Modified Titanium Oxide (TiO2) Nanocompos Review

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Modified titanium oxide (TiO2) nanocomposites and its

array of applications: A Review
a a
S. Ghosh & A. P. Das
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Bioengineering & Biomineral Processing Laboratory, Centre of Biotechnology, Siksha O
Anusandhan University, Khandagiri Square, Bhubaneswar, India
Accepted author version posted online: 21 May 2015.
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Publisher: Taylor & Francis
Journal: Toxicological & Environmental Chemistry
DOI: http://dx.doi.org/10.1080/02772248.2015.1052204
Modified titanium oxide (TiO2) nanocomposites and its array of applications: A Review
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S. Ghosh and A. P. Das*
Bioengineering & Biomineral Processing Laboratory, Centre of Biotechnology,
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Downloaded by [Shiksha O Anusandhan University] at 04:05 21 May 2015
Siksha O Anusandhan University, Khandagiri Square, Bhubaneswar, India
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Corresponding Author: Dr. Alok Prasad Das
Assistant Professor,
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Centre of Biotechnology,
Siksha ‘O’ Anusandhan University,
Bhubaneswar, Odisha, 751003
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Email: alokdas@soauniversity.ac.in
Phone: +919337048198
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Fax: 91-674-2350652
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1
Abstract
Titania (TiO2) has been the focus of attention of researchers since the first demonstration of its
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capability to generate photocatalytic splitting of water into hydrogen and oxygen. However there
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seems to be a recent surge in the research activity involving modified TiO2 nanoparticles (NP),
which are considered to be more effective due to different physicochemical properties in
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comparison to unmodified fine particle analogs. Several strategies have been employed to
modify titania to reduce recombination rates of photogenerated charge carriers to enhance
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optimal functioning of TiO2. Doping with cations and anions and coupling it with another
semiconductor are the most well-known modification methods used. Titania nanocomposites are
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known to have a plethora of applications. Photoexcitation of these particles are seen to be
extraordinarily effective in eliciting microbial death which makes it an attractive candidate for
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manufacturing of antimicrobial coatings. On the other hand, TiO2 induces oxidation of various
organic refractory compounds like tetracycline, sulfamethazine, and bisphenol. The photo-
electrocatalytic oxidation technique which amalgamates the principle of photocatalysis and
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electrolysis serves as a newer, unswerving and cost effective water treatment process. In the
biomedical arena, use is now acknowledged for photodynamic therapy of cancer, cell imaging,
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biological sensors, drug delivery system and as endonucleases. In the commercial front, it is
utilized in creams owing to its small particle size which facilitates absorption through skin. It is
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also employed as UV blocking agents in sunscreen and commonly encountered as a brilliant

white pigment in paint due to its brightness, high refractive index and resistance to discoloration.
Its use in solar cells has also been reported. This review aims to encompass the new progress of
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modified TiO2 nanocomposites for efficient applications, emphasizing the future trends of TiO2
in arenas like healthcare, environment, biomedical, food, personal care and pharmacy and also
highlights the commercial implications of this promising nanomaterial.
Keywords: Nanomaterials; Titania; Doping; Applications; Future scope
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Introduction
Titania (TiO2) is the naturally occurring form of titanium and occurs as three major crystal
structures: stable rutile, metastable anatase and brookite (Yin et al. 2013). Both rutile and
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anatase possesses tetragonal structure while brookite has a rhombohedral structure. However the
distinctive physicochemical properties of TiO2 crystals are a result of their intrinsic electronic
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structure and crystal structures, in addition to their shape, size and doping (Hagfeldt and Gratzel.
1995).This photocatalytic agent is most extensively studied among the different nanomaterials
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and acts a n-type wide band gap semiconductor with a band gap energy of 3.2eV (Stoyanova et
al. 2013).The scientific community raised their interest in studying TiO2 since the first report of
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photocatalytic splitting of water on a TiO2 electrode under ultraviolet (UV) light in 1972. Its
chemical stability, low cost and optical competent nature make it an attractive candidate for
photovoltaic cells, electrochromic devices and photodegradation (Yin et al. 2013). However,
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TiO2 nanoparticles (NP), i.e, particles of size <100nm have become the focus of researchers due
to exhibition of special properties by these NP, attributed to the fact that their band gap is
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inversely proportional to their size (Murakami et al 1999).Titanium NP are now known to have a
wider array of applications which includes application in healthcare, biomedical, environmental,
food and cosmetic industries (Yin et al. 2013). They are also quite efficient in destroying
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different group of microorganisms which includes fungi and bacteria (Josset et al. 2008; Linkous
et al. 2000, Sunada et al 2003).Modified TiO2NP are considered to be more effective due to
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different physicochemical properties in comparison to their fine particle analogs and used to
devise antimicrobial coatings. There are also environmental applications like water and air
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purification, dye removal and solar water splitting (Shon et al. 2008). Biomedical applications
include photodynamic therapy for cancer, drug delivery system, cell imaging, biosensors for
biological assay and as endonucleases in genetic engineering (Yin et al. 2013).
The photocatalytic property of TiO2 is the main driving force underlying all its applications.
WhenTiO2 is photoexcited with photons of energy greater than or equal to its band gap energy,
there is generation of electron hole pairs which lead to the induction of redox reactions at the
TiO2 surface resulting in formation of reactive oxygen species (ROS). This generated ROS forms
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the basis of its bactericidal activity by attacking the cell membrane of the microorganism (Fu et
al 2005). Alternate mechanisms include alterations in the coenzyme A-dependent enzyme
activities (Matsumaga et al. 1985) and hydroxyl radical induced DNA damage (Gogniat and
Dukan. 2007). Apart from destroying microorganisms, TiO2 has been expansively applied in the
process of oxidation of various organic refractory compounds like tetracycline, sulfamethazine,
and bisphenol. The photo-electrocatalytic oxidation technique which combines the principle of
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photocatalysis and electrolysis serves as a newer, unswerving and cost effective water treatment
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process. This is owing to its ability to remove detrimental organic compounds in aqueous phase
and eradicate stable organic species traces which is otherwise intricate to oxidize by
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conventional water treatment methods (Dawson and Kamat 2001).
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The photocatalytic efficiency of TiO2 may be enhanced by modifying the molecule in several
methods including (1) effect structure generation for induction of space-charge separation using
metal dopants, (2) surface area increase by engineering particle size and pore-size distributions
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and (3) modification of the TiO2 surface by doping it with a metal or semiconductor (Dawson
and Kamat 2001). The majority of the charge carriers are electrons and holes. However, these
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charge carriers show rapid recombination and this is the reason why single component
semiconductor NP show a comparatively poor photocatalytic activity. To overcome this
drawback, semiconductor-metal nanocomposites are used which show higher efficiency due to
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reduction in rate of recombination of charge carriers, which occurs as a result of better charge
separation between electrons that are accumulating on the surface of the photocatalyst. Several
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investigations demonstrated that overall photo efficiency of TiO2 may be enhanced with
addition of noble metals like gold and silver. Consequently, synthesis of several nanocomposites
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occurred with the aim of increasing photocatalytic efficiency of TiO2 (Haick and Paz 2003).
Figure 1 illustrates research papers published on modified TiO2 over a 10 years period
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obtained from SCI database. In this review, the properties, structural modifications and various
applications of TiO2 including its photocatalytic activity, antimicrobial coatings for surfaces,
waste water treatment, treatment of organic pollutants along with some added perspectives are
summarize. Table 1 lists the numerous of applications of TiO2 and modified TiO2 in various
fields.
Properties of TiO2
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TiO2 comprising approximately 0.62% of the earth crust, is one of the most plentifully
distributed element on the earth surface (Kennedy 1990). This compound is chemically inert in
nature, thermally stable and has three naturally occurring ores, namely (1) ilmenite, a black sand
or rock having a molecular formula FeTiO3 and having a TiO2 concentration of around 45% to
60%, (2) rutile, a brown or reddish black naturally occurring TiO2, containing iron (Fe)
compounds as its major impurities and a TiO2 concentration of 90 to 95% and (3) brookite (Shon
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et al. 2008). Band gap energy is the most electronic property of a semiconductor. Anatase has
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been found to have higher band gap energy of 3.2 eV in comparison to the other two phases, i.e,
rutile 3 eV and brookite. Anatase is more popular when it comes to its use as a photocatalyst,
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although rutile was also noted to effective under the influence of certain circumstances (Wang et
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al 2006). Table 2 enumerates the properties of TiO2.
Mechanism of photocatalytic activity
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The photocatalytic property of TiO2 is the basis of its popularity and involves three processes:
(1) excitation, (2) bulk diffusion and (3) surface transfer of the light induced charge carriers (Yin
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et al. 2013). Figure 2 depicts the schematic representation of the photocatalytic mechanism of
TiO2. Firstly, when the semiconductor is photoexcited, it absorbs energy larger than its band gap
which then triggers excitation of the valance band electrons of the photocatalyst to the
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conduction band and also generates holes in the valence band. Secondly, the generated charge
carriers, i.e, electrons and holes, migrate to the photocatalyst surface. This is affected by factors
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like particle size, crystallinity and crystal structure of the photocatalyst. However, there is
decrease in photocatalytic activity of the semiconductor when recombinations of charge carriers
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occur. Finally, the charge carriers lead to chemical reactions on the surface of the photocatalyst.
The holes react with the surface adsorbed H2O to produce hydroxyl ions while electrons are
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usually foraged by O2 to yield superoxide radical ions. These species further react in solution to
yield other cytotoxic ROS such as hydrogen peroxide and peroxy radicals (Yin et al. 2013; Shon
et al. 2008). ROS formation is depicted in a simplified way with the help of the following
equations (1-6):
TiO2 + hʋ →h+ + e-(1)
H2O + h+ →●OH + H+ (2)
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O2 + e−→O2● -(3)
O2● − + H+ →HO2●(4)
HO2● → H2O2 + O2 (5)
H2O2 + O2●−→●OH + OH- + O2 (6)
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Modification of TiO2
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TiO2 photocatalyst has a high band gap value which results in low conversion efficiency under
visible light. This implies that TiO2 may only be stimulated under UV radiation (Leary and
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Westwood. 2011). Thus, it becomes essential to develop a TiO2 photocatalyst which can be
stimulated by visible light for greater feasibility of its applications under minimal conditions. As
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mentioned earlier, the recombination of the charge carriers also reduces photoefficiency of the
photocatalyst. Modifications are thus required to ensure a lower rate of recombination for TiO2
to function optimally. Several strategies were employed for modification, however doping of
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pure TiO2 with either anions or cations remains one the most common methods used for its
sensitization to visible light and reduction in rate of recombination of charge carriers (Teh and
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Mohamed 2011; Wang and Lewis 2006)
Cation doped TiO2

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Cations such as rare earth metals, noble metals, poor metals, and transition metals have been
used to dope TiO2 (Zhu et al. 2006). Metallic ions doping to TiO2 results in widening of the light
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absorption range which is accompanied by augmentation in the redox potential of the photo
generated radicals and also in inhibition of recombination of the generated charge carriers.
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However, the nature, concentration of dopant, photocorrision process and induced space charge
layer length alter the surface property of the materials and influence the photocatalaytic property
accordingly.
Although, several studies depict the improvement of visible light absorption capabilities of
metal ion doped TiO2 (Zhu et al. 2006; Ghicov et al. 2007), it is important to mention that the
increase in visible light absorption is not the only sole factor to promote photoactivity of TiO2
(Dunnill et al 2012; Gracia et al 2004; DeTacconi et al. 2003). In fact, during cation
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implantation, a specific amount of defects might be created which act as centers of
recombination, which is the driving force underlying the reduction in photocatalaytic activity.
This undesirable effect might be avoided by the reannaling of doped TiO2 (Zhang et al 2009).
Moreover doping of TiO2 with cations displaying either higher or lower oxidation states
promotes the rise in electrical conductivity (Dunnill et al 2012). When TiO2 is doped with
metallic cations having lower oxidation state electron neutrality may be achieved by removal of
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electrons from the valence band (Bally et al 1998). The leaping of electrons generates holes in
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the valence band of the system which results in elevation in electrical conductivity. In
comparison, when TiO2 is doped with metallic cations possessing higher oxidation states, the
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electron neutrality in the system might be achieved by electron addition into the already empty
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conduction band. These electrons that are transferred into the conduction band result in
augmentation of electrical conductivity.
Doping of TiO2 with metallic cations displayed an augmentation of photocatalytic
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properties. Conversely, several studies showed that cationic doping of TiO2 has significant
drawbacks (Furubayashi et al. 2005; Nah et al 2010; Qiu and Burda. 2007). The photocatalytic
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activities of TiO2 decrease even under the influence of UV radiation. Metal doped materials were
reported to be thermally unstable and the metal centers act as electron traps which promote
recombination of photogenerated charge carriers (Choi et al 1994; Di Paola et al. 2001). The
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cationic dopant might be confined in the d-level deep TiO2 band gap, which eventually serves as
recombination centers of charge carriers resulting in dwindling photocatalytic activity.
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Anion doped TiO2

Among the various approaches that were undertaken to produce hindrace to the
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recombination of photogenerated charge carriers, doping of TiO2 with anionic non-metals like
carbon, sulfur, nitrogen and iodine were examined (Lu et al 2007). Daghrir et al (2013)
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demonstrated that non-metal dopants improve both photocatalytic performance of TiO2 and
morphology. Tan et al (2011) noted that anionic metal dopants possess the ability to lower the
band gap of TiO2 and shift its optical response to visible light region. Among all the anions, TiO2
doping with carbon or nitrogen proved to be more effective in ensuring higher photocatalytic
activity under visible light (Ren et al. 2007).
Several studies examined carbon doping of TiO2 (Burda et al. 2003). Carbon atom
substitution in TiO2 establishes new states (C 2p) close to the valance band edge of TiO2 (O2p).
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Consequently, the band gap narrows due to the edge shift of the conduction band. The
assimilation of carbon into TiO2 may result in formation of carbonaceous species at its surface
known to enhance visible light absorption (Chen et al. 2007).Moreover the higher surface area is
another reason for the elevation in photocatalytic activity of C-doped TiO2 due to the presence of
more reactive sites, which eventually promote adsorption of more target pollutants (Dunnill et al
2012).
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Doping of nitrogen into TiO2 changes the hardness, elastic modulus, refractive index,
electrical conductivity and photocatalytic activity towards visible light absorption (Lu et al
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2007). The TiO2 doping may result in two forms of nitrogen atom: an interstitial form, i.e, 0.73
eV above the valence band or a substitutional that is localized mostly above the valence band
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(Wong et al 2008). However, Di Paola et al (2001) observed that preparation methods of N-
doped TiO2 play a role in influencing the state of N in TiO2 and also its effectiveness in visible
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light absorption. Thus it becomes imperative to select a suitable method of preparation of N-
doped TiO2 for achieving superior photocatalaytic efficiency (Ren et al. 2007).
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Despite the advantages achieved by doping TiO2 with non-metal ions, the content of dopant
diminishes during the annealing process, thus lowering photoactivity under visible radiation.
This foremost disadvantage confines the integration of non-metallic anions for doping TiO2. The
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coupling of two semiconductors is one way to recompense the shortcomings of doped TiO2.
Coupled semiconductor photocatalyst

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Coupling between diverse semiconductors with different energy levels is an added appealing
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approach which was used to augment the competence of semiconductors (Asahi and Morikawa.
2007; Ouyang et al 2012).In photocatlytic systems, TiO2 coupling with other semiconductors
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was designed to extend the absorption wavelength of TiO2 in the visible region and also to
enable recombination of charge carriers which diminishes the efficiency of the photocatalyst
(Bessekhouad et al 2004). An appropriate matching of conduction and valence band of the two
semiconductors guarantees a competent relocation of the charge carrier from one to another.
When a small band gap semiconductor comprising of more negative conduction band level is
coupled with TiO2 having large band gap, the electron might be infused from the small band gap
of the semiconductor used as a sensitizer to the TiO2. The energy gap between the corresponding
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band levels ensures transfer of charge carriers from one particle to its neighboring particle and
encourages the separation between photogenerated electron−holes (Zhang et al 2009).The
efficient transfer of charge carriers between TiO2 and the sensitizer depends on the difference
between the potentials of the conduction and valence band of the semiconductors (Bessekhouad
et al 2004).The efficient transfer of electron between TiO2 and sensitizer occurs when the
conduction band of TiO2 is more anodic than the analogous band of sensitizer (Robert. 2007).
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Only the excitation of sensitizer arises under visible irradiation and the photo generated
electrons flows into the conduction band adjoining TiO2. On the other hand, if the valence band
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of the sensitizer is more cathodic than TiO2, the holes are photogenerated behind the valence
band of the sensitizer. Several studies suggested that the photocataytic activity of TiO2 coupled
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with metal oxides such as CdS, SnO2,WO3, and FeO3.Bi2S3 among others has been principally
used for improving the process under visible irradiation. (Bessekhouad et al 2004;,Kannaiyan et
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al. 2010; Shang et al. 2004; Ren et al. 2011; Kuang et al. 2009).
Applications of modified titania

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Different forms of modified TiO2 are now identified which includes copper, silver, iron,
carbon, and manganese. Due to its photocatalytic properties, TiO2 shows antimicrobial activities.
TiO2 also has several environmental applications like waste water treatment, soil purification and
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heavy meal removal especially reduction of hexavalent chromium. It also finds its application in
food and cosmetic industries. It also has a wide range of biomedical applications like cancer cell
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destruction, and biosensing. The applications of modified TiO2 are summarized in Figure 3.
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Antimicrobial activity
Antimicrobial materials are applied to produce coatings on the surfaces of various objects.
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TiO2 based antimicrobial nanocomposites have been developed in recent years. The biocidal
activity is a result of inflection of charge carriers at the external surface interface of the material.
Titania is advantageous over both chemical and metal based systems due to the fact that they
have a broad spectrum of activity against microorganisms, including bacteria and fungi and are
also environmentally friendly in nature. Several mechanisms are suggested for the bactericidal
activity of modified TiO2 based nanocomposites. The most well studied mechanisms of its
activity are the initial oxidative attack on the outer/inner cell membrane of the microorganism
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(Sunada et al 2003), alteration in coenzyme A-dependent enzyme activities (Matsumaga et al.
1985) and damage to DNA via hydroxyl radicals (Gogniat and Dukan. 2007).
A three step mechanism was proposed for the photodestruction of bacteria by TiO2 (Figure
4). (a) generation of ROS attacks the cell wall of bacteria; (b) fragmentation of the inner
cytoplasmic membrane and destruction of the cell; and (c) decomposition of toxic bacterial
ingredients (Sunada et al 2003). In the first stage, damage is produced to the outer membrane but
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this stage of attack does not principally influence cell viability. However it changes the bacterial
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cell permeability towards ROS. TiO2 enters the cell and attacks the cytoplasmic membrane by the
process of lipid peroxidation, i.e, the second step. It is at this step that that inner membrane gets
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disordered which leads to cell death. The final step is the one which separates the effectiveness
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of this photocatalytic sterilization from other classical bactericidal treatments. During long
exposure to TiO2, the damaged bacteria were completely mineralized to CO2 and H2O due to the
self-cleaning characteristic of photo-irradiated TiO2 surfaces.
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In a recent study Kubacka eta al (2014) suggested some other mechanisms of bactericidal
activity of UV irradiated TiO2. Data showed that there was alteration in the expression of a
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number of genes that encoded for enzymes involved in the cell wall and membrane composition
and integrity. Fourteen genes that encoded enzymes for the metabolism of lipids essential for cell
membrane structure were over-expressed whereas only 2 genes were expressed at a lower level.
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Other mechanisms reported include the effect on a restricted set of respiratory components,
effect on the ability of cells to assimilate and transport iron and inorganic phosphate (Pi), effect
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on cell-to-cell communication and effect on the growth-essential genes and operon linked
regulatory genes.
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Several investigations are being carried out based on the antibacterial activity of modified
TiO2. Delekar et al (2012) recently noted the antibacterial activity of nickel (Ni) doped TiO2NP
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against gram positive and gram negative bacteria. The Ni–TiO2NP displayed photocatalytic
antibacterial property towards gram positive, S. aureus, B. Subtilisand to a lesser extent of gram
negative E. coli and S. abony. Data indicated that Ni–modified TiO2 NP which were tested under
weak visible light are a promising way for future environmental and biomedical photocatalytic
disinfection applications (Table 3)
Energy and environmental applications
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Reduction of heavy metals
Cyanide and heavy metals are common waste byproducts from various industries which tends
to pollute the aquatic environment posing a threat to the residing life forms as well to the overall
environment (Ku and Jung 2001). The potential source of heavy metal pollution is manganese
(Mn) (Das et al, 2015) chromium (Cr) (Das and Mishra 2010), cobalt (Co), and lead (Pb).
Manganese pollution is mainly from hydrometallurgical wastes and biomining is used to
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remediate these wastes (Das et al 2011).The source of cyanide is ore extraction, metal fishing
and hydrometallurgical industries. Cyanide is also used in organic chemical production in nylon,
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acrylic plastics and nitriles. Electroplating, steel hardening, metal processing and synthetic
rubber production are some of its other applications. The customary treatment method is based
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on chlorination of simple cyanide and consequently the carcinogenic cyanogens gas (CNCl) is
usually produced (Farid et al 2013). The produced gas is harmful and needs further treatment. In
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contrast, heavy metals are present in process waste streams from electronic device manufacturing
units, mining operations, tanneries, metal plating, and power generation facilities (Afkhami et al
2010). The adsorption process is one of the accepted methods for removal of heavy metal ions
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due of ease and high removal efficiency (Stafiej and Pyrzynska. 2007; Afkhami et al 2007).
Traces of metals such as Hg, Cr, and Pb in addition to other metals are highly health hazardous,
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and hence eliminating these toxic metals are predominantly important for human health and
water quality. The environmental applications of heterogeneous photocatalysis for removing
various heavy metals such as Hg, Cr, Pb, Cd, As, Ni and Cu were noted by Harraz et al (2013).
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Harraz et al (2013) examined the TiO2 photocatalyst and evaluated degradation of cyanide ions
and removal of heavy metals (Cr(III),Co(II), Pb(II)).Varying amounts of the photocatalyst were
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utilized and efficiency investigated. Evidence indicated that cyanide removal efficiency
increased from 88.2 to 93.3% when degradation time rose from 1 to 3 hr. Different CN-
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contents(100, 75, 50 and 25 ppm CN - were consequently utilized in 500 mg catalyst weight and a
sample of the reaction mixture was taken for analysis after 3 hr. The results revealed that
decreasing CN-content from 100 to 25 ppm led to 5% rise in cyanide removal efficiency (93.3
increased to 99.4%).
The process of removal of CN- ions over TiO2–SiO2 catalyst are represented by the following
equations (Ding et al 1996):
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TiO2 + 2hʋ → TiO2 (2h + + 2e−)
1/2O2 + 2e − + H2 → 2OH −
2OH − + 2h+ →2OH
CN − + 2OH → OCN- +H2O
2OCN − + O2 →2CO2 + N2
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Overall reaction:
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It is worth mentioning here that the CN- might be converted to N2 and CO2, which are
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environmental friendly. Further, it was found that 1000 mg of TiO2–SiO2 catalyst is most
appropriate for removal of 100 ppm of each metal ion in nitrate solution over a 3 hr reaction time
to obtain 90, 91.9 and 98.6% photoactivity efficiency for Cr, Co and Pb, respectively. Similarly
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Parida et al (2005) analyzed the activity of unmodified and sulphate modified TiO2 towards
photocatalytic reduction of Cr(VI) under solar radiation and also compared between
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photocatalytic and adsorption processes. Data showed that % Cr(VI) reduction was negligible
without the presence of a catayst under solar radiation. An increase in reaction time up to 3 hr
resulted in rising % reduction and as well as quantity of adsorption which subsequently remained
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almost constant. While 80% of Cr(VI) reduction took place during photocatalysis only 23% of
adsorption took place under similar conditions.
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The role of organic species in the acceleration of the photocatalytic metal reduction process
was determined by using methanol, ethanol and ethylenediaminetetraacetic acid (EDTA) (Parida
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et al (2005). It was found that EDTA produced significant effect on photocatalytic reduction in
comparison to the other two compounds. This may be due to the potent chelating action of
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EDTA that forms stable complex with Cr(VI). Evidence indicated that sulphated TiO2 may be
effectively used for reduction of Cr(VI) under solar radiation and complete reduction of this
metal (20 ppm) in aqueous solution takes place using 0.8 g/L (2.5 wt.%) sulphated TiO2 prepared
at pH 3 for 3 hr. Thus the photocatalytic reduction of Cr(VI) can be enhanced in the presence of
complexing agent such as EDTA.
The reduction of Cr (VI) to Cr (III) occurs due to the generation of electron hole pairs under
illumination. After migration of these species to the surface of the particle, the photogenerated
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electrons reduce Cr (VI) to Cr (III) and holes oxidize water. The possible mechanism of the
photocatalytic reduction of Cr (VI) is as follows:
TiO2 → TiO2(h + + e−)
Cr2O72 − +H + +e−→ C r 3 + + H 2 O
H2O + h+→ O2 + H +
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Photocatalytic water treatment
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Photocatalytic water treatment using TiO2 nanocomposites is now a familiar advanced

oxidation process (AOP) for environmental remediation. Upon irradiation with light, the
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generation of electron-hole pairs occurs in TiO2 NP have the ability to convert a wide range of
organic compounds into harmless end products such as water, carbon dioxide and inorganic ions.
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Different doped TiO2 NP or their surface treatments augment the efficiency of photocatalytic
degradation reactions. Carefully designed photocatalytic reactors reduce the consumption of
energy or help in avoiding post-separation stages in photocatalytic water treatment processes
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(Lazar et al 2012).
Photocatalytic water purification is a predominant AOP because of its efficiency and eco-
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friendliness. Photo-Fenton technique is another method which produces oxidation of the

contaminants in water (Lofrano et al. 2009; Vilar et al. 2011). However the photo-Fenton process
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requires use of hydrogen peroxide (H2O2) and ferrous sulfate (FeSO4). In comparison, TiO2 NP
need not require any other reagent. The mechanism of action of destruction of pollutants in
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aqueous solution involves a cascade of hydroxylation reactions which is initiated by hydroxyl

radicals (●OH) (Medana et al. 2011; Stapleton et al. 2010). Electron-hole pairs are formed on the
surface of TiO2 photocatalyst when irradiated with UV light. Holes produce ●OH and H+ ions
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while electrons yield superoxide ions (O2−●), which react with water molecules to produce
peroxide radicals (●OOH) and hydroxide ions (OH-). The peroxide radicals bind with H+ ions to
form ·OH and OH−, and holes oxidize OH− to ●OH. Thus all species eventually facilitate
formation of ·OH, and these radicals attack the pollutants present in the aqueous solution.
Soil purification
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Volatile chlorinated organic compounds (VCOC) such as trichloroethylene and
tertachloroethylene, have been widely used as solvents for the purpose of dry cleaning of clothes
and washing of semiconductors. These chemicals are known to pollute soil and groundwater due
to indiscriminate disposal and pose a serious threat to the environment due to the fact that they
are carcinogenic and toxic in nature. The most common method of treating polluted soil had been
either simple replacement with or heating soil to volatize the VCOC into the air. However, these
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methods do not adequately prevent harmful effects on the environment. Hashimoto et al (2005)
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designed photocatlytic sheets containing TiO2NP to purify the polluted soil in presence of solar
energy. The polluted soil is dug up and covered with the photocatalytic sheet. Then the covered
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polluted soil is heated to volatilize the pollutant gas. The sheet is then allowed to remain
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undisturbed under sunlight, while TiO2 decomposes the pollutants completely to a non-toxic
form. The efficacy of this method was verified at an actual polluted field and was reported that
the VCOC became completely harmless after few weeks.
Hydrogen generation
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Photoelectrochemical cell oxidation reactions take place at the photoanode electrode and
reduction reactions at the cathode electrode. This spatial separation of reaction sites allows
alternative materials to be employed as reduction electrocatalysts. In the absence of oxygen and
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under appropriate conditions of gas collection, hydrogen may be produced at the cathode
electrode. In a photoelectrochemical cell, an electrical bias may also be applied that increases
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hydrogen production rate (Antoniadou et al. 2014; Pop et al. 2014). If the photoelectrochemical
cell is divided into two compartments by using an ion transfer membrane, a basic electrolyte may
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be used in the anode and an acidic electrolyte in the cathode compartment and this provides
chemical bias (Antoniadou and Lianos. 2009; Selli et al. 2007). Ravishankar et al (2015) found
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that TiO2: AgNP were successfully prepared using an ionic liquid assisted hydrothermal method.
These NP generated 2230 mmol H2 per 1 g of photocatalyst in 2.5 hr via the water splitting
reaction and also demonstrated photocatalytic activity in the degradation of trypan blue. In
another study Pop et al (2015) noted hydrogen was produced in an alkaline environment using
TiO2NP. Nanoparticulate TiO2 absorbs UV photons and is excited generating electron-hole pairs.
The overall reaction is given by the following equation, which presents ethanol photocatalytic
reforming in the absence of oxygen:
14
C2H5OH + 3H2O → 2CO2 + 6H2
Direct interaction of ethanol with photogenerated holes may also produce radicals, which may
inject electrons into the conduction band of TiO 2 producing the current doubling effect. The
consumption of holes liberates electrons, which escape recombination, while electron injection
by the current doubling effect increases the population of free electrons. This situation elevates
the electronegativity of TiO2NP. In the presence of ethanol, sufficient electric bias is generated
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between anode and cathode areas in the photoelectrochemical leaf, which makes the system
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functional and hydrogen is gemerated.
Food, personal care and pharmaceutical industry
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TiO2 is non-toxic and compatible with human skin and the basis for use in the pharmaceutical
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food processing industry. It is not only used as a white pigment for manufacturing drugs and
tablets but also as a filler and pigment (Siwińska-Stefańska et al. 2012). Therefore adsorption of
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dyes food and pharmaceuticals on precipitated inorganic materials raises concerns (Yang et al.
2009). The fact that TiO2 is not metabolized in humans makes it safe for usage in production of
packages which are to be in direct contact with food (bottles, milk boxes, packing foils) and of
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food products (candies, chewing gums) (Lockey. 1977). Food dyes either natural or synthetic
enhance the organoleptic properties and hence are extensively used. The most popular food dyes
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include riboflavin (E101), curcumin (E100), chlorophyll (E140), cochineal (E120) and natural
carotene (E160a). Dyes are usually added in small amounts at an early stage of food product
manufacture to enhance high thermal stability and high resistance to acids, oxygen and
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illumination with a long shelf-life. The synthetic dyes added for use in food products need to be
experimentally proven to be non-toxic (Yang et al. 2009).
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Titania has been used as a component in sunscreens as an inorganic physical sun blocker.
However, to solve the problem of undesired opaqueness, microsized TiO2 have been increasingly
Ac
replaced by TiO2NP. The decrease in particle size leads to transmission of visible light which
makes the particles appear transparent.TiO2 is also effective in absorbing UVB radiations which
is another reason why it is extensively used in sunscreens (Smijs and Pavel. 2011).
Biomedical applications
Cancer therapy
Compared with other forms of cancer therapy like surgery, chemotherapy, radiology and other
therapies, photodynamic therapy (PDT) is now recognized as a promising alternative form of
15
treatement which is also non-invasive. PDT involves administration to a localized tumor which is
followed by activation with the help of light of a specific wavelength (Dougherty et al. 1998).
When TiO2NP are irradiated by UV light of wavelength less than 385 nm, electron and hole pairs
are created (Triesscheijn et al. 2006) which further react with hydroxyl ions to form potent
oxidative radicals (e.g., -OH,-HO2) (Serpone et al. 2006) capable of destroying tumor cells, fungi
and bacteria. TiO2 has been used as a photosensitizer in PDT of cancer due to its reliable
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photostability, high photocatalytic efficiency and low toxicity.
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The photokilling activity of TiO2 to malignant cells was first reported on a TiO2 film
electrode by Fujishima et al. (1986) and Cai et al. (1992). Since the electrode system was not
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reliable, TiO2NP were applied, which integrated in the living cells, resulting in elevated reaction
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rates. The phototoxic effect in vitro of TiO2NP on a series of human cancer cells, including
cervical cancer cells (HeLa) (Cai et al. 1992), bladder cancer cells (T24) (Kubota et al. 1994),
monocytic leukemia cells (U937) (Huang et al. 1997) and adenocarcinoma cells (SPC-A1) (Xu et
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al. 1998), colon carcinoma cells (Ls-174-t) (Zhang and Sun. 2004), breast epithelial cancer cells
(MCF-7, MDA-MB-468) (Lagopati et al. 2010),glioma cells(U87) (Wang et al. 2011), and
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human hepatoma cells (Bel 7402) (Yang and Whang. 2007) were studied.
The anticancer effect of TiO2 was also demonstrated in vivo (Fujishima et al 2000). Cai et
al. (1992) injected HeLa cells under the skin of nude mice to induce tumors to form. When the
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size of the tumors grew to about 0.5 cm, a solution containing fine particles of TiO2 was injected
into the tumor. After 2 or 3 days, the skin covering the tumor was cut open to be exposed and
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irradiated by UVA. This treatment clearly inhibited tumor growth. After 13 more days, the
treatment was repeated and a further marked antineoplastic effect was observed. Further, TiO2NP
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significantly suppressed growth of bladder and glioma cancer cells implanted into nude mice
prolonging survival time (Wang et al. 2011).
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Chen et al (2011) recognized the cytotoxic effects of doxorubicin (DOX)- TiO2 in human
SMMC-7721 hepatocarcinoma cells and investigated the mechanism of anticancer efficacy
augmentation and side effect reduction. Doxorubicin is one of the most efficient anticancer drugs
to date, with a broad range of activity in different types of human cancers. However, its clinical
application is limited due to its harmful side effects, the most noteworthy of which is
cardiotoxicity, which leads to congestive heart failure. Counteracting its side effects is a
challenge for DOX before its clinical application. Therefore, there arises the need to develop new
16
drug delivery systems which minimize side effects, alter biodistribution, improve deposition at
the tumor sites, and enhance restorative efficiency. A novel drug delivery system based on
TiO2NP to reduce the side effects DOX was developed. Results showed that DOX- TiO2
nanocomposites may act efficiently as an anticancer drug delivery carrier. Thus potential range
of applications of TiO2 exists in the field of biomedical science and cancer therapy.
Biosensors for biological assay
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The design and production of uncomplicated and receptive electrochemical biosensors
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received attention for their extensive applications such as disease diagnosis, drug discovery, food
safety and environmental monitoring. However the limited utilization trend of electrochemical
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biosensors makes their operation challenging due to restricted active surface area of
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microelectrodes and the low recognition signal (Li et al. 2009). Amongst all the materials for
biosensors, TiO2 is a promising candidate due of its chemical and thermal stability, reliable
biocompatibility, environmentally benign nature and relatively high conductivity. Various forms
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of TiO2 have been used in devising biosensors. These include TiO2 nanotubes (Xie et al 2007),
NP (Shi et al. 2007), nanosheets (Wang et al. 2005),sol–gel matrices (Doong and Shih 2006) and
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three-dimensional macroporous matrices (Zhu et al 2009). TiO2 provide a promising boundary
for accumulating different types of proteins and capacity for manufacturing of electrochemical
biosensors. Data demonstrated that these biosensors qualitatively and quantitatively analyze
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biological molecules, such as tumor makers (CEA, AFP), glucose (Yuan et al. 2007; Huang et al.
2011).
pt
Ge et al (2013), presented the first report on the development of Fe3O4@ TiO2 magnetic
NP-based disposable test-strip immunosensor combining multi-enzyme labeled amplification
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strategy for sensitive and selective detection of organophosphorous (OP) pesticides–

butyrylcholinesterase adduct in human plasma. The principle of magnetic NP-based
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immunosensor is similar to traditional sandwich immunoassays except that the capture agent at
the test zone is performed by Fe3O4@ TiO2 magnetic NP instead of phosphoserine-BChE
antibody. Under the optimized conditions the developed NP- based test strip device was tested
with different concentration of OP–BChE and found that the proposed device was sensitive
enough to detect low-dose OP exposure.
TiO2 biosensors can not only be applied as substrate for detecting biological molecules, but
also for cell-capture assay. According to Zhang et al. (2012) an electrospunTiO2 nanofiber-based
17
cell capture assay was developed. By using these TiO2nanofibre-deposited substrates, it is
possible to capture Circulating Tumor Cells (CTC) from the blood samples of colorectal and
gastric cancer patients. CTC are of vital importance to early diagnosis and longitudinal
monitoring of cancer in clinic, therefore the TiNF deposited substrate has potential application.
Future scope
In spite of the hopeful applications of TiO2 there still remain some challenges that need to be
t
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undertaken, such thatTiO2 may be of benefit to humans. Only TiO2-blasted implants have been
successfully applied in clinic, especially in orthopedics and dentistry. Therefore it is imperative
cr
for investigators to select out the most favorable TiO2 or TiO2 nanocomposites, and then perform
in vivo and in vitro to ultimately successfully apply these compounds clinically in other
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conditions (Marincola. 2011). TiO2 can only be activated by UV light due to its energy gap.
However, UV light is harmful to humans. In order to extend the optical absorption of TiO2 to the
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visible light region, different methods have been developed. Dye adsorbed and doping methods
are the applied approaches (Tokuoka. 2006; Lopez. 2010). However further research on
developing more such strategies is required. The toxicological assessment of TiO2 is important
M
when assessing whether it could be used for humans. The ROS generation of illuminated TiO2 is
the basis of its biomedical applications, especially in PDT. However, ROS generation has also
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been suggested for cytotoxicity of TiO2NP. Previous investigations documented the adverse
effects thatTiO2 might have on human health (Schanen et al. 2009; Lu et al. 2008) Therefore, the
potential toxic effects of TiO2and its nanocomposites on human health and the mechanisms
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underlining the processes also need to be established.

Conclusions
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Among the different semiconductor photocatalystsTiO2 has been established to be the most
Ac
extensively used, due to its long-term photo stability, potent oxidizing capacity, ease of
availability and low toxicity. The main limitation includes poor response to visible light. In order
to be photo excited under visible light, several synthesis methods have been successfully applied
to achieve visual light activeTiO2photocatalysts. Non-metal doping, in particular nitrogen
doping, can be incorporated in the TiO2 lattice. Other non-metals including sulphur, carbon and
fluorine for doping and co-doping with nitrogen have been also investigated and shown visible
light photo-induced activity. TiO2nanocomposites have a wide range of activities. On one hand
18
TiO2 is highly efficient in destroying bacterial strains while on the other hand it aids in the
decomposition of a number of organic and inorganic pollutants. TiO2 plays an important role in
environmental radiation processes. The role in photocatalytic treatment of waste water has
gained a lot of interest due to its high efficiency and simplicity in comparison to other
remediating compounds. Photocatalytic bioreactors using TiO2nanocomposites have now
become a feasible option. TiO2 is also well recognized in heavy metal removal procedures and
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found to be quite effective in reducing highly toxic metals like Cr(VI) and cyanide.TiO2 is used
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as a pigment in food and personal care industries. Further, the use of TiO2NP is now being
contemplated to enhance the properties of the products which is aided due to the large available
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surface area of NP. The applications of TiO2 in biomedical arena highlight its vital importance in
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benefiting human health. Several studies performed demonstrated applications in this field which
includes mainly PDT for cancer and biosensing.
an
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ed
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19
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t
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ed
Figure 1: A graph depicting the increasing amount of work done and research papers published
pt
on modified TiO2 over a 10years period. Data obtained from SCI database.
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36
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pt
ed
37
M
an
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Figure 2: Schematic representation of the photocatalytic mechanism of TiO2
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Ac
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pt
ed
38
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Figure 3: Applications of TiO2 in various fields

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39
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Figure 4: Schematic representation of the annihilation of bacterial cell by TiO2
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Table 1: Application of Titania and modified titania in various arenas
Serial Titania/ Modified titania Applications Source

No.
Healthcare applications
1. TiO2 nanoparticles Photocatalytic Antibacterial ( Kong, Song
capability and Jang. 2010)
t
2. Fe-doped TiO2 nanoparticles Photocatalytic and antibacterial (Padervand et
ip
activity al. 2012)
3. Ag-doped TiO2 nanoparticles Photocatalytic antibacterial (Amereh and
cr
performance Afshar. 2010)

4. Cu-doped TiO2 nanoparticles Antimicrobial coating (Wei et al.
us
2014)
5. Ethylene-vinyl alcohol (EVOH)- Antimicrobial mechanism in (Kubacka et al.
6.
TiO2 nanocomposite film
TiO2/PLGA
an pathogenic bacteria
[poly(lactic-co- Antibacterial activity
2014)
(Wu et al.
M
glycolic acid)] 2014)
7. Copper-doped anatase photocatalytic antibacterial (Yadav et al.
TiO2nanoparticles activity 2014)
ed
8. TiO2/AgO2 nanoparticles Antimicrobial activity (Allahverdiyec

et al. 2011)
pt
9. Hydroxyapatite/titania Antimicrobial studies (Nathanael et

nanoparticles al. 2012)
ce
10. Nanosized AgBr/TiO2 composites Antibacterial and photocatalytic (Padervand et

activity al. 2012)
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Environmental applications
13. Silver Doped TiO2 nanoparticles Methyl Orange Degradation ( Girginov et al.
2012)
14. Nano-TiO2 powder Photodegradation of (Amereh and

acetophenone and toluene in Afshar. 2010)
40
water
15. Ag-doped TiO2 Humic acid degradation and (Lazau et al.
mineralizatio 2011)
16. Titanium dioxide–polypyrrole Hydrogen generation (Tan et al.
nano composites 2014)
17. Au-TiO2 nanoparticles Photocatalytic degradation of (Pugazhenthiran
t
ceftiofur sodium et al. 2014)
ip
18. TiO2 nanoparticles Dissolved organic matter (Daels et al.
cr
photodegradation 2014)
us
19. TiO2-BEW (Boron enrichment photocatalytic degradation of (Yola, Eren and
waste) atrazine Atar. 2014)
20. Nitrogen doped TiO2 Photocatalyst for water (Dolat et al.
21.
nanoparticles
TiO2-SiO2 nanoparticles
an remediation
Photo catalytic oxidation of (Ingale
2015)
et al.
M
TNT 2011)
ed
Additional thrust areas

22. TiO2 nanoparticles, Self cleaning dye-sensitized solar cell ( Zainudin et al.
pt
and color reduction in wool 2013)

23. PEGylated titanium dioxide Targeted paclitaxel drug ( Venkatasubbu
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nanoparticles delivery et al. 2013)

24. Doxorubicin and Drug delivery system, ( Chen et al.
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TiO2nanoparticles Overcoming drug resistance in 2011) ; Arora

cancer cells et al. 2012)
25. Peptide nucleic acid (PNA)- Assessing DNA hybridization (Brown et al.
titanium dioxide (TiO2) 2008)
nanoconjugates
26 TiO2 nanoparticle assisted mass Biosensor of Staphylococcus (Gopal,
spectrometry aureus Narayana and
41
Wu. 2011)
27. Gold Nanoparticle Encapsulated- Thiolated Enzyme Biosensors (Liu et al. 2013)
Tubular TIO2 Nanocluster
28. TiO2 nanotube Orthopedic applications, (Parcharoen et
Medical implants al. 2014)
29. TiO2 nanoparticles Self cleaning and color (Montazer and
t
reduction in wool Padkel. 2011)
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cr
us
an
Table 2: Properties of TiO2
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Property Anatase Rutile
Molecular Weight (g/mol) 79.88 79.88

ed
Cryatal structure Tetragonal Tetragonal

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3
Density (g/cm ) 3.79 4.13
Melting Point 1285 1285
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Boiling Point 2500-3000 2500-3000

Light absorption (nm) λ ≤ 385 nm λ ≤ 415 nm
Ac
Table 3: A table depicting the mechanism of TiO2 bacterial annihilation on diffret

bacterial strains
Serial Titania Target Mechanism of action Reference
42
No. microorganism
1. Copper- E. coli Oxidative attack on the (Sunada,
deposited TiO2 outer/inner cell membrane of the Watanabe and
thin film microorganism Hashimoto.
2003)
2. Fe-doped TiO2 E. coli Photo activated destruction of (Stoyanova et al.
t
nanoparticles cells 2013)
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3. Ag doped TiO2 S. aureus, Cell wall destruction (Lu et al. 2008)
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nanoparticles P. aeruginosa
and E. coli
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4. Cu-TiO2 E. coli Damage to the bacterial cell (Wei et al. 2014)
nanoparticle membrane
coating
5 TiO2
nanocomposite
based P. aeruginosa
anAlteration in gene expression of (Kubacka et al.
specific genes 2014)
M
film
6 TiO2-Biocidal S. aureus, synergic antibacterial (Kong, Song and
ed
Polymer E. coli performance Jang. 2010)

Nanocomposites
7 TiO2 E. coli Reduced adhesion on surface (Gupta et al. 013)
pt
nanostructured coated with TiO2

surfaces
ce
8 ZnO doped TiO2 E. coli & Disruption of bacterial cell wall (Seddiki et al.
S. aureus 2014)
Ac
9 TiO2 Co-doped E. coli Oxidative damage on bacteria (Sun et al. 2014)

with Nitrogen
and Silver
10 TiO2 E. coli DNA damage (Gogniat and
nanoparticles Dukan. 2007)
43

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Toxicological & Environmental Chemistry

Modified titanium oxide (TiO2) nanocomposites and its

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Siksha O Anusandhan University, Khandagiri Square, Bhubaneswar, India

also employed as UV blocking agents in sunscreen and commonly encountered as a brilliant

Keywords: Nanomaterials; Titania; Doping; Applications; Future scope

conventional water treatment methods (Dawson and Kamat 2001).

Mechanism of photocatalytic activity

TiO2 + hʋ →h+ + e-(1)

H2O + h+ →●OH + H+ (2)

HO2● → H2O2 + O2 (5)

H2O2 + O2●−→●OH + OH- + O2 (6)

Mohamed 2011; Wang and Lewis 2006)

Cation doped TiO2

Anion doped TiO2

Coupled semiconductor photocatalyst

Applications of modified titania

Energy and environmental applications

TiO2 → TiO2(h + + e−)

Photocatalytic water treatment using TiO2 nanocomposites is now a familiar advanced

friendliness. Photo-Fenton technique is another method which produces oxidation of the

aqueous solution involves a cascade of hydroxylation reactions which is initiated by hydroxyl

strategy for sensitive and selective detection of organophosphorous (OP) pesticides–

underlining the processes also need to be established.

Hazard Mater 181: 836–844.

Antoniadou, M., Sfaelou, S., Dracopoulos, V., Lianos, P. (2014) “Platinum-free

photoelectrochemical water splitting.” Catal Commun 43:72-74.

an available configuration for photocatalytic degradation of organic pollutant.”

doping in TiO2 nanoparticles.” Nano Lett 3:1049−1051.

cytotoxicity by photoexcited TiO2 particles.” Cancer Res 52: 2346.

matter photodegradation.” Separation and Purification Technology 133: 282-290.

Dawson, A., Kamat, P.V., (2001) “Semiconductor-metal nanocomposites. Photoinduced fusion

(2015) “Nitrogen-doped, metal-modified rutile titanium dioxide as photocatalysts for water

films.” ChemVap Deposition 18: 89−101.

methyl orange degradation.” Journal of Engineering Science and Technology Review 5:

surface and human nasal passage.” Biosens Bioelectron 27: 201-206.

of titanium dioxide.” Phys Chem B 107: 2319-2326.

Kennedy, B.A. (1990) “Surface Mining”: 2nd edition.

Environ Sci Technol 34: 4754–4758.

Mohapatra, P., Samantaray, S.K., Parida, K. (2005) “Photocatalytic reduction of hexavalent

chromium in aqueous solution over sulphate modified titania.” Journal of Photochemistry

Parcharoen, Y., Kajitvichyanukul, P., Sirivisoot, S., Termsuksawad (2014) “Hydroxyapatite

electrodeposition on anodized titanium nanotubes for orthopedic applications.”

nanoparticulatetitania and a novel Pt/carbon electrocatalyst: The concept of the

G. (2015) “Electrochemical detect ion and photochemical detoxicat ion of hexavalent

Appl Catal B 69:138−144.

Robert, D. (2007) “Photosensitization of TiO2 by MxOy and MxSy nanoparticles for

heterogeneous photocatalysis applications.” Catal Today 122: 20−26.

construct.” ACS Nano 3: 2523.

glass/SnO2/TiO2 interface composite film.” Appl Catal A 257: 25−32.

Engineering Chemistry 19: 1-16.

Siwińska-Stefańska, K.,Nowacka, M., Kołodziejczak-Radzimska, A., Jesionowski, T. (2012)

based on anatase titanium dioxide.” Dyes and Pigments 94: 338–348.

Stoyanova, A.M., Hitkova, H.Y., Ivanova, N.K., Bachvarova-Nedelcheva, A.D., Iordanova,

thin film under weak UV light illumination.”

hydrogen generation.” Synthetic Metals 189: 77-85.

solutions:” A review. J Alloys Compound 509: 1648−1660.

“Direct electrochemistry and electrocatalysis of heme proteins entrapped in agarose hydrogel