Catalysis Communications 10 (2009) 925929

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Synergetic effects of nitrogen doping and Au loading on enhancing

the visible-light photocatalytic activity of nano-TiO2
Baozhu Tian, Chunzhong Li *, Feng Gu, Haibo Jiang
Key Laboratory for Ultrane Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology,
130 Meilong Road, Shanghai 200237, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Nitrogen-doped together with gold-loaded TiO2 (Au/NTiO2) nanoparticles were prepared by a simple
Received 9 July 2008 wet-chemical method. The samples were characterized by XRD, TEM, XPS, UVvis diffuse reectance
Received in revised form 7 December 2008 spectroscopy, and photoluminescence (PL) spectroscopy. It reveals that Au was loaded on the surface
Accepted 11 December 2008
of TiO2 in the form of metallic Au, and nitrogen is introduced into TiO2 matrix in the form of substitu-
Available online 24 December 2008
tional nitrogen and interstitial nitrogen. Au/NTiO2 exhibits much higher visible-light photocatalytic
activity when compared with single N-doped or Au-loaded TiO2. A synergetic effect was proposed to
Keywords:
explain the effects of nitrogen doping and Au loading on enhancing the visible-light photocatalytic activ-
TiO2
Nitrogen doping
ity of TiO2.
Au loading 2008 Elsevier B.V. All rights reserved.
Photocatalytic activity
Synergetic effect

1. Introduction hinder the recombination of electrons and holes, but it almost

In recent years, TiO2-based photocatalysis has become the focus
of numerous investigations owing to its potential applications in
thoroughly decomposing undesirable organic contaminants in
waste water and air. Amongst various metal oxide semiconductor
materials, TiO2 has been most frequently employed as a promising
photocatalyst because of its various merits, such as opticalelec-
tronic properties, chemical stability, low cost and nontoxicity
[1,2]. However, the practical applications of TiO2 have been sup-
pressed by its two drawbacks, one of which is the low quantum
yield that arises from the rapid recombination of photo-induced
electrons and holes; the other is the poor solar efciency that is
determined by its band gap. Many studies have reported that load-
ing of noble metals (e.g., Pt, Au, or Ag) on the surface of TiO2 can
effectively promote the transfer of photo-induced electrons and
consequently hinder the recombination of photo-induced electrons
and holes, leading to the improvement of quantum yields of TiO2
[25]. Meanwhile, it was found that doping with nonmetals (e.g.,
boron [6], carbon [7], and nitrogen [8,9]), especially nitrogen, can
successfully tune the electron structure of TiO2, extending the pho-
toresponse of TiO2 into the visible light region.
Although nonmetal doping can extend the photoresponse of
TiO2 into the visible light region, it often decreases the quantum
yields of TiO2 [10]. Similarly, noble metal loading can effectively
* Corresponding author. Tel.: +86 21 64250949; fax: +86 21 64250624.
E-mail address: czli@ecust.edu.cn (C. Li).
has no effect on extending the photorespond of TiO2 to the visible
light region. Enlightened by the respective advantages of noble me-
tal loading and nonmetal doping, we speculated that the combina-
tion of noble metal loading and nonmetal doping might be useful
for overcoming the two drawbacks of TiO2. In this study, nitro-
gen-doped together with gold-deposited TiO2 (Au/NTiO2) was
prepared by a simple wet-chemical method. The photocatalytic
activities of photocatalysts under UV and visible light irradiation
were evaluated by measuring the degradation rates of methylene
blue (MB) and 2,4-dichlorophenol (2,4-DCP), respectively. The syn-
ergetic mechanisms of nitrogen doping and Au loading in enhanc-
ing the visible-light photocatalytic activity of TiO2 were tentatively
discussed.
2. Experimental
2.1. Preparation
Nitrogen-doped TiO2 was synthesized with following process:
under continuous stirring, Ti(OC4H9-n)4 dissolved in absolute eth-
anol, was added dropwise to NH4Cl aqueous solution. The mole ra-
tio of N/Ti was 2:1. After being continuously stirred for 24 h, the
mixture was transferred into a 100-mL Teon-inner-liner stainless
steel autoclave and kept at 180 C for 12 h. Then, the precipitate
was collected by centrifugation, washed with water and ethanol
for several times, and dried at 100 C for 6 h. Finally, nitrogen-
doped TiO2 was obtained by calcining the samples at 350 C for

1566-7367/$ - see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2008.12.029
926 B. Tian et al. / Catalysis Communications 10 (2009) 925929
1.5 h, designated as NTiO2. Pure TiO2 was synthesized with the
same procedure, except no NH4Cl was added. The Au loading was
carried out with depositionprecipitation method, in which
HAuCl4 was selected as gold precursor and the pH value of HAuCl4
solution was adjusted to 8.0 with 1 M NaOH solution. The detailed
process was similar to that of the reference [11]. In addition, it
must mentioned that the catalysts were calcined at 573 K under
a slow airow of N2 and O2 (the volume ratio of oxygen to nitrogen
was 1:8), which is different from the reference. The photocatalyst
samples with different Au loading were prepared by adjusting
the concentration of Au precursor, and labeled as x%Au/NTiO2,
where x stands for the mass percentage of Au in theoretical
product.
2.2. Characterization
X-ray powder diffraction (XRD) data were recorded at room
temperature with a Rigaku D/max 2550 VB/PC X-ray diffractome-
ter using Cu Ka radiation (k = 0.154056 nm), operated at 40 kV
and 100 mA. Transmission electron micrograph (TEM) images were
taken with a Hitachi H-800 transmission electron microscopy. UV
vis diffuse reectance spectra (DRS) were obtained using a Scan
UVvisNIR spectrophotometer (Varian Cary 500) equipped with
an integrating sphere assembly, using polytetrauoroethylene as
the reference material. The X-ray photoelectron spectroscopy
(XPS) measurements were carried out on a Perkin Elmer PHI
5000 C ESCA X-ray photoelectron spectrometer with Al Ka radia-
tion operated at 250 W. The shift of the binding energy due to rel-
ative surface charging was corrected using the C1 s level at
284.8 eV as an internal standard. The photoluminescence (PL)
spectra of the samples were measured with a Cary Eclipse spectro-
photometer by using 280 nm line of Xe lamp as excitation source at
room temperature.
2.3. Photocatalytic activity measurement
Because the dyes can be degraded under visible light irradiation
by self-photosensitization mechanism [6], here we selected 2,4-
dichlorophenol (2,4-DCP) which has no absorption in the visible
region as target pollutant to evaluate the photocatalytic activity
of the samples under visible light irradiation. Meanwhile, methy-
lene blue (MB) was used as model pollutant under UV light irradi-
ation. A 300-W high-pressure Hg lamp and a 1000-W tungsten
halogen lamp equipped with a UV cut-off lters (k > 420 nm) were
used as UV and visible light sources, respectively. Photodegrada-
Fig. 1. (A, B) XRD patterns of (a) pure TiO2, (b) 2%Au/TiO2, (c) NTiO2, and (d) 2%Au/NTiO2; (C) TEM imagine of pure TiO2; (D) TEM imagine of 2%Au/NTiO2.
tion reactions were carried out using a home-made set-up, in
which the lamp was cooled with owing water in a quartz cylindri-
cal jacket around the lamp, and a fanner was xed for maintaining
a constant temperature during the photocatalytic reaction. For
each test, 0.05 g of catalyst sample was added into an quartz tube
containing 50 mL of 20 mg/L MB (or 100 mg/L 2,4-DCP) aqueous
solution. Prior to light irradiation, the suspensions was sonicated
for 10 min and stirred for 30 min in the dark to attain the adsorp-
tiondesorption equilibrium for model pollutant and dissolved
oxygen on the surface of TiO2. At each given time interval, about
4 mL suspension was withdrawn, centrifuged and ltered to re-
move the remained particles. The residual concentration of MB
(or 2,4-DCP) was determined with a UVvis spectrophotometer,
and the degradation rate of MB (or 2,4-DCP) was calculated accord-
ing to the determined absorbance value.
3. Results and discussion
3.1. Crystallographic structures and morphologies
Fig. 1A shows the XRD patterns of pure TiO2, 2%Au/TiO2, NTiO2,
and 2%Au/NTiO2. Pure TiO2 and 2%Au/TiO2 consist of anatase as a
unique phase, while NTiO2 and Au/NTiO2 contain trace amount of
brookite. According to the previous reports [12,13], the formation of
brookite is probably related to the presence of chloride ions as well
as the acidity of NH4Cl aqueous solution. The average crystalline
sizes of the four samples were calculated to be 1012 nm (from
the half-width of the anatase (1 0 1) peak by using DebyeScherrer
equation), which is consistent with the TEM results (Fig. 2C and D).
Compared with pure TiO2 and NTiO2, 2%Au/TiO2 and 2%Au/NTiO2
exhibit new peaks emerged at 2h = 38.2, 44.4, 64.6, and 77.6,
which can be attributed to the diffraction peaks of (1 1 1) (Fig. 1B),
(2 0 0), (2 2 0) and (3 1 1) planes of polycrystalline Au, respectively,
demonstrating the formation of metallic Au [5,14]. The Au diffrac-
tion peaks are broad and low, suggesting that Au particles formed
on the surface of TiO2 show small crystalline size.
3.2. Light absorption and photoluminescence properties
Optical properties of solid materials are closely related to their
microstructure, such as electronic state, defect state, energy level
structure, etc. [15]. Fig. 2 shows the UVvis diffuse reectance spec-
tra of pure TiO2, NTiO2, 2%Au/TiO2, and 2%Au/NTiO2. Compared to
pure TiO2, the absorption edge of NTiO2 is obviously shifted to the
visible light region, together with a signicant enhancement of light
 B. Tian et al. / Catalysis Communications 10 (2009) 925929
Fig. 2. UVvis diffuse reectance spectra of (a) pure TiO2, (b) 2%Au/TiO2, (c) NTiO2,
and (d) 2%Au/NTiO2. Inset: XPS spectrum of N 1 s of 2%Au/NTiO2.
absorption in the visible region. The inset of Fig. 2 shows the XPS
spectrum of N 1 s of 2%Au/NTiO2. The N 1 s peaks appeared to be
broad and asymmetrical, suggesting the presence of different N spe-
cies. After tting of the curve, two peaks located at 399.1 and
401.3 eV were obtained. According the previous reports [1618],
the peak at 399.1 should be attributed to anionic N in OTiN link-
ages (substitutional nitrogen). The binding energy of this peak is
higher than that of TiN (6397.5 eV), which may be because nitrogen
in the TiO2 lattice can reduce the electron density on the nitrogen
due to the high electronegativity of oxygen. The other peak at
401.3 eV should be attributed to the formation of TiON bond
(interstitial nitrogen), which has been conrmed by the emergence
of a new peak of oxygen at 532 eV (not shown here). Both of substi-
tutional and interstitial nitrogen could affect the electronic band
structure of TiO2, enhancing the light absorption of TiO2 in visible
light region. In addition, it can be seen from Fig. 2 that both
2%Au/TiO2 and 2%Au/NTiO2 exhibit another absorbance band
around 550 nm when compared with pure TiO2 and NTiO2.
According to the previous Refs. [2,5,19,20], this band should be as-
cribed to the plasmon resonance of metallic Au particles. For metal
nanoparticles of Au0, Cu0, and Ag0, the plasmon absorption arises
from the collective oscillations of the free conduction band elec-
trons that are induced by the incident electromagnetic radiation.
PL emission spectrum are useful to investigate the efciency of
charge carrier trapping, migration and transfer, and to understand
the fate of electron-hole pairs in semiconductor particles since PL
emission mainly results from the recombination of free carriers
[2,21]. For nanostructured materials, the PL spectra are related to
the transfer behavior of the photo-induced electrons and holes so
that it can be used to evaluate the recombination rate of charge
carriers [22]. Fig. 3 shows the PL spectra of the prepared samples.
It can be seen that the PL intensities of these samples vary in the
following order: NTiO2 > pure TiO2 > 1%Au/NTiO2 > 4%Au/N
TiO2 > 2%Au/NTiO2 > 2%Au/TiO2. Since the PL emission results
from the recombination of photo-induced electrons and holes,
the lower PL intensity means the lower recombination rate of elec-
trons and holes. Furthermore, it is well known that Au favors the
transfer of photo-induced electrons and restrains the recombina-
tion of electrons and holes by forming Schottky barrier at the
TiO2Au interface [2,23]. Therefore, it is reasonable that the PL
intensities of Au-loaded samples were much lower than that of
samples without Au loading. The PL intensities of NTiO2 and
2%Au/NTiO2 are higher than those of pure TiO2 and 2%Au/TiO2,
927
Fig. 3. PL emission spectra of (a) pure TiO2, (b) NTiO2, (c) 2%Au/TiO2, (d) 1%Au/N
TiO2, (e) 2%Au/NTiO2 and (f) 4%Au/NTiO2.
respectively, implying that N doping promotes the recombination
of photo-induced electrons and holes. In fact, it has been reported
that N doping sites could serve as recombination centers when the
N concentration is excessive [10].
3.3. Photocatalytic activities and mechanism
Fig. 4A shows the degradation rates of MB under UV light irra-
diation for 1 h over different photocatalysts. It was found that Au
loading can evidently enhance the photocatalytic activity of both
pure TiO2 and NTiO2, and the variation of degradation rates is
consistent with PL result, indicating that the photocatalytic activity
is closely relative to the recombination rate of electrons and holes.
By forming Schottky barrier at the TiO2Au interface [2,23], Au
loaded on the surface of TiO2 favors the transfer of photo-induced
electrons from TiO2 conduction to adsorbed O2 and consequently
decreases the recombination rate of photo-induced electrons and
holes, nally resulting in the improvement of photocatalytic activ-
ity (Fig. 5). It is noteworthy that the photocatalytic activity doesnt
not always enhance with the increase of Au loading. In this study,
the optimal Au loading for achieving the highest photocatalytic
activity is 2.0 wt.%. When the Au loading is higher than this level,
the photocatalytic activity will decrease with increasing Au load-
ing. According to the previous reported [5,24], excess Au covered
on TiO2 surface can become the recombination centers of photo-in-
duced electrons and holes, consequently resulting in the decrease
of photocatalytic activity. Compared with pure TiO2, NTiO2 did
not show any improvement of photocatalytic activity in spite of a
signicant enhancement of light absorption in the visible region.
As mentioned above, excessive N dopant could act as recombina-
tion centers of photo-induced electrons and holes, leading to the
decrease of photocatalytic activity.
Fig. 4B shows the degradation rates of 2,4-DCP under visible
light irradiation for 5 h over different photocatalyst samples. It
can be seen that the photocatalytic activities of photocatalyst sam-
ples vary in the order: 2%Au/NTiO2 > 1%Au/NTiO2 > 4%Au/N
TiO2 > NTiO2 > 2%Au/TiO2  pure TiO2. The photocatalytic activity
of NTiO2 is much higher than that of pure TiO2, due to the
enhancement of light absorption in the visible region. An interest-
ing phenomenon is that Au loading can evidently improve the vis-
ible-light activity of NTiO2, but it cant effectively improve
the visible-light activity of pure TiO2. Combining the fact that Au
loading can greatly enhance the photocatalytic activity of both
928 B. Tian et al. / Catalysis Communications 10 (2009) 925929
Fig. 4. Photocatalytic degradation rates of MB under UV light irradiation for 1 h (A) and 2,4-DCP under visible light irradiation for 5 h (B) over different photocatalysts: (a)
pure TiO2, (b) 2%Au/TiO2, (c) NTiO2, (d) 1%Au/NTiO2, (e) 2%Au/NTiO2, (f) 4.0Au/NTiO2.
Fig. 5. Proposed mechanism for phototocatalytic degradation of organic pollutant
under UV and visible light irradiation over Au/NTiO2 photocatalyst. Au loading and
N doping exhibit synergetic effect on enhancing the visible-light photocatalytic
activity of TiO2.
pure TiO2 and NTiO2 under UV light irradiation, we speculate that
the effect of Au loading on improving photocatalytic activity is
probably related to the density of photo-induced electrons and
holes. Under UV light irradiation, a large amount of electrons and
holes were generated in short time, meaning high recombination
rate of electrons and holes. Therefore, Au loading can effectively
decrease the recombination rate of electrons and holes. Under vis-
ible light irradiation, the number of photoelectrons generated
within NTiO2 is much more than that within pure TiO2. Thus,
Au loading improves the photocatalytic activity of NTiO2 more
evidently when compared with pure TiO2. Fig. 5 illustrates the syn-
ergetic effects of N doping and Au loading on enhancing the visi-
ble-light photocatalytic activity of TiO2. Under visible light
irradiation, electrons are excited from the N impurity energy level
to the conduction band of TiO2. Subsequently, they are captured by
loaded Au and transferred to the adsorbed O2 on the surface of TiO2
to form superoxide anion radicals, which can further initiate the
degradation reaction. The presence of Au can restrain the recombi-
nation of photo-induced electrons and holes, resulting in the
enhancement of photocatalytic activity. However, excess amount
of Au not only inuences the penetration of visible light but also
acts as the recombination center of electrons and holes, leading
to the decrease of photocatalytic activity. Therefore, it is reason-
able that the photocatalytic activity of 4.0Au/NTiO2 is lower than
that of 2.0Au/NTiO2.
4. Conclusions
By a simple wet-chemical method, Au/NTiO2 nanoparticles
were successfully prepared. It was found that Au can be loaded
on the surface of TiO2 in the form of metallic Au, and nitrogen is
introduced into TiO2 matrix in the form of substitutional nitrogen
and interstitial nitrogen. Au/NTiO2 exhibits much higher visible-
light photocatalytic activity when compared with single N-doped
or Au-loaded TiO2. The enhancement of visible-light photocatalytic
activity of TiO2 might be ascribed to the synergetic effects of nitro-
gen doping and Au loading.
Acknowledgements
This work has been supported by the National High Technology
Research and Development Program of China (2006AA03Z358), the
National Natural Science Foundation of China (20706015,
50703009), the Shanghai Rising-Star Program (06QA14013,
07QA14014), the Major Basic Research Project of Shanghai
(07DJ14001), the Ph.D. Programs Foundation of Ministry of Educa-
tion of China (20070251022), the Special Projects for Key Laborato-
ries in Shanghai (07DZ22016, 06DZ22008), the Special Projects for
Nanotechnology of Shanghai (0752nm010, 0652nm034), and 973
Program (No. 2004CB719500).
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