Review

Physical Chemistry
June 2011 Vol.56 No.16: 1639–1657 doi: 10.1007/s11434-011-4476-1

SPECIAL TOPICS:

A review of TiO2 nanoparticles
GUPTA Shipra Mital* & TRIPATHI Manoj
University School of Basic and Applied Sciences, Guru Gobind Singh Indraprastha University, Sector 16C Dwarka, Delhi 110075, India Received August 29, 2010; accepted November 21, 2010

Climate change and the consumption of non-renewable resources are considered as the greatest problems facing humankind. Because of this, photocatalysis research has been rapidly expanding. TiO2 nanoparticles have been extensively investigated for photocatalytic applications including the decomposition of organic compounds and production of H2 as a fuel using solar energy. This article reviews the structure and electronic properties of TiO2, compares TiO2 with other common semiconductors used for photocatalytic applications and clarifies the advantages of using TiO2 nanoparticles. TiO2 is considered close to an ideal semiconductor for photocatalysis but possesses certain limitations such as poor absorption of visible radiation and rapid recombination of photogenerated electron/hole pairs. In this review article, various methods used to enhance the photocatalytic characteristics of TiO2 including dye sensitization, doping, coupling and capping are discussed. Environmental and energy applications of TiO2, including photocatalytic treatment of wastewater, pesticide degradation and water splitting to produce hydrogen have been summarized. nanoparticles, photocatalyst, TiO2, dye sensitization, doping, coupling, capping
Citation: Gupta S M, Tripathi M. A review of TiO2 nanoparticles. Chinese Sci Bull, 2011, 56: 1639−1657, doi: 10.1007/s11434-011-4476-1

1 Historical background
The growth of industry worldwide has tremendously increased the generation and accumulation of waste byproducts. In general, the production of useful products has been focused on and the generation of waste byproducts has been largely ignored. This has caused severe environmental problems that have become a major concern. Researchers all over the world have been working on various approaches to address this issue. Photoinduced processes have been studied and various applications have been developed. One important technique for removing industrial waste is the use of light energy (electromagnetic radiation) and particles sensitive to this energy to mineralize waste which aids in its removal from solution. Titanium dioxide (TiO2) is considered very close to an ideal semiconductor for photocatalysis because of its high stability, low cost and safety toward both humans and the environment.
*Corresponding author (email: shipra.mital@gmail.com) © The Author(s) 2011. This article is published with open access at Springerlink.com

In 1964, Kato et al. [1] published their work on the photocatalytic oxidation of tetralin (1,2,3,4-tetrahydronaphthalene) by a TiO2 suspension, which was followed by McLintock et al. [2] investigating the photocatalytic oxidation of ethylene and propylene in the presence of oxygen adsorbed on TiO2. However, the most important discovery that extensively promoted the field of photocatalysis was the “Honda-Fujishima Effect” first described by Fujishima and Honda in 1972 [3]. This well-known chemical phenomenon involves electrolysis of water, which is related to photocatalysis. Photoirradiation of a TiO2 (rutile) single crystal electrode immersed in an aqueous electrolyte solution induced the evolution of oxygen from the TiO2 electrode and the evolution of hydrogen from a platinum counterelectrode when an anodic bias was applied to the TiO2 working electrode. In 1977, Frank and Bard [4] examined the reduction of CN – in water using this technology. Schrauzer and Guth [5] reported the photocatalytic reduction of molecular nitrogen to ammonia and hydrazine over iron-doped TiO2. Schrauzer et al. [6] also performed experiments with desert sand and minerals to reduce nitrogen.
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7° 92. In 1998.0°–105° Properties Crystal structure Lattice constant (Å) Space group Molecule (cell) Volume/ molecule (Å3) Density (g cm–3) Ti–O bond length (Å) O–Ti–O bond angle . the prepared composite photocatalyst had tunable magnetic properties. Sreethawong et al.949 (4) 1. Watson et al. [12] found that TiO2 films coated with certain amount of silica acquired superhydrophilic properties after irradiation with UV light. Rocha et al. [19] prepared rutile TiO2 by anodic oxidation in a sulfuric acid electrolyte. There are four commonly known polymorphs of TiO2 found in nature: anatase (tetragonal). In 2004.172 3. [21] synthesized polymorphic TiO2 particles that were active under visible light using a water-based sol process followed by a solvent-based sol process with N-methylpyrrolidone as the solvent.184 b = 5. Diamandescu et al.23–28] to understand and summarize the progress in this field.154 Pbca 4 32. et al.6° Brookite Orthorhombic a = 9. two additional high-pressure forms have been synthesized from the rutile phase.3 times higher than that of commercial TiO2 (Kronos VLP7000). Fujishima et al.0° Anatase Tetragonal a = 3. [22] carried out oil sludge treatment using heterogeneous photocatalysis (H2O2/UV/TiO2) by applying black and white light reactors.784 c = 9.13 1. [15] reported Fe-doped TiO2 films that could photodegrade up to 95% of methyl orange in a solution after exposure to sunlight for 3–4 h.9587 P42/mnm 2 31. The photocatalytic activity for the degradation of phenol was improved under both visible and UV light by codoping. Saccharomyces cerevisiae and Escherichia coli. Besides these polymorphs. [20] synthesized TiO2-coated magnetic silica that showed enhanced photocatalytic activity for the degradation of reactive brilliant red X-3B compared with Degussa P25 under both UV and visible light irradiation. The TiO6 octahedron Table 1 Crystal structure data for TiO2 [31–33] Rutile Tetragonal a = 4. Rutile: Rutile TiO2 has a tetragonal structure and contains 6 atoms per unit cell (Figure 1). Sulfur doping played an important role in the response of the product to visible light by narrowing the band gap of TiO2. [16] synthesized nanocrystalline mesoporous TiO2 using sol-gel techniques combined with surfactant-assisted templating and evaluated its photocatalytic activity of the evolution of hydrogen from an aqueous methanol solution. only the crystal structures (Table 1) [31–33] and properties of the rutile.2160 4. Folic acid was bound to TiO2 nanoparticles to provide cell targeting specificity. producing a novel magnetic photocatalyst that was easy to separate from a slurry-type photoreactor by application of an external magnetic field. all performed under ambient conditions. the properties of TiO2 that make it suitable to act as a photocatalyst and various methods including dye sensitization. Heterogeneous photocatalysis provided efficient degradation and mineralization of a large part of the organic matter in the oil sludge. O’Regan and Grätzel [11] reported an efficient solar cell containing nanosized TiO2 particles coated with organic chromophore groups active under visible light. and TiO2 (B) (monoclinic) [23]. In 1986. In the present review. rutile (tetragonal). [10] used TiO2 for photokilling tumor cells (HeLa cells). the first organic photosynthetic reaction was presented as an alternative photoinduced Kolbe reaction (CH3COOH → CH4 + CO2).99 1. Sonawane et al. eliminating 100% of the PAH content from the oil sludge sample after 96 h of UV irradiation. These nanoparticles exhibited higher cytotoxicity under photoexcitation.2° 90. A significant amount of research on TiO2 has been performed over the last five decades and a number of reviews on various aspects of TiO2 have been published [12. [13] developed highly hydrophilic TiO2 surfaces with excellent anti-fogging and self-cleaning properties.061 3. It proved to be an alternative treatment for removing polyaromatic hydrocarbons (PAHs) from oil sludge.04 77. These are TiO2 (II) [29] with a PbO2 structure and TiO2 (H) [30] with a hollandite structure. The photocatalytic activity under visible light was approximately 3.79 1. [9] reported the photocatalytic activity of TiO2 as a microbiocide effective at photokilling Lactobacillus acidophilus. pesticide degradation and water splitting by TiO2 to produce hydrogen are summarized. In 1991. Wang et al. including photocatalytic treatment of wastewater.447 c = 5. In 2009. Chinese Sci Bull June (2011) Vol. anatase and brookite polymorphs are considered. Mizukoshi et al. Fujishima et al.87–2. In this review. brookite (orthorhombic). In 2008. [17] reported a hydrothermal synthesis of iron and europium codoped TiO2 materials under mild conditions.965(2) 77. 2 Chemical structure of TiO2 TiO2 belongs to the family of transition metal oxides. coupling and capping that are used to improve its efficiency are discussed. allowing the photocatalyst to effectively bleach an aqueous solution of methylene blue under irradiation with visible light of >413 nm. Environmental and energy applications. In 2005. Ollis and coworker [8] showed the extent of adsorption of several chlorinated hydrocarbons in terms of the Langmuir adsorption isotherm.56 No. Lai and Lee [18] revealed the ability and mechanism of photoexcited TiO2 nanoparticles modified with folic acid to kill cells. Wang et al. In 1995.515 I41/amd 2 34.937(4) 1. Kaeugun et al.980 (2) 81. In 1985. Matsunaga et al.5936 c =2. doping. [14] used the sol-gel technique to coat magnetic particles with TiO2.1640 Gupta S M. In 1983. In 2002. Furthermore.16 In 1978. which opened the field of photosynthetic reaction [7].

lower capacity to adsorb oxygen and higher degree of hydroxylation in the anatase phase [38]. with the rutile phase becoming more stable than anatase for particle sizes greater than 14 nm. Sclafani et al [36]. depending on its preparation conditions. but the energy difference between these two phases is small (∼2 to 10 kJ/mol). with band gaps of 3.2. Selloni [39] reported that the reactivity of (001) facets is greater than that of (101) facets in an anatase crystal. When TiO2 is exposed to near-UV light. et al. leading to a reduction in the probability of e–/h+ recombination [43].Gupta S M. The anatase structure is preferred over other polymorphs for solar cell applications because of its higher electron mobility.96 eV for the anatase.56 No. Once the rutile phase formed. Brookite: Brookite TiO2 belongs to the orthorhombic crystal system.16 1641 Figure 1 Crystal structures of the rutile and anatase phases of TiO2 [27]. Anatase TiO2 is considered to be the active photocatalytic component based on charge carrier dynamics. and is also the least dense of the 3 forms and is not often used for experimental investigations [26]. The activity of the rutile phase as a photocatalyst is generally very poor. 3. chemical properties and the activity of photocatalytic degradation of organic compounds. Its unit cell is composed of 8 formula units of TiO2 and is formed by edge-sharing TiO6 octahedra (Figure 2). concluded that the rutile phase can be active or inactive. Anatase: Anatase TiO2 also has a tetragonal structure but the distortion of the TiO6 octahedron is slightly larger for the anatase phase [28. Muscat et al. However. Chinese Sci Bull June (2011) Vol. low dielectric constant and lower density [23]. [37] found that the anatase phase is more stable than the rutile at 0 K. The rutile phase is stable at most temperatures and pressures up to 60 kbar. It is more complicated. rutile and brookite phases. The increased photoreactivity is because of the slightly higher Fermi level.33]. it grew much faster than the anatase. [35] found that anatase and brookite structures transformed to the rutile phase after reaching a certain particle size. as depicted in Figure 1. and 2. Zhang et al.02. Yang et al. electrons in the valence band are excited to the conduction band leaving behind holes (h+). is slightly distorted [25–27]. [40] synthesized uniform anatase crystals containing 47% (001) facets using hydrofluoric acid as a morphology controlling agent. respectively [41]. the transition probability of e– to the valence band decreases. The excited electrons (e–) in the conduction band are now in a purely 3d state and because of dissimilar parity. while the conduction band is only the 3d orbitals of titanium [42]. has a larger cell volume Figure 2 Lattice structure of brookite TiO2 [33]. The valence band of TiO2 is composed of the 2p orbitals of oxygen hybridized with the 3d orbitals of titanium. It has inherent surface band bending that forms spontaneously in a deeper region with a steeper potential compared with the rutile phase (Figure 4) [44] thus surface hole trapping dominates . TiO2 is a large band semiconductor. as shown in Figure 3. where TiO2 (II) becomes the thermodynamically favorable phase [34].

oxygen vacancies and the primary particle size of the anatase phase. Recently. The transformation was also . and causing a decline in surface area. precursors.16 Figure 3 Mechanism of light absorption by TiO2 [72]. a large surface area for absorbing substrates and high crystallinity to reduce the rate of photoexcited e–/h+ recombination. The two requirements are partially satisfied at a moderate calcination temperature. nanotubes and nanorods. TiO2 containing both the rutile and anatase phases enhanced the effect of absorbed visible light than either of the pure phases. the rate constant of charge transfer in the normal Marcus region increases [52]. Mill and Le Hunte [53] reported that because the absorption edge blue shifts with decreasing particle size. Ohtani et al. thin films. Hu et al. As a result of this confinement. affected by factors such as preparation conditions. affecting morphology. TiO2 has been prepared in the form of powders. However. loss of surface hydroxyl groups and inducing phase transformation. Photocatalytic activity per unit mass of TiO2 bulk reached a broad maximum at a calcination temperature of around 400°C. However. reached a maximum after 60 min and then decreased upon further heat treatment. [47] investigated the relationship between the phase transformation and photocatalytic activity of nanosized anatase powder and found that the highest photocatalytic activity for the degradation of acid red B under irradiation with visible light occurred when the rutile phase was on the point of appearing. [46] have reported that TiO2 normally undergoes an anatase-to-rutile phase transformation in the range from 600–700°C. namely.1642 Gupta S M. [49] showed that the duration of heat treatment also affected the photocatalytic activity of TiO2 films. [48] proposed that TiO2 with high photocatalytic activity could be achieved by fulfilling two requirements. in the rutile phase. crystals. so only holes very close to the surface are trapped and transferred to the surface. When TiO2 films were heat-treated at 500°C.56 No. 4 TiO2 nanoparticles Various investigations have established that TiO2 is much more effective as a photocatalyst in the form of nanoparticles than in bulk powder [50]. (400°C and above) the removal of organic materials takes place. Wang et al. the photocatalytic activity began to decrease rapidly. At high temperatures. In other words. Because of the increased driving force and the unchanged solvent reorganization free energy. Crystallinity increases and the surface area decreases with calcination temperature. et al. crystallinity and porosity. the band gap increases and the band edges shift to yield larger redox potentials [51]. impurities. When the diameter of the crystallites of a semiconductor particle falls below a critical radius of about 10 nm. Using size-quantized semiconductor particles increases the photoefficiency of systems in which the rate-limiting step is charge transfer. Once the rutile phase TiO2 formed separately. each charge carrier appears to behave quantum mechanically [11] as a simple particle in a box (Figure 5). Figure 4 Surface band bending of the anatase (a) and rutile phases of TiO2 (b) [44]. the bulk recombination of electrons and holes occurs. Slow heating rates provide relatively mild conditions for phase transformation [45]. Chinese Sci Bull June (2011) Vol. 3 Heat treatment of TiO2 Heat treatment has a vital role in the synthesis of particles. the redox potentials of the photogenerated electrons and holes in quantized semiconductor particles increased. the rate constant first increased as the heat treatment time lengthened. quantized particles show higher photoactivity than macrocrystalline semiconductor particles. Yu et al. the solvent reorganization free energy for charge transfer to a substrate remains unchanged. Liquid because spatial charge separation is achieved by the transfer of photogenerated holes towards the surface of the particle via the strong upward band bending. The surface area of TiO2 decreases with calcination time and heating rate because of the collapse of pores in the TiO2 powder caused by the transformation of amorphous TiO2 to the anatase phase.

while most particles were deposited at 600°C and a thin coating was formed at 400°C. upper edge of the valence band. some disadvantages exist including expensive precursors. as well as the standard potentials of several redox couples. Dawson et al.e. However. [54] subjected mixed phase TiO2 powders with different compositions and particle sizes to hydrothermal reaction with NaOH. The anatase phase component of the starting material was easily converted to trititanate nanotubes at 140°C.e.. The lower edge of the conduction band. nitrate. long processing times. Uniform nanorods of approximately 45–200 nm in diameter and 10–60 μm in length were grown over large areas with almost unidirectional alignment. Among the products and byproducts of AR18 photodegradation. Nanorod growth was observed at 500°C. [56] prepared modified titanate nanotubes (TNTs) via a hydrothermal method and focused on their application for the decomposition of Acid Red 18 (AR18) in water. thus systems using these materials require application of an external electrical bias to complete the water splitting reaction and achieve phase processing is one of the most convenient and commonly used methods in chemical synthesis. However. [55] synthesized pure rutile nanotubes by a hydrothermal process in NaOH water-ethanol solution starting from rutile-anatase TiO2 particles. The photocatalytic experiments revealed that the most active sample towards the decompo- . an ideal semiconductor should also be easy to produce and use.. other materials as a photocatalyst The primary criteria for an efficient semiconductor photocatalyst is that the redox potential of the charge couple. Most of the reported photocatalysts possess limitations. Post-treatment calcination of the TNTs was carried out at temperatures of 400–700°C. density of states) varies among systems [51]. The nanotubes were up to several micrometers in length and had diameters of less than 20 nm. and WO3 possess a conduction band edge at an energy level below the reversible hydrogen potential. SnO2.Gupta S M. The ordinate represents the internal energy not the free energy. [59] fabricated aligned anatase and rutile TiO2 nanorods and nanotubes with diameters of about 80–130 nm. Chinese Sci Bull June (2011) Vol. The spacing of the energy levels (i. ammonia and sulfate) were detected. i.56 No. effectively activated by solar light and able to catalyze the reaction effectively [23]. The diameter and length of the nanorods were about 50–100 nm and 0. cost effective. the rutile phase reacted to form trititanate plates and belts.g. Apart from possessing a suitable band gap energy. Limmer et al. respectively. and band gap of some of these sensitizers. lies within the band gap domain of the photocatalyst. 5 TiO2 vs. homogeneous products and allowing the formation of complex shapes and preparation of composite materials.5–2 mm. the photocatalytic activity of the calcined titanate nanotubes. was lower than that of P25 regardless of the annealing temperature. [57] grew TiO2 nanorods on a Tungsten carbide-Cobalt (WC–Co) substrate by metal-organic chemical vapor deposition. Attar et al. [58] used sol electrophoretic deposition for template-based growth of TiO2 nanorods.16 1643 sition of AR18 was TNTs calcined at 600°C. GaAs. photostable. are presented in Figure 6 [60]. The rutile nanotubes exhibited different optoelectronic properties to those of the raw TiO2. Mozia et al. acetic and oxalic) and inorganic ions (nitrite. PbS.. et al. and CdS are not sufficiently stable for catalysis in aqueous media as they readily undergo photocorrosion and are also toxic [53]. and the presence of carbon as an impurity. Figure 5 Molecular orbital model for particle growth of N monomeric units. Fe2O3. organic acids (formic. When the reaction time was increased to 7 d. The energy level at the bottom of conduction band determines the reducing ability of photoelectrons while the energy level at the top of valence band determines the oxidizing ability of photogenerated holes [23]. all of the TiO2 was converted to trititanate and the morphology of the resulting product was exclusively nanoplates and belts. nonhazardous for humans and the environment. ZnO is unstable because it readily dissolves in water [61] to yield Zn(OH)2 on the ZnO particle surface. At 170°C. with no nanotubes. The free energy of an e–/h+ pair is smaller than the band gap energy because e–/h+ pairs have a significant configurational entropy arising from the large number of translational states accessible to the mobile carriers in the conduction and valence bands. This method provides the advantages of controlling the stoichiometry. Yana et al. e–/h+. Pradhan et al. which inactivates the catalyst over time. The type of alcohol and the ratio to water had a great impact on the morphology and structure of the final products. e.

several approaches including dye sensitization. Its holes are strongly oxidizing and redox selective. Photosensitization of semiconductors by various dyes has been monitored by nanosecond and picosecond flash photolysis as well as femtosecond spectroscopy.1644 Gupta S M. This occurs through excitation of the sensitizer followed by charge transfer to the semiconductor. doping. photostable in solution and nontoxic. An overview of these approaches is presented in the following sections. which improved the anchoring geometry of the dye on their surfaces and led to faster electron injection. et al. Nishikiori et al. The electron injection and back electron-transfer rates from the dye to the photocatalyst depend upon the nature of the dye molecules.56 No. Chinese Sci Bull June (2011) Vol.16 Figure 6 Band positions of several semiconductors in contact with an aqueous electrolyte at pH 1 [60]. TiO2 is cheap. The single drawback is that it does not absorb visible light [23]. 6 Dye sensitization Surface sensitization of a wide band gap semiconductor photocatalyst such as TiO2 via chemisorbed or physisorbed dyes can increase the efficiency of the excitation process and expand the wavelength range of excitation for the photocatalyst. or more commonly. several novel heterogeneous photocatalytic reactions have been reported at the interface of illuminated TiO2 photocatalyst. Charge carriers can form in semiconductor particles by exciting a dye attached to the surface of the photocatalyst. and TiO2-based photocatalysis has been researched exhaustively for environmental cleanup applications. To overcome this problem. which decreases the quantum yield of photon-to-current conversion. was also enhanced as the crystallinity of the TiO2 nanoparticles was . TiO2 is close to being an ideal photocatalyst and the benchmark for photocatalysis performance. This sensitization increases the range of wavelength response of the photocatalyst. [64] found that an increase in the overall crystallinity of TiO2 nanoparticles increased the surface quality of the nanoparticles. hydrogen evolution at the cathode [62]. However. The excited state can inject either a hole. For these reasons. which is very important for photocatalyst to operate under natural sunlight. back electron transfer via recombination with oxidized dye molecules. coupling and capping of TiO2 have been studied extensively. properties of the TiO2 nanoparticles and the interactions between the dye and nanoparticles [63]. Highly efficient charge injection is observed when a monolayer of a dye is dispersed on a photocatalyst with a high surface area. an electron to the particle.

the impurity energy levels formed in the band gap of TiO2 can also lead to an increase in the rate of recombination between photogenerated electrons and holes. Its high dielectric constant provides effective electrostatic shielding of the injected electron from the oxidized dye molecule. Nd is the number of dopant donor atoms. Chinese Sci Bull June (2011) Vol. Photocatalytic reactions can only occur if the trapped electron and hole are transferred to the surface of the photocatalyst. Its conduction band edge lies slightly below the excited state energy level of many dyes. The differences in photoactivity derive from the change in the diffusion length of the minority carriers [76]. tris(bipyridyl) ruthenium.. Localized d-states act as trapping sites that capture electrons from the conduction band or holes from the valence band. the magnitude of the potential drop across the space-charge layer should not fall below 0. coumarin) as a sensitizer [11]. Dopants such as Fe(III). a decrease of the band gap or introduction of intra-band gap states. when metal ions or oxides are incorporated into TiO2 by doping. the . This means that metal ions should be doped near the surface of the photocatalyst to allow efficient charge transfer. where the oxidation of Ti3+ species is kinetically fast compared with the oxidation of Ti4+. which results in the absorption of more visible light. [66] reported efficient photocatalytic decomposition of 2. The dopant content directly influences the rate of e–/h+ recombination by the equation: W = (2 εεoVs /eNd). and Mo by electron paramagnetic resonance.. TiO2 is a preferred semiconductor for dye-sensitized solar cells because it is a stable photoelectrode in photoelectrochemical cells even under extreme conditions. However. εo is the static dielectric constant in a vacuum. Grätzel developed a highly porous TiO2 substrate electrode called a “Grätzel cell” containing a dye (e. Doping may lead to photocatalytic systems that exhibit enhanced efficiency [23].56 No. and e is the electron charge [78]. et al.2 V [77]. Re(V) and V(V) substantially enhanced the photochemical reactivity of TiO2 for the oxidation of CHCl3 and reduction of CCl4. The main objective of doping is to induce a bathochromic shift. As the concentration of the dopant increases.4-DCP by TiO2 sensitized with various dyes decreased in the following order: eosin Y ≈ rose bengal > erythrosine > rhodamine B. Li et al. The high refractive index of TiO2 results in efficient diffuse scattering of the light inside the porous photoelectrode. Mo(V).16 1645 increased. However. thus preventing its recombination before reduction of the dye by the redox electrolyte. Electron transfer from one of these levels to the conduction band requires lower photon energy than in the situation of an unmodified semiconductor. where W is the thickness of the space-charge layer. Choi et al.g. giving a relatively slow recombination rate. the surface modification of TiO2 nanoparticles appears to be more beneficial than the modification of bulk TiO2 [71]. Os(III). TiO2 catalysts can make full use of visible light to realize photocatalytic reactions. Nanomaterials show a higher tolerance to structural distortion than bulk materials due to their inherent lattice strain.4-dichlorophenol (2. Joshi et al. After increasing the crystallinity of the TiO2 particles. which is one condition required for efficient electron injection. Enhancing the rate of photoreduction by doping a semiconductor with metal ions can produce a photocatalyst with an improved trapping-to-recombination rate ratio.1 Doping with transition metal cations 7 Doping Doping of TiO2 has been an important approach in band gap engineering to change the optical response of semiconductor photocatalysts. V. For optimal e–/h+ separation. Dye-sensitized TiO2 has received much attention in photovoltaic applications. As a result.Gupta S M. i. [75] reported the adverse effect of doping TiO2 with transition metal ions on photocatalytic activity because of the formation of localized d-states in the band gap of TiO2. to substitute O2– with another anion because of the difference in the charge states and ionic radii [24]. The efficiency of decomposition of 2.4-DCP) under visible light irradiation by TiO2 using xanthene dye as a sensitizer. In the case of doping at a high concentration. the trapping states were mostly eliminated [65] and surface states formed that increased the rate of back electron transfer to the oxidized dye. [74] carried out a systematic investigation of the photoreactivity of TiO2 doped with 21 different metal ions. ε is the static dielectric constant of the semiconductor. It is desirable to maintain the integrity of the crystal structure of the photocatalyst while changing its electronic structure by doping. such as dye-sensitized cells [11] and photolysis of water to generate hydrogen [67]. Ru(III). 7. It is easier to replace Ti4+ in TiO2 with a cation than Transition metal ions can provide additional energy levels within the band gap of a semiconductor. [73] studied the effect of doping TiO2 with transition metals such as Fe. TiO2 doping is equivalent to the introduction of defect sites like Ti3+ into the semiconductor lattice. Grätzel et al. When sensitized by dyes. Amorphous TiO2 containing some alkoxide groups causing defects inside and outside the amorphous particle-like units served as trapping states with long lifetimes for electrons injected from the excited dye molecules. From a chemical point of view. Such cells are a cheap alternative to amorphous silicon solar cells. which significantly enhances light absorption [68].e. TiO2 has been doped with many different transition metals [72–86]. However. dyes themselves can undergo photodegradation or form intermediates that need to be disposed of ulteriorly [70]. Vs is the surface potential. very few dyes are stable towards photodegradation and can provide a high photocurrent quantum yield [69]. metal ions can behave as recombination centers.

the rate of recombination of photogenerated electron-hole pairs in the semiconductor increases because there is no driving force to separate them. Khan et al.1646 Gupta S M. Xin et al. Wu and Lee [92] reported that deposition with Cu particles . Decontamination reactions were carried out at room temperature. Adachi et al. Rupa et al. The Cu-TiO2 catalyst yielded. M = Ag. et al. A Gd doping content of 4% provided optimal photocatalytic activity for the degradation of Reactive Brilliant Red. Periyasami et al. Rh and Cu have been reported to be very effective at enhancing photocatalysis by TiO2 [87–92]. The loading method. When the size of the metal particles is less than 2. The photoactivity of the Fe-doped TiO2 nanorods was much higher than that of Degussa P-25. They also synthesized Ce-doped TiO2 hollow spheres using carbon spheres as a template and Ce-doped TiO2 nanoparticles as building blocks [86]. smallest particle size and the highest surface area and pore volume of the samples. The dopant lanthanide ions enhanced the photocatalytic activity of TiO2 to some extent compared with pure TiO2 and Gd3+-doped TiO2 was the most effective photocatalyst. Papp et al. [85] prepared Gd-doped TiO2 hollow spheres were using hydrothermally prepared carbon spheres as a template. dispersion and composition. El-Bahy et al. resulting in efficient separation and higher photocatalytic activity. Wong et al. Gd3+ and Yb3+) by a sol-gel method. Wang et al. Noble metals including Pt. Doping with Fe caused a significant shift in absorption towards the visible region compared with that of Degussa P-25 and pure TiO2. methane and ethylene. Au. Gd3+-doped TiO2 had the lowest band gap. Ni. [84] synthesized TiO2 nanoparticles doped with lanthanide ions (La3+. The photocatalytic activity of TiO2 doped with Fe exceeded those of undoped commercial and synthesized pure TiO2 for the oxidative degradation of 2. [79] reported enhanced photocatalytic activity of TiO2 containing a low doping concentration of Fe3+ (Fe/Ti ≤ 0. This greatly reduces the possibility of electron-hole recombination. Thampi et al. [88] found that the addition of palladium to TiO2 powder by either photodecomposition or thermal decomposition increased its photocatalytic activity towards the degradation of 1. [90] reported CO2 reduction using copper-doped TiO2 powder at ambient temperature. It has been suggested that too high a concentration of metal particles reduces photon absorption by TiO2 and allows the metal particles to become electron-hole recombination centers. there is an optimum concentration of dopant ions where the thickness of the space-charge layer is similar to the depth of light penetration. The photocatalytic degradation of acetic acid and formaldehyde by the doped nanorods was investigated under irradiation with UV light. Mn2+ and Ru3+-doped TiO2 nanotubes. the composites display exceptional catalytic behavior [93].56 No. More recently. where sulfur mustard sulfoxide was formed. while photogenerated holes in the valence band remain on TiO2. Numerous studies have found that the properties of these kinds of composites depend strongly on the size of the metal particle. [89] reported that Rh/TiO2 samples exhibited a high activity for CO2 photoreduction using hydrogen to selectively produce CH4. Therefore. [82] synthesized TiO2 nanotubes hydrothermally and doped them with ruthenium using an ion exchange method. [91] observed that visible light induced H2 production from an aqueous methanol solution over a Cu-ion doped TiO2 photocatalyst. [80] prepared zero-valent Fe-doped TiO2 nanorods by an in situ reduction route using templareTiO2 nanorods that were pre-synth. when the concentration of doping is high. exhibiting higher photocatalytic activity (>80%) for the degradation of methylene blue than undoped nanotubes. [87] synthesized TiO2 nanoparticles by the sol-gel technique and doped the nanoparticles with about 1% noble metal (M/TiO2. Prasad et al. Chinese Sci Bull June (2011) Vol. Li et al.03 mol) and reduced photocatalytic activity at higher concentrations. the space-charge region is very narrow so the penetration depth of light into TiO2 greatly exceeds the width of the space-charge layer. M/TiO2 catalysts showed remarkable photocatalytic activity towards the decolorization of tartrazine even under visible irradiation. specifically.4. Nd3+. size of ruthenium particles and metal dispersion pattern at the surfaces of the nanotubes had a great influence on their photocatalytic performance. The order of the photocatalytic activity of the different catalysts was: Au/TiO2 > Ag/TiO2 ∼ Pt/TiO2 > Synthesized TiO2 > TiO2 (P-25 Degussa). resulting in lower efficiency [94]. The resulting photocatalyst was active under visible light. photoexcited electrons can be transferred from the conduction band of TiO2 to metal particles deposited on the surface of TiO2. Because the Fermi levels of these noble metals are lower than that of TiO2. The rate constant for the degradation of the dye X-3B at with a Ce doping content of 4% was almost 31 times higher than that of Degussa P25. Ag. Hydrolysis of sulfur mustard was accelerated on Ag+-doped TiO2 nanotubes compared with Cu2+.4-dichlorobenzene.6-trichlorophenol. Thiodiglycol and 1.esized using a traditional alkaline hydrothermal method. Eu3+. However. Ni2+. [83] studied modified TiO2 nanotubes as powder decontaminant for sulfur mustard. Co2+.2 Addition of noble metals Addition of noble metals is another approach for the modifying photocatalysts. a deadly chemical warfare agent. The photocatalytic activity of the as-prepared hollow TiO2 spheres was determined from their degradation of the dye Reactive Brilliant Red under irradiation with visible light.16 space-charge region becomes narrower and the electronhole pairs within the region are efficiently separated by the large electric field before recombination. 7. Sm3+. Consequently. [81] synthesized pure and Fe-doped nanocrystalline TiO2 by combining a sol-gel technique with hydrothermal treatment. Au.4-oxathiane were observed to be the major products formed except for on the Ru3+-doped TiO2 nanotubes.0 nm. Pd. and Pt) through photodeposition.

56 No. S or C) with the O 2p states shifts the valence band edge upwards. undoped TiO2 and Degussa P25 because cerium doping slowed the radiative recombination of photogenerated electrons and holes in TiO2. N. The photocatalytic activities of the samples showed the following order: B-doped TiO2 (hydrothermal method) > B-doped TiO2 (sol-gel method) > pure TiO2 > Degussa P25. 7. It was revealed that the photocatalytic activity of the hollow TiO2 spheres was almost 22 times greater than that of Degussa P25. [101] found that F-doped TiO2 exhibited higher photocatalytic activity for the oxidation of acetone into CO2 than undoped TiO2.103]. increasing the rates of anodic and the cathodic processes via improved interfacial charge transfer. [106] reported that Fe. when exposed to visible light. Diwald et al. [103] reported that TiO2–xCx nanotube arrays exhibit much higher photocurrent densities and more efficient water splitting under irradiation with visible light than pure TiO2 nanotube arrays. Various reports state that C-doped TiO2 is also remarkably effective at catalyzing this reaction [102. Unlike metal cations. and were dispersed on the surface of .Gupta S M. Yu et al. This modified catalyst exhibited an unexpected blue shift in the O2 photodesorption compared with that of undoped crystals of TiO2.3 Doping with metalloids Xu et al. the doped sample exhibited stronger absorption in the visible region and also showed a larger surface area. molecular dopants like NO and N2 gave rise to bonding states below the O 2p valence band and antibonding states deep in the band gap (Ni and Ni+s) that were well screened and hardly interacted with the band states of TiO2. Codoping of TiO2 with N and Cu extended absorption upto 590 nm and gave higher photocatalytic activity than pure Nor Cu-doped TiO2 for the photocatalytic degradation of xylenol orange. [107] prepared (Cu. [99] prepared N-doped TiO2 hollow spheres by a one-pot hydrothermal method using urea as precursor of nitrogen. Compared with pure TiO2. [98] incorporated nitrogen monoanions into single crystals of TiO2 by sputtering with N2+/Ar+ mixtures and subsequent annealing to 627°C under ultrahigh vacuum conditions. Sakthivel and Kisch [102] showed that C-doped TiO2 was five times more active than N-doped TiO2 toward the degradation of 4-chlorophenol by artificial light (λ ≥ 455 nm). Ao et al.5% Eu3+) showed significantly enhanced photocatalytic activity compared with undoped TiO2.4 Doping with anions activity than undoped TiO2 hollow spheres and commercial Degussa P25. Chinese Sci Bull June (2011) Vol. Park et al. The dopant cerium atoms existed in the form of Ce2O3. The photocatalytic activity of the spheres was determined by degrading Reactive Brilliant Red dye X-3B under irradiation with visible light and showed higher photocatalytic Codoping of TiO2 may be used as an effective way to improve charge separation. et al. The array exhibited enhanced photocatalytic efficiency for the photocatalytic degradation of methyl orange under visible light irradiation compared with undoped nanotubes because nitrogen doping narrowed the band gap of the nanotubes. F. In addition. narrowing the band gap energy of TiO2. For these anion-doped TiO2 photocatalysts. are more effective at enhancing the photocatalytic activity of TiO2 [104]. The photocatalytic activity of these TiO2 spheres was determined by degrading Reactive Brilliant Red under visible light irradiation. The photocatalytic activity of (Ce. P and S. thus revealing a potential application in degrading organic pollutants. C)-codoped TiO2 for degradation of Reactive Brilliant Red X-3B under visible light was significantly improved compared with that of C-doped TiO2. Song et al. Nitrogen atoms were incorporated into the TiO2 crystal structure and narrowed the band gap energy. The photocatalytic activity was evaluated by measuring the degradation of Reactive Brilliant Red and 4-chlorophenol under irradiation with visible light. Substitutional doping with N narrowed the band gap most significantly because its p state mixed with the O 2p states.16 1647 greatly enhanced the photocatalytic activity of TiO2 for producing H2 from aqueous methanol solution. [105] reported that monocrystalline TiO2 codoped with optimal concentrations of Eu3+ and Fe3+ (1% Fe3+ and 0. [109] prepared a (N. Dong et al.5 Codoping Many studies have been devoted to the development of TiO2 that is responsive to visible light by doping it with various anions [97–103] as a substitute for oxygen in the TiO2 lattice. Shen et al. Ce)-codoped TiO2 photocatalyst by the sol-gel route that could degrade nitrobenzene under irradiation with visible light. Yang et al. the mixing of the p states of the doped anion (N. [108] synthesized (Ce. Vasiliu et al. [97] calculated the electronic band structures of TiO2 containing different substitutional dopants including C. Xu et al.and Eu-doped TiO2 showed a red shift in its absorption spectrum and high photoactivity for the degradation and catalytic oxidation reactions of styrene and phenol. [100] synthesized N-doped TiO2 nanotube array by annealing anodized TiO2 nanotubes with ammonia at 500°C. 7. Fe3+ serves as a hole trap and Eu3+ as an electron trap. anions are less likely to form recombination centers and therefore. C)-codoped TiO2 using a modified sol-gel method under mild conditions. 7. respectively. N)-codoped TiO2 nanoparticles and investigated the influence of the amounts of Cu and N codoped into TiO2 on the photocatalytic activity. The same group also prepared B-doped TiO2 hollow spheres [96] using hydrothermally prepared carbon spheres as a template. [95] prepared TiO2 photocatalyst that was active under visible light by doping with boron using sodium borohydride at 55°C under hydrothermal conditions. Asahi et al.

the absorbance started at 800 nm. It acted as a support for WO3. diethylsulfide degradation and hydrogen production by this system were reported. also attracts much interest. it is possible to irradiate CdS with light of lower energy than that needed to electronically excite TiO2 particles. As illustrated in Figure 7.56 No. TiO2-SnO2.4 eV and its electron affinity is about 0. [115] observed that loading of WO3 on the TiO2 surface improved the decomposition of 1. Grandcolas et al. which extended the absorption to the visible region and improved the photocatalytic performance. TiO2-WO3. Appropriate placement of the individual semiconductors and optimal thickness of the covering semiconductor are crucial for efficient charge separation. it was deduced that electrons in the conduction band of TiO2 could be easily accepted by WO3.28 eV are a good material for the photosensitization of nanocrystalline TiO2. Coupled semiconductor photocatalysts exhibit very high photocatalytic activity for both gas and liquid phase reactions by increasing the charge separation and extending the energy range of photoexcitation. The electrons in WO3 would then be transferred to the oxygen molecules adsorbed on the surface of TiO2. in which illumination of one semiconductor produces a response in the other semiconductor at the interface between them [53]. pure TiO2. Yang et al. The geometry of particles. [118] reported that the rate of photocatalytic degradation of several textile azo dyes increased by 10 times using an SnO2/TiO2 composite system as a result of improved charge . Vinodgopal et al. 8 Coupled/composite TiO2 It is possible to create coupled colloidal structures. The conduction band of Bi2S3 nanoparticles is less anodic than the conduction band of TiO2 and the valence band is more cathodic than the valence band of TiO2 [113]. Both the upper edge of the valence band and the lower edge of the conduction band of WO3 are lower than those of TiO2. so the photogenerated electron can be injected from CdS to TiO2 while hole remains in CdS [53]. There has been much interest in coupling different semiconductor particles with TiO2. and TiO2-Fe2O3 being reported [111–118].4-dichlorobenzene in aqueous solution by up to 5. The resulting Ag/V-TiO2 three-component junction system exhibited the highest photocatalytic activity for the degradation of rhodamine B and Coomassie Brilliant Blue G-250 under both visible and UV light exceeding that of Degussa P25. [116] reported porogen templateassisted sol-gel synthesis of coupled rutile-anatase TiO2 with a high surface area. The electron transfer from CdS to TiO2 increases the charge separation Figure 7 Schematic illustration of the photoinduced charge injection process that occurs upon excitation of the CdS component of a CdS/TiO2 colloid in the presence of a sacrificial electron donor D and electron scavenger (methyl viologen. Methyl viologen was almost completely reduced using coupled CdS/TiO2 as a photocatalyst under irradiation with visible light [112].03 V. TiO2-MoO3. enhancing electron injection from the excited state of Bi2S3 into TiO2.5 eV larger than that of TiO2. and particle size play a significant role in interparticle electron transfer. The Fermi energy level of TiO2 is higher than that of SnO2 because of its smaller work function so electron transfer occurs from the conduction band of TiO2 to the conduction band of SnO2 and hole transfer occurs from the valence band of SnO2 to the valence band of TiO2 (Figure 8) [117]. Song et al. Because the standard reduction potential between W(VI) and W(V) is only –0. et al. The coupled system WO3/TiO2 has been used as a photocatalyst for decades.1648 Gupta S M.16 TiO2. [114] studied a Bi2S3/TiO2 junction prepared by precipitation of different concentrations of Bi2S3 onto TiO2. WO3 can be excited by illumination with visible light and the photogenerated holes can transfer from WO3 to TiO2. The separated electron and hole are then free to undergo electron transfer with adsorbates on the surface of the catalyst. singly-doped TiO2 (Ag/TiO2 or V-TiO2) as well as a P123-free-Ag/V-TiO2 codoped system. Chinese Sci Bull June (2011) Vol. Bi2S3-TiO2. Bi2S3 nanoparticles with a direct band gap of 1. where TiO2 plays the role of photosensitizer for SnO2. CO oxidation. The work function and electron affinity of TiO2 are both around 4. The improvement in the photocatalytic activity was ascribed to the synergistic effects of nitrogen and cerium codoping. with coupled samples such as TiO2-CdS. Bessekhouad et al. MV2+) [53] and the efficiency of the photocatalytic process.8 eV) is not sufficient to initiate photocatalytic reactions. even after UV illumination. The coupled structure that has received the most attention is that consisting of CdS and TiO2 colloidal particles. The coupled system SnO2/TiO2.5–3. [110] codoped TiO2 with metallic silver and vanadium oxide using a one-step sol-gel solvothermal method in the presence of a triblock copolymer surfactant (P123). as illustrated in Figure 6.9 times compared with pure TiO2.2 eV while the work function of SnO2 is around 4. Pure SnO2 shows little catalytic activity compared with TiO2-based photocatalysts because the band gap of SnO2 (3. Bi2S3 absorbed a large portion of visible light and when the junction contained 10 wt% Bi2S3. surface texture.

The photocatalytic performance of C60-hybridized TiO2 under UV irradiation was enhanced four times compared with that of a P25-TiO2 photocatalyst. E 0 (CdS) and E 0 (S–TiO2(x)) are the standard reduction potentials of the conduction band electrons of CdS and S−TiO2(x). [123] fabricated a photoelectrode photocatalyst that was active under visible light by modifying TiO2 nanotubes with CdS and S6+. Thus. To further improve the photocatalytic performance. [120] also obtained an efficient TiO2 photocatalyst by surface hybridization with a thin layer of C60 molecules. enhancing the photoactivity. it is clear that doping of TiO2 can enhance its visible light activity significantly by changing the position of the conduction or valance bands by introducing impurity energy levels. TiO2 with a carbon shell with a thickness of three molecular layers showed a photocatalytic activity that was twice as high as that of Degussa P25 TiO2 under UV irradiation. 10 Doped and coupled TiO2 9 Hybridization Conjugated materials are excellent candidates for improving the transportation of photocarriers in photocatalysis by forming electronic interactions with TiO2 because of its unique electron and hole transport properties. suggesting that electron transfer between TiO2 and CdS occurred more readily so the amount of carriers is increased. In addition.56 No.16 1649 Figure 8 Schematic diagram showing the energy band structure and electron-hole pair separation in a SnO2/TiO2 heterostructure [117] rod-shaped hydroxyapatite crystals with surfaces covered by nanosized TiO2 particles. resulting in better charge separation in the illuminated photocatalyst by enhancing the lifetimes of the e− and h+. Consequently. Ji et al. highly porous. TiO2 nanoparticles hybridized with hydrophobic zeolite adsorbents and TiO2 thin films responsive to visible light. Zhang et al. a promising photocatalyst can be produced. S6+ doping narrowed the band gap to enhance the visible light response of TiO2 and reduced the potential of the conduction band of TiO2. Some efforts have been made to electronically combine conjugated materials with photocatalysts in recent years. the active anatase surface was retained effectively and they operated as three-dimensional. The free energy (ΔG) for electron transfer between a donor and acceptor is a useful predictor of the activity of a coupled photocatalyst. where F is Faraday’s constant (96486 C/mol). size-controllable small reactors. and “x” denotes the concentration of S6+. respectively. Microstructure analysis indicated that the granule contained From the above discussion. [119] have demonstrated that surface hybridization of TiO2 with a few molecular layers of graphite-like carbon yielded an efficient photocatalyst exhibiting photo-induced electrons with high mobility at the graphite-like carbon/TiO2 interface because of the electronic interactions between the materials. et al. Takeuchi et al. A blue shift of the absorption edge of 16 nm was observed upon hybridization of TiO2 and hydroxyapatite. The increase in photocatalytic activity strongly depended on the coverage of C60 molecules on the surface of TiO2. Zhang et al. [122] prepared various Ti oxide-based photocatalysts such as highly dispersed Ti oxide species within zeolite frameworks. accelerating the electron transfer between TiO2 and CdS. In the composite granules. various attempts have been made to study the combined effect of coupling and doping. Quantitative analysis of the decomposition of methylene blue as a target pollutant compound indicated that the photocatalytic reaction rate constant was greatly increased compared with that of bulk TiO2.Gupta S M. Increasing the concentration of S6+ caused ΔG to decrease. [121] fabricated a TiO2/hydroxyapatite composite granular photocatalyst with a novel microstructure from commercially available α-tri-calcium phosphate and TiO2 powders using a process based on the liquid immiscibility effect followed by precalcination and hydrothermal treatment. Zhang et al. it was concluded that decreasing ΔG was one of the reasons for the high activity of CdS/S−TiO2(x). ΔG for electron transfer between S-doped TiO2 and CdS was determined according to the following equation [124]: ΔG = − F (E 0 (S–TiO2(x)) − E 0 (CdS)). the response of TiO2 was extended into the visible range due to the electronic coupling of p states of the graphite-like carbon and conduction band states of TiO2. Chinese Sci Bull June (2011) Vol. separation. The coupling of TiO2 with other narrow band gap semiconductors could also enhance its visible light activity because electrons or holes photogenerated in the narrow band gap materials could be injected into TiO2. A high photocatalytic reactivity was observed for the photocatalytic decomposition of NOx and the photocatalytic reduction of CO2 with H2O using the TiO2 semiconducting photocatalysts. . by such modification.

and SnO2 samples. [132] reported anatase/rutile core-shell structured TiO2 particles synthesized by controlled heat treatment of poly(ethylene oxide)-TiO2 hybrid particles. capped semiconductors have a core-shell geometry. The mechanism of core-shell structure formation was based upon volume shrinkage.1650 Gupta S M. Bedja and Kamat [129] prepared TiO2-capped SnO2 and SiO2 colloids. interfacial charge transfer and charge collection in this multicomponent semiconductor system are significantly different. By depositing a relatively thick shell of the second semiconductor with a thickness is similar to the core radius it is possible to maintain the individual identities of the two semiconductors. The photocatalytic activity was greatest for the thickest shells but did not correlate precisely with specific surface area. Matijevic and coworker [128] prepared spherical ZnO particles coated with uniform layers of TiO2. thermal expansion coefficient differences and further decomposition of organic components. Semiconductor nanoparticles are coated with another semiconductor with a different band gap in a core-shell geometry to passivate the surface of the initial nanoparticle and enhance its emissive properties. SiO2. most probably because of the increased surface area of the nanoporous. these materials showed a lower efficiency than Degussa P25 for the photocatalytic oxidation of acetaldehyde. et al. In coupled semiconductor systems.16 Kumar and Jain [125] investigated the effect of addition of metal ions on the photoactivity of CdS-TiO2 composite photocatalysts. Chinese Sci Bull June (2011) Vol. Such a capping process provides an economical way to deposit expensive semiconductor material on an inexpensive support and is convenient for building tandem semiconductor structures. The improved charge separation in this system was confirmed from the enhanced efficiency of hole trapping monitored by the absorption peak at 360 nm.88 to 2. Doping either Cd(OH)2-coated Q-CdS or TiO2 with Ag+ prior to their coupling (Ag+-doped Cd(OH)2-coated Q-CdS coupled with TiO2 and Ag+-doped TiO2 coupled with Cd(OH)2-coated Q-CdS) produced a three component composite catalyst [CdS-TiO2-Ag2S] system. The presence of Ag+ in the TiO2 lattice promoted the charge separation by scavenging shallowly trapped electrons from the conduction band of CdS and causing the trapped holes to move to deeper traps. the two particles are in contact with each other and both holes and electrons are accessible for selective oxidation and reduction processes on different particle surfaces. On the other hand. thus improving the selectivity of the interfacial transfer and enhancing the oxidation or reduction reaction [126] (Figure 9). only one of the charge carriers is accessible at the surface. However. [131] synthesized TiO2/MoO3 core-shell nanocrystalline materials. Lim et al. taking into account that many of these semiconductors (especially group II–VI compounds) are prone to anodic photocorrosion in aqueous media [127]. These core-shell particles showed enhanced rates of photodecomposition compared with spherical and other commercially available particles. The capped semiconductor system was useful for the oxidation of I– and SCN– and the quantum efficiency for I– oxidation was improved by a factor of 2–3 upon capping SnO2 with TiO2. The TiO2-capped SnO2 particles were 80- 100 Å in diameter and exhibited improved photochromic and photocatalytic efficiencies compared with TiO2-capped Figure 9 Electron transfer in a core-shell geometry [126]. 11 Capping The coating of one semiconductor or metal nanomaterial on the surface of another semiconductor or metal nanoparticle core is called capping. The photoabsorption energy of this system systematically shifted from 2. while opposite charge transfer to the inner semiconductor occurs. SiO2. [130] synthesized monodisperse silica/TiO2 core-shell photocatalysts of varying thickness via a sol-gel route and measured their photocatalytic activity using the decolorization of methylene blue.60 eV as the size of the composite nanoparticle was tuned from 80 to 40 Å.56 No. Under these circumstances. While the mechanism of charge separation in a capped semiconductor system is similar to that in coupled semiconductor systems. nanocrystalline structure of the anatase core. TiO2. A new series of photocatalysts has been designed by . Elder et al. Core-shell geometry has an important consequence in terms of imparting enhanced photoelectrochemical stability to the system. Sung et al. The Ag-doped coupled photocatalyst system was found to be about twice as photocatalytically efficient as the undoped Q-CdS-TiO2 composite for performing synthetic photochemistry.

Sekiguchi et al. Photocatalysis occurs in the presence of light with the energy corresponding to the band gap energy of the photocatalyst and causes the coating to chemically break down the organic particles adsorbed on the surface of the photocatalyst. no waste solids to dispose of and mild temperature and pressure conditions. creating oxygen vacancies. Also. [136] carried out multifrequency electron paramagnetic resonance studies on TiO2 nanocrystals capped with organic moieties prepared by both nonhydrolytic and hydrolytic procedures. Various research groups have studied TiO2 capped with organic molecules. producing adsorbed OH groups that tend to make the surface hydrophilic. After about 30 min under a UV light source of moderate intensity. [140] made TiO2-coated silicone catheters for clean intermittent catheterization. [134] reported that Ag core/TiO2 shell clusters were able to store electrons under UV irradiation and discharge them on demand in the dark. water and mineral acids. the smaller the contact angle of water becomes. algae and fungi disfigures the facades of buildings and results in mechanical weakening and eventual destruction. The photocatalytic degradation of phenol has been extensively studied because of .56 No. They examined the photocatalytic antibacterial effect using light energy and the safety of this type of catheter for practical clinical use. In recent years. cations to Ti(III). polymers. a blue shift in the plasmon absorption band from 480 to 420 nm was observed.4 V) such as silver and gold are good electron acceptors and facilitate rapid electron transfer from excited TiO2. The growth of organisms. Pseudomonas aeruginosa and Serratia marcescens in the liquid inside the TiO2 catheter decreased to a negligible level within 60 min of exposure to UV irradiation. et al. Water molecules can then occupy these oxygen vacancies. The electrons tend to reduce the Ti(IV) Over the last two decades. The photocatalytic activity of oleic acidTiO2 nanocrystals was shown to be even higher than that of Degussa P25 [135]. This behavior indicates a direct involvement of the interface of the materials in photocatalytic reactions. However. Staphylococcus aureus. buildings can be coated with a layer of photocatalyst. Hirakawa et al. These catheters were easily sterilized under sunlight. photocatalysis with TiO2 nanoparticles has been shown useful for the degradation of wastewater pollutants. [139] reported the degradation of gaseous nitrogen oxide pollutants like NO and NOx by sprayed TiO2 coatings (around 52% for NO and 34% for NOx). several review articles [51. Au. The photocatalytic investigation of TiO2 nanocrystals capped with different organic molecules have been performed.2 Wastewater treatment 12 Applications 12. The general concept of the self-cleaning capacity of TiO2 is well known and the application of TiO2 coatings to buildings for self-cleaning purposes is of considerable interest [138]. unpleasant odors and colored matters present in wastewater. the contact angle approaches zero.78] have been published on photocatalytic water treatment with generally positive results. TiO2 powders have higher photocatalytic efficiency than a coating because of their higher specific surface area.1 Photoinduced hydrophilic coatings and self-cleaning devices The deposition of dirt. Metal particles with a favorable Fermi level (0. surfactants. In this case. it allowed highly efficient decomposition of harmful organic substances. To prevent this. and the holes oxidize the O2− anions. If a TiO2 film is prepared with a certain percentage of SiO2.Gupta S M. electrons and holes are still produced but they react in a different way than normal photocatalysts. aromatics. Because the reaction area was large. contact angle of water is increased.16 1651 capping noble metal particles of Ag. making the surface superhydrophobic which would allow dirt to be washed away easily [137]. Photocatalysis with TiO2 nanoparticles uses two kinds of reaction systems. soot. and also the depth of penetration of UV light is limited because of strong absorption by both catalyst particles and dissolved organic species. When these clusters were subjected to UV irradiation. or Pt [133] with a semiconductor shell. The transfer of electrons from the excited semiconductor to the metal is an important aspect that dictates the overall energetics and hence the efficiency of photocatalytic reduction. which reflects an increased electron density in the Ag core during photoirradiation. This process has several advantages including complete mineralization of organic pollutants like aliphatics. These difficulties can be overcome and the application of TiO2 nanoparticles can also be expanded by employing various materials as substrates [139]. The presence of paramagnetic species (carbon radicals) on the surface of the TiO2 nanocrystals was suggested to account for the high catalytic efficiency of such a nanostructured material. Glass beads or fiberglass mesh structures may increase the surface area available for catalysis. such as bacteria. In this process. Taoda [142] developed photocatalytic silica gel by coating a transparent film of TiO2 on beads of silica gel. Chinese Sci Bull June (2011) Vol. Fittipaldi et al. dyes. the separation of powder from the liquid state used in water treatment and recycling processes is troublesome because of the formation of aggregates. 12. oxygen atoms are ejected. Toma et al. it acquires superhydrophilic properties after UV illumination. indicating the potential of photocatalytic oxidation technologies for neutralizing very diverse categories of toxic compounds in water. The survival rate of Escherichia coli. namely suspension and immobilized systems [141]. meaning that water has a tendency to spread perfectly across the surface [12]. vehicular exhaust and other particulates results in the necessity of cleaning the surfaces of buildings. pesticides and herbicides to CO2. The longer the surface is irradiated with UV light.

For this purpose.O-diethyl O-4-nitrophenyl phosphorothiate 2-chloro-4-ethylamino-6-isopropylamino-1.3. Cr(VI).5-triazin-2-yl)-3-[2-(2-methoxyethoxy)phenylsulfonyl]urea 1-[2-(2-chloroethoxy)phenylsulfonyl]-3-(4-methoxy-6-methyl-1. The ability of TiO2 to remove metals was found to depend on the standard reduction potential of the metal. fungal diseases and weeds.4-dichlorophenyl)O. whereas Cd(II).O-dimethyl O-4-nitrophenyl phosphorothiate .3. reducing its toxicity. and are considered cumulative and toxic.3.5-triazin-2-yl)urea Parathion methyl O.O-diethyl phosphorothioate Bromophos ethyl O-4-bromo-2. et al.5-triazine 2-(methylthio)-4-(tert-butylamino)-6-(cyclopropylamino)-striazine 2.5-triazine 3-(3-chloro-4-methylphenyl)-1.5-triazine 2-chloro-4. A thin film of TiO2 was coated on one side of a Ti plate. Mahmoodi et al. photocurrent flowed from the platinum counter electrode to the TiO2 electrode through the external circuit.143]. Photocatalysis using solar energy has been widely studied as a possible system to produce hydrogen from water ever since the Honda-Fujishima effect was first reported in 1972 [3].56 No.6-bis(isopropylamino)-1.O-diethyl phosporothioate Bromophos methyl O-4-bromo-2. Pesticides are usually applied as formulations to such targets in the field.5-dichlorophenyl O. Various reports have been made on the degradation of pesticides using TiO2 or modified TiO2 in solution.5-dichlorophenyl O. [141] studied the photocatalytic degradation of a textile dye (Acid Blue 25) in a photocatalytic reactor containing immobilized TiO2 nanoparticles at pilot scale and showed that immobilized TiO2 nanophotocatalysis was capable of degradation of Acid Blue 25 in textile wastewater. and Ni(II) were not removed. 12.6-dimethoxy-1. Cu(II). Prairie et al.1 3-(4-bromophenyl)-1-methoxy-1-methylurea 3-(4-isopropylphenyl)-1. When the surface of the TiO2 electrode was irradiated with near-UV light. showing that water can be decomposed into Category organophosphorus insecticide organophosphorus pesticides (insecticide-acaricide) pyrrole group of pesticides (insecticide-miticide) organophosphate insecticide insecticide insecticide insecticide organophosphorus insecticide organophosphorus insecticide herbicide herbicide herbicide herbicide herbicide herbicide/ herbicide derivative herbicide herbicide herbicide herbicide Reference [147] [148] [149] [150] [151] [151] [151] [151] [151] [151] [151] [151] [151] [151] [152] [152] [152] [153] [153] 2-(dimethoxyphosphinothioylthio) butanedioic acid diethyl ester (O.S-dimethyl phosphoramidothioate) 4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl5-(trifluoromethyl)pyrrole-3-carbonitrile.1-dimethylurea 1-(4. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Degradation of pesticides using TiO2 or modified TiO2 in solution Pesticide Malathion Methamidophos chlorfenapyr Phoxim Dichlofenthion Chemical name wide variety of structures and have been developed to exhibit an intended efficacy to specific pests. They concluded that Ag(I). [144] completely mineralized two azo dyes.1-dimethylurea.3.16 its high toxicity and ubiquity [36. insecticides. as listed in Table 2 [147–153]. Asmussen et al. Hg(II). Bui et al. H2 should be produced from renewable resources and natural energy sources.3. [145] treated water contaminated with metal and organic species with TiO2. Their presence as contaminants in aquatic environments may cause serious problems for human beings and other organisms.1 wt% TiO2. The use of TiO2 for environmental cleanup of organic pollutants through photooxidation has received much attention in the past decade. while an electrocatalyst (thin film of Ta2O5-IrO2) was coated on the other side.4 Production of hydrogen fuel H2 has great potential as a source of energy from the aspects of environmental preservation and energy security to realize a sustainable society in the future. and fungicides) have a Table 2 No.1652 Gupta S M.3 Degradation of pesticides Pesticides (herbicides.5-triazine 2-chloro-4-(1-cyano-1-methylethylamino)-6ethylamino-1. 12.O-dimethyl phosporothioate Parathion ethyl Atrazine Cyanazine Irgarol Prometryne Propazine Chlorotoluron Metobromuron Isoproturon Cinosulfuron Triasulfuron O.4-bis(isopropylamino)-6-methylthio-1.3. The possibility of solar photoelectrolysis was demonstrated for the first time with a system in which an n-type TiO2 semiconductor electrode was connected through an electrical load to a platinum black counter electrode [154]. These bifunctional electrodes exhibited superb activity for the degradation of common persistent toxic pollutants (4-nitrophenol and 2-nitrophenol) in industrial and agricultural wastewater. [146] reported wastewater remediation using bifunctional electrodes that performed both photocatalytic degradation and electrochemical oxidation. Reactive Red 4 (Cibacron Brilliant Red 3B-A) and Reactive Black 5 (Remazol Black B) to determine the potential of photocatalysis for the treatment of water using TiO2 powder. Chinese Sci Bull June (2011) Vol. N-Diethoxyphosphinothioyloxybenzenecarboximidoyl cyanide O-(2. and Pt(II) were easily treated by photocatalytic reduction with 0.

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