would tend
to disperse them, but also localize them and thus protect them
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.4. Modified band diagram for photocatalysis, showing that the cathodic
reduction of O2 takes place through surface states, with no impediment from the
increasingly alkaline pH at these sites.
from recombination. These processes are being considered more
quantitatively and will be reported elsewhere.
The insertion of hydrogen atoms would tend to increase
the volume, as already mentioned in Section 3.6, as confirmed
theoretically by Koudriachova et al. [160]. This could help in
explaining results that have been reported recently involving
the effects of compressive vs. tensile stress and others involving
changes in volume and roughness (see Section 5).
Several specific cases can be envisioned (Fig. 4.5). First, as a
reference case, let us say that only water, either liquid or vapor,
is present at the surface (Fig. 4.5a). A photoproduced electron is
shown hitting a hydrogen-rich region and being conducted along
it to the surface, where it reacts with water, producing another
interstitial hydrogen atom, which is essentially a kind of trapped
electron.
If a hole trapping agent such as an alcohol is present at the
surface, the holes will be more effectively trapped, and there will
be less recombination (Fig. 4.5c). In this case, the photoproduced
electrons will have a greater opportunity to react and produce
interstitial hydrogen. If this process continues indefinitely, a large
portion of the TiO2 particle, or even macroscopic solid, can be
reduced, so that the blue color produced by the presence of Ti3+ is
visible. This explains the first early report of Renz in which is noted
the discoloration of TiO2 samples exposed to organic compounds
and sunlight [17].
When oxygen is present as well, it can be reduced to superoxide
or hydrogen peroxide by the photoproduced electrons. In this case,
conventional photocatalysis can take place, since the superoxide
can participate in the photocatalytic reactions (Fig. 4.5d). When
oxygen is present but no organic compound (Fig. 4.5c), the
situation becomes like that for the photo-induced hydrophilic
effect (see Section 5). The superoxide produced by oxygen
reduction and the hydroxyl radicals produced by water oxidation
can both react further, the superoxide via disproportionation, and
the hydroxyl radicals likewise via disproportionation, to produce a
surface that has a high coverage of hydrogen peroxide. In this case,
again, the hole trapping process is not perfect, and recombination
can occur, and also some electrons are removed via oxygen
537
reduction, so the H-rich region does not have an opportunity
to grow.
The scenario described here could be considered to be an
example of a simple self-organizing system, i.e., a system that
spontaneously organizes itself into an array (in this case, two-
dimensional) of two different types of regions with distinct
properties. There are a number of examples of such systems
in chemistry [237]. The ideal system does not assume any pre-
existing heterogeneity; this ideal could be approached on a single
crystal surface. It is quite likely that the pattern formation that
we observed on a rutile single crystal surface (see Section 5) was
of this type, in which cathodic and anodic regions might have
formed spontaneously. However, on a perfectly homogeneous
surface, the pattern formation may not be robust, and the regions
might tend to move around, based on statistical fluctuations. In
a real photocatalytic film, heterogeneity does in fact exist and
can affect the pattern of regions that might develop. The process
of formation of small conductive regions might involve a kind of
nucleation and subsequent growth, as in the deposition of crystals
or electrodeposition of metals. If the nucleation is based on specific
conditions that tend to favor it, for example, a particular crystal
face or the presence of trace impurities, the pattern could be quite
robust. This is an area that will be developed further.
As mentioned above, this is basically a modification of the
Gerischer–Heller model, in which relatively small areas on the
surface trap electrons, which subsequently react with oxygen
to produce superoxide [226,234–236]. These authors envisioned
single, stationary surface traps on titania nanoparticles. They argue
that the rate of electron transfer from surface traps to solution-
phase oxygen is significantly below the rate at which holes are
produced, and therefore, the number of electrons builds up within
the particle to levels at which most of the holes are consumed by
recombination. They argue further that, in order to accelerate the
oxygen reduction reaction, electrocatalysts such as Pd or Pt could
be used.
The merits of this approach were also demonstrated by
Kesselman et al. in their work with rutile single crystal electrode,
in which they showed that the oxygen reduction current–potential
behavior on a Pt-covered rutile electrode surface was indeed
increased to the point where it matched the anodic photocurrent
[204]. Aside from the practical problems of this approach, one
of the fundamental chemical problems is that it ignores the
need to produce superoxide as a reaction intermediate in the
photocatalytic process. In fact, Heller and co-workers [226,
234–236] and other groups, including our own, have proposed
mechanisms for catalysis in which superoxide plays a key role.
We propose here that oxygen reduction to superoxide and
hydrogen peroxide can occur at TiO2 at significant rates under
certain conditions, specifically, those under which small near-
surface regions become sufficiently highly doped that the electron
transfer approaches the limit predicted by the Marcus theory. This
can involve doping with either oxygen vacancies, as in the case of
bulk electrodes, or it can involve hydrogen doping, which can, in
principle, be induced electrochemically, as already discussed.
In summary, this slightly modified Gerischer–Heller model
takes into account the requirement of electroneutrality, i.e., that
both oxidation and reduction must take place at exactly equal
rates. It explains how oxygen reduction can proceed even at
significant rates without an added catalyst, and even though the
local pH might tend to slow down the reaction. It also explains
how photogenerated electrons can be channeled to the surface
efficiently, avoiding recombination with holes. Finally, it helps
in explaining changes in bulk lattice parameters, which would
otherwise be difficult to explain.
538 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

Fig. 4.5. Combined reductive–oxidative model for the photo-induced hydrophilic (PIH) effect, in which reducing and oxidizing regions are spontaneously formed: (a) in
the absence of oxygen, protons are reduced to produce interstitial hydrogen atoms (no organic compound present). (b) in the presence of oxygen, the latter is reduced to
superoxide or hydrogen peroxide (no organic compound present); (c) in the absence of oxygen, protons are again reduced, while an organic compound is oxidized; (d) in
the presence of oxygen, the latter is again reduced, while an organic compound is oxidized. In (a) and (b), holes react with water to produce a variety of possible hydrophilic
moieties.

Fig. 4.6. Processes occurring on bare TiO2 particle after UV excitation.

4.1.2. Time scales
When a TiO2 photocatalyst absorbs a photon with energy equal
to or greater than its band-gap, an electron–hole pair is generated;
subsequently, the pair is separated into a free electron and a free
hole. The electron and hole ‘‘walk randomly’’ to the surface of
the photocatalyst and are trapped there (Fig. 4.6); the trapped
electron e− +
tr and hole htr react with acceptor (step c) or donor
molecules (step d), respectively, or recombine at surface trapping
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582 539

Table 4.1
Some measured characteristic time for primary processes in TiO2 photocatalysis.
Primary process Characteristic time Sample description References

Charge carrier generation

TiO2 + hν → e− + h+ fs
Charge trapping
h+ → h+ tr <200 fs
e− → e−tr <150 fs
Nanoporous TiO2 film Tamaki et al. [262]
+
hs−tr → h+ d−tr (relaxation) ∼100 ps
e− −
s−tr → es−tr (relaxation) ∼500 ps
Charge recombination
tr , h + etr , or e + h
e− + h+ 1 µs
+ − − +
Nanoporous TiO2 film (water) Yoshihara et al. [246]
→ heat (or hν ) 25 µs Nanoporous TiO2 film (air) Peiro et al. [238]
Interfacial charge transfer
∼300 ps (methanol oxidation) Nanoporous TiO2 film Tamaki et al. [264]
∼3 ns (2-propanol oxidation) Nanoporous TiO2 film Tamaki et al. [264]
<2 µs (water oxidation) Degussa P25 powder Yamakata et al. [256]
h+ (or h+
tr ) + Red →Red
+
No water oxidation within 80 µs Nanoporous TiO2 film Murai et al. [609]
e−
tr + O2 → O2
−
<100 ns Nanoporous TiO2 film Yoshihara et al. [246]
e− + O2 → O− 2 10–100 µs Degussa P25 powder Yamakata et al. [256]
e− (or e− −
tr ) +O2 → O2 ∼10 µs Nanoporous TiO2 film Peiro et al. [238]
e− + Pt → Pt · · · e− 2.3 ps Degussa P25 powder Iwata et al. [265]

Fig. 4.7. Time scales in photocatalysis.

sites (step a). The electron and hole can also be trapped at bulk
trapping sites and recombine there with the release of heat (b).
The processes of back-reaction between the oxidized donor and
electron, or reduced acceptor and hole, can occur after the initial
charge transfer, especially when the species are strongly adsorbed
on the TiO2 surface [238–240]. These processes together with the
characteristic surface reactions, as illustrated in Fig. 4.6, occur at
the time scales shown in Fig. 4.7 and listed in Table 4.1. Since the
band-gap transition is of an indirect nature, deexcitation through
light emission is not an important process for TiO2 [6,74].
The photogenerated charge carriers, either free or trapped,
can be probed by various spectroscopic techniques. Trapped
holes and electrons absorb light in the visible and near-infrared
spectral regions [238,241–253], whereas free electrons absorb in
the infrared or microwave regions [254–260]. These absorptions
allow one to accurately measure the time scale of photocatalytic
processes by means of transient spectroscopies, such as transient
absorption (TA) spectroscopy [238,243–249,252,253], transient
diffuse reflectance (TDR) spectroscopy [242,250,251,255,256,258],
and time-resolved microwave conductivity (TMRC) measurements Fig. 4.8. Absorption spectra of (a) trapped holes in Refs. [252,253,261], and
[254,259,260]. Typical spectra for these species are shown in (b) trapped electrons in Refs. [243,245,252,253]. (c) The spectra of trapped holes,
free electrons, and trapped electrons identified by Yoshihara et al. [246].
Fig. 4.8. © 2004, American Chemical Society.
540 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
In an early study, Serpone et al. compared the TA results of three
TiO2 sols excited by a 30-ps-width UV laser, with particle sizes of
2.1, 13.3, and 26.7 nm [247]. They observed that for all three kinds
of sols, the transient spectra were fully developed and comprised
spectra of trapped holes and trapped electrons at the end of the
30 ps laser pulse. Thus, they estimated that the trapping times
for electrons and holes should be in the ≤ 1–10 ps range. Later,
Yang et al., by means of femtosecond TA spectroscopy, estimated
the hole trapping within 50 fs and electron trapping within 260 fs
for TiO2 particles of several-nm diameter [261]. The ultrafast hole
trapping was interpreted in terms of the difference in the effective
mass of hole (0.8me ) and electron (>10me ) that results in a 40
times faster transit time from the interior to the surface of the TiO2
nanoparticle for the hole than that for the electron. Very recently,
Tamaki et al. studied the trapping dynamics of electrons and
holes in a nanoporous TiO2 film by femtosecond TA spectroscopy
[262,263]. They observed that shallowly trapped electrons and
holes were generated at a time constant of 100 fs, deeply trapped
electrons at 150 fs, and deeply trapped holes at 200 fs. In addition,
they assigned the time constant of 100 ps to trapped holes relaxing
from shallow traps to deep ones, and the time constant of 500 ps to
trapped electrons relaxing from surface shallow traps to bulk deep
traps. These results suggest that in TiO2 photocatalysis the species
that lead to surface redox chemistry should be the trapped, rather
than free, charge carriers.
Yoshihara et al. studied the transient adsorption of TiO2
nanoporous film in a wide wavelength range (400–2500 nm)
[246]. They used a low-intensity pulsed laser to excite a TiO2
film so that less than one electron–hole pair was generated in
each particle, on average, per pulse; this ensured them obtaining
information of the transient species under conditions close to
those in a real photocatalytic system, i.e., with UV light below the
1 mW cm−2 level. They found that, for a nanocrystalline TiO2 film,
the half-life for electron–hole recombination is ca. 1 µs for a film
dipped in N2 -saturated deuterated water. This result is in contrast
to the fast electron–hole recombination (∼10 ns) suggested by
the earlier transient spectroscopic studies on TiO2 colloids and
powders in which high power laser pulses are used [6,259,260],
but is consistent with recent studies by Durrant and co-workers
[238] and Yamakata et al. [256], in which similar low-intensity
laser pulses were employed for excitation.
Yoshihara et al. identified the characteristic absorption of
trapped and free electrons in nanoporous TiO2 films: trapped
electrons showed a broad absorption centered at 770 nm, whereas
free electrons showed a structureless absorption in the near-
infrared and infrared region whose intensity increased with
wavelength (λ) by a function of λn [246]. They found that trapped
electrons reacted with oxygen more rapidly than free electrons:
the absorption of trapped electrons decreased clearly at 100 ns
after excitation when the TiO2 film was immersed in air-saturated
methanol, whereas no change was observed for free electrons at
the same time scale.
Durrant and co-workers studied the photochemical reduction
of oxygen adsorbed on nanoporous TiO2 film by means of TA
spectroscopy [238]. They observed that in a nitrogen atmosphere,
the TA signal probed at 900 nm decayed with a half-life of
about 25 µs. The signal, however, exhibited a decay with a
half-life of about 12 µs in air, indicative of oxygen reduction
competing directly with the electron–hole recombination reaction.
Yamakata et al. studied the water-induced and oxygen-induced
decay kinetics of free electrons in TiO2 by means of time-resolved
infrared absorption spectra [256]. They observed that on TiO2
(Degussa P25), O2 from the gas-phase captured the electrons and
accelerated the decay rate at a delay time of 10–100 µs, and water
vapor reacted with holes within 2 µs.
Tamaki et al. studied the oxidation of adsorbed alcohols with
trapped holes by means of femtosecond TA spectroscopy (Fig. 4.9)
Fig. 4.9. (a) Absorption spectra of TiO2 nanocrystalline film in the ground state and
of trapped hole in the film. (b) Time profiles of transient absorption of TiO2 in air,
water, methanol, ethanol, and 2-propanol at 400 nm [264].
© 2006, American Chemical Society.
[264]. They recorded the time profile at 400 nm after a laser
pulse (160 fs pulse width); at this wavelength, deeply trapped
holes contributed 90% of the absorption, while trapped electrons
contributed another 10%. In the case of the TiO2 nanoporous film in
air, where there is no scavenger for trapped holes, the time profile
showed an additional rise in TA up to 20 ps as a minor contribution
after the instantaneous rise within the time-resolution (200 fs) of
instrument. They attributed this additional rise to the relaxation
from shallowly trapped holes to deeply trapped holes. A similar
rise was observed for a film immersed in water. The TA did not
show a decay up to 1 ns, either in air or in water, suggesting
that electron–hole recombination and the oxidation of water are
negligible on this time scale. However, in alcohol media, the TA
of trapped holes decayed after excitation, clearly indicating that
trapped holes reacted with the alcohols, and the reaction was
competitive with the trapping of holes. The lifetimes of trapped
holes in the films in methanol, ethanol, and 2-propanol were
300, 1000, and 3000 ps, respectively; the reaction efficiencies
were close to unity. The decay kinetics of the trapped holes that
react with alcohols is monoexponential on the nanosecond order,
different from the non-exponential recombination kinetics for the
film in air. This suggests that the hole transfer from trapping sites
to alcohol molecules is the rate-limiting step for the former.
There were several studies that dealt with the electron transfer
within Pt/TiO2 photocatalysts. In a femtosecond TDR study, Furube
et al. observed a new decay component of a few ps under 390 nm
excitation in addition to the normal charge recombination kinetics
for Pt/TiO2 photocatalyst; the larger the Pt loading on the TiO2
surface, the more efficient the electron migration observed [241].
They thus assigned the fast decay process to the migration of
electrons in TiO2 to Pt. Iwata et al. measured the femtosecond TA
spectra of Pt-loaded TiO2 in the spectral region of 0.9–1.5 µm. They
observed a decay process of 2.3 ps, which represents the transfer
of electrons from TiO2 to Pt. Despite this fast electron transfer,
Iwata et al. suggested that a fraction of the electrons remain in the
TiO2 particle, since considerable signal intensity remains even after
hundreds of ps [265]. Yamakata et al. traced the absorption of free
electrons in TiO2 and Pt/TiO2 particles after a 10-ns-width laser
pulse by means of time-resolved IR absorption spectra [256]. They
observed that the absorbance on Pt/TiO2 decreased more quickly
in the 0–1 µs range than that on TiO2 . The rapid decay on Pt/TiO2
suggests that the migration of electrons to Pt clusters occurred
within 1 µs, and the electrons were equilibrated among the Pt
clusters and TiO2 substrates after 1 µs. The three studies coincide
with each other on the fact of fast electron transfer from TiO2 to Pt
clusters.
The above-mentioned studies focused on TiO2 nanoparticles
and nanoporous films. Further studies need to be conducted on
polycrystalline TiO2 films, which are also important photocatalyst
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
materials. However, their results are still valuable for us to
determine some important time scales in TiO2 photocatalysis,
as summarized in Fig. 4.7 and Table 4.1. These time scales,
as summarized in the table, suggest that: (1) the charge
recombination in TiO2 photocatalysts could be a slow process
due to the efficient charge trapping; (2) the interfacial charge
transfer processes are competitive to charge recombination; (3)
photocatalytic reactions could be completed within µs to ms
after the generation of the electron–hole pair. The last point
suggests that in the photocatalytic processes under low-intensity
UV illumination (1 mW cm−2 , ∼1015 photons s−1 cm−2 ), a photon
is absorbed by the TiO2 photocatalyst only after the electron–hole
pair generated by the previously absorbed photon has already
undergone reaction or charge recombination.
4.1.3. Trapping of electrons and holes
Charge carrier trapping is needed in the photocatalysis
process to suppress recombination and increase the probability
of interfacial charge transfer [6,74]. As mentioned before, the
recombination can be delayed, with a lifetime on the scale of
µs in nanocrystalline TiO2 films [238,246]. This makes the slow
charge transfer of electrons to molecular oxygen competitive with
the recombination. The electron paramagnetic resonance (EPR)
technique is frequently used to trace trapped electrons and holes
in TiO2 nanoparticles after UV illumination [266–271]. At low
temperature, trapped electrons can be detected in the form of
Ti3+ . Adsorption of O2 at surface has been found to remove the
Ti3+ signal. Trapped holes are also observed and are considered
to be localized deep trap states. However, there is no consensus
on the exact nature of the state: several types of species, such
as sub-surface oxygen radicals connected to surface hydroxyls
(Ti–O• –Ti–OH) [266,271] surface oxygen radicals (Ti–O–Ti–O• )
generated from basic surface hydroxyls [267,270], lattice O•
− vapor into the IR system caused a decrease of the background
radical, etc. [266,268] are postulated to exist in various cases. In a
− the result of the formation of surface hydroxyls by dissociative
recent EPR study by Berger et al., a lattice O• radical was observed
on the surface of dehydrated 13-nm TiO2 nanocrystals; the signal
− that clearly merits further study.
of O• was completely removed by the addition of a large amount
of O2 due to the exchange effect between the O2 molecule and the
−
O• species [268].
The energetics of electron trap states of various TiO2 materi-
als have been evaluated by a variety of experimental methodolo-
gies. For example, for single crystal rutile, trap sites have been
shown by thermoluminescence and thermally stimulated current
measurements to exist 0.21–0.87 eV below the conduction-band
edge [272–274]. For nanocrystalline TiO2 film, trap states at about
0.5–0.7 eV below the conduction-band edge have been reported
[197,201,275]. By time-resolved photoacoustic spectroscopy, elec-
tron trapping states in nanocrystalline colloidal titanium dioxide
were determined to exist on average 0.8 eV below the conduction-
band edge [276]. Photoluminescence measurements on anatase
nanoparticles revealed the presence of four shallow electron trap-
ping levels at energies of 0.4, 0.5, 0.64 and 0.86 eV below the
conduction-band edge, ascribed to the presence of oxygen vacan-
cies [277,278]. Rutile particles show almost the same photolumi-
nescence from shallow traps as anatase particles, indicating the
same origin of shallow traps, i.e., the presence of oxygen vacancies
in rutile as well as anatase particles.
The energetics of deeply trapped holes has been evaluated
indirectly by several methods. Lawless et al. studied the reaction
of TiO2 particles with • OH radicals that were generated by pulse
radiolysis [249]. The product of the • OH reaction with the particles
was identified as a deeply trapped hole at the particle surface,
whose redox level was approximately 1.3 eV above the valence
band. Nakamura et al. observed a photoluminescence centered at
840 nm from the atomically smooth TiO2 (100) surface, ca. 1.5 eV
541
Fig. 4.10. Schematic diagram of the reaction of trimethylacetic acid (TMA) on a
rutile (110) single crystal via adsorption at two adjacent 5-coordinate Ti4+ sites,
with simultaneous reduction of 6-coordinate Ti4+ sites to Ti3+ and subsequent re-
oxidation by O2 to Ti4+ [280].
© 2003, American Chemical Society.
above the valence-band edge, and assigned it to the recombination
of conduction-band electrons with deeply trapped holes [219,220].
No energetics information for shallowly trapped holes is available,
probably due to their short lifetime.
Two different types of surface Ti–OH groups have been
proposed to play important roles in trapping charge carriers,
forming Ti4+ –• OH radicals (hole trapping) or Ti3+ –OH groups
(electron trapping) [257]. This point has been investigated both
experimentally and theoretically recently. In an IR spectroscopic
study, Panayotov et al. observed the depletion of conduction-
band electrons in reduced TiO2 powders with water adsorption
[279]. Compared with the oxidized TiO2 sample, the reduced
sample shows an increase in the background absorbance due to the
production of free conduction-band electrons. Introducing water
absorption. This apparent electron withdrawal was believed to be
absorption of water on defects on the TiO2 surface. This is an issue
In another study, Henderson et al. sought to identify surface
sites associated with charge transfer and trapping during the
photodecomposition of a trimethyl acetate (TMA) adlayer on the
rutile (110) surface, using scanning tunneling microscopy (STM),
electron energy loss spectroscopy (EELS), and photodesorption
(Fig. 4.10) [280]. In ultra-high-vacuum (UHV) conditions, they
observed the decomposition of a TMA molecule that bridged two
Ti4+ sites into isobutene and CO2 , with the accumulation of Ti3+
cations bound to surface bridging OH groups. The Ti3+ signal,
detected as a feature at about 0.8 eV in the EELS spectra, was largely
removed by postexposure to O2 .
By means of density functional theory (DFT) calculations on
hydroxylated and reduced rutile TiO2 (110) surfaces, Di Valentin
et al. [281] demonstrated the electron trapping nature of bridging
Ti–OH groups, which is consistent with Henderson’s study [280],
but found no evidence that these groups should also act as hole
traps by formation of Ti4+ –• OH radicals. As calculated, the oxygen
vacancy introduced two localized Ti3+ 3d1 states about 1 eV
below the conduction-band edge (Fig. 4.11). These states were not
removed upon dissociation of a water molecule and formation
of a pair of hydroxyl groups. Instead, the excess electrons of
the hydroxylated surface were trapped by two Ti4+ ions, which
were reduced to Ti3+ . These two ions were found to be of two
types: a six-fold-coordinated Ti located between the two bridging
hydroxyls, with an energy 1.6 eV below the conduction band
(3.4 eV band-gap calculated) denoted as Ti3br+−OH , and a nearby five-
fold-coordinated Ti, with an energy 1.2 eV below the conduction
band, denoted as Ti35c+ . The O 2p states of the bridging OH
groups were spread within the O 2p band, providing very little
542 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.11. Total and projected density of states for the hydroxylated (top) and
reduced (bottom) TiO2 (110) surface, calculated using the B3LYP hybrid functional.
The Ti3+ states are localized on: (a) the Ti ion between the two bridging OH groups,
Ti3br+−OH ; (d) the Ti ion nearest to the oxygen vacancy, Ti3br+−v ; (b),©Ti35c+ , top view.
The vertical dotted line in the PDOS denotes the position of the Fermi energy [281].
© 2006, The American Physical Society.
contribution to the top of the band. This suggests that these
OH groups are not very efficient hole traps. On the contrary,
the Ti atom of the Ti–OH group is a good electron trap, as the
corresponding energy level for Ti3br+−OH was found 1.6 eV below the
CB by calculation. Once the electron is trapped, the Ti3+ –OH can
attract and neutralize a hole, i.e., behave as a recombination center.
These studies have provided solid evidence for the contribution
of surface Ti–OH groups to electron trapping. For the stoichiomet-
ric (unreduced), hydrated TiO2 surface, there are at least two dif-
ferent types of surface Ti–OH groups: one is the bridging Ti–OH
(actually, considered to be adsorbed protons, i.e., Ti–OH+ –Ti, as
discussed in Section 5.2.4), and the other is the terminal Ti–OH,
(considered simply as OH− ions that are adsorbed at 5-coordinate
Ti4+ sites, as discussed in Section 5.2.4, or, alternatively, as the
product of the dissociative adsorption of water at these sites (see
also Section 3.4) [282]. The former is more acidic than the latter,
which leads to different reactivities. One can consider two path-
ways for electron trapping at bridging oxygens (given formally as
Eq. (3.2)): either the electron is trapped first and the proton trans-
fer follows, or vice versa. As outlined above, there is a consensus
that the neutral bridging Ti–OH group is the final product, with the
electron itself trapped at the 6-coordinate Ti4+ site. There is also
evidence that some electron density exists at the 5-coordinate Ti4+
sites (see Sections 3.5 and 4.1.5), since both superoxide and hydro-
gen peroxide can adsorb at these sites.
More controversial is the role of the more basic terminal
Ti–OH− group, which has been postulated to trap holes by
some workers, but this has been disputed by others (see
Section 4.1.4). At this point, we should note that the role of
hydroxyl groups in general can become complicated, because,
Fig. 4.12. Correlation of O− and Ti3+ EPR signal intensity as a function of UV
exposure time at 90 K. The intensity values for the Ti3+ and O− species were
normalized with respect to equal integral intensities of the respective spin center
signals [268].
© 2005, American Chemical Society.
under real photocatalytic conditions nanosize TiO2 photocatalysts
with highly hydrated surfaces are used. Under these conditions,
there are large numbers of hydroxyl groups in a variety of different
environments, as shown by the infrared spectra in Fig. 3.10. More
work is still needed to unravel the roles of the various surface
Ti–OH groups in photocatalytic processes.
One important point is that, whereas almost all of the
photogenerated holes are trapped in deep or shallow trapping
sites, a large fraction of the photogenerated electrons are in a
nearly free, untrapped state in the interior of the TiO2 particle,
as observed by a structureless absorption in the near-IR and IR
region [258]. In a recent EPR and IR study, Berger et al. found
that even at the low temperature of 90 K, the major fraction,
over 90%, of photoexcited electrons remained in the conduction
band and was silent in EPR spectra under high-vacuum conditions
(Fig. 4.12) [268]. This may explain the slow oxygen reduction on
the irradiated TiO2 surface, since trapped electrons react with
molecular oxygen much faster than free electrons [246]. The
reaction of the trapped electron with O2 will be discussed also in
Section 4.1.5.
4.1.4. Oxidizing species at the TiO2 surface
Many efforts have been devoted to clarifying the oxidizing
species generated at the irradiated TiO2 surface, which is
essential for understanding the mechanism of photocatalysis and
for designing photocatalyst systems for environmental cleanup
applications. The ever-clarified oxidizing species include holes,
either free or trapped, • OH radicals, O•− 1
2 , and O2 , among others [6,
10,22,283,284]. H2 O2 and O2 are also involved in the photocatalytic
oxidation processes in various mechanisms [5,6,10].
Holes. Holes are the primary oxidizing species in photocatalytic
reactions. As mentioned above, photoproduced holes are trapped
within picoseconds at the TiO2 photocatalyst surface [262]; this
indicates that most of the primary oxidation processes are caused
by trapped holes. TA studies have revealed that at least two
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.13. Sum-frequency generation (SFG) spectral evolution of methanol on TiO2 (a) with introduction of water vapor (b) and subsequent evacuation (c) [291].
© 2004, American Chemical Society.
kinds of different trap sites exist for holes on the surface of
TiO2 nanocrystalline photocatalysts: the deep hole exhibits an
absorption around 520 nm, while the shallow hole exhibits an
absorption around 1200 nm [246]. The shallowly trapped holes are
easily excited thermally into the valence band so as to establish
equilibrium with the free holes [252]. Shallowly trapped holes will
therefore have a comparable reactivity and mobility to free holes.
The deeply trapped holes, however, are more or less localized at
deep traps and exhibit lower oxidizing potential [252,277]. The
precise chemical nature of these is still in question, however.
Shallowly trapped holes react very rapidly with chemisorbed
substances; the oxidation process is even competitive to the
ultrafast charge trapping [264]. Deeply trapped holes, however,
prefer to react with more mobile physisorbed substances, due
to their localized nature; the reaction is often a slower process.
For instance, NMR studies by Xu and Raftery showed that for the
oxidation of ethanol and 2-propanol, the chemisorbed species,
i.e., ethoxide or propoxide, were oxidized much more rapidly than
the H-bonded species [285,286]. Shkrob et al. observed the rapid
photo-oxidation of glycerol by the holes on TiO2 nanoparticles;
ca. half of these holes are scavenged within the duration of a
3.3-ns fwhm (full width at half maximum), 355-nm excitation
laser pulse; the others are scavenged at a slower rate over 200 ns
after the photoexcitation pulse [287,288]. They suggested that the
reaction with chemisorbed and physisorbed glycerol may account
for the prompt and the slow hole decays, respectively. Tojo et al.
studied the one-electron oxidation processes of aromatic sulfides
in TiO2 colloidal solution by laser flash photolysis [289]. They found
that the 4-methylthiophenylmethanol cation radical showed a
broader absorption at 1 µs after excitation than that at 10 µs
after excitation. They assigned the former to the absorption due to
surface-bound cation radicals and the latter to the absorption due
to free cation radicals in solution.
One important point is that even for the same substance, the
adsorption states may change, depending on the environment. By
means of NMR, Nosaka et al. studied the adsorption of ethanol on
TiO2 photocatalysts [290]. When there was a physisorbed water
layer on the surface of the photocatalyst, ethanol was found to
prefer to stay in the mobile water physisorbed water layer, and
thus the NMR signal for ethanol was sharp. When the physisorbed
water molecules vaporized completely at elevated temperature,
ethanol molecules reached the surface and reacted with the surface
titanols to form ethoxide, resulting in remarkable line broadening
due to the restricted mobility. With rehydration and recovery of
the water layer, the ethoxide was hydrolyzed to form ethanol
molecules, which moved back to the physisorbed water layer and
produced sharp NMR signals.
In another study related to this, Wang et al. observed the
competitive adsorption between methanol and water on TiO2 film
543
by means of in situ sum-frequency generation (SFG), a highly
sensitive surface characterization technique (Fig. 4.13) [291].
When only methanol vapor was in contact with the TiO2 film,
two kinds of species, molecular methanol and methoxide, which
were produced by dissociative chemisorption of methanol, were
detected on the TiO2 surface. When a relatively large amount of
water vapor (water–methanol ratio, ca. 300) was introduced into
the system, the surface methoxide signal dropped below the SFG
detection limit, but physisorbed methanol remained. Evacuating
the system containing a large amount of water and a relatively
small amount of methanol caused the water SFG peak to drop
below the SFG detection limit. The methanol peak remained.
Interestingly, a substantial methoxide SFG peak reappeared. These
workers suggested that the oxidation pathway of methanol in the
presence of water should depend on the ratio between water and
methanol.
In a purely photoelectrochemical study, Villareal et al. found
that the oxidation of methanol was never mediated by holes,
because the conditions were aqueous solution, so that there was
sufficient water available to shift the adsorption equilibrium away
from methanol. In contrast, they found that formic acid oxidation
was always mediated by holes, due to strong chemisorption of the
acid on the TiO2 surface [223].
•OH radicals. Previous product analyses on various photocatalytic
reactions led to the postulate that •OH radicals, produced by
oxidation of surface hydroxyl or adsorbed water, play an important
role in initiating oxidation reactions, especially for substances that
adsorb weakly on the TiO2 surface [6,11]. This oxidation pathway
is sometimes designated as indirect oxidation, in comparison to
the direct oxidation by holes. The presence of •OH radicals at
the irradiated TiO2 surface was demonstrated by spin trapping
experiments with EPR spectroscopy [292–295].
Some recent studies, however, suggest that the role of the
•OH radical is probably overestimated. The photocatalytic one-
electron oxidation studies by Fox and co-workers [296,297] and
Tachikawa et al. [298–300] showed that for many substances the
primary oxidation should be initiated by free or trapped holes.
A fluorescence probe investigation by Ishibashi et al. showed
that free •OH radicals, detected by terephthalic acid probe, were
produced in a quantum yield three orders smaller than that of
trapped holes, detected by iodide ions [301]. Nosaka et al. argued
that the common spin trapping reagents, such as 5,5-dimethyl-
1-pyrroline-N-oxide (DMPO), might simultaneously detect both
trapped holes and surface-adsorbed •OH radicals [302]. They
suggested that water reacts with the one-electron oxidation
product of the spin trapping reagent (Eqs. (4.4), (4.5)) and should
give the same product as the adduct formation between •OH
544 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.14. Reaction scheme for the oxygen photoevolution reaction on TiO2 (rutile)
in contact with an aqueous solution of pH of 1 to about 12 [219,220].
© 2004, American Chemical Society.
), and mixture of water–ethanol
radicals and the spin trapping reagent (Eq. (4.6)) [302].
DMPO + h+ → DMPO•+
+ −
DMPO• + OH → DMPO–OH •
•OH + DMPO → DMPO–OH • .
Similarly, some reactions, which were considered to be initiated by
•OH radicals previously, could be initiated by trapped holes with
the production of the same products [302]. One such example is
the oxidation of methanol (Eqs. (4.7)–(4.10)):
By •OH radicals:
CH3 OH + •OH → •CH2 OH + H2 O
•CH2 OH → HCHO + H+ + e− .
By trapped holes:
CH3 OH + h+ → + CH3 OH → •CH2 OH + H+
•CH2 OH → HCHO + H + e . + −
•OH radicals have been proposed to be generated by the
oxidation of either water or adsorbed hydroxide ion with
photogenerated holes [6,215,216,303,304]. Nakato and co-workers
and others have found problems with this simple electrochemical
process (e.g., failure to explain the 840-nm photoluminescence
peak) [111,217–220,305] and have proposed an alternative
pathway in which •OH radicals are produced by a nucleophilic
attack of water on a hole trapped at a surface lattice oxygen
((4.11)–(4.14)).
[Ti–O–Ti]s + h+ + H2 O → [Ti–O • HO–Ti]s + H+
+ TiO2 aqueous suspension system by means of a gated photon
[Ti–O • HO–Ti]s → [Ti–O–O–Ti]s + H
[Ti–O–O–Ti]s + H2 O → [Ti–O–OH • HO–Ti]s .
When the O–O bond in TiO–OH breaks
[Ti–O–OH • HO–Ti]s → [Ti–O • HO–Ti]s + •OH.
A similar scheme is shown in Fig. 4.14, in which the overall water
oxidation process is shown. Quantum mechanical calculations
have also been carried out by Qu and Kroes recently to check these
proposed pathways [222]. These authors examined a large number
of different possible geometries for adsorbed oxygen atoms and
peroxide groups. Neumann et al. examined this mechanism
experimentally with electrochemical mass spectroscopic and
photovoltage measurements and found problems with it [221].
They proposed a slightly modified pathway for water oxidation.
Moreover, there are several reactions of H2 O2 , produced by
reduction of molecular oxygen or the disproportionation reaction
of superoxides, could produce •OH radicals (Eqs. (4.15)–(4.19)) [6,
306]. It should be noted that reaction (Eq. (4.17)) only produces
surface-adsorbed •OH radicals, whereas reactions (4.18) and (4.19)
Fig. 4.15. Emission spectra observed after the laser pulse irradiation at 355 nm
for TiO2 (P25) suspension in water (), ethanol (
(M). Copyright The Owner Societies 2004. (b) Schematic illustration of the possible
formation mechanism of singlet 1 O2 on UV-excited TiO2 particles.
(4.4)
can produce both surface-adsorbed •OH radicals and free •OH
(4.5) radicals.
(4.6)
O2 + 2e− + 2H+ → H2 O2 (4.15)
•− •−
O2 + O2 + 2H +
→ H 2 O2 + O2 (4.16)
− −
H 2 O2 + e → •OH + OH (4.17)
H 2 O2 + O2 •−
→ •OH + OH + O2 −
(4.18)
H2 O2 + hν → •OH + •OH. (4.19)
(4.7) •− •−
O2 . Superoxide O2 is less important in initiating oxidation
(4.8) reactions. Although there are several reports that suggested that
O•−
2 initiated some type of oxidation reaction, for example, the
oxidation of trichloroethylene [307], the examples are quite few
compared to those concerning holes and •OH radicals. The role of
(4.9) O•− in photocatalytic oxidation processes was discussed mainly
2
(4.10) within the framework of participation in the total mineralization of
organic substances through reaction with organoperoxy radicals,
the production of H2 O2 by disproportionation reaction, and the
anti-microbial activities [5,6,10]. Recently, Nosaka et al. proposed
that the reaction between O•− 2 and a trapped hole would produce
singlet oxygen 1 O2 , a strong oxidant (see below) [283].
1
O2 . Singlet oxygen 1 O2 is an important reactive oxygen species
in atmospheric, biological and therapeutic processes, and is also
used as a reagent in organic synthesis. The formation of 1 O2 in
TiO2 photocatalysis was predicted twenty years ago [308], but
only recently 1 O2 generated on irradiated TiO2 surface could be
detected. Nosaka et al. first reported the detection of the near-
(4.11) infrared phosphorescence at 1270 nm of 1 O2 in a photocatalytic
(4.12)
counting method (Fig. 4.15a) [283]. They suggested that oxidation
(4.13)
of O•− 2 with holes at the TiO2 surface should be a plausible
mechanism to produce 1 O2 (Fig. 4.15b). The lifetime of 1 O2 was
determined to be 2 µs, which is rather short as compared with
(4.14) those of •OH radicals (ca. 10 µs) and trapped holes, possibly due
to the fast deactivation of 1 O2 at TiO2 surfaces.
Daimon and Nosaka measured the quantum yields for 1 O2 over
ten commercial TiO2 photocatalysts in air, and found they ranged
from 0.12 to 0.38, while the lifetimes ranged from 2.0 to 2.5 µs
[309]. The short lifetime suggests that the generated 1 O2 mainly
remains on the TiO2 surface without being released to the air or
solution. Since the quantum yield is significantly high, 1 O2 may
contribute to the oxidation of organic molecules at the irradiated
TiO2 surface.
Hirakawa et al. studied the generation of 1 O2 by the photocat-
alytic reaction of TiO2 particles, either anatase or rutile, dispersed
in solvents [310]. The estimated quantum yield by both types of
TiO2 was about 0.02 in ethanol. The 1 O2 emission was completely
quenched by the addition of superoxide dismutase, suggesting that
1
O2 is produced via oxidation of O•− 1
2 . The O2 was found to be
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
adsorbed at the TiO2 surface and could not oxidize nicotinamide
adenine dinucleotide, which has no affinity for the TiO2 surface.
However, it can oxidize the water-soluble protein bovine serum al-
bumin, which can be adsorbed on the TiO2 surface. The generation
of 1 O2 was enhanced in the phospholipid membrane, suggesting
that the phospholipid membrane is an important environment for
the phototoxic reaction mediated by 1 O2 generation in TiO2 pho-
tocatalysis.
Janczyk et al. reported the generation of 1 O2 at surface-modified
TiO2 particles [311]. They found that TiO2 particles, after surface-
modification with organosilane, could oxidize cyanuric acid, a
stable material resistant to TiO2 photocatalysis. They concluded
that cyanuric acid was oxidized by 1 O2 and suggested an energy
transfer pathway for the generation of 1 O2 on hydrophobically
modified TiO2 particles.
4.1.5. Role of molecular oxygen
Molecular oxygen plays an indispensable role in TiO2 photo-
catalysis, especially in reactions related to environmental cleanup
applications [5,6,10]. It assists the charge separation in TiO2 by
capturing TiO2 electrons; it generates active species such as O•−
H2 O2 , 1 O2 , etc. that participate in reactions; it itself participates
in the reaction and accelerates the mineralization of organic sub-
stances; it also helps the TiO2 photocatalyst to maintain stoi-
chiometry during photocatalytic reactions. These effects have been
either postulated or already demonstrated for many years, but re-
cent progress in both theoretical simulations and experimental
techniques have greatly improved our understanding.
Improved charge separation. Berger et al. found that molecular
oxygen could not only capture the photogenerated electrons
to suppress charge recombination, but also improve the photo-
stimulated charge separation in TiO2 nanoparticles, i.e., more holes
could be trapped within the particles in the presence of molecular
oxygen [312]. They designed two experiments to demonstrate
this idea: in one experiment, they illuminated dehydrated TiO2
nanocrystals (13 nm) and recorded the EPR spectra before and
after the addition of molecular oxygen; in another experiment,
they illuminated dehydrated TiO2 nanocrystals and recorded the
EPR spectra in the presence of molecular oxygen. They observed
that, in the former experiment, the concentration of trapped holes
(O− ) was the same as the superoxide, indicative of the depletion
of photogenerated electrons with molecular oxygen; thermally
stable charge separation could be maintained for quite a long time
after the formation of superoxide. In the latter experiment, they
observed that the concentrations of O•− −
2 and O were related to the
oxygen pressure during UV excitation, first increasing with oxygen
pressure, and finally saturating at 25 mbar O2 (Fig. 4.16). This
indicates that either the number of adsorption sites for O•− 2 ions
on the nanocrystal surface or the surface capacity for hole trapping
and O− formation limits the final concentration of EPR-active
species. Most interestingly, at 140 K, a maximum concentration
of ten O− /O•−2 pairs per particle was obtained after O2 photo-
adsorption, but, under high-vacuum conditions, UV excitation
resulted in only one e− /O− pair per particle.
Ishibashi et al. quantitatively studied the kinetics of pho-
togenerated O•− 2 under very low-intensity light illumination
(1 µW cm−2 ) at the air–TiO2 interface as well as the water–TiO2
interface by measuring the chemiluminescence from luminol so-
lution pipetted onto TiO2 film photocatalysts [313,314]. The total
number of steady-state O•− 2 on the TiO2 surface was determined
from the chemiluminescence intensity: about 1 × 1014 cm−2 at
the air–TiO2 interface and 2 × 1014 cm−2 at the water–TiO2 inter-
face. These steady-state concentrations were independent of light
intensity (1 µW cm−2 –15 mW cm−2 ), indicating that the amount
of O•−
2 is restricted by the number of adsorption sites on TiO2 . The
545
Fig. 4.16. Time-resolved accumulation of trapped holes and scavenged electrons
upon UV exposure at different oxygen pressures: (a) 0.1 mbar O2 and (b) 10 mbar
O2 . (c) UV exposure at P < 10−6 mbar and subsequent addition of O2 . Note that
the profiles of O− and O•− − •−
2 coincide for a given pressure, as the ratio of O to O2
equals unity throughout all experiments [312].
© 2005, Wiley-VCH Verlag GmbH & Co.
2 ,
greater concentration of O•− 2 at the water–TiO2 interface compared
to the air–TiO2 interface was thought to be due to the lower inter-
facial energy barrier for the electron transfer in water.
As discussed in Section 3.7, the reaction of TiO2 electrons with
molecular oxygen is a process that is still poorly characterized,
varying over many orders of magnitude in rate, even for samples
that are nominally identical. It has been considered as the rate-
determining step in photocatalytic processes [234,236], although
this is still not certain. The kinetics for oxygen reduction on the
TiO2 surface can probably be improved by depositing a noble metal
co-catalyst [226], although this is a far from practical solution.
It will be interesting, both fundamentally and practically, to try
to understand the detailed reasons for the wide variations in
rate. As discussed in Section 3.8, the driving force for electron
transfer is quite low, as the potential difference between the
conduction-band edge of TiO2 and the potential for O2 reduction
to superoxide is quite small, which may result in a slow electron
transfer [238]. This driving force is most likely decreased even
further, due to the fact that the electron transfer takes place from
surface electron traps.
Generation of active oxygen species. Superoxide (O•−2 ) and hydrogen
peroxide are two main products of O2 reduction in TiO2
photocatalysis and are involved in the production of other active
oxygen species such as •OH, 1 O2 , as described in Section 4.1.4.
While superoxide is the product of one-electron reduction of
molecular oxygen, hydrogen peroxide can be produced by either
two-electron reduction of molecular oxygen or disproportionation
of two superoxides [6]. The generation of superoxide has been
recognized for a long time based on the EPR [268,269,312,315,316]
or chemiluminescence studies [313,314,317,318]. The detection
of surface-peroxo species, however, is difficult, and only recently
was achieved by Nakamura et al. by means of multiple internal
reflection infrared spectroscopy [319].
Tilocca et al. studied the adsorption of O2 on hydroxylated
rutile TiO2 (110) using density functional theory total energy
calculations and first principles molecular dynamics simulations
[320]. Their results suggested that the electron transfer from Ti–OH
to O2 does not need to pass through a chemisorbed O2 state.
Instead, scavenging by O2 starts as soon as the oxygen molecule
captures two hydrogen atoms from the bridging hydroxyls
(Fig. 4.17, a–c); this produces a hydroperoxide species, which
is eventually chemisorbed onto the five-fold-coordinated surface
Ti (Ti5c ) atoms (Fig. 4.17, d–f). The H2 O2 –Ti5c molecule was
further transformed to HO2 –Ti5c after transferring a proton back
546 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

Fig. 4.17. Selected snapshots from the MD trajectory started with an O2 molecule above the surface, illustrating the formation of H2 O2 , its adsorption and further
transformation. Slab Ti and O atoms are represented as white and dark sticks, while adsorbed O and H atoms are represented as large dark and small white spheres,
respectively; dashed lines denote hydrogen bonds [320].
© 2005, American Chemical Society.

to a bridging oxygen (Fig. 4.17, g–i). The theoretical calculations

support the experimental hypothesis of Henderson that electron
scavenging could happen between weakly bound (physisorbed) O2
and bridging hydroxyls [143].
Atwood et al. compared the oxygen-centered radicals gener-
ated on surfaces of Degussa P25 powder and two rutile powders
by EPR spectroscopy [321]. They found that stable superoxide
radicals are generated on either dehydroxylated P25 powder or
dehydrated rutile powders under UV excitation; the signal can per-
sist up to several days. On the fully hydrated P25 surface, no signals
(O− , O•−
2 , •O2 H) are observed in the EPR spectrum, even after pro-
longed UV irradiation at 100 K. On the partially hydrated P25 sur- Fig. 4.18. Photocatalytic decomposition of several kinds of organic compounds
face, the dominant signal of O− ; and traces of O•− 2 and •O2 H are
through the tetraoxide mechanism suggested by Schwitzgebel et al. [235].
observed; both were thermally unstable and quickly decayed to © 1995, American Chemical Society.
diamagnetic species such as H2 O2 upon warming to 300 K. How-
ever, thermally stable O•−2 and •O2 H could be observed on rutile
Although valence-band holes of TiO2 were required for the
powders, even in the case of full hydration. It was believed that on oxidation to be initiated, the actual oxidizer was molecular
the P25 surface, which is mainly anatase, superoxide anions can be oxygen. O2 was suggested to react with organic radicals, generated
sufficiently mobile on the fully and partially hydrated surfaces such upon the hole or •OH radical reaction with the reactant, to
that disproportionation reactions (forming H2 O2 ) occur. However, produce an organoperoxy radical (ROO•), and subsequently the
on the hydrated rutile surface, some surface sites capable of O•− 2 reactant was degraded and mineralized through thermochemical
stabilization remain. reactions, probably by the tetraoxide pathway (Fig. 4.18). A similar
Consistent with Atwood’s study, Goto et al. reported a conclusion was also drawn from photoelectrochemical studies
preferred generation of hydrogen peroxide on anatase during [230,231] and isotope studies [323].
the photocatalytic degradation of 2-propanol in water, while for Although the existence of the organoperoxy radical was
rutile photocatalysts, the generation of superoxide was preferred predicted in photocatalytic processes, its detection was difficult
[322]. They observed this trend on several anatase and rutile due to its short lifetime [324–326]. In a recent EPR study, Murphy
photocatalysts; the data are shown in Table 4.2. et al. observed that a number of different organoperoxy species
Participation in reactions. Heller suggested that the photocatalytic are involved in the heterogeneous decomposition of ketones over
oxidation of organic pollutants is mostly mediated by molecular dehydrated polycrystalline TiO2 [327]. These radical intermediates
oxygen, not by photogenerated holes or •OH radicals [5,235]. were identified as organoperoxy-based species of general formula
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582 547

Table 4.2
Physical properties and estimated production rates of hydrogen peroxide and superoxide ion on several TiO2 powders [322].

TiO2 powder Anatase component (%) Surface area (m2 /g) Purity (%) H2 O2 (10−7 mol min−1 ) 2 (10
O•− −7
mol min−1 )

NS-90 <1.0 0.9 >99 0 1.0

CR-EL <0.1 7.1 >99 0.1 0.9
TIO-3 <1.0 48 >99 0 1.6
TIO-2 >99.9 18 98.5 2.9 0.4
ST-21 >99.9 56 95 5.3 0.2
ST-11 >99.9 71 95 2.7 0.5

reactions [329–337]. Under O2 -deficient conditions, these O atoms

Fig. 4.19. High-resolution transmission electron micrograph of the hydrocarbon/
TiO2 films that were illuminated with UV light for 3 h. (1) A low-magnification
image and the corresponding selected area electron diffraction pattern (inset).
(b) A high-magnification image. Additional lattice fringes (d = 0.45 nm and 0.69
nm) which do not appear in a perfect rutile crystal, were observed in the inset of (a)
(marked by arrows) and (b) [333].
© 2006, American Institute of Physics.
ROO• and RCO3 •. They were formed by reaction of photogenerated
charge carriers with the adsorbed ketones in the presence of
molecular oxygen. The organoperoxy intermediates are thermally
unstable and decompose at temperatures in the region of
180–250 K. This work demonstrates the importance of free-radical
pathways involving both organoperoxy and superoxide radicals for
the photo-oxidation processes over TiO2 photocatalysts.
Maintenance of the stoichiometry of TiO2 . Surface coordinatively
unsaturated O atoms of TiO2 photocatalysts, especially those at
surface irregularities such as kinks and edges, are labile under
UV illumination due to hole trapping, and could be exchanged
with molecular oxygen [328] or abstracted during photocatalytic
would gradually be lost during photocatalytic reactions; this
results in a loss of stoichiometry of the TiO2 photocatalyst
and also its photocatalytic activity [329–333]. Yoshida et al.
recently studied the structural changes of a TiO2 film during
the photocatalytic oxidation of an organic film in vacuum by a
unique in situ TEM/ EELS system [331–333]. The organic film
was deposited on a 60-nm-thick TiO2 film supported on a Cu
grid for TEM observation. During UV irradiation, the organic
material was oxidized and decomposed, desorbing from the TiO2
surface (Fig. 4.19). At the same time, single crystalline TiO2
was transformed into polycrystals, and additional lattice fringes,
belonging to substoichiometric forms of TiO2 , appeared. The TiO2
film gradually became a network of aggregates after one week of
irradiation. A detailed EELS analysis revealed that the structural
changes were associated with the loss of oxygen atoms in the TiO2
crystal lattice [331–333].
Muggli and Falconer studied the photocatalytic oxidation of
formic acid and acetic acid in a helium atmosphere [329,330]. They
observed the fast deactivation of the TiO2 photocatalyst and the
recovery of activity by storage in O2 in the dark. They suggested
that the loss of surface lattice oxygen caused the deactivation of
the photocatalyst, and O2 was able to replenish the lattice oxygen
vacancies.
4.1.6. Effect of crystal face
Morris Hotsenpiller et al. studied the photochemical reduction
of Ag+ ions in an aqueous solution on oriented TiO2 (rutile)
surfaces [338]. They observed the oriented photochemical reaction
rates and quantum yields, i.e., the (101), (111), and (001)
surfaces had higher Ag-deposition rates than the (100) and (110)

Fig. 4.20. (a) AFM image (1 × 1 µm2 ) of ultra-smooth TiO2 (110) surface. (b) Ag formed on as-polished (dark bar) and ultra-smooth (slashed bar) TiO2 surfaces with various
orientations. The Ag/Ti intensity ratio was evaluated by EDX [340].
© 2005, The Japan Society of Applied Physics.
548 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.21. (a) A SEM image of n-TiO2 (001) surface of (001) after photoelectrochemical etching under 2.0 V anodic polarization [218]. (b) A SEM image of TiO2 polycrystalline
electrode after photoelectrochemical etching under 1.0 V anodic polarization [344].
© 1998, The Electrochemical Society, Inc.
Fig. 4.22. (a) SEM image of a rutile particle on which Pt fine particles were
deposited selectively on (110) face by photocatalytic reactions. (b) SEM image of
an anatase particle (center) on which Pt fine particles (indicated by arrows) were
deposited by photocatalytic reactions. (c) and (d) SEM images of rutile and anatase
particles, respectively, co-deposited with Pt and PbO2 by photocatalytic reactions.
© 2002, The Royal Society of Chemistry and the Centre National de la Recherche
Scientifique [345].
surfaces. In a later study, Lowekamp et al. used polished and
annealed surfaces of randomly textured rutile polycrystals to
photochemically reduce Ag+ to Ag metal in an aqueous solution
[339]. By correlating the surface orientation of more than 100
individual crystallites with the amount of deposited Ag, they
concluded that the most reactive orientations lie near the (101)
surfaces. These studies, however, did not involve atomically
smooth surfaces, and thus might be open to question (see below).
In a recent study, Yamamoto et al. reconsidered the anisotropic
photochemical reactivities of rutile with atomically smooth rutile
single crystal surfaces (Fig. 4.20) [340]. They observed only little
orientation dependence of the photochemical reactivity for Ag+
reduction on the group of as-polished surfaces. In contrast, the
photo-reactivity on the group of ultra-smooth surfaces exhibited
strong orientation dependence, although their reactivities were
one to two orders of magnitude smaller than those on the as-
polished surfaces. The reactivity of ultra-smooth surfaces for Ag+
reduction followed the sequence: (101) > (100) > (001) >
(111) > (110) [340]. Note that the Ag reduction reaction
is accompanied by water photo-oxidation in their experiments.
Thus, the above reactivity sequence should represent the sum of
reduction and oxidation reactions. In another study, Nakamura
et al. measured the flat-band potential of atomically smooth TiO2
rutile single crystal surfaces [111]. They found that the flat-band
potential of the (100) surface is 0.1 V more negative than that of
the (110) surface, indicative of the higher reduction ability of the
former surface.
Nakato et al. observed the anisotropic etching of TiO2 single
crystal surface during anodized polarization in H2 SO4 electrolyte
solution [217,341,342]. The etching left rectangular holes on the
rutile (001) surface (Fig. 4.21a) [218]. The holes, 50–200 nm wide,
extend in the (001) direction, with the (100) face or equivalent
exposed selectively at the walls. For the (110) surface, long
rectangular grooves were produced at the surface in the (001)
direction, with the (100) face or equivalent exposed at the walls
of the grooves. For the (100) surface, the results were quite
similar to those for the (110) surface, except that the walls of
the photoproduced grooves were either parallel or perpendicular
to the electrode surface. This also shows that the (100) face or
equivalent is exposed at the walls. A similar phenomenon was also
observed on polycrystalline TiO2 electrodes during anodization
polarization in H2 SO4 solution, with uniform rectangular cells
created on the surfaces of microcrystals (Fig. 4.21b) [343,344].
These etching results were considered to be abnormal, since the
(110) face is the most stable for rutile, rather than the (100) face,
but this could be explained by the difference in hole reactivity with
water for various crystal faces [218].
Matsumura and co-workers studied the crystal-face-dependent
photocatalytic reactivity of rutile and anatase particles [345]. The
TiO2 powder used in their study consisted of 1-µm size rutile
and anatase particles with well-developed crystal faces. The rutile
particles showed a tetragonal prism structure with four planes,
which are assigned to the (110) faces. Each end of the prism is
capped by four planes, which were assigned to the (011) faces. The
anatase particle had a tetragonal bipyramid structure consisting of
eight (011) faces. Both vertexes were removed and capped by (001)
faces. After photocatalytic oxidation of water on the powder using
hexachloroplatinate ions as the electron acceptors, Pt deposits
were observed mostly on the rutile particles, especially on the
(110) face, indicating that the reduction sites of rutile particles
were on the (110) face (Fig. 4.22a). When 2-propanol was added
to the solution, Pt was deposited on both the anatase (Fig. 4.22b)
and rutile particles. Using the thus-prepared Pt-deposited TiO2
powder, Pb2+ ions were photocatalytically oxidized to PbO2 , which
were deposited on the TiO2 particles (Fig. 4.22, c, d). They observed
the selective deposition of PbO2 on the (011) face of rutile particles,
and for anatase particles, PbO2 was deposited in a larger amount on
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.23. SEM images of (a) an anatase particle after UV irradiation in aqueous
solution containing 1 mM H2 PtCl6 and 0.52 M 2-propanol and (b) an anatase particle
after sequential UV irradiation in the same solution as in (a) and then in an aqueous
solution of 0.1 M Pb(NO3 )2 [346].
© 2003, The Royal Society of Chemistry and the Centre National de la Recherche
Scientifique.
Fig. 4.24. Active oxygen species and some processes related to remote
photocatalysis. Neutral species including H2 O2 , HO2 , and 1 O2 are supposed to
diffuse farther away from irradiated TiO2 surface than the highly reactive •OH,
through air, water, or surface.
the (001) face than on the (011) face. This means that the (011) face
provides the oxidation site for rutile particles, while for anatase
particles the (001) face is more oxidative than the (011) face.
In another study, Matsumura and co-workers etched the
same anatase particles with HF solution [346]. By this process,
the edge between two (011) faces was selectively etched and
as a result, eight new faces were generated on each particle,
which were assigned as (112) faces. The new anatase particles
were photocatalytically deposited with Pt and PbO2 in sequence.
Interestingly, most of the Pt was deposited on the (011) faces,
while PbO2 was deposited on the newly generated (112) faces, as
shown in Fig. 4.23, indicating the reductive function of the (011)
faces and the oxidative function of the (112) faces for the anatase
particles. These results suggest that crystal faces could assist in the
separation of electrons and holes, and thus, it may be possible to
obtain high photocatalytic activity through control of the surface
atomic arrangement of TiO2 photocatalysts. More work needs to be
Fig. 4.25. Time course of water contact angle of (a) octadecyltriethoxysilane (ODS) modified glass surface and (b) polystyrene-coated glass surface during the remote
oxidation experiment. The polyimide spacer was 50 µm thick and the light source was an Hg–Xe lamp (light intensity 10 mW cm−2 ) [350].
© 2001, American Chemical Society.
549
carried out in which highly well-defined experimental results are
compared with high accuracy quantum mechanical calculations.
4.1.7. Remote photocatalysis
Recent studies have shown that photocatalytic reactions could
be initiated at a distance away from the TiO2 photocatalysts. Some
examples include the remote killing of bacteria [347], the remote
decoloration of dye films [348–352], the remote decomposition
of organic or polymeric films [350,353–358], and the remote
oxidation of inorganic materials (Cu, C, SiC, etc.) [359,360]. In
these examples, the impact distance of the TiO2 photocatalyst was
found to be as long as several millimeters, and the reaction media
could be air, water, or solid surfaces; in addition, several types
of oxidizing species were involved in the photocatalytic reactions
(Fig. 4.24).
Tatsuma et al. first observed the remote oxidation of methylene
blue film at a distance of 500 µm away from a TiO2 film [352].
Later studies showed that aromatic or even aliphatic substances
can be oxidized and decomposed into CO2 remotely by TiO2
films (Fig. 4.25), and the impact distance could be up to 2.2 mm
[350]. It was clear that the oxidation could not be caused by
holes on the TiO2 surface. Similarly, it was hard to believe that
hydroxyl radicals generated on the TiO2 surface could travel such
a long distance in air, considering their high activity [350]. Some
neutral oxygen species generated on illuminated TiO2 surfaces,
such as HO2 , H2 O2 , can diffuse a long distance in air. However,
these species are not reactive enough with aliphatic hydrocarbons
to produce CO2 . Tatsuma et al. thus postulated that hydroxyl
radicals should participate in the remote photocatalytic reactions
described above, but a major proportion of these hydroxyl radicals
should be generated in the gas phase by the UV-photolysis of H2 O2
[350]. The possible remote oxidation mechanism thus includes
(1) the diffusion of H2 O2 in the gas phase, (2) the photolysis of
H2 O2 into hydroxyl radicals in the gas phase under UV irradiation
(λ < 365 nm), and (3) oxygenation and decomposition of target
materials by hydroxyl radicals. Also, H2 O2 can be generated in the
disproportionation of HO2 . Thus, either H2 O2 or HO2 can be the
diffusing species [350].
Kubo and Tatsuma designed several experiments to verify
the proposed double-excitation mechanism. In one of these
experiments, air was forced to flow through a TiO2 -loaded cell that
was irradiated with UV light and an aqueous solution of peroxidase
in sequence. By this experiment, they proved the existence of
H2 O2 in the gas phase, released from the irradiated TiO2 film
[361]. In another work, they observed that H2 O2 vapor, when
illuminated with UV light shorter than 365 nm, could oxidize
ODS-modified glass [362]. Importantly, the reaction rates of the
H2 O2 –UV system were in close agreement with those for the
550 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.26. Correlations between the remote oxidation ability and the H2 O2
generation ability for various photocatalysts (). TiO2 ‘‘A’’ and ‘‘B’’ are anatase sols,
with average particle sizes of 20 nm and 7 nm, respectively. Pt (1.0 wt%) and
Ag (0.0055 wt%) were deposited photocatalytically. The correlation between the
oxidation ability and the H2 O2 amount for the H2 O2 –UV reaction is also shown (4)
[362].
© 2006, American Chemical Society.
photocatalytic remote oxidation, suggesting the similarity of the
active species in both systems (Fig. 4.26). They also compared the
remote oxidation of octadecyltriethoxysilane (ODS)-modified glass
with various photocatalysts, and found that the oxidation rates
followed the sequence: Pt-loaded TiO2 > TiO2 > ZnO > WO3 ,
the same sequence for the decomposition activity of methylene
blue in conventional photocatalysis [362]. Thus, they suggested
that the conventional photocatalytic activity could be a measure
for roughly predicting the remote oxidation activity of a given
photocatalyst [362].
Naito et al. studied the remote photocatalysis by means of
single-molecule fluorescence microscopy [348,351]. They found
that the double-excitation process described above should be
Fig. 4.27. Fluorescence images of single terrylenediimide (TDI) molecules spin-coated on a polymethyl methacrylate (PMMA)-coated coverslip before (a) and after (b) UV
irradiation for 5 min (scale bars are 10 µm). The air gap between TDI layer and TiO2 film is 12.5 µm. The bright spots correspond to TDI diepoxide. The UV irradiation area
is inside the white circle in the images, in this area TDIs are bleached by direct UV irradiation. (c) Scheme for the fluorescent detection of airborne 1 O2 with TDI [348].
© 2006, American Chemical Society.
involved in the bleaching of the fluorescence of dye molecules
[351]. But they also argued that it is hard to exclude the
contribution of other active oxygen species, such as 1 O2 . They
designed an experiment that used terrylenediimide (TDI) as a
fluorescent probe for 1 O2 . The molecule reacts to 1 O2 to form
a strongly fluorescent TDI diepoxide with blue-shifted emission.
They found that 1 O2 generated on UV-excited TiO2 film could
diffuse in air over 2 mm distance, and oxidize TCI molecules at that
distance (Fig. 4.27) [348].
Haick et al. reported another type of remote photocatalytic
oxidation by surface diffusion of oxidizing species [357,358]. They
prepared microstripes of TiO2 on an Si substrate and observed
the mineralization of aliphatic chains anchored to inert silicon
domains within minutes, even when these chains were located as
far as 20 µm away from the TiO2 microstripes [358]. The hydroxyl
radical is believed to be the oxidizing species in this system. In
another study, they covered the TiO2 film with a photomask and
observed the decomposition of aliphatic chains in the dark region
[357]. Very interestingly, the occurrence of the photocatalytic
reaction in the dark region did not cause any decrease in the
reaction rate in the illuminated region, even though competition
may exist in sharing the oxidizing species. Kawahara et al. studied
the surface diffusion behavior of photogenerated oxidizing species
on TiO2 films and concluded that the diffusion length was as long
as 75 µm [356].
The observation of remote photocatalysis, especially that
induced by surface diffusion of oxidizing species, may have a
significant effect on the design of photocatalytic materials. The
efficiency of photocatalysis is restricted by recombination. In
the illuminated state, on the TiO2 surface, electrons, holes, and
active oxygen species maintain a dynamical equilibrium. When
there is spillover of an oxidizing species, light can be utilized
more efficiently for chemical conversion. This implies that a
hybrid of TiO2 and an adsorbent (e.g., zeolite, active carbon) may
exhibit performance better than that of pure TiO2 . The role of the
adsorbent is not restricted to the adsorption of pollutants; it can
also act as a reaction site via the out-diffusion of oxidizing species.
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.28. (a) Quantum yield dependence on absorbed photons at various initial 2-propanol concentrations; (b) quantum yield dependence on normalized absorbed photon
number (Inorm ) at various initial 2-propanol concentrations [366].
© 1997, American Chemical Society.
The observation of remote photocatalysis may cause concern
regarding the safety of TiO2 photocatalysts. However, the reaction
rates for remote photocatalysis are lower than those for ordinary
photocatalysis, and they decrease with distance. For a 50-µm
diffusion distance, the rate of remote photocatalysis via air
diffusion is ca. 2 orders of magnitude lower than that of ordinary
photocatalysis, while that through surface diffusion is ca. 1 order of
magnitude lower, as roughly estimated by the published data [350,
356,357]. Therefore, the TiO2 surface should not be harmful even
when human skin is in close proximity to it, in the low-intensity
UV light contained in solar light or interior illumination.
Remote photocatalysis through air diffusion of oxidizing species
may have applications in lithographic techniques. Tatsuma et al.
[360,363] have investigated the feasibility of this new technique
and have observed the patterning of copper plates and organic
monolayer-modified glass, with a resolution of 10 µm or better, by
placing a TiO2 film on the surface to be patterned and irradiating
the film through a photomask. The technique requires neither
photo-resist nor special equipment other than a light source.
4.2. Photocatalytic reactions
As mentioned above, several kinds of active oxidative species,
−
including free and trapped holes, •OH radicals, O•2 , and 1 O2 , are
involved in the initiation of photocatalytic oxidation reactions [6,
11,15,16,283,302,311,317,364]. This offers the TiO2 photocatalyst’s
superior ability to oxidize almost all kinds of organic and polymer
materials, kill microbes, and mineralize these substances with
the aid of molecular oxygen. These reactions mainly occur on or
very close to the surface of the TiO2 photocatalyst. The remote
photocatalysis also contributes to the oxidation reactions, but as
mentioned above, at rates one or two orders of magnitude lower.
4.2.1. Decomposition of gaseous pollutants
Under UV illumination, TiO2 is able to oxidize gaseous
pollutants in quantum yields ranging from 1% to over unity, which
has important applications in cleaning indoor and outdoor air [11].
Given that there is a sufficient supply of O2 and UV illumination,
gaseous organic substrates can be completely degraded into CO2 ,
H2 O, and mineral acids on a TiO2 thin film. However, the removal
rate is influenced by numerous parameters; these include light
intensity, substrate concentration, O2 partial pressure, humidity,
substrate type, and so on. Also, in many cases, the generation of
relatively stable reaction intermediates lowers the removal rate
and even stops the reaction through blocking active sites [365].
Air–solid photocatalytic reactions are influenced by substrate
concentration and incident light intensity in a cooperative
551
way. Ohko et al. measured the quantum yield (QY) of a
simple photocatalytic reaction, 2-propanol oxidation, on a TiO2
film in ambient air, for a series of 2-propanol concentrations
(1–1000 ppmv) and a wide range of light intensity (tens of
nW cm−2 –1 mW cm−2 ) [366]. They found that the QY increased
gradually with decreasing light intensity I, and reached a
maximum value when the light intensity was extremely low. They
designated the condition for maximum QY as light-limited. They
also found that when the 2-propanol concentration was decreased,
the maximum QY was obtained at lower light intensity. They
replotted QY as a function of a normalized light intensity (Inorm ),
which was defined as the ratio of the number of photons absorbed
per second to the number of adsorbed 2-propanol molecules,
both normalized to the geometric area. The plots obtained for
different initial concentrations of 2-propanol fell on the same
curve, which is a very interesting result (Fig. 4.28). QY increased
as Inorm decreased and finally became constant at ∼28% for Inorm
values below 10−4 s−1 . The maximum QY varied from film to
film, which indicated that there are recombination losses that are
intrinsic to each film. As interesting as these results are, they are
yet to be adequately explained.
The mechanism of photodecomposition of 2-propanol does
not involve chain reactions. Only one photon participates in
the generation of one molecule of acetone. Interestingly, the
QY of acetaldehyde degradation, for which there is the possible
involvement of radical chain reactions, exhibited the same trend
as 2-propanol [367]. The curves for both acetaldehyde and 2-
propanol coincided over a wide range of Inorm values (>10−4 s−1 ),
except for the region of Inorm below 10−4 s−1 , where the QY
values for acetaldehyde degradation continued to increase with
decreasing Inorm and reached 180% for the value of Inorm of 3 ×
10−5 s−1 due to the involvement of the radical chain pathway.
It should be pointed out that, aside from the light-limited con-
dition, over a wide range of experimental conditions, photocat-
alytic reactions on TiO2 follow reasonably well-known behavior,
i.e., first-order kinetics in the adsorbed concentration of the organic
compound and an order of α in light intensity [6].
r = kΓ I α . (4.20)
Here, r is the reaction rate, k the first-order rate constant, Γ the
concentration per unit real surface area, and I the light intensity.
Under light-rich conditions, the value of α is between 0 and
1 [239]. This was explained by considering the recombination
of charge carriers to surface-adsorbed intermediate products
[239]. Conversely, the light-limited reaction rate is represented
as α = 1. Many organic compounds, as well as noxious gases
such as H2 S and NH3 , follow Langmuir adsorption behavior, so
552 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
that this simple equation can be converted into the familiar
Langmuir–Hinshelwood form by substituting the expression for Γ :
Γ −1 = Γ0−1 + (Keq c )−1 (4.21)
where Γ0 is the surface concentration at full coverage, Keq the
adsorption equilibrium constant and c the gas-phase or liquid-
phase concentration [6,11,15].
The O2 concentration also greatly influenced the mineralization
of gaseous organic substances. Durrant et al. suggested that
an oxygen concentration of 5% is sufficient to suppress charge
recombination through capture of photogenerated electrons [238].
However, the study of Lichtin et al. clearly showed that high O2
concentration facilitates the complete mineralization of organic
pollutants [368]. Lichtin et al. measured the molar ratio of CO2
produced to vaporized CH3 OH removed after 15 min of irradiation
in different O2 concentrations. They observed that in 20% O2 ,
generation of the stoichiometric yield of CO2 took twice as long
as complete removal of CH3 OH, while in 100 mol% O2 the times
required for complete removal of CH3 OH vapor and for formation
of CO2 were similar. This supports the Gerischer–Heller proposal
that the photocatalytic oxidation of organic pollutants is mostly
mediated by molecular oxygen, as mentioned in Section 4.1.5.
Humidity influences the removal rate in a complicated way
and appears to be dependent on the concentration and type of
organic compound. Obee et al. reported that ethylene oxidation
rates decreased significantly as the water vapor concentration was
increased from 1000 ppmv [369]. The influence of water vapor on
the reaction rate derived from the low adsorption of ethylene due
to its low adsorption affinity relative to water. Sano et al. observed
that the removal rate of acetaldehyde was higher in dry air than in
humidified air (50% relative humidity) [370]. However, Einaga et al.
found that in the cases of benzene, toluene, and hexane, removal
rates decreased with decreasing humidity, due to the increasing
amounts of carbon deposits on TiO2 [371]. Blount and Falconer
also observed the same phenomenon in toluene photocatalytic
oxidation [372]. Recently, Jo and Park reported that in the case
of very low-level contamination in indoor air (ppb level), there is
no appreciable dependency on humidity for removal of volatile
organic compounds (VOCs), which results from the competitive
adsorption of water and the substrate compounds on the TiO2
surface [373].
The removal rate is also influenced by the type of substrate com-
pound. A comparison of reaction rates between 0.1 to 100 ppmv for
toluene, n-butane, 1,3-dichloroethene, n-hexane, methyl-ethyl-
ketone, n-decane, propanal, 1-butanol, trichloroethylene, ethy-
lene, ammonia and phosgene showed that the rates, from the most
to least reactive, differed by about a factor of fifteen at any particu-
lar concentration [11]. Substrates such as trichloroethylene, whose
degradation concerns radical propagation, are often degraded at a
high rate. The degradation of aromatic substrates is slow and suf-
fers photocatalyst deactivation due to the accumulation of reaction
intermediates.
As often mentioned in the literature, photocatalyst deactivation
is a general problem in the removal of gaseous pollutants, due
to the accumulation of intermediate products or products on the
TiO2 surface [8]. Some deactivations are reversible; the deactivated
photocatalyst could recover activity after UV illumination in clean
humid air [8,372,373]. Some deactivations are irreversible; these
are often observed in the removal of gaseous pollutants containing
heteroatoms such as S, N, P, and Si, etc. [374–377]. In such cases,
mineral acid products block the active surface sites, and thus water
washing is needed to regenerate the deactivated photocatalyst.
Loading noble metals can retard the deactivation of TiO2
photocatalysts. Einaga et al. reported that Rh0 could greatly
improve the catalyst durability in benzene photo-oxidation [378].
The role of Rh0 supported on the TiO2 surface is to reduce the
amounts of carbonaceous intermediates and byproducts on the
catalyst surface. Sano et al. reported that Pt–TiO2 could be free from
deactivation in the removal of acetaldehyde and toluene through
a combination of photocatalysis and thermocatalysis [371]. They
combined Pt–TiO2 photocatalysts with a solar concentrator, by
which the photocatalyst could be heated to about 200 ◦ C. At
this temperature, Pt could effectively decompose the intermediate
products and prevent the TiO2 from deactivating.
4.2.2. Decomposition of aqueous pollutants
Most of the organic pollutants in water can be completely de-
composed and mineralized at the surface of UV-excited TiO2 pho-
tocatalysts; these include alkanes, haloalkanes, aliphatic alcohols,
carboxylic acids, alkenes, aromatics, haloaromatics, polymers, sur-
factants, herbicides, pesticides, and dyes [11,365,379–382]. While
only UV light and O2 are necessary for the reactions, many factors
such as light intensity, pH, ions, photocatalysts, kinds and concen-
trations of substrates, etc., have a great influence on the efficiency
of the mineralization process. As in the gas–solid system, photocat-
alytic reactions in water work best at room temperature, and thus
no heating is needed.
Serpone and co-workers studied the quantum yields of
liquid–solid photocatalytic reactions on TiO2 slurry photocatalysts
[239,383–385]. Similarly to the study of Ohko et al., they found
that maximum quantum yields could be obtained under light-
limited conditions, that is, low light intensity and relative high
substrate concentration [239]. The maximum QY (365 nm) for
phenol degradation was measured as 14% using Degussa P25
as a photocatalyst at pH 3, and this value varied over a range
of 3.5%–30% for six types of TiO2 photocatalysts tested [383,
384]. Aside from the light-limited condition, over a wide range
of experimental conditions, liquid–solid photocatalytic reactions
on TiO2 can also be described by Eq. (4.20), the same as for
gas–solid photocatalytic reactions [239]. The QYs measured in
these conditions varied over the wide range of 0.1%–10%, which
was several times lower than those of gas–solid photocatalytic
reactions [4,11,379]. The low QY should restrict the applications
of TiO2 photocatalysis in water purification. The intrinsic reasons
for the lower QY in water vs. air are yet to be explained in detail.
Pichat et al. studied the influence of the sintering process on the
photocatalytic removal rate of various organic pollutants in water
[386–388]. While the increase of sintering temperature is expected
to decrease the recombination rate of charge carriers; it does re-
sult in a decrease in surface area. Their purpose was to examine
the net effect of the sintering process on photocatalytic reactions.
In one study, they compared the removal rate of three chlorophe-
nolic compounds and one chloroaliphatic acid compound on four
TiO2 samples, which were all obtained identically by TiOSO4 ther-
mohydrolysis with subsequent calcinations at various tempera-
tures [388]. They found that the removal rate increased with the
sintering temperatures for the three chlorophenolic compounds,
whereas it was the opposite for the aliphatic acid compound. They
suggested that the hole attack mechanism for carboxylic acids is
much more sensitive to surface area variation than would be the
•OH radical mechanism for cholorophenolic compounds, which
can react in the near-surface solution phase. Their studies demon-
strate suggest the difficulty in finding a high-efficiency photocata-
lyst versatile for all types of pollutants in water [386].
Generally, loading of noble metal co-catalysts such as Pt, Au, and
Pd, etc., enables accelerating liquid–solid photocatalytic reactions
[389]. These co-catalysts could enhance the charge separation
and catalyze the oxygen reduction reaction. Recent studies
suggest that addition of electron receptors, such as hydrogen
peroxide, ozone, persulfate, etc., also works well for improving
reaction rates [382,390,391]. These electron receptors are more
reducible than molecular oxygen. Moreover, when accepting an
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582 553

Table 4.3
Photodecomposition of various organic compounds on TiO2 film [400].
Samples Stoichiometric formula Melting point (◦ C) Light intensity (mW cm−2 ) Rate constants (µg cm−2 h−1 )

Octadecane C18 H38 28.28 0.8 0.70

Stearic acid C18 H36 O2 69.3 0.8 0.75
Glycerol trioleate C57 H104 O6 −5 1.1 6.6
Glycerol C3 H8 O3 17.8 1.1 31
Liquid paraffina – −12.5 1.1 7.6
Salad oilb – −5 to −10 1.1 6.2
PEG (MW 600 D) (C2 H6 O2 )n 15–25 1.1 17
PEG (MW 500kD) (C2 H6 O2 )n 57–65 1.1 12
a
Including 15–20-carbon hydrocarbons, alkyl naphthalene hydrocarbons.
b
Including oleic, linoleic, linolenic, palmitic acids and stearic acid.

Fig. 4.29. (a) Pots of weight changes vs. illumination time for the photodecomposition of octadecane under 0.8 mW cm−2 UV illumination. (b) Plots of weight changes vs.
illumination time for the photodecomposition of glycerol trioleate (•), glycerol (), liquid paraffin (+), and salad oil (×) under 1.1 mW cm−2 UV illumination [400]. ©2000,
Elsevier Sciences B.V.

electron, these chemicals will dissociate into highly reactive
radicals in subsequent reactions, which can also participate in the
photocatalytic reactions [382,390,391]:
H2 O2 + e− → OH− + •OH
O3 + e + H− +
→ O2 + •OH
S2 O28− +e →−
SO24− + SO4•− .
4.2.3. Decomposition of liquid and solid films
The photocatalytic decomposition of monolayers, multi-layers,
and thin films of organic substances has been well studied for
the purpose of development of self-cleaning surfaces [5,9,10,
392–404]. Minabe et al. compared the decomposition of several
liquid and solid organic films (∼500 nm thick) on TiO2 surfaces,
under about 1 mW cm−2 UV illumination (Table 4.3) [400]. All
of the compounds exhibited pseudo-zero-order kinetics in the
initial stage of the reactions. This is reasonable, since the effective
concentration of reactant is high and can be approximated by a
constant value. Carbon dioxide was the only detectable gaseous
product during the experiments. The weight change vs. time
behavior during the initial stages for octadecane and stearic
acid yielded similar rates, i.e., thinning rates of 9–11 nm h−1
(Fig. 4.29). The decomposition rate (ca. 70 nm h−1 ) for glycerol
trioleate, however, was much higher than those for octadecane
and stearic acid. Other liquid compounds, including liquid paraffin,
salad oil, glycerol, and even polyethylene oxide, etc., exhibited
degradation rates similar to that for glycerol trioleate. Thus, the
degradation rates of organic films are dependent on their physical
states, i.e., solid or liquid film. The higher rates for liquid organic
compounds are reasonable, since organic compounds in the liquid
state can remain in more intimate physical contact with the TiO2
surface than those in the solid state.
The decomposition rates of oily compounds were found to
be dependent on the square root of light intensity [400]. Even
in a dry atmosphere, the organic compounds were effectively
decomposed, suggesting that the water that is generated during
(4.22) the decomposition can be effectively used. The decomposition
(4.23) was believed to occur through a mechanism in which tetraoxide
intermediates are involved (Fig. 4.18). The hydrocarbon chains can
(4.24) be attacked at any point along their length, with C–C bond scission
and subsequent decomposition via the resulting aldehydes [235].
The decomposition process proceeds at significant rates, with the
evolution of CO2 as the only detectable gas-phase product. The
quantum yield for stearic acid decomposition could be over 20%,
as estimated by Mills et al. [404].
Lee et al. studied the solid-phase photocatalytic reaction on
the carbon black soot/TiO2 interface [353]. They observed that
the bulk of the soot layer with ∼2 µm thickness was completely
oxidized to CO2 over a 30-h irradiation. The presence of O2 was
essential in the photocatalytic soot oxidation. In another study,
Cho et al. studied the solid-phase photocatalytic degradation of
polyvinylchloride–TiO2 polymer composites [355]. Irradiating the
composite film for 300 h in air reduced its average molecular
weight by two-thirds and weight by 27%. The photocatalytic
degradation of the composite film was accompanied by an increase
in the FT-IR carbonyl peak intensity, the evolution of CO2 and
H2 O, and whitening due to visible light scattering from growing
cavities. SEM images of the irradiated composite films showed the
development of cavities around the imbedded TiO2 particles and
indicated that active oxygen species which were photogenerated
on TiO2 surface desorbed and diffused across a few micrometers to
react with the polymer matrix.
4.2.4. Photocatalytic sterilization
TiO2 photocatalysts have been found to kill cancer cells,
bacteria, viruses, and algae under UV illumination [10,405–410].
554 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

Fig. 4.30. AFM images of E. coli cells on a TiO2 film: (a) no illumination; (b) illumination for 1 day; (c) illumination for 6 days; light intensity was 1.0 mW cm−2 . The outermost
layer, labeled as ‘‘A’’ in (a), disappeared after 24 h of illumination, with no layer visible in image (b) at the designated positions [414]. ©2003, Elsevier Science S.A.

Fig. 4.31. Schematic illustration of the three stages in the process of E. coli photokilling on a TiO2 film. In the lower row, part of the cell envelope is magnified [414]. ©2003,
Elsevier Science S.A.

This results in important applications in the disinfection of
air, water, and surfaces with TiO2 photocatalysis. Kikuchi et al.
studied the killing of Escherichia coli on TiO2 thin films [347]. A
typical experiment involves placing 150 microlitres of an E. coli
suspension, containing 3 × 104 cells, on an illuminated TiO2 -
coated glass plate (1 mW cm−2 UV light). Under these conditions,
there were no surviving cells after only 1 h of illumination. Even
when the cells were separated from the TiO2 film by a 50-µm
PTFE membrane, with 0.4 µm pores, the cells were still killed
remotely: after 4 h, there were none remaining. By contrast, after
4 h under UV illumination without a TiO2 film, only 50% of the
cells were killed. Further studies showed that various bacteria,
E. coli, Staphylococcus aureus, and Pseudomonas aeruginosa, etc.,
were killed rapidly on TiO2 surfaces under UVA illumination
(320–380 nm, ∼1 mW cm−2 ) [9]. Kühn et al. observed that the
killing rates of bacteria were dependent on the thickness and
structure of cell walls [411]. Bacteria having thin cell walls, such as
E. coli, and P. aeruginosa were killed much faster than bacteria such
as Candida albicans that have a thick eukaryotic cell wall [411].
Sunada et al. observed that not only bacteria are killed on the
TiO2 surface by photocatalytic action, but also the toxic ingredient
of bacteria can be decomposed [412]. If the UV illumination
continued for a sufficiently long time, the bacteria were found
to be mineralized completely into CO2 , H2 O and other mineral
substances [413–415]. This is a unique property of photocatalytic
sterilization compared to that of other antibacterial agents.
Besides bacteria, viruses and fungi can also be killed and totally
mineralized by photocatalytic action [408,413], but the killing of
fungi sometimes is much slower than that of bacteria because of
their chemical stability [413].
Sunada et al. studied the photokilling process of E. coli by
means of AFM (Fig. 4.30) [414]. They found that the photokilling
of bacteria on the illuminated TiO2 surface could be divided into
three stages (Fig. 4.31): (1) disordering of the outer membrane of
bacteria cells by reactive species (•OH, H2 O2 , O•−
2 ); (2) disordering
of the inner membrane (the cytoplasmic membrane) and killing of
the cell; and (3) decomposition of the dead cell. In the first stage,
the outer membranes of E. coli cells were decomposed partially by
the reactive species produced by the TiO2 photocatalyst. During
this stage, cell viability was not lost very efficiently. The partial
decomposition of the outer membrane, however, changes the
permeability to reactive species. Consequently, reactive species
easily reach and attack the inner membrane, leading to the
peroxidation of the membrane lipid. The structural and functional
disordering of the cytoplasmic membrane due to lipid peroxidation
led to the loss of cell viability and cell death. If the illumination
continued for a sufficiently long time, the dead cells were found to
be decomposed completely.
Ordinary TiO2 surfaces do not work well in killing bacteria
under low-intensity UV illumination. However, when there are
Cu particles dispersed on the TiO2 surfaces, the hybrid surfaces
exhibit excellent self-sterilizing properties even under room light
that contains only a very small amount of UV light (∼1 µW cm−2 )
(Fig. 4.32) [416]. Although metallic Cu is a kind of antibacterial
material that works even in the dark, it is not the only reason for
the observed antibacterial effect of the hybrid films, since some Cu-
resistant bacteria can be effectively killed on the TiO2 –Cu hybrid
surface under indoor illumination [416]. Comparative studies
showed that metallic Ag also enhanced the antibacterial effect of
TiO2 film, but metallic Pt did not, even though Pt could improve the
photocatalytic performance of TiO2 . Based on these observations,
Sunada et al. proposed a mechanism for the enhanced antibacterial
performance of TiO2 –Cu hybrid film that emphasizes the effect
of cuprous ions [416]. Under UV illumination, cuprous ions may
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.32. Changes in survival of copper-resistant E. coli cells on a Cu/TiO2
film under dark condition (•) and under UV illumination at light intensities of
7 µW cm−2 () and 1 µW cm−2 (N) [416].
© 2003, American Chemical Society.
exist on the TiO2 surface through the oxidation of metallic copper
with photogenerated holes. The cuprous ion may play two roles
in killing bacteria: (1) it increases the yield of hydroxyl radical
through a photo-Fenton process by reaction with photogenerated
H2 O2 ; and (2) it diffuses into the cytoplasmic membrane of the
bacteria and accelerates the lethal effect after the outer membrane
of the bacteria is destroyed by oxidizing species.
4.3. Visible-light-induced photocatalysis
Due to their wide band-gaps, pristine anatase and rutile TiO2
photocatalysts mainly absorb ultraviolet photons. However, solar
light only contains a small amount of ultraviolet photons (about
5%), and room light lamps emit mainly visible photons. Therefore,
starting one decade ago, efforts have been devoted to extending
the spectral response of pure TiO2 material (mainly anatase TiO2 )
to visible light. These efforts have included doping TiO2 with
metal impurities [417–425], coupling TiO2 with narrow band-gap
semiconductors [426,427], preparing oxygen-deficient TiO2 [428–
433], and doping TiO2 with non-metal atoms (anion doping) [434–
462,221,463–487]. Especially in recent years, non-metal doping
has become the most attractive; various non-metallic elements
Fig. 4.33. (a) Optical absorption spectra of TiO2−x Nx and TiO2 films. (b) N 1s XPS spectra of TiO2−x Nx and TiO2 films. (c) CO2 evolution as a function of irradiation time (light
at zero) during the photodegradation of acetaldehyde gas under UV irradiation and visible irradiation [435].
© 2001, The American Association for the Advancement of Science.
555
such as N [434–464], C [221,465–474], S [475–481], B [482], P
[483], and F [484–487], were reported to shift the absorption
threshold of TiO2 into the visible range and provide the TiO2
material with photocatalytic activity under visible illumination.
Various mechanisms have been postulated to explain the shift of
absorption threshold and the photocatalytic activity of non-metal-
doped TiO2 photocatalysts [435,449,450,452,459]. These will be
summarized in the sections below.
4.3.1. Non-metal doping
N-doped TiO2 . In a paper published in 1986, Sato described
that impurity NH4 Cl shifted the absorption threshold of TiO2
into the visible light region upon calcination [434]. The as-
calcined material, assigned to NOx -doped TiO2 , showed higher
photocatalytic activity for oxygen isotope equilibration and the
oxidation of carbon monoxide and ethane than pristine TiO2 in
the visible light region. This work, however, was not noticed for
quite a long time. Fifteen years after Sato’s paper, Asahi et al.
reported visible light photocatalysis with N-doped TiO2 [435].
They prepared the photocatalysts by two methods: one was by
sputtering a TiO2 target in an N2 /Ar gas mixture; the other was
by calcining TiO2 powder in an NH3 /Ar atmosphere. Both methods
produced yellowish TiO2 photocatalysts that noticeably absorbed
light at less than 500 nm and showed activity under visible
illumination for decomposition of acetaldehyde and decoloration
of methylene blue solution (Fig. 4.33). Nitrogen atoms were
believed to substitute for lattice oxygen atoms, as evidenced by the
peak at 396 eV in the N 1s XPS spectra.
Asahi’s work is considered as a breakthrough in visible light
photocatalysis. After that, researchers started to consider the
doping TiO2 with non-metal atoms in order to obtain visible light
photoactivity, with N-doped TiO2 being the most studied system.
There have been a great volume of publications that deal with
the preparation of N-doped TiO2 by physical or chemical methods,
including sol-gel [437,442,445,448,449,452,461], sputtering [440,
453], ion implantation [455,456], and plasma-enhanced chemical
vapor deposition method [454]. Either substitutional or interstitial
nitrogen is assigned to the observed photocatalytic activity
under visible illumination. Various spectroscopic techniques [449,
451,452,457,462,463], surface analysis techniques [455,456], as
well as theoretical calculations [435,447,449,450,456] have been
applied to N-doped TiO2 in order to elucidate the origin of the
visible light photoactivity and to develop visible-light-responsive
photocatalysts with higher activity.
C-doped TiO2 . Khan et al. reported in 2002 that the controlled
combustion of Ti metal in a natural gas flame could produce
556 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
C-doped TiO2 with an absorption threshold that was extended
into the visible spectral range [465]. The preparation method
was similar to that first used by Fujishima and Honda in the
early 1970s for the photoelectrochemical splitting of water [54].
Khan et al. claimed that carbon substituted for some of the
lattice oxygen atoms in their sample. Besides the lower band-
gap energy than rutile (2.32 vs. 3.00 eV) estimated from the
absorption spectrum, the C-doped TiO2 material was reported
to photoelectrochemically split water with the unbelievably high
photoconversion efficiency of 8.35% under Xe lamp illumination
[465]. Their work was critically commented on by several groups
[221,466–468]; the main criticism was the high photoconversion
efficiency. It should be noted that, in their paper Khan et al.
did not provide any evidence of carbon doping or photoactivity
under visible illumination. A later study by Bard and co-workers
showed that TiO2 nanotube arrays annealed under controlled CO
gas flow could split water under visible illumination, but they did
not try to estimate the photoconversion efficiency [470]. Recently,
Grimes and co-workers have actively investigated carbon-doped
TiO2 nanotubes for photoelectrochemical water splitting and have
reported efficiencies as high as 6.8% [488–490].
Irie et al. reported the preparation of carbon-doped TiO2
by oxidative heating of TiC powder [469]. Either anatase or
rutile type C-doped TiO2 was prepared through control of the
heating temperature. The prepared materials were yellowish with
noticeable shifts of the absorption threshold to the visible spectral
region. The carbon dopant showed a peak at 281.8 eV in the
C 1s XPS spectra, which was assigned to substituted carbon. A
similar peak was also observed on the C-doped TiO2 samples
prepared by reactive sputtering [473] and ion-assisted electron-
beam deposition methods [474]. The photocatalytic activity of C-
doped TiO2 under visible illumination was quite weak, as evaluated
by the decomposition of gaseous 2-propanol [469].
S-doped TiO2 . Umebayashi et al. reported that sulfur doping was
unable to extend the absorption of TiO2 into the visible region
[475–477]. They prepared S-doped TiO2 either by oxidative heating
of TiS2 powder [475,476] or by sulfur-ion implantation [477]. In
either case, a red-shift of the absorption threshold was observed
compared to pristine TiO2 , and the prepared materials were able
to generate photocurrent and to decolor methylene blue solution
under visible illumination. Umebayashi et al. explained the
observed photoactivity in the visible spectrum to the substitution
of oxygen atoms with sulfur, which caused the narrowing of the
band-gap [477].
Ohno et al. found that S-doped TiO2 could be easily prepared by
a chemically modified sol-gel process [478–480]. They prepared
the precursor powder by mixing titanium isopropoxide with
thiourea; heating the powder produced yellow-colored S-doped
TiO2 . The oxidation states of sulfur in Ohno’s samples, however,
were S4+ and/or S6+ , inconsistent with the results of Umebayashi
et al. [479]. Sakthivel and Kisch followed the experiments of Ohno
et al.; however, they did not find any evidence of sulfur doping.
Instead, they claimed the formation of N-doped TiO2 [442]. This
disagreement suggests the complexity of the chemistry involved
in the preparation, and the possible misreading of characterization
results.
Others. There are several reports that deal with doping TiO2 with
B [482], P [483], or F [484–487] atoms by the sol-gel method.
The doped TiO2 materials are all yellowish, similar to N-, C-, or
S-doped TiO2 , and have been reported to exhibit activities for
decomposition of organic substances.
TiO2−x , the oxygen-deficient form of TiO2 , has also been
studied extensively as a visible-light-responsive photocatalyst
[428–433]. Nakamura et al. reported the preparation of TiO2−x
through the H2 plasma treatment of TiO2 powders [428]. The
TiO2−x photocatalysts showed weak absorption in the region
of 400–500 nm, and were able to oxidize nitrogen oxides
under visible illumination. Justicia et al. prepared TiO2−x films
by metal-organic chemical vapor deposition, using titanium
tetraisopropoxide as a Ti precursor and N2 as the carrier gas [430].
Their preparation condition was quite similar to several chemical
preparations of non-metal-doped TiO2 materials, i.e., a reducing
atmosphere was involved in the preparation [470,471].
4.3.2. Origin of visible light photoactivity
Although there has been much published work on non-metal-
doped TiO2 materials, the origin of visible light photoactivity
of these materials is still in debate [435,449,450,452,459]. The
controversies are focused on two issues: (1) the origin of
the absorption in the visible light region; and (2) in what
state the non-metal atoms are doped in the TiO2 lattice. As a
representative, N-doped TiO2 has been examined intensively by
various experimental and theoretical methods. In particular, recent
works that combine density functional theory calculations with
surface analysis techniques and spectroscopic characterization
have shed light on the origin of the visible light activity of N-doped
TiO2 [449,452,456]. These also aid the understanding of other non-
metal-doped TiO2 materials.
Origin of absorption in the visible light region. In their paper in
2001, Asahi et al. suggested that the N 2p level could mix with
the valence band of TiO2 , which is mainly made up of O 2p, and
this resulted in the narrowing of the band-gap and photocatalytic
activity in the visible light region (Fig. 4.33) [435]. They calculated
the densities of states of the substitutional doping of C, N, F, P, or
S or O in the anatase TiO2 crystal by the full-potential linearized
augmented plane wave (FLAPW) formalism in the framework of
the local density approximation (LDA). Their calculation supported
the idea of band-gap narrowing with N doping.
The model of band-gap narrowing was soon challenged by
several experimental and theoretical studies on N-doped TiO2
materials [437–441,443,447,459]. As commented by Serpone, it
is hard to believe that a low level of doping (<2 atomic %) can
rigidly shift up the valence band [459]. Irie et al. reported that
the quantum yields of gaseous 2-propanol decomposition on N-
doped TiO2 powders under visible illumination were several times
lower than those under UV illumination [438]. This observation
could not be explained by the band-gap narrowing model. Instead,
it suggested that nitrogen doping led to the formation of localized
midgap states above the valence-band edge (Fig. 4.34). Torres
et al. studied the photoelectrochemical behavior of N-doped TiO2
for water oxidation [440]. They observed that UV light gives a
higher probability than visible light for the electrons and holes to
leave the electrode and contribute to a photocurrent and oxidizing
water, which is consistent with the conclusion of Irie et al. [438].
Nakamura et al. observed that an N-doped TiO2 photoelectrode
could oxidize SCN− and Br− under UV illumination; however,
no oxidation was observed under visible illumination [439]. This
study also points out the possibility that the doped nitrogen species
gives rise to a midgap level slightly above the top of the valence
band. A similar conclusion was drawn by Tachikawa et al. in
transient spectroscopy studies on N-doped TiO2 [457], as well as
C- and S-doped TiO2 [481].
Lin et al. used the spin-polarized plane-wave pseudopotential
method, based on density functional theory, to calculate the
electronic-band structures and the optical absorption spectra of
nitrogen-doped TiO2 [450]. According to their calculation results,
substitutional nitrogen should give rise to localized N 2p acceptor
states above the valence band, and absorption in the region
between 400 and 500 nm in the calculated spectrum. Moreover,
the calculation reveals that even for high nitrogen concentration
(12.5% doping), the N 2p states are still localized, lying slightly
above the top of the O 2p valence band. Their conclusion is in
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.34. Various schemes illustrating the possible band-gap electronic structure
and excitation processes of visible-light-responsive TiO2 materials: (a) pure TiO2 ;
(b) band-gap narrowing model for non-metal-doped TiO2 ; (c) oxygen-deficient
TiO2 ; (d) localized midgap level model for non-metal-doped TiO2 ; (e) oxygen
vacancy levels and non-metal-doped midgap levels are considered together.
Fig. 4.35. Valence-band spectra for Ar+ -reduced and N-implanted rutile TiO2
(110), acquired with a photon energy of 325 eV. Dashed lines denote the reference
spectrum from stoichiometric TiO2 (110) [456].
© 2006, American Institute of Physics.
contrast to the spin-restricted FLAPW calculation of Asahi et al.
[435], but is consistent with spin-polarized calculations [447] and
several experimental results [437–441]. They also found that at
least 20% N doping is needed to mix the N 2p state with the O 2p
valence band, but in practice such a high doping level would result
in the formation of TiN [448,462].
The formation of localized midgap states is further proven
by recent UV-photoelectron spectroscopy (UPS) studies on N-
implanted TiO2 single crystals [455,456]. Batzill et al. doped
rutile and anatase single crystal surfaces by low energy nitrogen
ion implantation (N. 3 at.%); the single N 1s peak at a binding
energy of 396 eV suggests that the doping is of a substitutional
type [455]. Ultraviolet photoemission studies show that N doping
induces localized N 2p states within the band-gap just above
the valence band, but no evidence of band-gap narrowing is
observed in this study. For the rutile (110) surface, N doping shifts
the edge up by 0.4 eV; for the anatase surface, the N-derived
states span the region in the band-gap from the valence band
maximum up to the higher lying Ti 3d defect states [455]. In
557
later synchrotron-based photoemission studies, Nambu et al. also
reached the same conclusion on the N-doped rutile (110) surface
[456]. They compared the valence-band spectra of Ar+ -reduced
and N-implanted rutile TiO2 (110), and found that both spectra
contained new states just below the Fermi level EF that could be
assigned to the occupied 3d states of Ti3+ , but for the N-implanted
TiO2 , they observed extra features above the top of the O 2p band,
which shifted the edge by ∼0.5 V towards EF (Fig. 4.35) [456].
Considering that the conduction-band edge is little influenced by
nitrogen doping [442], the N-derived states should result in a red-
shift of the absorption edge of N-doped TiO2 materials.
The doping of nitrogen facilitates the formation of oxygen
vacancies in TiO2 materials, which is observed as midgap
states below the conduction band [440,449,451,452,455,456]. This
explains why N doping does not change the n-type semiconducting
TiO2 to p-type. In the case of the rutile (110) surface, N doping led
to a 1 × 2 type surface reconstruction, triggered by the increased
formation of oxygen vacancies [455]. EPR and UPS studies, and
DFT calculations revealed the existence of attractive interactions
between the dopants and the O vacancies [449,452,456]. The
presence of nitrogen dopants was found to reduce the formation
energy of oxygen vacancies [451,452]. At the same time, the
existence of O vacancies stabilized the N impurities [449,452,456].
When oxygen vacancies and N impurities are together, there is an
electron transfer from the higher energy 3d band of Ti3+ to the
lower energy 2p band of the nitrogen impurities [449,452,456].
Oxygen vacancies also contribute to the absorption in the
visible light region (Fig. 4.36) [450]. This point was often neglected
in studies on non-metal-doped TiO2 [459,460]. Lin et al. calculated
the absorption spectra of oxygen-deficient TiO2 and found that the
entire absorption edge of oxygen-deficient TiO2 is red-shifted by
about 20 nm with the dominant visible light absorption occurring
above 500 nm (Fig. 4.36) [450].
Doping states of nitrogen atoms. As the direct evidence of
nitrogen doping, XPS studies on N-doped TiO2 materials often give
two kinds of N 1s peaks, one at about 396 eV, and the other one at
about 400 eV [452]. Sato observed a peak at 400 eV for TiO2 powder
heated in the presence of ammonium chloride and assigned the
peak to an NOx species [434]. Asahi et al., however, observed an
additional peak at 396 eV for a TiO2 film prepared by the sputtering
method in addition to the peak at 400 eV [435]. They assigned
the 396 eV peak to substitutional N doping, and argued that
only substitutional N is responsible for the observed photoactivity
under visible illumination, since the 400 eV peak is also observable
for pristine TiO2 powders. In later studies, the peak at about 400
eV was frequently observed, in particular for the samples prepared
by chemical methods [438,442,444,452,461]. In some cases, only
the peak at 400 eV was observed for N-doped TiO2 materials
that exhibited photocatalytic activity under visible illumination
[442,452,461]. It was thus believed that at least two kinds of
nitrogen doping are responsible for the visible light photoactivity.
The 396 eV peak is generally assigned to substitutional nitrogen
doping; while the 400 eV peak is believed to related to interstitial
nitrogen doping.
Di Valentin et al. studied N-doped TiO2 powder prepared by the
sol-gel method with EPR combined with DFT calculations [449].
They observed the presence of two slightly different nitrogen
species in the EPR spectra. On the basis of comparison with the DFT
calculations, one of the two species was assigned to substitutional
nitrogen atoms, and the other was assigned to interstitial nitrogen
in the form of NO (Fig. 4.37). In another study, Reyes-Garcia
et al. studied N-doped TiO2 photocatalysts with 15 N solid state
NMR and EPR characterization [461]. Their samples were prepared
by high temperature nitridation of TiO2 nanoparticles in the
presence of urea, or by a sol-gel preparation with various N-
containing chemicals as nitrogen sources. Interstitial nitrogen
558 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

Table 4.4
Preparation and characteristics of N-doped TiO2 films.
Author (Ref.) Preparation method Description Photocatalytic activity

Asahi et al. [435] Sputtering deposition in N2 /Ar, Or
annealing TiO2 powders in NH3 at
873K
Burda et al. [446] Nitriding TiO2 nanoparticles with
triethyl amine.
Sakthivel Sakthivel et al. [443] Hydrolyzing TiCl4 in water with
addition of ammonia, post-annealing
at 673 K.
Irie et al. [438] Annealing TiO2 powders in NH3
Mrowetz et al. [441] One sample (a) was prepared by
Burda’s method, the other sample (H)
was prepared similarly to Asahi’s and
Irie’s works.
Diwald et al. [444] Annealing rutile (110) in NH3 at 873 K.
Maeda et al. [454] PECVD in NH3 /Ar using Ti(Oi Pr)4 as
precursor; post-annealing over 673 K.
Kitano et al. [453] RF Magnetron sputtering in N2 /Ar
Yates et al. [491] Chemical vapor deposition in NH3 /N2 ,
using TiCl4 and ethyl acetate as
precursor.
Absorption onset: 500 nm; N1s peaks
at 396 eV and 400 eV; nitrogen
concentration: 1–1.4 atomic %.
Absorption onset: 600 nm, N1s peak at
401.3 eV
Absorption onset: 520 nm; a weak N1s
peak at 404 eV
N-substituted for oxygen: 0.5–1.9%
Increased absorption in the visible
light region for both sample A and
sample H.
N1s peaks at 399.6 and 396.7 eV;
increased absorption in the range of
2.4–3.0 eV.
N1s peaks at 396 eV and 399.3 eV,
Area ratio of the two peaks is 4:1.
N-substituted for oxygen: 2–16.5%;
photo-response up to 550 nm.
Nitrogen atomic concentration: 1.5–5%
Decompose methylene blue and acetaldehyde in
visible irradiation, with similar activity in UV
irradiation as non-doped TiO2 .
Decompose methylene blue in solution by visible
laser.
Degradation of 4-chlorophenol, benzene and
acetaldehyde with visible light (λ > 455 nm),
Degradation of gaseous 2-propanol under visible
light irradiation; UV light activity was weaker for
doped samples than non-doped. Visible light
activity was several times lower than UV light
activity.
Both samples A and H showed no apparent
activity for degradation of HCOO− and NH3 · H2 O
in visible irradiation; sample A was bleached
with UV irradiation.
Photodeposition of Ag from AgNO3 solution in
visible irradiation.
Degradation of stearic acid molecules under
visible irradiation.
Degradation of 2-propanol solution with visible
irradiation; 6% N-substitution is the best.
No visible light activity for degradation of stearic
acid molecules; weak UV-activity.

atoms were observed in their studies, and these were assigned to
nitrates (NOx ).
Di Valentin et al. calculated the electronic-band structures for
substitutional and interstitial N-doped anatase TiO2 [449]. For both
of these N-doped model systems, the formation of localized states
in the band-gap was predicted (Fig. 4.37). Substitutional nitrogen
states lie just above the valence band, while interstitial nitrogen
states lie higher in the gap [449]. The localized nature of the
N-induced states has the consequence that the hole generated
by visible irradiation is less mobile than that generated by UV
irradiation. In particular, the interstitial N impurities, which give
rise to the higher energy states in the gap, might behave as stronger
hole trapping sites, reducing the direct oxidation power of the
sample in the photocatalytic process [449]. The calculations of
Di Valentin et al. also suggested that there is a cost to induce
substitutional nitrogen formation starting from the interstitial one.
In an excess of oxygen and nitrogen, interstitial nitrogen doping is
definitely preferred. However, under highly reducing conditions,
as is the case after annealing at high temperature, substitutional
nitrogen species in parallel with oxygen vacancies could be favored
[449].
4.3.3. Activity and stability of N-doped TiO2 photocatalysts
Asahi reported that nitrogen doping offered visible light (VL)-
photocatalytic activity to TiO2 , without any loss of UV-activity, for
the decoloration of methylene blue solution and degradation of
gaseous acetaldehyde [435]. However, many studies after Asahi’s
work showed that nitrogen doping only offered modest VL-activity
to TiO2 , but at the same time lowered the UV-activity (Table 4.4)
[438,442,443,463,464]. Some studies even showed almost no VL-
activity for N-doped TiO2 (Table 4.4) [441,491]. It thus seems that
the preparation history, which dictates the types and level of
nitrogen doping and the concentration of oxygen vacancies, greatly
influences the photocatalytic activity.
Mrowetz argued that the often-used probe, methylene blue,
is not a good indicator for photocatalytic activity [441]. Methy-
lene blue solution could be decolored via several pathways, in-
cluding oxidation with holes or hydroxyl radicals, reduction with

Fig. 4.36. (a) Calculated optical absorption spectra for various N concentrations in the polycrystalline TiO2 : (I) undoped TiO2 ; (II) 12.5% nitrogen doped; (III) 6.2% nitrogen
doped; and (IV) 3.1% nitrogen doped. (b) Calculated optical absorption spectra of polycrystalline TiO2 with different O vacancy contents: (I) undoped TiO2 ; (II) 12.5% oxygen
vacancies; (III) 6.2% oxygen vacancies; (IV) 3.1% oxygen vacancies [450].
© 2005, American Chemical Society.
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 4.37. Schematic sketch and electronic-band structure for (a) substitutional and
(b) interstitial N-doped anatase TiO2 . The calculated value of the band-gap is also
reported [449].
© 2005, American Chemical Society.
conduction-band electrons, sensitized photodegradation, and ad-
sorption on catalyst surfaces [492–495]. Thus, they studied the
VL-activity of N-doped TiO2 by the oxidation of HCOO− anions in
water [441]. They used two samples: the first, designated ‘‘A’’, was
prepared by Burda’s method, that is, nitriding TiO2 nanoparticles
with triethyl amine [445,446]; the second, designated ‘‘H’’, was
prepared by annealing TiO2 powders in NH3 with a post-annealing
in air. They found that sample A suffered bleaching under UV irra-
diation. They inferred that the reaction between the TiO2 nanopar-
ticles and triethyl amine at room temperature led to the formation
of surface organotitanium complexes, rather than to substitutional
N-doped TiO2 , the former being readily degraded by UV light [441].
Sample H, although doped with nitrogen atoms, did not show ap-
preciable VL-activity for the degradation of HCCO− and NH+ 4 ions
[441]. Moreover, no appreciable hydroxyl radicals were detected
with ESR for H under visible irradiation. Their results are contrast
to those of Asahi [435] and Irie [438], who used similar methods
to prepare N-doped TiO2 materials. One possible reason is that the
post-annealing in Mrowetz’s work might re-oxidize the surface of
sample H, which has a detrimental influence on VL-activity.
Livraghi et al. studied the VL-activity of N-doped TiO2 by means
of EPR spectroscopy [452]. They found that nitrogen dopants form
either diamagnetic (Nb− ) or paramagnetic (Nb• ) bulk centers. Both
Fig. 4.38. (a) EPR signal intensity of Nb• (substitutional and interstitial N) and O•−
2 in various conditions. I0 is the Nb intensity in the non-irradiated sample. ‘‘Blue’’ indicates
437-nm irradiation, while ‘‘Green’’ indicates 500-nm irradiation. (b) Sketch of the proposed mechanism for the processes induced by visible light irradiation of the N-doped
sample in O2 atmosphere [452]. Nb− and Nb• are nitrogen dopants forming paramagnetic and diamagnetic bulk centers, respectively.
© 2006, American Chemical Society.
559
types of Nb• centers give rise to localized states in the band-
gap of the oxide. The diamagnetic Nb− species are expected to
be more abundant than the paramagnetic Nb• ones, since they
are energetically favored. Irradiation with visible light at 437 nm
promotes electrons from these states to the conduction band and
thus leads to the increase of paramagnetic Nb• centers, as shown
in Fig. 4.38. When the irradiation at 437 nm is performed in an
oxygen atmosphere, the increase of the Nb• signal is accompanied
by the simultaneous appearance of new EPR lines corresponding to
a surface superoxide O•−2 radical species (Fig. 4.38), suggesting that
the photoexcited electrons are available for chemical interactions
at the surface [452]. The holes, formed by charge separation,
remain localized on the Nb• centers, which limits the VL-activity of
N-doped TiO2 [452].
Emeline et al. measured the QYs of phenol degradation over a
commercial VL-responsive TiO2 photocatalyst [458]. They found,
under optimum conditions, where recombination losses were
minimal, that the QYs at 365 nm and 436 nm were 12% and
8%, respectively. The QY of phenol degradation over Degussa P25
was 14% at 365 nm measured by the same experimental system
[458]. Emeline’s work was done under ‘‘light-limited’’ conditions,
which is by far different from the ‘‘light-rich’’ conditions of actual
photocatalytic systems. However, this suggested that the VL-
activity of N-doped TiO2 could be comparable to the UV-activity,
provided that the recombinative losses introduced by oxygen
vacancies were suppressed and the absorption of visible light were
improved.
Intense efforts have been devoted to the development of prepa-
ration methods for highly efficient N-doped TiO2 materials in terms
of increasing both the VL-absorption and the activity. Maeda and
Watanabe developed a plasma-enhanced chemical vapor deposi-
tion method to prepare N-doped TiO2 [454], which ensured the
substitutional doping of nitrogen, in contrast to the sol-gel method
or annealing in NH3 , which often produced predominantly inter-
stitially doped nitrogen [434,441,452,461]. Their film photocata-
lysts were able to decompose stearic acid molecules under visible
irradiation, suggesting promising applications in VL-activated self-
cleaning materials [454].
Kitano et al. developed a RF magnetron sputtering technique
to prepare N-doped TiO2 films [453]. By their method, nitrogen
atoms were able to substitute oxygen in the range of 2–16.5%.
Such a high-level doping was not achieved previously and resulted
in a steep absorption edge in the visible light region [453]. A
film photocatalyst with a nitrogen concentration of 6% (strong
absorption up to 500 nm) exhibited the highest reactivity for
the photocatalytic oxidation of 2-propanol in water under visible
•
560 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

irradiation (λ > 450 nm). Higher nitrogen concentration would

introduce large amounts of oxygen vacancies in the films and result
in lower VL-activity [453].
The stability of N-doped TiO2 is also an important issue
concerning actual applications. It was reported that N-doped TiO2
exhibited better thermal stability than oxygen-deficient TiO2 , as a
result of the interaction between the nitrogen dopants and oxygen
vacancies [437]. The latter lost VL-absorption due to oxidation
upon heating at 473 K [437]. However, Kitano et al. observed
that N-doped TiO2 lost VL-absorption gradually upon heating
at 573 K, accompanied by a decrease in nitrogen concentration
[453]. Kitano et al. also examined the stability of N-doped TiO2
film under irradiation [453]. They found that the film after
photoelectrolysis of water under visible irradiation showed a
decreased N concentration at the surface layer, indicating that the
surface of the film was oxidized during photoelectrolysis. These are
challenges for the further development of these types of materials.

5. Fundamentals of the photo-induced hydrophilic (PIH) effect

5.1. Overview

Our group first reported, along with co-workers from the TOTO
Corp., in 1997 on the phenomenon that we termed the ‘‘light-
induced amphiphilic surface’’ [496]. When a titania film was
illuminated with UV light, the contact angle for water decreased
to near 0◦ , and the same occurred also with organic liquids. We
expected that there would be several applications for this new
effect, including self-cleaning surfaces and anti-fogging mirrors.
With friction force microscopy, it was observed that there was
a spontaneous formation of a pattern of two different types of
areas with hydrophobic and hydrophilic properties (Fig. 5.1). We
hypothesized that the presence of two types of surfaces at the tens
of nanometer scale was responsible for the high affinity for both
water and organic liquids, hence the term ‘‘amphiphilic surface’’.
The following year, we published a more detailed article
and included a proposed concept for the mechanism, based
in part on the observed infrared spectrum, which showed the
reversible growth and decay of a peak (3695 cm−1 ) assigned to the
formation of hydroxyl groups, presumably at sites where there had
been dissociative adsorption of water at oxygen vacancies [514].
Even though the ideas have become much more detailed in the
meantime, the same basic idea is still valid. The large number
of studies that have been described in Section 3.4 have led to
a consensus that water is adsorbed molecularly under neutral
pH conditions on the stoichiometric rutile (110) surface. Thus,
the interaction with water is not particularly strong, and the
introduction of hydroxyl groups would be expected to lead to a
surface with a stronger interaction with water.
The effect of enhanced hydrophilicity was found to slowly
revert to the normal, hydrophobic state during storage of the film
in the dark, this process requiring varying amounts of time. It was
found that ultrasonication of the film accelerated the reconversion
to the initial state; with low-intensity agitation (0.6 mW cm−2 ),
the process was found to take ca. 140 min, while, with high-
intensity agitation, it required only 20 min [497]. Subsequent UV
illumination served to make the surface hydrophilic again.
Most of the experiments that were carried out involved pure
anatase TiO2 films, but it was found that the addition of 10–30 wt%
SiO2 to a TiO2 film improved the hydrophilic properties [498]. The
presence of SiO2 helped the films to retain higher surface area and
to suppress the thermal conversion of anatase to rutile during film
heat treatment.
One of the first mechanisms proposed included a step in which
bridging oxygens, such as those on the rutile (110) surface, were
thought to be removed from the surface during UV illumination
Fig. 5.1. (a) Friction force microscopic (FFM) image (5 × 5 µm) for a rutile (110)
surface before UV illumination; (b) FFM image (5 × 5 µm) of the same surface after
illumination; (c) a medium scale FFM image (1000 nm × 1000 nm) of the framed
area in (b); (d) a higher-magnification topographic image (240 × 240 nm) of the
framed area in (c). For (d), the sample stage was rotated 45◦ from the position in (c)
(taken from Wang et al. [514]).
© 1998, John Wiley & Sons.
(see later), and thus it was of interest to examine the influence of
the crystal face exposed. Our study with single crystals of rutile
found that the (110) and (100) faces had similar characteristics,
i.e., both became hydrophilic at about the same rate under UV
illumination [499,500]. However, the (001) surface was found
to be much slower in becoming hydrophilic. Under a pure O2
atmosphere, it was found that, for all three surfaces, (110), (100)
and (001), the effect was partly suppressed; indeed, with the
(001) surface, the effect was almost completely suppressed. X-
ray photoelectron spectra showed that the (110) and (100) faces
acquired a small peak in the Ti 2p spectrum that was attributable
to Ti3+ sites, while the (001) face did not. Thus, the idea of UV
induction of oxygen vacancies was supported. However, other
possible explanations exist, as discussed later.
The photo-induced hydrophilic (PIH) effect was initially
thought to involve simply the photocatalytic removal of hydro-
carbon contamination films, but this was found to be an inade-
quate explanation. One of the experiments that underscored this
involved the comparison of TiO2 and SrTiO3 (501). These were both
prepared as polycrystalline films on glass. Both were found to pho-
tocatalytically decompose methylene blue, but the SrTiO3 film did
not become hydrophilic under illumination (Fig. 5.2).
In an effort to continue improving the characteristics of the PIH
effect, variations were examined. One of the most promising ones
involved the deposition of a thin film of WO3 on the TiO2 surface
[427]. An amorphous film was found to be more effective than a
crystalline film. With the former, a PIH conversion was observed
to reach completion after 100 min at the surprisingly low UV light
intensity of 1 µW cm−2 .
The amphiphilic effect is unique for TiO2 : no other oxide that
has been examined thus far exhibits this behavior. In further
exploration of this effect, it was found that, the oleophilic behavior
of TiO2 films was actually reconverted to oleophobic after about
10 h of continuous UV illumination at 1 mW cm−2 [502], while
the hydrophilic character remained. It was speculated that this
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582 561

Fig. 5.2. Comparison of the photocatalytic and PIH behavior of TiO2 and SrTiO3 : (left panel) time dependence of absorbance under UV irradiation of methylene blue adsorbed
on TiO2 (solid diamonds), on SrTiO3 (open squares), and on an uncoated glass substrate (open triangles); (right panel) time dependence of water contact angle under UV
irradiation of TiO2 (solid diamonds), and SrTiO3 (open squares). UV irradiation was 1 mW cm−2 under ambient conditions (295 K; relative humidity, 60%, air) (taken from
[501].

behavior resulted from a redistribution of the nanometer-scale

hydrophobic (oleophilic) domains with time.
The effect of repeated cycles of UV illumination followed
by ultrasonication was studied for rutile (110) and (001) films
[503]. Interestingly, although the (001) surface was found to be
quite slow compared to the (110) surface in reaching hydrophilic
behavior, taking about three times as long, it exhibited an
increasingly rapid effect with cycling; by the third cycle, it reached
a fully hydrophilic state after less than 50 min under a UV light
intensity of 40 mW cm−2 . This was thought to be the result of
restructuring of the surface to expose more bridging oxygens.
The influence of electrochemical potential was examined, and
it was found that more positive potentials were effective in
accelerating the PIH effect [504]. This effect reached a plateau in
the 0.4–0.8 V vs. Ag/AgCl range in aqueous pH 6.86 buffer. As the
potential was held at increasingly negative potentials, starting at
about −0.2 V, the PIH effect began to be suppressed, with the
suppression increasing with negative potential. This phenomenon
led to a modification of the mechanism; it was concluded that
photogenerated holes are trapped at bridging oxygens, causing Fig. 5.3. Trace of water contact angle (WCA) vs. time for an anatase film sample,
them to be ejected from the surface, thus allowing a water showing reversible lowering of WCA under UV illumination and increasing WCA
molecule to dissociate at the resulting oxygen vacancy. This under visible light illumination (taken from [506]).
mechanism will be discussed in more detail below. It should © 2002, Elsevier Science.
be noted that the type of film studied in this work begins to
absorb light at longer wavelengths (monitored at 700 nm) as the generated over a wide range of potential under illumination at
film is maintained at potentials below about −0.8 V vs. Ag/AgCl, 360 nm and an intensity of 50 mW cm−2 , whereas the anatase
which is an indication that electrons are building up, either in the film generated about 1.5 mW cm−2 photocurrent at 0.8 V. The
conduction band or in electronic states close to the conduction hydrophilic effect for the amorphous film was thought to involve
band. In this region, it becomes more difficult to separate the Eq. (3.2), thus generating surface hydroxyl groups, which should be
photogenerated electrons and holes, since the film behaves more more hydrophilic. This is still not a complete explanation, however,
like a metal and less like a semiconductor. because, if the effect just involves the surface, the anatase film
The electrochemical potential was also found to have an should also produce nearly the same degree of hydrophilicity.
effect even in the dark, but this effect was rather weak for There is clearly some other factor involved, for example, roughness.
conventional polycrystalline anatase films [505]. However, for It was discovered that visible light illumination, without
amorphous titania films, the effect was much more obvious. In the UV, is actually effective in reconverting anatase films from a
potential region below −0.6 V vs. Ag/AgCl, the amorphous film hydrophilic state back to a semi-hydrophobic state (Fig. 5.3)
began to absorb light (monitored at 700 nm). At this potential, [506]. This effect was found to result from the visible-light-
the contact angle also began to decrease in the dark for the induced heating of the film. The highly reversible alternation of
amorphous film. At more negative potentials, the effect was more the hydrophilic and hydrophobic character is one of the most
pronounced: at −1.0 V, the contact angle approached 0◦ after convincing demonstrations that this effect is not simply due to
20 min. In contrast, for the polycrystalline film, even at a potential the build-up and destruction of contamination layers. These results
of −1.2 V, the contact angle only approached 12◦ after 20 min. were also confirmed by Stevens et al. [507].
The photo-response of the amorphous film to UV light was found The PIH effect has also been examined on other metal oxides,
to be very small, with only a small µA cm−2 photocurrent being for example, ZnO [508]. This oxide also exhibits a pronounced
562 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
effect. Initially, the ZnO surface is much more hydrophobic than
the TiO2 surface, exhibiting a water contact angle of ca. 110◦ . The
contact angle for these films also increases during storage in the
dark in a manner similar to that for TiO2 . It was proposed that the
ZnO surface can also be induced by UV light to generate oxygen
vacancies. This point will be discussed later. As with TiO2 , ZnO also
reconverts to a hydrophobic state at different rates according to the
type of atmosphere. For example, the conversion is fastest in pure
O2 . This is thought to be due to a competition between O2 and H2 O
for reaction with oxygen vacancies.
A number of other metal oxides were also examined for their
PIH activity and photocatalytic activity [509]. The following oxides
were found to exhibit the photocatalytic effect: TiO2 , SrTiO3 and
ZnO, with SnO2 exhibiting only a slight effect. The following were
found to exhibit a PIH effect: TiO2 , SnO2 , ZnO, WO3 and V2 O5 .
Other oxides studied were: CeO2 , CuO, MoO3 , Fe2 O3 , Cr2 O3 and
In2 O3 . All of the latter group exhibited neither effect. These results
are also one of the most convincing with regard to distinguishing
the two effects. As already noted, SrTiO3 is the clearest example
of an oxide that exhibits the photocatalytic effect but not PIH;
in this work, there are two examples of oxides that exhibit PIH
but not photocatalysis: WO3 and V2 O5 . Similar to TiO2 , these
oxides are able to lose oxygen, creating oxygen vacancies to the
point where the structure can change, as in the Magneli phases.
However, an exception to this correlation is MoO3 , which is also
known to be able to convert to Magneli phases. This explanation
requires modification, because the loss of substantial amounts of
oxygen can also lead to metallic conduction, which suppresses
photoeffects that normally occur in semiconductors.
In an effort to make the PIH measurements more precise, Sakai
et al. used the reciprocal of the water contact angle to quantify
the conversion rates from hydrophobic to hydrophilic and back
[510]. In this work, a correlation was found between strongly
adsorbed water, as observed as a component in the O 1s XPS
spectra, and the reciprocal of the contact angle. Temperature-
programmed desorption was also used to measure the amounts
and types of adsorbed water. The reconversion of the surface to
hydrophobic was found to exhibit a clear transition between a fast
and a slow process, the latter being thought to involve a structural
reconstruction process.
The influence of tensile and compressive stress on the PIH effect
is surprising [511]. Tensile stress applied to a TiO2 film enhances
the effect, while compressive stress suppresses the effect. This
interesting phenomenon was explained in terms of the intrinsic
stress created when the surface undergoes the reconstruction
discussed above. Related to this is a study in which it was observed
that a TiO2 film became significantly rougher under illumination
and then reverted to its smooth texture in the dark, as reported by
Watanabe and coworkers [521].
Another related study, carried out with in situ grazing angle
incidence X-ray diffraction, showed that illumination of a rutile
single crystal in the presence of various alcohols led to a reversible
expansion of the lattice [512]. One possible explanation is the
electrochemical intercalation of protons Eq. (3.8), leading to the
type of lattice expansion shown in Fig. 3.15. A more recent study
carried out with the X-ray truncation rod technique in aqueous
solution without an organic compound present to trap holes, led
to a disordering of the single crystal surface [513]. This result was
considered to be consistent with the type of domain formation
reported by Wang et al. in our early papers on the PIH effect [496,
514].
More recent work has focused on new ways to enhance the PIH
effect. For example, Gu et al. found that nanotexturing of the TiO2
surface can lead to an extremely long-lived hydrophilic character,
lasting more than one year, in comparison to the conventional film,
which becomes completely hydrophobic within 50 days [515]. The
texturing was carried out by first forming a layer of polystyrene
spheres (250 nm), followed by intrusion of a suspension of 15-
nm TiO2 particles, with the polystyrene spheres finally being
removed by heat treatment in air (Fig. 5.4). Other recent work,
including that aimed at enhancing the visible light sensitivity, will
be discussed later.
5.2. Mechanisms of the PIH effect
Some indications have already been given regarding the pos-
sible mechanisms for the PIH effect. These will now be discussed
in more detail: they include the original mechanism, which essen-
tially says that the PIH effect and photocatalysis are identical; the
reductive mechanism, which was originally proposed, the later ox-
idative mechanism, and finally, a new combined redox mechanism,
which is again similar to photocatalysis but includes both.
5.2.1. Decomposition of organic films
The initial thought that has occurred to almost everyone
when learning about the PIH effect is that it is a simple
process of photocatalytic removal of organic contamination films,
which are notorious and ubiquitous. Our group first assumed
this mechanism, but later evidence, as outlined above, made it
increasingly clear that the two effects, while very closely related
indeed, are separate.
Several groups during the past several years have revisited this
issue. White et al. used the rutile (110) surface and found that the
presence of oxygen vacancies, produced by heating the crystal, did
not produce a noticeable effect on the TPD behavior for water [516].
Both the stoichiometric and the slightly reduced surfaces were
highly hydrophilic. After the surfaces are covered with a monolayer
of trimethylacetic acid, they become highly hydrophobic, as
evidenced by TPD curves that indicate the presence of liquid rather
than adsorbed water. After these surfaces are illuminated with UV
light for 300 s in the presence of 5 × 10−6 Torr O2 , they became
much more hydrophilic and again exhibited the behavior of the
clean surface, i.e., with first-layer, second-layer and multi-layer
water TPD peaks.
The main conclusions of this work were that (1) the original
TiO2 surface is highly hydrophobic, without UV illumination,
because it is clean; (2) the presence or absence of oxygen vacancies
has no discernable effect on the apparent interaction with water;
and (3) the photocatalytic removal of an organic monolayer leads
to a recovery of hydrophilic properties.
A second major work that advocated the contamination layer
mechanism was that of Zubkov et al. [517]. This paper shows
convincingly the effect of additions of hexane to the gas phase
above the sample. For example, with 120 ppm hexane present in a 1
atm O2 atmosphere, there is an induction time of about 150 s; up to
that time, the contact angle is relatively constant at 20◦ , and then
it drops suddenly to the range in which it is difficult to measure
the contact angle (0◦ –7◦ ), as shown in Fig. 5.5. However, it is also
significant that, in the absence of hexane, the clean crystal initially
shows a contact angle of ca. 25◦ (see curve for 0 ppm hexane). After
the initiation of UV illumination, it requires only ca. 12 s to reach
the 0◦ –7◦ range. This result is further substantiated by results that
are shown for the effect of the presence vs. absence of O2 (Fig. 5.6).
There is no doubt that contamination films cause the surface to
be hydrophobic; this issue is important and must be kept in mind
in the proper design of experimental measurements in this area.
In very recent work, it has become increasingly evident that there
are actually two distinct effects, the first being the destruction of
organic contaminants, which lowers the contact angle from higher
ranges (e.g., 60◦ ) to the 20◦ –35◦ range and a separate effect that
lowers the value down to the 0◦ –5◦ range [518]. Consistent with
this is the result already cited by Zubkov et al., as well as the recent
work of Hennessy et al. [513].
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 5.4. Nanostructured TiO2 surface (a) microscopic image and (b) WCA vs. time for the conventional TiO2 (upper curve) and nanotextured (lower curve) surfaces.
© 2004, American Institute of Physics.
Fig. 5.5. Traces of WCA vs. time under various atmospheres: 1 atm O2 containing
added hexane (taken from Zubkov et al. [517]).
© 2005, American Chemical Society.
5.2.2. Reductive mechanism
In our papers prior to 2001, we focused on what could be called
a reductive mechanism, in which UV light was thought to produce
oxygen vacancies, at which water then dissociated, creating two
hydroxyl groups. There are several papers in which it is reported
that UV light can create oxygen defects, but, as already mentioned,
Mezhenny et al. showed the lack of an effect of reasonable light
intensities on the appearance of rutile (110) surfaces with STM
[139]. Thus, it seems clear that this mechanism would have to be
modified. One modification that is sensible is simply to recognize
that an electron with the reducing power of hydrogen, or even
slightly less, can directly reduce a bridging oxygen on rutile (110)
to produce a single OH group (reaction (3.2)). This product is
very similar, if not identical to that produced via reaction of
a thermally produced oxygen vacancy with water. The degree
of sameness or difference should in fact be carefully examined,
but, to a first approximation, it should be identical. Our report
on results obtained with cathodic polarization enhancement of
hydrophilicity [505] seems to support this, but further work needs
to be carried out.
As White et al. point out, even in the case in which there are
indeed oxygen vacancies present on the surface, they do not have
a measurable effect on the hydrophilic properties [516]. Intuitively,
we expect that the presence of bridging hydroxyls should lead
to an enhanced interaction with bulk water, and this supposition
appears to be valid from the experiments just cited with cathodic
polarization [505]. However, the effect with anatase film is not
563
pronounced and is clearly not the dominant one in the PIH effect.
Thus, it is clear that the mechanism needs to be modified.
5.2.3. Oxidative mechanism
The report that positive polarization has a strong effect on the
attainment of a hydrophilic surface demonstrates the importance
of photogenerated holes in any broadly useful mechanism for
the PIH effect [504]. The mechanism that was proposed in that
paper again invoked the production of oxygen vacancies, and this
indeed appears to be a weakness, for the same reasons already
discussed. In this case, we cannot argue that the direct product
of the reaction of a vacancy with water could be the same as
that obtained electrochemically, but there is almost certainly a
structure that is produced photochemically that could be similar
to the one obtained electrochemically. This point also needs to be
examined in further research. The recent work of Nakato and co-
workers on the photoproduction of peroxo species on the titania
surface is important in this regard [219,220,519,520].
5.2.4. Combined redox mechanism
The mechanism already given for the general photocatalytic
processes (see Section 4.1.1 and Fig. 4.5) is also proposed for the PIH
effect, because it combines both reductive and oxidative elements,
both of which are important. Specifically, Fig. 4.5a, which involves
water as an electron donor, without an organic present, may be
useful. Panel A includes water as an electron acceptor, while panel
B includes O2 as an electron acceptor. Either may be appropriate
under specific conditions. From the result of Zubkov et al. (Fig. 5.6),
however, it can be seen that O2 is necessary to accelerate the
PIH process. It is important to keep in mind, however, that O2
accelerates the recovery of the original hydrophobic behavior in
the dark.
As mentioned earlier, this type of mechanism might be
consistent with a report in which the effect of tensile stress
was discussed [511]. The presence of localized areas in which
hydrogen is inserted electrochemically is consistent with the idea
of volume expansion, as discussed theoretically by Koudriachova
et al. (see Fig. 3.15a, b) [160]; volume expansion can certainly
lead to compressive stress, which would be alleviated by tensile
stress. Volume expansion was also indicated in the work of
Matsushige and co-workers [512], in which in situ X-ray diffraction
measurements were made on a rutile single crystal under UV
illumination in the presence of organic hole trapping agents. This
idea is also consistent with the report of Watanabe and co-workers
on increased surface roughness during illumination [521]. More
recently, an in situ X-ray truncation rod study showed an increase
in apparent roughness during UV illumination in the absence of a
564 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

Table 5.1
Possible unitary reactions that might be involved in the PIH effect.

Fig. 5.6. Traces of WCA vs. time under inert atmosphere (no O2 ) and under 10% O2
(taken from Zubkov et al. [517]).
© 2005, American Chemical Society.

hole trapping agent [513]. This was suggested to be consistent with

the original reports of Wang et al., in which surface nanostructures
were observed on a rutile single crystal during UV illumination
(Fig. 5.1). It is likely that the presence of hole trapping agent in the
earlier X-ray study [512] allowed the regions of proton injection to
increase in size and thus to be observed easily.
The development of a general mechanism for photocatalysis
and a specific one for the PIH effect is an ongoing endeavor. At
this point, we would like to recommend that a focused effort be
undertaken to understand the possible reactions occurring on the
TiO2 rutile (110) surface, both experimentally and theoretically,
that might lead to PIH effects. As already mentioned, there are
several candidates for surface entities that might enhance the
hydrophilic properties, including bridging OH groups, as in the
reductive mechanism [496,505,514], and surface-trapped holes
of various types, as in the oxidative mechanism [504]. On the
oxidative side, the intermediates involved with the O2 evolution
reaction could also be important [111,218–220]. The attack of a
surface-trapped hole on adsorbed water can in principle produce
an adsorbed •OH radical in an electrochemical reaction, or can
lead to a bond breakage, which might be more likely in the case
of a bridging oxygen. We have attempted to assemble as many as
possible of the reasonable unitary reactions, i.e., a single reaction
event, including electron transfer, proton transfer, bond breaking
and bond making (Fig. 5.7, Table 5.1.). Such unitary reactions might
also be useful in building more complicated mechanisms. We
present these as a possible starting point for further guidelines in
stimulating both experimental and theoretical studies that would
try to finally be directed at achieving a deep understanding of the
most studied oxide surface, rutile (110). If good agreement can
be achieved between experiment and theory on such a surface, it
should also be a great impetus toward the achievement of similar
understanding of other important rutile and anatase surfaces.

5.2.5. Visible-light-induced PIH effect

Several reports have appeared concerning the development of
visible-light-induced hydrophilicity, encouraged by the boom in
studies on visible light photocatalysis [454,473,474,522]. These
studies focusing on N, or C-doped TiO2 films and showed quite The locations of each of the moieties are indicated by the letters in the titles for each
scattered results on the rate of hydrophilic conversion due to reaction, referring to Fig. 5.7. The listed reactions are a sampling of the possible ones
for the TiO2 rutile (110) surface.
differences in the preparation methods of the films. Some studies
stated that the hydrophilic conversion rates were slow and the
superhydrophilic state were not obtainable even in reasonably studies stated that the superhydrophilic state could be obtained for
long period (over 100 h) of visible irradiation [473,522], but some N-, or C-doped TiO2 films within hours of visible irradiation [454,
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 5.7. Schematic top view of the rutile (110) surface, showing the structures that
are used in Table 5.1 regarding the possible reactions involved in the PIH effect. The
red rectangle corresponds to the designation ‘a’ in Table 5.1, the blue rectangle to
‘b’, and the green rectangle to ‘c’. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)
474]. However, all of the studies have reached the same conclusion,
i.e., the rate of hydrophilic conversion is much slower under
visible irradiation than UV irradiation even when the absorbed
photons are in same number for both cases, the same as what
was observed in visible light photocatalysis. Also, it appears that
films that are more photocatalytically active undergo, hydrophilic
conversion more easily and rapidly under the visible irradiation
[454,473,474,522].
6. Brief review of applications
6.1. Self-cleaning surfaces
The TiO2 surface can decompose organic contamination with
the aid of ultraviolet light. This observation suggests the applica-
tion of TiO2 photocatalysis to a novel ‘‘self-cleaning’’ technique,
i.e., a surface coated with TiO2 can maintain itself clean under
ultraviolet illumination (Fig. 6.1) [5,9,10,392]. This technique is
obviously of great value, since it can utilize freely available so-
lar light or waste ultraviolet emission from fluorescent lamps,
save maintenance costs, and reduce the use of detergents. Watan-
abe, Hashimoto and Fujishima first demonstrated this self-cleaning
concept on a titania-coated ceramic tile in 1992 [392]. A simi-
lar idea was conceived independently by Heller [5]. One of the
first commercialized products using this technique was the self-
cleaning cover glass for highway tunnel lamps [9,14,523]. This type
of lamp, which is often a sodium lamp in Japan, emits UV light of
about 3 mW cm−2 at the position of the cover glass. This UV light
is of no use for lighting, but it is sufficient to decompose the con-
tamination from exhaust compounds. As a result, the cover glass
can maintain transparency for long-term use.
The efficacy of self-cleaning surfaces was found to be dependent
on the relative rates of decontamination vs. contamination.
The TiO2 photocatalyst can maintain the surface clean only
when the photocatalytic decontamination rate is greater than
that of contamination. Wang et al., however, observed that the
self-cleaning effect of TiO2 surfaces could be enhanced when
water flow, such as natural rainfall, was applied to the surface
[514]. They attributed this enhancing phenomenon of water
565
Fig. 6.1. Schematic diagram of the decontamination process occurring on the
superhydrophilic self-cleaning surface [15]. ©2006, Elsevier Science Ltd.
flow to the superhydrophilic property of TiO2 surface, i.e., water
penetrated the molecular-level space between the stain and
the superhydrophilic TiO2 surface [14,15]. In other words, this
phenomenon has effectively removed the limitation of the self-
cleaning function of TiO2 photocatalysis set by the number of
incident photons. Even though the number of photons may
be insufficient to decompose the adsorbed stain, the surface
is maintained clean when water is supplied there. Thus, they
suggested that the best use of self-cleaning TiO2 surfaces should
be exterior construction materials, since these materials could be
exposed to abundant sunlight and natural rainfall [9,14,15]. Such
materials, including tiles, glass, aluminium siding, plastic films,
tent materials, cement, etc., have already been commercialized in
Japan since the late 1990s and in other countries in recent years
[15,524]. Some examples are shown in Fig. 6.2.
As estimated by TOTO, Ltd., the pioneer of self-cleaning
technology, a building in a Japanese city covered with ordinary
tiles should be cleaned at least every five years to maintain
a good appearance, while that covered with self-cleaning tiles
should remain clean over a span of twenty years without any
maintenance. Therefore, self-cleaning technology can lead to large
decreases in maintenance costs. We have been examining the
efficacy of self-cleaning technology at the Photocatalyst Museum
of our Institute. Fig. 6.3 shows the results of one test on a self-
cleaning tent material produced by Taiyo Kogyo Co. The tent
material, made from PVC film, was coated with TiO2 photocatalyst
material on the left half. The test was started on July 22nd, 2004;
on that day, both the non-coated and TiO2 -coated halves had
the same white appearance, as shown in Fig. 6.3a. The photo
shown in Fig. 6.3b was taken on April 23rd, 2007. The TiO2 -
coated part remains white in the photo, whereas the non-coated
part, however, is dark grey. Note that the tent was placed in a
location surrounded by tall buildings, where little direct sunlight
illumination could reach the surface. Nevertheless, even under
such conditions, the self-cleaning effect is obvious. On clear days,
contaminants accumulate on the whole surface, but during a rain,
these are washed off the TiO2 -coated part of the surface.
In Japan, several thousand tall buildings have been covered with
TOTO’s self-cleaning tiles. The Central Japan International Airport,
which opened in February, 2005 near Nagoya, Japan, used over
20 000 m2 of self-cleaning glass manufactured by the Nippon Sheet
Glass Co. Self-cleaning tent materials have been widely applied for
storage structures, business facilities, bus and train stations, sports
centers, sunshades in parks and at the seaside. The PanaHome
Company, one of the major house manufacturers in Japan, has
marketed ‘‘eco-life’’-type houses since 2003; self-cleaning tiles and
windows, in addition to a solar cell-covered roof-top, are utilized.
New applications of self-cleaning technology are also under
examination. Zhang et al. recently reported on antireflective
TiO2 –SiO2 self-cleaning coatings that may find application for
the cover glass of solar cells [525,526]. Conventional TiO2 -based
coatings are highly reflective due to the large refractive index of the
566 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

Fig. 6.2. Applications of self-cleaning exterior building materials. (a) Picture of the MM Towers, in Yokohama, coated with self-cleaning tiles (courtesy of TOTO). (b) Picture
of the Matsushita Denso building covered with self-cleaning glass (courtesy of Nippon Sheet Glass). (c) Picture of the self-cleaning sound-proof wall (courtesy of Sekisui).
(d) Eco-life-type houses using self-cleaning tiles and glass (courtesy of PanaHome). (e) Self-cleaning roof of a train station in Motosumiyoshi (courtesy of Taiyo Kogyo).

Fig. 6.3. Outdoor exposure test for a PVC tent material manufactured by Taiyo Kogyo done in the Photocatalyst Museum, KAST. The left half part of the tent material was
coated with TiO2 . (a) Picture taken in July 22, 2004. (b) Picture taken in April 23, 2007.

material, and thus the loss of transmittance by TiO2 can be larger the coating enhanced the transmission of the glass to exceed 97%
than that caused by contamination layers. Zhang et al. prepared for visible light, greater than the 90–92% usual for glass (Fig. 6.4)
nanoporous TiO2 –SiO2 coatings that have a low refractive index; [525,526].
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 6.4. Transmission spectra of a bare glass and a glass coated with TiO2 –SiO2
composite film. The maximum transmittance for the coated glass could be over 99%
[525].
© 2005, American Chemical Society.
TiO2 -coated textiles are another promising application of self-
cleaning technology. Recent studies by Kiwi and co-workers have
shown that coffee and wine stains on TiO2 -treated cotton or
synthetic textiles can be decolorized under sunlight [527,528].
6.2. Water purification
As noted in our historical overview, the earliest reports of
the cleaning properties of TiO2 were those of Frank and Bard in
1977, in which they found that suspensions of TiO2 powder in
contaminated water were able to photocatalyze the conversion of
cyanide to cyanate, thus detoxifying the water [56,57].
One of the advantages of TiO2 photocatalysis for water
decontamination is that only the TiO2 photocatalyst (immobilized
or suspended) and UV light, either from solar light or artificial
light sources, are needed and thus its cost can be lower than other
kinds of advanced oxidation techniques (UV/O3 , UV/H2 O2 , photo-
Fenton). Moreover, no toxic intermediate products are generated
in the photocatalytic decontamination process; this makes it very
attractive for cleaning the water environment, even for cleaning
drinking water [379,380,382,529].
However, it is generally accepted that TiO2 photocatalysis
is feasible only for the treatment of wastewater that contains
contaminants at low to medium pollutant concentrations, because
of its relatively low efficiency and the limited flux of ultraviolet
photons [382,530]. Malato and co-workers studied the solar
decontamination of industrial [390], agricultural [531,532] (3,4),
and municipal wastewater [533] at the pilot-plant scale, using
compound parabolic collector (CPC) reactors and TiO2 slurry
photocatalysts. They observed the complete mineralization of
organic matter at concentrations of ca. 50 mg L−1 within hours
under sunlight. However, the decontamination rate was generally
lower for TiO2 photocatalysis than for the photo-Fenton process
in their studies [534,535]. Herrmann and co-workers reported
a solar photo-reactor design based on the multi-step cascade
falling-film principle to ensure good exposure to sunlight and good
oxygenation of the effluent to be treated [536]. These workers used
an immobilized TiO2 photocatalyst that was prepared by coating
non-woven paper with anatase paste using aqueous SiO2 colloid
as a binder material in order to avoid the filtration procedure
required in slurry photo-reactor. This film photo-reactor was
found to be as efficient as the CPC slurry photo-reactor for 4-
chlorophenol, formetanate, and a mixture of pesticides in terms of
total degradation under identical solar exposure.
One interesting application of TiO2 photocatalysis is to remove
endocrine disruptor chemicals (EDC) in the aqueous environment
567
[537–540]. These chemicals, including natural hormones, dioxins,
biphenol-A, etc., in the aquatic environment have been implicated
as health hazards for both humans and wildlife. They are assumed
to disrupt normal endocrine functions through interaction with
steroid hormone receptors, even at very low concentrations.
Conventional biological methods to remove these EDCs require
long periods of time, and chemical oxidation methods are in
general not economical because of the low concentrations of the
EDCs. Nakashima et al. designed a photocatalytic reactor using
TiO2 -modified-PTFE mesh sheets as photocatalysts and utilized
this to treat the water discharged from the Kitano sewage-
treatment plant, which is located next to the Tama River near
Tokyo [540]. Concentrations of estron in the discharged water were
140 ng L−1 . Under UV illumination (1.2 mW cm−2 ), about 90%
of the initial estron was decomposed in a very short time, with
good reproducibility (Fig. 6.5). Thus, TiO2 photocatalysis can be
applied in the treatment of sewage effluent as a safe method for
removing natural and synthetic estrogens. This approach should
also be suitable for the removal of other low-level EDCs in the
aquatic environment.
Hashimoto and co-workers recently reported the application
of photocatalytic technology to the hydroponic cultivation of
tomatoes [14]. In conventional hydroponics, tomato plants are
planted in an organic culture medium. The culture solution,
containing nitric acid, phosphoric acid, potash, etc., flows through
the culture medium in a circulated mode and provides nutrients
to the plants. However, organic substances are released into
the culture medium during circulation, and as a result, plant
pathogens can be propagated in the system and can cause diseases
in the plants. The researchers connected a photocatalytic-water-
treatment tank to the circulation system and used sunlight to
decompose organic substances in solution. The method is effective,
as evidenced by the apparent decrease in the total organic carbon
in solution and the increased yields of tomatoes.
Other important water-purification applications of TiO2 pho-
tocatalysis include water disinfection [406,408,541–545], re-
mediation of metal contamination [546,547], and oxidation of
arsenite [548]. For developing countries, solar photocatalytic dis-
infection appears to be a promising process to produce drinking
water, which could help in improving public health. Rincón et al.
reported that real lake water contaminated with E. coli K12 at a
level of 106 CFU mL−1 could be disinfected completely within 3 h
on a clear day in summer, using a CPC reactor and a TiO2 slurry
catalyst [549]. In comparison, solar light alone is unable to effec-
tively disinfect the contaminated water. The mechanism for photo-
catalytic disinfection is still under debate (see Section 4.2.4) [408].
Various active oxygen species, such as hydroxyl radicals, superox-
ide, hydrogen peroxide, singlet oxygen, etc., may participate in the
disinfection process. In addition, the self-repair action of microbes
complicates the disinfection process [408].
There have been several types of water-purification facilities on
the market for various purposes. One of these is designed to re-
move volatile organic compounds (VOC), such as trichloroethylene,
tetrachloroethylene, 1,3-dichlorobenzene, and dichloromethane,
etc., from underground water or soil. These substances are widely
used as extracting solvents in industrial processes and in dry clean-
ing and are released into the environment in large quantities. The
facility basically involves suctioning up underground water from
a deep well dug in the polluted area, spraying the water to evap-
orate the VOCs into the gas phase, and decomposing the gaseous
VOCs with a photocatalytic air-cleaning unit. VOCs at concentra-
tion levels ranging from several hundreds to several thousands of
parts per million can be decomposed almost completely to carbon
dioxide and hydrochloric acid with such a facility, with a maximum
treatment capability of 5 kg VOCs per day for a 15-kW facility.
568 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

Fig. 6.5. (a) Concentration change of estron (E1) in water discharged from a sewage-treatment plant during photocatalysis. The measurement was repeated three times
(UV light intensity, 1.2 mW cm−2 ; water temperature, 15 ◦ C) [540]. ©2003, Elsevier Science Ltd. (b) Picture of a photocatalytic reactor for treatment of sewage water. The
reactor consists of two 34-L columns, 100 pieces of TiO2 -coated PTFE mesh sheet, and 12 black-light (40 W) lamps which gave a light intensity of about 1.2 mW cm−2 .

Fig. 6.6. (a) Photographic images of a honeycomb-type air-cleaning filter (left) and a three-dimensional porous ceramic air-cleaning filter (right); (b) Schematic diagram of
the microscopic structure of the air-cleaning filter; the substrate materials (ceramics, paper, fabrics) are coated with a composite of TiO2 and adsorbent.

6.3. Air purification type construction or a three-dimensional porous structure for

One of the most important applications of TiO2 photocatal-
ysis is to decontaminate, deodorize, and disinfect indoor air.
Low-concentration volatile organic compounds (VOCs), such as
formaldehyde, and toluene, emitted from interior furnishings and
construction materials, may lead to the ‘‘sick building syndrome’’
and other diseases. Besides, the indoor air of public facilities, which
is normally contaminated with bacteria, fungi, etc., threatens the
health of users. Conventional air-purification systems often adapt
filter-type components for the cleaning of polluted air. Pollutants
are accumulated in the active carbon filters, and the filter becomes
saturated with adsorbed substances and loses its function after a
certain period of use. Treatment of the used air filters may cause
the risk of secondary pollution. Photocatalytic air-cleaning filters,
however, can decompose the organic substances instead of accu-
mulating them and, as a result, exhibit better performance than
conventional ones [9,15,373,550–552]. Moreover, the photocat-
alytic filter can kill the bacteria floating in indoor air, which is also
important for indoor air purification [553,554].
Fig. 6.6 shows images of two types of photocatalytic filters used
in air-purification devices. The filters feature either a honeycomb-
minimum pressure drop. TiO2 nanoparticles are coated on the body
of the filter with active carbon, zeolites, etc., as co-adsorbents.
The co-adsorbents facilitate the adsorption of VOCs on the filter,
and ensure that no intermediate gaseous compounds diffuse into
the ambient atmosphere. The adsorbed substances diffuse on the
surface of the adsorbent until they reach the TiO2 and then undergo
photodecomposition. The oxidizing species on the photocatalyst
can also diffuse to the surface of the adsorbent and participate
in oxidation reactions there. UV light, illuminated on the filter
surface from black-light lamps, is generally at the level of several
mW cm−2 ; this ensures the rapid mineralization of VOCs that
typically exist in concentrations of about 1 ppm or even lower.
After long-term use, the filter may be poisoned by HNO3 or H2 SO4
formed during removal of ammonia or hydrogen sulfide. In such
a case, the poisoned filter can be regenerated by simply washing
with water.
The available air-cleaning devices based on photocatalytic
filters include air cleaners, air conditioners, air-cleaning units
for refrigerators, etc. Among these application groups, the air
cleaner is the largest. There are more than thirty companies
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 6.7. Usage of TiO2 -based photocatalytic material on roadway surfaces to convert nitrogen oxides (NOx ) to nitrate: (left) application of the coating; and (right) finished
roadway, with the coated surface showing a lighter color (courtesy of Fujita Road Construction Co., Ltd.).
manufacturing photocatalyst-type air cleaners in Japan, with over
one hundred product types available on the market. The consumers
of photocatalyst-type air cleaners include hospitals, institutions for
the elderly, pet stores, offices, smoking rooms, sports clubs, hotels,
schools, restaurants, food manufacturers, or in any location where
indoor air purification is necessary. In addition to air cleaners,
deodorizing sheets that are composed of TiO2 photocatalyst and
active carbon adsorbents are also available on the market. The
sheet is able to remove malodorous substances in kitchens,
refrigerators, vehicles, and shoes through the adsorption function
of the activated carbon. Placing the used sheet in sunlight readily
decomposes the adsorbed pollutants by the action of the TiO2
photocatalyst and regenerates the sheet.
Nitrogen oxides (NOx ) exhausted from automobiles have be-
come a serious source of air pollution in urban areas. Photocatalytic
TiO2 has the capability of removing nitrogen oxides [555,556]. It
has been suggested that the nitrogen oxide (NO) in the air is oxi-
dized when the catalyst is exposed to light. Then, through the in-
termediate stage of nitrogen dioxide (NO2 ), it is finally converted
to nitric acid, which must then be stored. At the nitrogen dioxide
stage, part of the gas may escape from the photocatalyst surface,
but, with an adsorbent like activated carbon mixed with the cata-
lyst, this gas may be effectively trapped [9].
The range of concentrations of air pollutants that can be
efficiently removed is from 0.01 ppm to 10 ppm. These concentra-
tions correspond to the range from those in the ordinary environ-
mental atmosphere to those in highway tunnels. Some companies
in Japan are now considering covering roads with TiO2 photocata-
lyst, and removing the NOx exhausted from automobiles with sun-
light. TiO2 -coated road bricks, which are used to cover pavement,
have become available on the market. Interestingly, TiO2 coatings
for roadways are being prepared by mixing colloidal TiO2 solutions
with cement. Nitric acid, formed during the oxidation of nitrogen
oxides, reacts with the cement to form calcium nitrate, which can
be washed off by rainwater. This method, which has been termed
‘‘photo-road’’ technology, has been tested in more than fourteen
places in Japan over the past nearly ten years (see Fig. 6.7). One
of the places tested is on the 7th belt highway in Tokyo, with
an area of about 300 m2 . Nitrogen oxide removed from this test-
ing area was estimated to be 50–60 mg per day, corresponding
to the amount of nitrogen oxide discharged by 1000 automobiles
passing by.
More recently, this idea has been developed to a great extent
in Europe. In particular, the Italian cement company Italcementi
has created several demonstration projects, for example, in Rome
and Paris, to check the actual photocatalytic effect of a TiO2 -coated
highway in the conversion of NOx and SOx to more environmentally
benign forms, i.e., NO− 2−
3 and SO4 [557].
569
6.4. Self-sterilizing surfaces
TiO2 photocatalysts can kill bacteria on their surfaces, and
therefore self-sterilizing surfaces can be prepared [9,10,530]. Such
materials are particularly useful for hospitals and elder care
facilities, where the control of surface and airborne bacteria and
viruses is important. In cooperation with TOTO Ltd., Fujishima
et al. developed a type of antibacterial tile made by covering
ordinary tiles with a TiO2 –Cu composite coating [9,530]. In a test
experiment, the bacteria on these tiles were killed completely in
one hour under illumination equal to the brightness of the surface
of a study desk (UV light: ∼4 µW cm−2 ). On the basis of these
results, such tiles were tested on the floor and walls of a hospital
operating room where sterile conditions are crucial [9,530]. After
installing the tiles, the bacterial counts on the walls decreased to
negligible levels in a period of one hour. Surprisingly, the bacterial
counts in the surrounding air also decreased significantly. TOTO
Ltd. has marketed the antibacterial tiles in Japan. Its users include
hospitals, hotels, and restaurants, among others.
One advantage of photocatalytic sterilizing surfaces is that
they operate in a passive fashion, that is, without the need for
electrical power or chemical reagents, only light and oxygen being
required. Unlike chemical antibacterial agents, TiO2 surfaces are
non-poisonous and will not result in environmental pollution.
It is thus expected in the near future that self-sterilizing TiO2
materials may have many medical applications. At least, hospital
room walls, medical instruments, and hospital uniforms can all
be coated with self-sterilizing TiO2 materials. In a recent study,
Ohko et al. coated flexible silicone catheters with a TiO2 thin
film [558]. The film, as shown in Fig. 6.8, strongly adhered to
the body of the catheter: it was able to sustain repeated bending
without cracking and peeling observed macroscopically; it was
able to pass an adhesive tape test, and it was resistant to scratching
with a 3H pencil. The TiO2 -coated silicone catheter exhibited good
self-sterilizing properties under 1 mW cm−2 UV illumination, as
shown in Fig. 6.9, and was shown to be safe in an experiment
using cultured cells and animal experiments [559]. Clinical studies
showed that the antibacterial capability of TiO2 -coated catheters
was superior to that of conventional catheters, and suggested
the promising clinical use of the self-sterilizing catheter as an
intermittent (self-)catheterization catheter for neurogenic bladder
patients [559]. The self-sterilizing catheter can be disinfected in
a specially designed portable sterilizer box, or by direct sunlight.
The intra-corporeal use of TiO2 -coated catheters is also under
examination. In this case, metallic Ag is deposited on the TiO2
surface to enhance the antibacterial action under dark conditions.
570 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 6.8. Scanning electron micrographs of (a) the surface and (b) the cross-section of the TiO2 -coated silicone catheter. There is a thin intermediate SiO2 layer between TiO2
and catheter substrate [558].
© 2000, John Wiley & Sons, Inc.
Fig. 6.9. (a) Survival rate of E. coli inside several kinds of catheters under
ultraviolet-A irradiation. The catheters were filled with a 0.1 mL aliquot of E. coli
suspension, as follows: N, control 1, original silicone catheters, no UVA irradiation;
, control 2, TiO2 -coated catheters, no UVA irradiation; , original silicone catheters,
with UVA irradiation (1 mW cm−2 ); ×, TiO2 -coated catheters, with UVA irradiation
(1 mW cm−2 ) [559].
© 2007, The Japanese Urological Association.
6.5. Anti-fogging surfaces
The fogging of the surfaces of mirrors and glass occurs when
moist air cools down on these surfaces, forming many water
droplets. These droplets, ranging from micrometer to millimeter
size, tend either to scatter light or simply to reflect or refract it
randomly. In both cases, visual clarity is impaired drastically. In
a serendipitous discovery, Watanabe and co-workers found that
a TiO2 –SiO2 surface could become extremely hydrophilic under
UV illumination [500,560]. The result of this property is that
water spreads evenly across the surface. If the amount of water is
relatively small, the water layer becomes very thin and evaporates
quickly. If the amount of water is larger, it forms a sheet-like layer
that also has high visual clarity (Fig. 6.10). The first commercial
Fig. 6.10. Photographs of fogged surfaces of usual glass (a) and TiO2 -coated glass after sufficient UV illumination (b), typically > 150 min at an intensity of 1 mW cm−2
[500]. ©1999, Elsevier Science Ltd.
application of this phenomenon has been for automobile side-view
mirrors. The TOTO Ltd., in Japan currently is supplying TiO2 -treated
glass for such mirrors to major automobile manufacturers [9,14].
In addition, it has marketed adhesive TiO2 -coated plastic films or
TiO2 -containing sprays for the conversion of existing mirrors.
The uses of anti-fogging technology, however, are not limited to
mirrors and glass. One example in our daily life is air conditioners.
When an air conditioner is operating to cool during the summer,
air that is cooled on the heat exchanger of the air conditioner
often has moisture condensing out of it, except in an extremely
dry climate. For an ordinary plate heat exchanger, the condensed
water droplets fog the fins and large water droplets often form,
often bridging between the adjacent fins; this can reduce the heat
exchange efficiency and increase the resistance to air flow. Coating
the heat exchanger surface with superhydrophilic TiO2 , however,
can hinder the fogging and the formation of water bridging, and
remove the condensed water more effectively. This has been
proven by the recent studies of Takata et al. [561]. They observed
that the volume of water flowing off superhydrophilic TiO2 -coated
fins was 20% greater than that from ordinary fins, when humid
air (RH 90%, 40 ◦ C) was passed through the cooled fins (surface
temperature: 15 ◦ C).
As the properties of superhydrophilic films continue to be
improved, there will be many other possible applications of
the anti-fogging phenomenon. Research activities have been
focusing on: (1) increasing the rate of superhydrophilic conversion
[427,515]; (2) prolonging the superhydrophilic states of the
films [515,526,562]; and (3) activating the films at longer
wavelengths [473,522]. A rough TiO2 surface morphology has
the advantages of fast superhydrophilic conversion and long
persistence of the superhydrophilic state, but it can do harm to
film transparency. A mixed film of TiO2 and SiO2 (or Al2 O3 ) has
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
the advantages of long persistence of the superhydrophilic state,
but an excessive SiO2 –TiO2 ratio can have a negative effect on
the rate of superhydrophilic conversion. To develop a desirable
anti-fogging film, one obviously should strike a balance between
film composition and surface roughness. Extending the response
wavelength of TiO2 materials into the visible light region is
considered important for the design and actual applications of
superhydrophilic anti-fogging materials, but until now, only very
few reports have appeared on the superhydrophilic conversion
of visible-light-responsive TiO2 films (N-, or C-doped TiO2 ) under
visible illumination (see Section 5.2.5).
6.6. Heat transfer and heat dissipation
Superhydrophilic surfaces may improve the heat transfer
accompanied by liquid–vapor-phase transition. Takata et al.
studied the heat transfer properties of superhydrophilic TiO2
surfaces. They found that a TiO2 -coated Cu cylinder exhibited
excellent heat transfer characteristics in the nucleated boiling
regime, and its critical heat flux (CHF), a condition where liquid
cannot rewet the heater wall because of the rate of vapor
production impeding the liquid flow back to the hot surface,
was about two times higher than that of the uncoated surface
[561,563]. They also compared the falling-film evaporation on
a superhydrophilic surface with that on an ordinary surface
[564]. In this work, water was sprayed on the heated surface
through nozzles to form a water film. They found that on the
superhydrophilic surface, a stable water film was formed for
much smaller water flow rates than those on an ordinary surface.
Since the heat transfer rate increases for thinner water films, the
superhydrophilic surface is expected to improve the performance
of falling-film evaporators, which are widely used in seawater
desalination units and milk and juice concentrators. They observed
that the superhydrophilic surface performed 40 times better
than the ordinary surface in low water flow and low heat flux.
For high water flow, a thick water film formed on both the
superhydrophilic and the ordinary surface, and thus no difference
in heat transfer rate was observed. These workers suggested that
the superhydrophilic surface could be an ideal heat transfer surface
and would be applicable to various heat transfer phenomena that
are affected by surface wettability [561,563,564].
Hashimoto et al. reported recently the cooling of the exterior
walls of buildings with a falling-water film, with the intent to
help resolve the urban heat island problem for major cities and to
reduce the electricity consumption by air conditioners in summer
[14,565]. In their experiments, water was continuously sprinkled
onto the surfaces of buildings that were covered with TiO2 films.
Due to the superhydrophilic property of the material, water was
able to spread on the surfaces in the form of a thin water film
(∼0.1 mm). The evaporation of the water film can effectively cool
the building surface and also the surrounding air. They observed
on a clear day in the middle of summer that the temperature
drops were 15 ◦ C on window glass and 40–50 ◦ C on black-roof-tile
surfaces. The cooling of the building surfaces is expected to result
in the reduction of electricity consumption by air conditioners.
As estimated by Hashimoto et al., this reduction could be ten
to several tens of percentage for a real house. Therefore, TiO2 -
coated building materials could contribute much to energy-saving
technologies in the future (Fig. 6.11). The water film is so thin that
only a small amount of water is required to cover the building
surfaces. Moreover, natural rainwater can be collected and stored
in specially designed reservoirs for this purpose so that the cost of
the water can be reduced. The water film also helps in maintaining
the building surface clean by the self-cleaning effect.
571
Fig. 6.11. Energy-saving system using solar light and stored rainwater [14].
6.7. Anticorrosion applications
In general, metals are protected from corrosion in several
ways, for example, by a corresponding passive metal compound
layer, by a paint layer, or by a sacrificial metal coating (with a
less positive corrosion potential). Of these, the passive layer and
the paint layer are effective only when the coating covers the
metal surface perfectly. As for the sacrificial metal coating, its
lifetime is limited, because the metal coating dissolves gradually.
Recently, the application of photocatalytic technology in corrosion
prevention for metals has been examined [566–574].
In cooperation with the Koyo Electrical Construction Co.,
Ohko et al. studied the anticorrosion effects of a TiO2 coating
for Type 304 stainless steel [566]. Under UV irradiation, TiO2
injected electrons into the steel and as a result protected it from
corrosion, while the photogenerated holes decomposed organic
contaminants to provide a self-cleaning function. Interestingly,
the coating remained effective even if perforated with pinholes.
Later, the same group observed that TiO2 , when coupled with
WO3 , maintained an anticorrosion effect even in the dark for
a period of time after UV irradiation ceased [567,570,571]. This
phenomenon can be explained by the energy storage ability of
WO3 , as illustrated in Fig. 6.12. Under UV irradiation, electrons in
the valence band of TiO2 are excited to the conduction band. The
excited electrons are injected into the metal so as to maintain its
potential more negative than the corrosion potential. The excess
electrons can be accumulated in the ‘‘electron pool’’ of WO3 due
to the lower conduction-band edge of WO3 compared to TiO2 . The
reduced WO3 then reacts with protons adsorbed on the surface
or sodium cations in the electrolyte solution to form metastable
tungsten bronze (Mx WO3 , M: H+ , Na+ ; x ≤ 1) so that the reductive
energy generated at the irradiated semiconductor can be stored
as in a battery. After the UV light is turned off, the metastable
tungsten bronze gradually releases electrons into the metal via a
self-discharge process, and as a result the metal remains protected
from corrosion in the dark until the discharge process is completed.
Similarly, MoO3 also exhibited an electron pool function when
composited with TiO2 [572].
Research activities are continuing in order to extend the
anticorrosion period of TiO2 -based coatings in the dark [573,
574]. Recent studies have shown that phosphotungstic acid (PWA)
exhibits a longer self-discharge time than WO3 [574]. The TiO2 -
PWA coating can maintain an anticorrosion effect over 12 h in
electrolyte solution, after being illuminated with 1 mW cm−2 UV
light for 1 h. This is a very promising result for the development of
practical semiconductor coatings for metal corrosion protection.
572 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
Fig. 6.12. Schematic diagram of an energy storage-type photocatalytic anticorro-
sion system, which can protect metal from corrosion even in the dark [567].
© 2001, American Chemical Society.
6.8. Environmentally friendly surface treatment
In conventional technology for manufacturing printed circuit
boards (PCBs), insulating resin materials are first etched with
strong oxidants such as permanganate and hexavalent chromium
to prepare rough surfaces followed by electroless plating of a
copper layer on the whole surface and removal of the unwanted
copper after applying a temporary mask. The surface treatment
procedure is of vital importance for the strong adherence of the
copper layer to the resin substrate. However, the use of those
oxidants can cause serious environmental problems. Moreover,
the roughness of the etched surfaces is often of the order
of micrometers, which can lead to technical problems in the
fabrication of fine copper wires. Honma and co-workers recently
reported a novel environmentally friendly surface treatment
technique for PCB manufacture by treatment of resin surfaces
with TiO2 photocatalyst, replacing conventional etchants [575].
They found that an aqueous TiO2 suspension was able to oxidize
an epoxy resin surface within a depth of 30–50 nm under UV
illumination but did not affect surface roughness appreciably.
Palladium and tin catalysts for the electroless deposition of copper
penetrated into the surface-modified layer and electroless copper
plating was initiated at the bottom of this layer. As a result, the
copper layer showed excellent adhesion (1.15 kN m−1 ) to the
epoxy surface, even better than that obtained by conventional
technology. By using this new surface treatment technique, Honma
et al. succeeded in fabricating fine patterns of copper with lines and
spaces of 10 µm/10 µm, as shown in Fig. 6.13.
Honma and co-workers also applied this new surface treatment
technique to modify the ABS resin surface, which is often etched
with hexavalent chromium in conventional technology [576]. The
1, 2-polybutadiene distributed in the ABS matrix was preferentially
reformed by photocatalytic oxidation and induced hydrophilicity
on the reformed surface. The ABS resin surface was reformed down
to the depth of a few µm and the catalyst (Pd and Sn) penetrated
into the surface to the extent of 30–40 nm. Metal layers deposited
on the modified ABS surface showed adhesive strengths of about
1.0 kN m−1 . They concluded that the superior adhesion strength
was derived from a nano-anchor effect by the deposition of metal
inside the 30–40 nm reformed resin layer.
6.9. Photocatalytic lithography
The active oxygen species such as the hydroxyl radical or singlet
O2 generated during the photocatalytic process are so active that
they can oxidize not only organic materials but also inorganic
materials such as copper, silicon, carbon, and SiC etc. [353,359,
360]. The oxidation can occur either on the TiO2 surface or at a
distance away from the surface. Therefore, it is possible to develop
a novel photocatalytic lithographic method based on the above-
mentioned oxidation reactions to fabricate surface patterns with
Fig. 6.13. SEM mapping of 10 µm/10 µm L/S copper wiring. (a)–(c) PCB substrates
were treated by TiO2 photocatalyst. (d)–(f) PCB substrates were etched with
permanganate etching process. (c) and (f) are reflection mode images. As shown, the
photocatalytic treatment did not change the surface morphology of PCB much, and
could be used to prepare finer copper wires than those obtained by the conventional
etching method [575].
© 2006, Surface Finishing Society of Japan.
composition/wettability contrast. This novel method would have
the advantages of simplicity and low cost: it does not require
expensive photo-resist materials and special equipment.
Tatsuma and co-workers first examined the concept of
photocatalytic lithography based on the remote oxidation effect of
TiO2 [360]. They placed a TiO2 -coated quartz substrate in contact
with a glass plate modified with an ultrathin organic layer, or
silicon, copper, or silver plate, separated by a small gap. The TiO2
was irradiated with UV light in air through a photomask. As a
result, two-dimensional images corresponding to the photomask
were obtained; those images were based on the contrast of non-
oxidized to oxidized surfaces. In a following study, Kubo et al.
examined the resolution of their novel lithography technique and
found that the resolution of remote oxidation-based photocatalytic
lithography deteriorated slightly due to the lateral diffusion of
active oxygen species in the air [353] They obtained a resolution of
10 µm by optimizing the TiO2 film/photomask assembly (Fig. 6.14)
and suggested that the theoretical resolution should approach the
scale of the light wavelength, namely the submicrometer level,
provided that a highly collimated light beam and a highly uniform,
non-light scattering TiO2 film were available [353].
Lee and Sung combined photocatalytic lithography and selec-
tive atom layer deposition (ALD) to prepare patterned ZrO2 thin
films on Si substrates [577]. In their study, a patterned TiO2 thin
film (line width, 400 nm; line space, 580 nm) on quartz was used
as the lithographic tool. The TiO2 film was placed on an octadecyl-
siloxane self-assembled monolayer (SAM)-modified Si substrate,
and the assembly was irradiated with 254-nm UV light. The SAM
was selectively removed, retaining the dimensions of the TiO2 pat-
tern without noticeable line spreading. By means of the ALD tech-
nique, a ZrO2 thin film was selectively deposited in the region with-
out the SAM, with a 430-nm linewidth, through reaction with the
silanol groups of the Si substrate.
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582 573

Fig. 6.14. (a) Micrograph of the Cu plate surfaces patterned by the photocatalytic lithography. (b) Micrographs of masked TiO2 film (upper) and heptyldecafluorode-
cyltrimethoxysilane (HDFS)-coated glass plates patterned by photocatalytic lithography (below) [360].
© 2004, American Chemical Society.

Fig. 6.15. Micrographs of a drop of polystyrene microsphere suspension pipetted on a preheated superhydrophobic–superhydrophilic pattern, which were taken at (a) 5 s,
(b) 5 min, (c) 8 min, and (d) 9 min after pipetting the drop. Polystyrene microspheres were selectively deposited in the superhydrophilic stripes. The scale bar in pictures is
400 µm [585].
© 2007, American Chemical Society.

Photocatalytic lithography has also been applied to prepare
chemical affinity/wettability patterns on surfaces [578–580].
Spencer and co-workers irradiated an alkanethiol monolayer on an
Au substrate through a TiO2 film and a filter with a transmittance
gradient [580]. Thus, these workers were able to prepare a
concentration gradient of alkanethiol on the Au surface, since
the oxidized alkanethiol molecule was removed from the surface.
Adsorption of other types of alkanethiol molecules led to the
formation of chemical affinity/wettability gradients on the Au
surface.
In addition to remote oxidation-based photocatalytic lithogra-
phy, there have also been some efforts to prepare chemical affin-
ity/wettability patterns directly on TiO2 surfaces. The patterned
TiO2 surfaces were used to assemble colloidal crystal films [581]
and to site-selectively immobilize semiconductor quantum dots
[582]. There have been several studies concerning the pattern-
ing of superhydrophobic TiO2 films by photocatalytic lithogra-
phy [583,584]. The resulting superhydrophobic–superhydrophilic
surface patterns were shown to guide the evaporation of a la-
tex suspension (Fig. 6.15) or to be filled site-selectively with
electroless-plated metal or polymer hydrogel, due to the extremely
large wettability contrast in the pattern [585,586] In these cases,
the diffusion of holes in TiO2 and the surface diffusion of active oxy-
gen species should restrict the lithographic resolution to the mi-
crometer scale, as suggested by the studies of Haick and Paz [357,
358] A recent study by Kobayashi et al., however, showed that a
feature with 30-nm linewidth was able to be produced in a stearic
acid monolayer deposited on a TiO2 substrate by photocatalytic
574 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

Fig. 6.16. (a) Photochromism of the Ag–TiO2 film. Absorption spectra of Ag deposited on the TiO2 film by ultraviolet light irradiation (300–400 nm, 1 mW cm−2 , 15 min) and
after visible light irradiation (>400 nm, 50 mW cm−2 , 1 h). Corresponding photographs are also shown. (b) Multicolor photochromism of the Ag–TiO2 film. A–D, Differential
absorption spectra of the Ag–TiO2 film after visible light irradiation (10 mW cm−2 , 5 min) using a xenon lamp with bandpass filters [588].
© 2003, Nature Publishing Group.

lithography, aided by a local electrical field applied by a conduc-

tive AFM cantilever [587]. The positive bias (10 V) applied to TiO2
substrate lowered the local charge recombination, which led to the
rapid decomposition of the stearic acid molecules at the site to
which bias was applied.

6.10. Photochromism

Photochromic materials, which change their colors reversibly

in response to light, can be applied to smart windows, displays
and memories. Conventional photochromic materials respond
in a monochromatic way, so that multicolor photochromism
has required several different materials or filters combined
appropriately. If multicolor photochromism could be achieved
with a simple material, photochromic devices would find a greater
number of applications, including a rewritable color copy paper
or electronic paper and a high-density multi-wavelength optical
memory. Ohko et al. recently reported the interesting multicolor
photochromism of TiO2 films loaded with silver nanoparticles
[588–591]. The film color, initially brownish-grey, changed under
monochromatic visible light to almost the same color as that of
the light (Figs. 6.16 and 6.17); the apparently uniform Ag–TiO2
film can take on almost any color. The color reverted to brownish-
grey under ultraviolet light, and these processes were found to be
repeatable.
Ohko et al. proposed the following model for the multicoloring
process [588]: on irradiation with monochromatic visible light,
the corresponding Ag nanoparticles adsorb the light, and the
electrons thus excited are accepted by O2 , resulting in oxidation
of the Ag nanoparticles to Ag+ and an absorption decrease
appears at the corresponding wavelength, i.e., the color of the
excitation wavelength. The most important role of the TiO2 film
is the repeatable generation of Ag nanoparticles with diverse
sizes and shapes due to the ‘‘molding effect’’ of the nanoporous
TiO2 film; this resulted in different plasmon resonance absorption
wavelengths of the Ag particles in the whole visible light spectrum.
Later studies by Kawahara et al. showed that not only TiO2 but
Fig. 6.17. A thick multicolored Ag–TiO2 film. Each spot (6 mm diameter) was
irradiated successively with a blue, green, red, or white light.
© 2004, American Chemical Society [591].
also ZnO films were able to work as the substrate material for Ag-
based multicolor photochromism [589]. SiO2 and ITO, however, did
not work. These workers suggested that both TiO2 or ZnO play
an important role in the charge separation between the excited
electrons and the Ag+ . Actually, a fraction of the excited electrons
on Ag were transferred to oxygen molecules via TiO2 or ZnO and
non-excited Ag.
The color image is bleached gradually in air by ambient white
light, which is detrimental to practical applications. Naoi et al.
showed that a stable color image can be obtained by either
modifying the Ag nanoparticles with thiols [592], or washing the
photogenerated Ag+ ions off the film [591]. Interestingly, the color
image fixed by washing off the Ag+ ions could be maintained as a
‘‘latent image’’, that is, the image can be recovered after a cycle of
white light bleaching and UV coloration due to the ‘‘molding effect’’
of the nanoporous TiO2 film [591].
6.11. Microchemical systems
Microchemical systems using microchannels as reaction fields
provide many technical advantages over conventional technolo-
gies for chemical synthesis as well as analysis. Coating the in-
ner walls of microchannels with TiO2 provides photocatalytic
reactivity to microchemical systems. Possible applications in-
clude the photocatalytic degradation of organic pollutants [590,
 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582
593], photocatalytic synthesis of organic compounds [594], site-
selective introduction of functional metal nanoparticles [595],
photo-controllable wettability of channels [596,597], and self-
cleaning microchannels, among others.
Takei et al. employed a TiO2 -modified microchannel chip for
the photocatalytic synthesis of L-pipecolinic acid from L-lysine
[594]. They observed that the conversion rate in the chip was 70
times larger than that in a cuvette with almost the same selectivity
and enantiomeric excess [594]. They suggested that the large
surface area of the microchannels, together with the short diffusion
distance, should improve the efficiency of photocatalytic reactions
within the channels.
Castellana et al. reported a simple method to introduce
noble metal nanoparticles inside sealed microfluidic channels
that were coated with a TiO2 photocatalyst [595]. Under UV
illumination, metal ions, for example, Ag+ , were reduced from
solution to the area covered with TiO2 to form an Ag nanoparticle
film. In cases in which photomasks were used, a patterned Ag
film was readily prepared. The Ag nanoparticle film could be
biofunctionalized to capture proteins with good discrimination
between addressed locations and background. Their method
appears to be quite general, and films of Au, Pd and Cu could
also be patterned. The ability to address individual ligands atop
nanoparticle films inside microfluidic devices can be combined
with such technologies as transmission surface plasmon resonance
spectroscopy or surface-enhanced fluorescence. This allows for
the development of powerful lab-on-a-chip devices with label-
free detection or fluorescence detection with enhanced sensitivity.
Moreover, the metal nanoparticle films can be used to immobilize
patches of oriented enzymes inside microfluidic devices, which
have promising applications in enzymatic microreactors.
Kim and co-workers applied photocatalytic reactions to control
the wettability of microchannels, by which pressure barriers, so-
called Laplace valves, were introduced to microchannels at desired
positions [596]. They modified the inner walls of the microchan-
nels with TiO2 nanoparticles; afterwards they modified the TiO2
nanoparticles with a hydrophobic self-assembled monolayer. The
walls of the microchannel became superhydrophobic (water con-
tact angle > 150◦ ) after these procedures. When UV illumination
was applied to the superhydrophobic microchannel, TiO2 nanopar-
ticles decomposed the hydrophobic monolayer, which led to the
gradual decrease of the water contact angle to 0◦ , the so-called
superhydrophilic state. Since the water contact angle of the TiO2 -
modified microchannel wall was adjustable between 150◦ and 0◦ ,
the pressure barrier was found to be tunable over a wide range; the
latter was determined by the Laplace pressure P = −2γ cos θ /r,
where γ is the surface tension of the liquid, r the channel radius,
and θ the contact angle. They demonstrated the preparation of
4-step wettability-based Laplace valves having different pressure
barriers in one channel (Fig. 6.18), and also the construction of a
batch operation system consisting of two sub-nL dispensers and a
reaction chamber.
Thus, given the number of promising approaches already
reported, it appears likely that photocatalysis will find increasing
application in microchemical and microfluidic devices.
7. Summary
We have tried to provide an overview of the field of
photocatalysis from its very beginning in 1921 [17] through its
developments in fundamental studies, both experimental and
theoretical, which have been strongly tied to applications. Of
course, it is impossible to do justice to this vast field in a review
of even this length, and new work is emerging every day. This
is the nature of the field. We have also tried to focus on some
of the aspects of the field that would not be treated in a general
575
Fig. 6.18. (a) Irradiation time for preparation of the 4-step Laplace valve in one
channel and (b) fluorescence microscope images of fluorescein aqueous solution in
the photopatterned and tuned channel [596].
© 2007, The Royal Society of Chemistry.
review or in a pure surface science-oriented review, for example,
electrochemistry and photoelectrochemistry.
The early work in the field can be inspirational and still teach
us much. For example, the work of Baur in the 1920s shows us the
power of imagination in the development of science. His idea of the
pairing of oxidation and reduction reactions is still a central one
[23,24,598]. The work of Goodeve and Kitchener in 1938 could be
published today with only slight modification [26], but the fact that
it was done at that time should inspire us to even greater efforts.
Fundamental studies in spectroscopy have led to a much better
understanding of the processes occurring in TiO2 in its various
forms, including single crystals, powders and films. There is so
much information available now that it is a challenge to make
sense of it all. One of the points that we have learned is that the
nature of the sample itself, i.e., its preparation, handling, history,
and chemical and physical characteristics must be specified in
as great detail as possible, because all of these are important in
determining the observed behavior.
The dual use of experimental studies with single crystal stud-
ies and theoretical studies on the same surfaces is becoming
an extremely powerful approach. It is hoped that this approach
will be extended and deepened, with increasingly sophisticated
techniques, until a convergence can be reached even for photocat-
alytically related reactions on the rutile (110) surface, which we
venture to say is still not completely understood. As a convergence
is achieved for this surface, we can become more confident that our
experimental and theoretical techniques can be applied to other
surfaces. Of course, this is not to say that we should wait to study
the other surfaces, but the point is that we cannot be truly confi-
dent until we can obtain convergence for this most studied system.
The work of Henderson has provided an excellent example [113,
114,130,141–143,280,516,599–608].
The recent STM work on reactions of water and oxygen with the
rutile (110) surface is truly impressive and provides an example
of what can be learned at the atomic scale [129,133,137]. The
realization that trace water, even in ultra-high vacuum, can react so
readily with oxygen vacancies to produce OH groups should cause
us to examine carefully any work in which vacancies are discussed,
576 A. Fujishima et al. / Surface Science Reports 63 (2008) 515–582

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