Materials Science Forum Vol. 734 (2013) pp 186-214 Online available since 2012/Dec/27 at www.

scientific.net © (2013) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/MSF.734.186

Recent development on titania based mixed oxide photocatalysts for environmental application under visible light Noor Aman, Trilochan Mishra*
CSE Division, CSIR-National Metallurgical laboratory, Jamshedpur-831007, India E. mail: drtmishra@yahoo.com Key words: Titania, mixed oxide, doping, photocatalyst, visible light, environmental, selenium.

Abstract: In the recent years most of the studies are confined to the mixing of ZrO2, SiO2, WO4 or ceria with titania in different composition so as to stabilize anatase phase, maintain high surface area and increase visible light absorption for better photocatalytic activity. Method of synthesis also helps in effective doping and enhancing surface area of the resultant materials. Nonmetal doping of oxide semiconductor materials facilitates the visible light application of photocatalysis. Based on the recent literature this review elaborately discuss on the development of titania based mixed oxide catalyst with or without different doping for visible light application. In addition this review deals with critical analysis of these materials towards photocatalytic oxidation of organics and reduction of pollutants like toxic metal ions and nitrates. 1. Introduction Since the discovery of photo-induced water decomposition under UV light [1] titania has received much attention as a potential photocatalyst for future environmental application. Due to the presence of a small amount of oxygen vacancies, which are compensated by the presence of Ti3+ centres, TiO2 is an n-type semiconductor. The valence band of this is mainly formed by the overlapping of the oxygen 2p orbitals, whereas the lower part of the conduction band is mainly constituted by the 3d orbitals. Among various semiconductors tested till date, TiO2 is the most promising photocatalyst because of its appropriate electronic band structure, photostability, chemical inertness, and commercial availability [2]. TiO2 exists in three main crystallographic forms anatase, brookite and rutile [3-5]. All the three polymorphs of titania can be described in terms of distorted TiO6 octahedra with different symmetries or arrangements [6, 7]. The band gap of anatase and rutile are 3.2 and 3.0 eV, respectively. Anatase has been usually found to be photocatalytically more active than other polymorphs [8, 9]. Fermi level position, electron mobility, surface hydroxyl concentration are the main factors responsible for its higher activity. Rutile has larger crystallite size which increases the electron-hole recombination. However, it is widely accepted that the mixed phase of titania is beneficial in reducing the recombination of photogenerated electrons and holes and it always results in enhancement of photocatalytic activity [10-12]. Commercially available Degussa P25 TiO2 containing anatase and rutile mixture in 80:20 ratio possesses an excellent photocatalytic activity [13]. Rutile is the stable phase at high temperatures, but anatase and brookite are common in fine grained (nanoscale) natural and synthetic samples [3, 4, 14-16]. In general the crystallite phase, porosity, surface area and surface hydroxyl groups primarily determines the photocatalytic activity of a material. To improve these parameters, a number of synthetic strategies have been adopted by the researchers. Even the synthetic technique helps in increasing the visible light absorption of photocatalysts. The synthesis methods have a lot of influence in controlling the surface properties as well as activity of a particular photocatalyst. It is now well understood that the surface area of pure titania can be increased through different synthetic techniques. But the stability of anatase phase and porosity at high calcination temperature still remains a concern for the material chemists. Therefore, the concept of another metal ion doping and use of titania based binary oxides have been getting more and more importance to overcome the above shortcomings. In addition to the metal-anatase system, the oxideAll rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP, www.ttp.net. (ID: 103.6.236.38-03/02/13,16:16:22)

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anatase system corresponds to the most broadly applied composite materials in the field of photocatalysis. It is well known that binary oxide catalysts often exhibit higher catalytic activity and selectivity than what one can predict from the properties of their components. It is established in the literature that mixing two dissimilar oxides adds another parameter since they are liable to form new stable compounds, which can lead to totally different physicochemical properties and catalytic behaviour. In addition mixed oxides system helps in the development of Z scheme photocatalyst which helps in increasing the activity by delaying the e/h recombination. Effect of different semiconductors with anatase has been reviewed recently in relation to solar photocatalysis [17]. Details about the structural interfaces between oxides such as WO3, Cu2O, CeO2 or Fe2O3 with anatase are essentially unknown from a structural point of view. This is essential to understand the electronic properties of the mixed oxides. However, pure titania can only work under ultraviolet (UV) light due to its wide band gap, which means only about 2-4% of the incoming solar energy on the earth surface can be utilized. Therefore the development of visible-light photocatalysts has become one of the most important topics in photocatalysis research. In most of the case non-metal doping helps in increasing the visible light absorption. So it is of interest to look into the development of non-metal doped binary oxide systems as potential photocatalyst for future environmental application. Another approach for achieving this objective is to sensitize TiO2 by using a narrow band gap semiconductor with a higher conduction band than that of TiO2. CdS and CdSe with band gap energy of .3.0 eV are considered to be potential sensitizers used for large band gap semiconductors because of the ideal position of its conduction and valence band edges. So CdS and CdSe sensitized TiO2 system were also investigated by some researchers [18, 19]. CdSe, CdS, PbS, PdS, and PbSe with titania are among the most used composite systems for visible light photocatalysis. However, lack stability in specific environments due to anodic photocorrosion by holes and the subsequent release of cations into the media. [20-25] restrict their prospective use. So here we will discuss about the recent development on binary oxide photocatalyst. Titania based binary oxide systems are limited in the literature and mostly talks about the systems like TiO2-SiO2, TiO2-ZrO2, TiO2-WO3 and TiO2-CeO2 etc. In addition limited studies are carried out on TiO2-NbO [26], TiO2-Fe2O3 [27] and TiO2-GeO2 [28] systems. Highly transparent TiO2-In2O3 composite film [29] and hollow sphere [30] systems were also investigated by some researchers as visible light sensitive photocatalyst. Comparative structure–activity relationship in Ti–M (M = V, Mo, Nb, W) mixed-metal oxides with anatase structure are studied for the photoelimination of toluene under sunlight type excitation [31]. The result indicates the suitability of TiO2-WO3 systems as efficient photocatalyst in comparison to others. However, some of these systems are rarely studied and reported in the recent time. So we will discuss in detail about the development of only extensively studied four systems with or without non-metal doping. 2. Binary oxides 2.1 Titania-Silica materials Mixed metal oxides of TiO2-SiO2 and TiO2-ZrO2 are of special interest because of their common valency (+4). Titania-silica mixed oxides have a large number of applications in catalysis, either as catalyst by themselves or as catalyst support [32-34]. Titania-silica mixed oxide is reported to be more active than pure titania photocatalyst. The unique chemical and physical properties exhibited by titania-silica binary oxides depend on both the composition and the degree of homogeneity. Therefore, strategies have been developed to synthesize the mixed oxides in a uniform manner and typically include co-precipitation, flame hydrolysis and sol-gel hydrolysis. Synthesis in presence of surfactant and other complexing agents results in the formation of homogenous distribution having high porosity. Desired arrangement of TiO2 and SiO2 species in the binary TiO2-SiO2 particles can be achieved by appropriate synthesis conditions. Introduction of SiCl4 vapour during oxidation of TiCl4 in a laminar diffusion flame reactor at reaction temperatures of 935 and 1068°C [35, 36] slows down the sintering rate of titania, resulting in decrease of primary particle size and in increase of anatase phase fraction. In sol-gel process, alkoxides of Ti are

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typically hydrolyzed in water at a much faster rate than the standard Si alkoxide which leads to the formation of separate titania-rich phases. This problem can be mitigated by prehydrolyzing the tetraethyl orthosilicate before adding the titanium alkoxide [37, 38] and by controlling the acidity/basicity of the medium [39]. In particular surfactant mediated synthesis of mesoporous photocatalysts with improved activity are reported [40-43] in the literature. Recently Mishra et al reported the synthesis of spherical titania silica material through modified sol-gel techniques in presence of CTAB [44]. CTAB concentration plays an important role in controlling the shape and size of the material. Only 2mol% of CTAB can form spherical titania particles (Fig-1) with mesoporosity. Same method can be used to prepare spherical titania based other binary oxides (Fig2) also.

A

B

C

D

Fig.1. SEM micrographs of TiO2 prepared with varied CTAB concentration. A: without CTAB, B: 1mol% CTAB, C: 2mol% CTAB and D: 4mol% CTAB The crystallinity of titania is a critical factor for the photoactivity. The addition of silica in titania enhances thermal stability by suppressing phase transformation of anatase to rutile and also increases the surface area and surface acidity. Suitable addition of silica in titania can stabilise anatase phase of titania with high degree of crystallinity and smaller crystalline size and reduce the bulk defects even at high calcination temperature. Addition of 30 mol% silica is found to increase the phase transformation temperature of anatase to rutile by about 180 °C [84]. At higher silica content (50 mol%) in the mixed oxides, the activity is, however, significantly dropped down due to the presence of amorphous titania covered with photocatalytically inactive silica on the surface [39]. Stabilisation of anatase phase up to 900°C is reported with 10-20 wt% silica in the materials [45]. Interestingly presence of silica not only stabilises the anatase phase at high temperature but also maintains the porous structures [45]. Whereas pure titania transforms to rutile phase even at 700 °C calcination thus decreasing the surface area and the photocatalytic activity.

Surface area of titania-silica mixed oxide proportionally increases with increasing the silica content [52].2. It is found that the thermal stability of mesoporous structures in the composite matrix is improved due to the introduction of silica which acts as glue and links anatase nanoparticles together. At high temperatures. Effect of silica on the surface area and crystallite size is presented in Table-1 with respect to calcinations temperature. Low crystallite size of silica mixed titania even at 900 °C calcination is well marked indicating the controlling effect of silica on the size of the materials. have also reported a similar trend [50]. 734 189 A B C Fig. This may also be one of the reasons for high anatase phase stability of SiO2 mixed titania [48].Materials Science Forum Vol. (B) Si (10%)TiO2 and (C) Si(20%)TiO2 after calcinations at 900°C. Silica modified titania prepared by sol-gel process retains its high surface area even at higher calcination temperature [53]. However. associated with the formation of Ti–O–Si hetero linkages where tetrahedrally coordinated silica is chemically mixed with the octahedral titania matrix. 3. the increase of surface area by making materials porous does not always increases photoactivity [54]. Itoh et al.042 nm) allows it to enter into the TiO2 lattice easily. Stabilization of the anatase phase by the surrounding SiO2 phase is reported to be through the Ti-O-Si interface [46]. In another study. [47]. Moreover. Fig-3 shows the change in shape and size of the spherical material due to heat treatment at 900 °C. The SiO2 lattice locks the Ti-O species at the interface with the TiO2 domains preventing the nucleation. (B) Titania-silica and (C) titania-zirconia synthesized in presence of 2mol% of CTAB. silica desolutes from the anatase lattice due to its smaller ionic radius. (A) TiO2 . may also have important contribution to enhance the photocatalytic activity of titania– silica mixed oxides. Similar findings have also been reported by Ding et al. Materials (A) Titania. The Brønsted acidity. The photocatalytic activity increases due to the increased anatase . Hierarchically macro/mesoporous TiO2-SiO2 oxides photonic crystal with highly efficient photocatalytic activity has been synthesized by combining colloidal crystal template and amphiphilic tri-block copolymer. A B C Fig.5 mol%) has been observed for coprecipitated titaniasilica catalysts [51]. smaller ionic radius of Si4+ (0. The highest Brønsted acidity is achieved in a material having 10 mol% silica in titania [49]. It has been found that the new acidic sites created by lattice substitution exhibit Brønsted acid character instead of Lewis acid character [49]. increased acidity with increasing titania content up to nearly pure titania (99.

There are two types of combinations between TiO2 and ZrO2: physically mixed (mixture of two oxides) and chemically bonded having Ti–O–Zr type linkages. It indicates that the spherical shape still retains with partial sintering of particles after calcinations at . 67]. However. profound acid-base properties. 72] and reverse microemulsion [73] techniques. A recent study [56] indicates that the physical mixing of silica with Degussa P25 titania can enhance the photocatalytic activity under UV light to a large extent due to the change in the electronic property of the material with increased band gap. only anatase phase is observed in the temperature range of 500– 700 °C. The most widely employed methods for synthesis of TiO2-ZrO2 mixed oxides are co-precipitation [57-62] and sol-gel [53.15 2 Crystallite Size(nm) 2. due to heat treatment at 900°C (Fig-4) [45]. 63-67]. The more-negative conduction band (-1. 5. zirconia is segregated within the matrix of the titania crystallites whereas. Anderson et al. For the Zr-doped TiO2 materials with less than 30% of Zr. The sample containing 30 % of Zr remains amorphous when calcined at 500 °C and transforms into anatase when the calcination temperature increases to 600 and 700 °C. The degree of interaction or in other words the homogeneity largely depends on the preparation techniques and parameters. neutral amine [71.05 15. a high thermal stability and strong mechanical strength.and Zr-alkoxides is a major problem in the preparation of mixed oxides. TiO2-ZrO2 mixed oxides exhibit high surface area.98 12. zirconia is segregated on the surface of the titania crystallites [74]. Sample code Titania Wt% Silica (Wt%) Zirconia (wt%) 500˚C Ti TiSi-10 TiSi-20 TiZr-10 TiZr-20 100 90 80 90 80 10 20 10 20 91 126 138 105 96 BET Surface area (m /g) 700˚C 48 106 112 84 80 900˚C 30 85 88 75 68 500˚C 14.75 21. prepared titania and zirconia sols separately prior to their combination [53. Presence of nearby zirconia inhibits densification and crystallite growth by providing dissimilar boundary.0 V vs NHE) makes ZrO2 a promising alternative photocatalyst for the degradation of a great variety of pollutants. In homogeneous colloids. Both TiO2 and ZrO2 are n-type semiconductors with similar physicochemical properties. Other less frequently applied procedures include the super critical fluid extraction [68].49 16. Physicochemical and catalytic properties of titania-zirconia mixed oxides vary depending on the type of bonding takes place in a mixed oxide.190 Photocatalytic Materials & Surfaces for Environmental Cleanup-II crystallinity and surface area [55]. Several preparation methods have been employed to synthesize the TiO2-ZrO2 composite oxides. Particle size of TiO2-ZrO2 mixed solution is found to be lower than the Zr-doped TiO2. in the heterogeneous colloids.9 900˚C 48. [69] have suggested that a higher temperature is required for crystallisation of binary oxides than the individual oxides.17 9.2 Titania-zirconia binary oxide Titanium and zirconium belong to the same group (IVB) of elements in the periodic table. This is also supported by the fact that anatase TiO2 and tetragonal ZrO2 are not compatible with each other. In sol-gel processes.13 24.1 12. separate domain formation due to the difference in the hydrolysis and condensation rates of Ti.85 10. prepared in presence of CTAB. The excess Zr4+ ions are accumulated at the surface of the anatase TiO2 because of slow condensation of Zr4+ ions [65].0 V vs NHE) and more-positive valence band potential (4. Partial substitution of Ti4+ by Zr4+ has also been reported in Zr-doped TiO2 [73]. citric acid complexation [70].3 700˚C 40. So zirconium doping retards the amorphous–anatase and anatase–rutile phase transition processes. non-hydrolytic modified sol-gel [69]. In fact. Recently Mishra et al reported the change in shape and size of the spherical TiO2-ZrO2 material. Table-1: Textural properties of synthesized TiO2 and binary oxide materials.6 15.0 eV) in comparison to those of TiO2.17 24. In yet another approach. ZrO2 has a wide band gap (ca. Chang et al.4 12.02 12.

Zr(10%)TiO2 and (B) Zr(20%)TiO2 after calcinations at 900°C. associated with heterometallic bonding formation. These study shows the prospect of titania based binary oxide as stable and effective photocatalysts. Codoping of Zr4+ and F.Materials Science Forum Vol. A B Fig. Increasing surface acidity of the material helps to improve the photocatalytic activity. Wu et al. The role of ZrO2 in enhancing the visible light photocatalysis of TiO2-xNx towards oxidation of gaseous organic compounds has been evaluated recently [76]. However. UV-Vis absorption shifts to lower range on increasing the Zr-content. So the presence of CTAB not only controls the particle size and shape but also increases the porosity of the materials. As a result the amount of lattice nitrogen on the surface of TiO2-xNx-ZrO2 is more than that on the TiO2-xNx. 734 191 900°C. 53]. no extra phase formation is observed at high calcinations temperature. These methods are usually performed at relatively low temperature as the prepared N-doped TiO2 materials usually have a low thermal stability. In another study ZrO2 modified S-doped TiO2 visible light photocatalysts has been successfully prepared by simple sol-gel method [77]. The introduction of ZrO2 into TiO2-xNx considerably inhibits the undesirable crystal growth during calcination and thus preserves the lattice nitrogen. Moreover with 10 wt% zirconia samples. surface area of the titania increases drastically due to the presence of 2 mol% CTAB during synthesis. However. (A).ions within anatase hollow microspheres promotes lattice substitution of Ti4+ ions by Zr4+ and facilitates the transformation of surfacesegregated amorphous ZrOx clusters into Zr-F species [78]. Unlike silica mixed samples zirconia mixed samples shows mostly uniform particle size. [75] observed slight decreased band gap of the mixed oxide. In addition. 2. 4.3 Non-metal doped TiO2-ZrO2 and TiO2-SiO2 materials In general. Interstitially N doping of TiO2-SiO2 2 . The increment of surface acidity in mixed oxides has been generally attributed to a charge imbalance.) has been proved to be an effective route to improve the thermal stability and UV light photocatalytic activity of TiO2 [45. Yu et al. The introduction of ZrO2 could effectively suppress phase transformation of anatase-to-rutile and stabilize the sulphur in the STiO2-ZrO2 matrix which in turn enhances the visible-light absorption compare to the corresponding non-modified S-TiO sample. at 900 °C calcination still spherical particles (Fig-4) are observed with little sintering effect for all the binary oxide materials. the preparation of N-doped TiO2 powder mainly includes wet chemical methods such as co-precipitation and sol-gel. It was concluded that the presence of zirconia not only helps in anatase phase stabilization but also controls the sharp decrease in surface area by restricting the particle aggregation. ZrO2 etc. The average particle size increases from 1100nm to 1150nm with the increase in zirconia content. At 900 °C calcinations only pure TiO2 completely loses the spheroid shape due to sintering of the particles. The introduction of a second metal oxide (SiO2. Only small zirconium titanate phase is observed particularly at 900°C calcination in case of 20 wt% zirconia sample. [70] have observed a decrease in iso-electric point of the mixed oxide with increase in the Zr4+ substitution in the TiO2 lattice. Nitrogen doping in the TiO2 lattice has been done by the thermal treatment of NH3-adsorbed TiO2 hydrous gels.

Besides. Nitrogen doped titania-zirconia material exhibit high surface area and enhanced visible light mediated photocatalytic activity in comparison to nitrogen doped pure titania. XPS analysis of Ti 2p and O1s spectra confirm the presence of Ti3+ and oxygen vacancy in N doped materials. All these factors are responsible for an enhancement in photogenerated electron-hole separation and thus increased photocatalytic activity.%) helps in phase stabilization and maintains the porous structure even at higher calcination temperatures in comparison to that of pure titania.5eV signifies the doping in the matrix and the formation of NO species. thermally stable Ndoped zirconium titanium mixed oxide with enhanced photocatalytic activity towards reduction reactions under visible light employing hydrazine as a source of nitrogen. and surface area. effect of hydrazine to metal oxide ratio on the overall activity is investigated so as to have better understanding on the optimum composition. respectively. Aman et al [80] used a simple approach for the synthesis of high surface area.192 Photocatalytic Materials & Surfaces for Environmental Cleanup-II mixed oxide. but the rise of SiO2/TiO2 ratio in the mixed oxides led to a decrease in the amount of surface sulphate species. Surface area and pore volume increases with the increasing hydrazine amount to 298 m2/g and 0. Synthesis at low pH of 2 results in the formation of nanomaterials (Fig-5). Presence of low amount of zirconium oxide (10 wt. . Even if NF co-doping of binary oxides is found to be beneficial in comparison to only N doped titania [81]. The reported results revealed a decrease in the size of TiO2 particles with increasing the SiO2 content. a b c Fig. oxygen vacancy and substantial N doping. Amount of nitrogen doping and the visible light absorption (Fig-6a) capacity of the material increase with the increasing hydrazine amount up to an optimum value. TEM micrographs of (a) titania-zircona and (b) & (c) N doped titania-zircona materials at different magnifications. The photoactivity was initially affected by factors such as the amount of inactive surface SiO2.5 eV which is somewhat prominent in the case of TiZr-6N material. This peak is rarely observed in the N doped materials. Fig-6b shows the presence of three different peaks with varying intensity in case of both N doped materials. Still another low intensity peak is observed in the range of 402. Presence of peaks at 397 and 400. Mainly addition of SiO2 results in the improvement of thermal stability of the catalystand the formation of Brønsted acid sites. Amount of hydrazine plays an important role in nitrogen doping as well as formation of porous structure in the material. TiO2 particle size.5. respectively in the material. leads to increased visible light absorption [79]. Decreased particle size due to the presence of silica is also reported earlier [53]. It is observed in between the standard position of NO and NO2 (405 eV) so it can be due to the formation of more electropositive NO type species. Enhanced photocatalytic reduction and oxidation activity of N doped titania–zironia material under visible light was attributed to the synergistic effect of high surface area.323 cm3/g.

which may accelerate the photoelectron and holes recombination rate and decrease the photocatalytic activity. a strong size effect is expected for sunlight excitation and positive effects arising from interphase charge transfer can only be envisaged in a narrow size domain mainly governed by WO3 characteristics. But theWO3 band gap energy is large enough to limit visible photon absorption. and correspondingWO3 surface phases on anatase gives an idea of the complexity of the situation [82].4 Titania-tungsten oxide materials Titania-tungsten oxide system is studied by several researchers due to some inherent interesting properties of WO3 in combination with titania. there should be further improvement in their works since these preparation processes were too complicated and the TiO2N-WO3 material prepared from immerging TiO2-N into tungstic acid may result in most of WO3 adsorbed on TiO2 surface instead of inserted into the TiO2 lattice. u T iZ r-6 N T i-6 N T iZ r 390 395 400 405 410 B in d in g e n e rg y (e V ) Fig. This includes the presence of anomalous oxidation (W5+) states mostly at the surface layers or defects sites. (A) N1s spectra and (B) diffused reflectance spectra of N doped materials. the band modification of the solid should allow efficient hole transfer from WO3 to anatase upon light absorption.8 eV [83]. a full analysis of surface and electron-hole recombination as a function of the particle size still remains to be explored. So there is a need to look into new method of synthesis for tungsten and nitrogen co-doped TiO2 as a potential catalyst under visible light. Present knowledge of understanding cannot rationalized the defects formation as a function of size. Thus in case of TiO2-WO3 system. For particles well below 10 nm. is therefore in case of WO3. anion vacancies.6. However. Nanosized WO3 is mostly crystallized into monoclinic or orthorhombic phases on contact with titania. 2. the presence of gap states may allow electron transfer from TiO2 to WO3 and adequate charge separation. . TiZr denote the zirconium titanium mixed oxide and the number indicates different mole of hydrazine (N) used. Energy diagram indicates that the bulk contact between anatase and WO3 allows energy transfer between two components but inefficient in promoting charge separation in case of both UV and sunlight excitation.Materials Science Forum Vol. WO3 is considered to be mainly amorphous and hence the capability to absorb visible photons and handle charge carriers to produce useful chemistry is essentially lost. The presence of several W oxidation states. particularly acidity constitute one of the important factors controlling the photocatalytic activity enhancement. The defect chemistry of WO3 is remarkably interesting. surface properties. For WO3 particles below 10 nm size. 734 193 A Intensity/ a. Typically the monoclinic polymorph exhibits a band gap of 2. Gao et al prepared a series of N-doped TiO2 coupled with WO3 showing higher photocatalytic activity under both UV and visible light [84].7-2. However. However.

To overcome these limitations. Authors believe that these nanotube structures based on TiW alloy anodization can find applications. However separate WO3 phase in addition to anatase phase was not detected in the material. numerous efforts have been made to improve the photocatalytic activity by modifying the surface or bulk properties of TiO2 through mixing of two semiconductors as described above. Such surfaces have a higher affinity to the species with unpaired electrons and can easily adsorb the hydroxyl groups and water. Compared to titanium oxide nanotubes. which are necessary for the hydroxyl radical generation thus facilitating the photocatalytic process. Hierarchically nanostructured cerium-doped titania materials having anatase phase with a squamalike morphology . Photocatalytic efficiency can be remarkably enhanced by the introduction of rare-earth metal elements. Recently noodle shaped. It was observed that the visible light absorption increases with the increasing tungsten amount. TEM image of the N doped titania-tungsten oxide material. In addition composite Ti-W oxide nanotubes have been successfully fabricated through anodization of TiW alloy [87]. In particular. In this context hierarchically nanostructured Ce/TiO2 is found to increase the photodegradation of RhB under visible light [99]. the catalytic properties of ceria have received much attention due to two features (i) the redox couple Ce3+/Ce4+ with the ability of ceria to shift between CeO2 and Ce2O3 under oxidizing and reducing conditions. Ce-doped TiO2 materials have been preferentially prepared by the sol– gel and hydrothermal methods [93-98]. Keller et al [86] reported that tungsten doping of the TiO2 leads to the appearance of Lewis and Brønsted acid sites and therefore an increase of the surface acidity is observed. the photocatalytic activity of TiO2 can be significantly enhanced by doping with lanthanide ions/ oxides because lanthanide ions can form complexes with various Lewis bases through interaction of the functional groups with their f orbital [88-90].194 Photocatalytic Materials & Surfaces for Environmental Cleanup-II 20 nm 100n Fig. Among the lanthanide oxides. mesoporous N doped TiO2-WO3 system was reported [85] with increased visible light activity.5 Titania-Ceria materials Continuous improvement of the photo-reaction rate and the solar efficiency via adjusting the band structure of TiO2 is a meaningful work at the present stage. 7. Alternatively. photoelectrodes in photocatalytic devices or photoelectrochemical solar cells. and (ii) the easy formation of labile oxygen vacancies with the relatively high mobility of bulk oxygen species [91]. Obtained nanotubes show straight wall morphology and are well vertically aligned on the substrate. The noodles of 150-200nm are composed of nanoparticles of 10-20 nm (Fig7). Surface area and the photocatalytic activity varies with the variation in WO3 content in the material.2 wt% WO3 are present. in electrochromic devices. Even pure ceria nanomaterial is reported recently as an efficient photocatalyst [92]. the composite Ti-W oxide nanotubes showed highly improved ion insertion and electrochromic properties even when only small amounts such as 0. 2. Ti-W oxide nanotubes have a much higher electrochromic contrast and lower onset voltage and exhibit a good cycling stability.

Activity is found to depend on the presence of Ce4+/ Ce3+ rather than only visible light absorption. Recently synthesis and photocatalytic activity of Ce/TiO2 varying the cerium oxide content from 2-10wt% with respect to TiO2 was studied by Aman et al. The exceptionally high phase stability. Only a few groups studied this nanocomposite system for visible [110] or UV-visible [111. 114] is useful in the context of their interaction with titania for improved photocatalytic activity. 112] light excitation. However. 734 195 have been reported through a simple O/W emulsion technique using Span-60 as an emulsifier.TiO2 with high surface area. 109]. Material calcined at 600ºC shows better activity than that calcined at 400ºC even though surface area decreases. systematic studies of the anatase/hematite material as a function of the particle size are missing from the literature. . Therefore an optimum amount of cerium with appropriate heat treatment is required so as to have best photocatalytic result under visible light. Other complex oxides such as LaVO4 or Bi oxyhalides are also very useful in this context because of similar electron-hole charge separation [115. 116].6 Other binary oxides systems The interaction of Cu2O/CuO with titania as a photocatalyst has not been well studied till date.Materials Science Forum Vol.0 eV which limits the absorption of visible light photons. However. The latter is particularly well suited as valence-conduction relative band positions is capable of promoting visible-photon generated electron transfer from Bi2O3 to titania and UV-photon generated hole transfer from titania to Bi2O3. This leads to the development of highly active sunlight-driven photocatalysts. Sol-gel synthesis of titania doped with 5-mole% CeO2 after calcining to 500°C. Highest photocatalytic activity is observed for TiCe5 having 5wt% cerium oxide calcined at 600°C. to date studies on copper oxide based photocatalysts is limited [108. Synthesis of a novel thermally stable mesoporous ceria−titania phase using a neutral templating route was reported [100] with high removal of volatile organic compound like toluene. Other oxide like Bi2O3 [113. The UV-vis diffuse reflectance spectra show that the cerium-doped samples exhibit obviously enhanced absorbance in the visible light region compared with pure titania. [101] Surface properties and the photocatalytic activity under visible light towards methylene blue oxidative decomposition and selenium (IV) reductive removal reaction are studied to correlate the surface properties with respect to optimum cerium concentration. The toluene removal performance was further enhanced for Pt impregnated mesoporous ceria−titania. Combination of Fe2O3 lacks adequate electronic characteristics to efficiently separate the charge carrier for visible light excitation. It is also understood that the presence of cerium helps in better separation of hole-electron pair. Moreover. However. It was demonstrated that the oil in water emulsion method is practical to produce a hierarchical nanocomposite structure of Ce. Similar to the above observation [101] 5mol% Ce gives better photocatalytic activity. possesses specific surface area of 97 m2 g–1 and has anatase phase stability up to 900C [102]. narrow mesopore size distribution and good thermal stability [99]. the band energy levelling is adequate for enhancing charge separation mostly with UV light [103]. Role of oxygen vacancy created due to mixed oxidation state can not be ruled out. In fact the latter studies indicate that defect rich nanosized iron oxide transfer visible light excited electrons to the titania. Anatase crystallinity mostly decides the photocatalytic activity rather than only surface area. 2. Change in particle size plays an important role in photocatalysis of these materials. The only positive effect might be derived from UV-excited electrons on anatase which may be efficiently transferred to the Fe2O3 phase. Below 10 nm size the band gap is expected to reach a value close to 3. the beneficial effect of Ce doped TiO2 catalysts depends on the Ce content in the material. crystallinity and high surface area are due to the extremely fine particle size and effective doping achieved by the specific synthesis method. Modification of the Cu2O band gap and the nanocomposite Fermi level position with 10mm size provide an effective way to transfer visible light excited electrons from the copper oxide to anatase and promote electron-hole separation [104-107].

decontamination of soil. Photodegradation of chlorinated organics (chlorophenol. The option for recovery of valuable metals. water disinfection and hazardous waste remediation in addition to hydrogen energy generation. acetaldehyde decomposition under visible light also emphasized the significance of N-doped TiO2 [129]. has been reviewed recently [2]. destruction of malodorous compounds. the photocatalysis allows us to carry out both oxidation and reduction type of reactions. 4- . possibly because of the back electron transfer from the active sites on the photocatalyst surface. The complete mineralization of a variety of aliphatic and aromatic chlorinated hydrocarbons via heterogeneous photo-oxidation on TiO2 has been reported [120]. in the recent year development of various new materials with enhanced activity for direct water splitting in visible/solar light stimulated the researchers to improve the process for a prospective technology [117]. Titanium dioxide supported on glass has been found most effective in removing methyl orange while chicago sky blue 6B is most stable against photodegradation process. chicago sky blue 6B have been studied as a test reaction in the presence of titanium dioxide [120. purification and decontamination of indoor air. higher degree of water and hydroxyl groups adsorbed on the surface of nano-TiO2 [126]. dissolved oxygen etc. [1]. Ethylene oxidation is found to increase over silica and zirconia mixed TiO2 in comparison to pure titania [130]. methyl orange. high surface area. The recently developed photocatalysts like In1-xNiTaO4 [118] and ruthenium chromium modified solid solution of (Ga1-xZnx)(N1-xOx) [119] with improved efficiency in presence of visible light have opened a new direction and hope for the direct water splitting. ZrO2TiO2 [58] and CdS-TiO2 [132] with increased efficiency mostly at higher pH. reduction of COD (chemical oxygen demand).196 Photocatalytic Materials & Surfaces for Environmental Cleanup-II 3. The treatment of hazardous wastewater containing heavy metals and organic compounds by photocatalysis with respect to various parameters such as pH. Asahi et al. However. mineralization of hazardous organics. have emerged as a focus of environmental remediation efforts [123]. Significant works have been reported in the field of degradation of textile dyestuff in presence of other cations and anions into non-hazardous end products under visible light radiation [124.1 Photocatalytic oxidation The major applications investigated for this technology are mostly confined to colour removal and destruction of dyes. light intensity. Later. [128] succeeded in degrading methylene blue under visible light using N-doped TiO2. Higher degradation rate of dyes by combustion synthesized nano-TiO2 in comparison to Degussa P25 was explained on the basis of reversible adsorption. Photodegradation of different common dyes like methylene blue. Photoassisted water electrolysis using UV light was demonstrated over 30 years ago by Fujishima et al. 121]. 125]. Majority of the recent research works have focused on the generation of hydrogen as a clean and renewable fuel to fulfil the ultimate objective of producing hydrogen in large scale using solar energy. However. Textile dyes. Photocatalytic applications Semiconductor photocatalysis appears to be a promising technology with wide applications in environmental systems such as air purification. The photodegradation of oil in water was carried out using slightly crystallized titanates [131]. after converting to their less-toxic/nontoxic metallic states through reduction was explored. Similarly. In another study. Promising degradation of crystal violet and methylene blue has been reported on the vanadium doped TiO2 [127]. Feasibility of a reaction depends on the redox potential of the reactant and the semiconductor used. destruction of hazardous inorganics such as cyanides. 3. Degussa P25 has been found more effective than ZnO for the photomineralisation of Chrysoidine Y [122]. Moreover. It is often found that photocatalytic oxidation process is nearly suppressed in the absence of oxygen. disinfection of water. our work in this dissertation will mostly focus on the importance of environmental applications of photocatalysis. tricloroethylene) in aqueous solution has also been investigated using mixed semiconductors like SiO2-TiO2 [52]. being the major constituent of total dyestuff used. indigo carmine.

acetaldehyde and carbon monoxide. Effect of boria doping was also investigated for vapour phase Beckmann rearrangement of cyclohexanone oxime [62]. These metallic couples are also influenced by the solution pH. In addition CO oxidation with appreciable results [99] was reported on cerium doped titania. Se(IV)) or their protonated forms (HSeO4−. have reported the degradation of phenol over metal (Fe and Pt) doped TiO2 to find out the optimum level of metal doping [135].4 V can be reduced on pure TiO2. . Accordingly the photoreduction of several inorganic cations and anions investigated for removal or recovery applications has been discussed below. Se(VI)). 8. C-doped TiO2 is also found to increase the oxidation of gaseous benzene. In this case. Prairie et al. In another study.2 Photocatalytic reduction For photo-reduction of a metal ion Mn+ to M0. 734 197 chlorophenol. Se(VI) is more mobile and stable towards reduction than Se(IV). Decomposition of other organics like methylcyclohexanone [73]. 134] under visible light. the comparative activity of TiO2.Materials Science Forum Vol. tetrazene and 3-benzene sulfonic acid by Ag-doped TiO2 photocatalyst has been reported [136]. 3. such as selenate (SeO42−. 140] have demonstrated that only metal ions with redox potentials more positive than 0. selenite (SeO32−. ZnO and Fe2O3 towards degradation of phenol under concentrated solar light has been studied [137]. 2-propanol are completely mineralised by carbon modified TiO2 [133. photogenerated electrons are utilized to reduce the toxic Cr(VI) to the environmentally benign and immobile Cr(III) species. 3. Ceria doping has improved the decomposition of 2mecaptobenzothiazole in aqueous solution [93]. hence it is harmful and difficult to remove it from wastewater [141]. Positions of the redox potentials of various metallic couples related to the energy levels of the conduction and valence bands of TiO2 at pH ~ 0. HSeO3−). Brezova et al. the energy of the cb electron must be more negative than the E0 of the Mn+/M couple. Schematic presentation of cb and vb of TiO2 with respect to different cations is given in Fig-8. This strategy is particularly relevant to practical remediation scenarios involving wastewater effluent streams containing both toxic metal ions and organic pollutants. Dye photooxidation along with simultaneous photoreduction of Cr(VI) has also been investigated [138]. The photocatalytic reduction of Se(VI/IV) species using TiO2 has been initiated by Sanuki et al. The toxicity of Se compounds is related to their oxidation states. V Fig.1 Selenium and copper The most common selenium species in wastewater exist as mobile ions. salicylic acid and tcinnamic acid [88] was studied using titania based mixed oxides. Comparative degradation of acid orange 7.2. [139.

Among all the synthesized materials. They found that the adsorption of Se(VI/IV) species onto titanium dioxide and the presence of suitable hole scavenger is essential for an effective reduction process. Degussa P25 performs slightly better than titanium zirconium mixed oxide. It is reported that 25ppm of Se(VI) can be reduced to elemental Se in only 45min of reaction under visible light [80].198 Photocatalytic Materials & Surfaces for Environmental Cleanup-II [142. Chen et al. Studies on photocatalytic activity of all the commercially available titania show that Millenium PC-500 with highest surface area as the best photocatalyst for complete reduction of Se(VI) and Se(IV) into elemental selenium [146]. Selenium reduction is also studied on TiO2-ZrO2 systems. sodium oxalate or alcohols in the aqueous phase [147. Present study shows that 100ppm of mixed solution can be removed under visible light in 40minutes of reaction using titanium zirconium mixed oxide as catalyst. This indicates that the waste water containing copper and selenium ions can be efficiently treated under visible or solar light. sulfates and chlorides has inhibitory effect on copper reduction due to irreversible adsorption on photocatalyst surface. high surface area and presence of oxygen vacancy. Solution pH plays an important role in the photocatalytic performance as observed in Fig-9. which interferes with copper reduction. Generally the rate of reduction increases with the increase of the concentration of hole scavenger. However. EDTA. [144146] have studied the effects of a range of hole scavengers on photocatalytic reduction of Se(VI/IV). electron scavenging by O2 is a thermodynamically favoured process. titania-zirconia mixed oxide performs as the best photocatalyst for both Cu(II) and Se(IV) reduction. another group [152] has reported the synergistic photoreduction in mixed solution of Cu(II) and Cr(VI). concentration. modification of TiO2 by silver has resulted in simultaneous generation of H2Se along with elemental selenium [145]. Photodeposited material is found to be copper selenide rather than pure copper and selenium metal. Similarly cyanide degradation along with copper reduction is also possible [150]. only EDTA (ethylene diamine tetraacetic acid) and formic acid are found to be the most active hole scavengers for the reduction reaction. Noor et al studied for the first time simultaneous photocatalytic reduction of Cu(II) in presence of Se(IV) over some spherical binary oxide catalysts [154]. out of which latter showed the best result for Se(VI/IV) reduction due to competitive adsorption of formate anion [144]. In a mixed solution both EDTA and formic acid perform very well under visible light irradiation. The presence of phosphates. Photochemical copper ion reduction proceeds only in presence of hole scavenger like sodium formate. In a mixed Cu(II)/Fe(III)-EDTA system. In addition. 143]. For a single contaminant. Highest photocatalytic reduction in a mixed solution is observed at pH 3. Increased photocatalytic activity under visible light is correlated to the synergistic effect of substantial nitrogen doping. 148]. pH etc. Fe(III) has been selectively removed over Cu(II) due to reduction potential difference [151]. . When the ethyl lactate and phenol contaminated waste-water contains copper ions. Under aerobic conditions. Photoreduction has been shown only in the presence of methanol. EDTA is found to be the best for Cu(II) reduction whereas formic acid is the best for Se(IV) reduction. heterogeneous photocatalysis is able to remove both copper and organic compounds simultaneously [149]. SEM images in Fig-10 show the catalyst before reaction. Amal et al. However. Electron mediation from TiO2 to selenium via silver greatly enhances the electron density in the selenium particles leading to the formation of H2Se by reduction of Se(0). Among a range of organic additives. after 15min and 35min reactions. This clearly indicates that deposition of the metal gradually increases with the reaction time and ultimately completely covers the catalyst surface thus deactivating the catalyst. ethanol and formic acid. [153] have observed a significant enhancement in photoreduction of copper in presence of alanine over TiO2 nanoparticles. A comparative study is reported using both the hole scavengers varying reaction time. However under UV light.

Fig.403 V. Cadmium is used in electroplating.126 V). (b) after 15minutes and (c) after 45minutes of reaction.5 Solution pH 3. with a relatively negative E0 value (E0(Pb2+/Pb0) = 0.5 2.5 1. Surface modification of TiO2 particles with adsorbents has been used for improving the efficiency of the reduction process [158. Tanaka et al. 3. In a solution containing nitrobenzene and Pb(NO3)2 at pH 6. Linkage of alanine and histidine to TiO2 has possibly shifted the conduction band cathodically so as to make electron transfer possible.5 Cu(II) Se(IV) Total Fig. Similar results have also been observed by Skubal et al. In a recent study the surface modified TiO2 with histidine and alanine has shown complete photoreduction of cadmium into its metallic form [162]. batteries and as a neutron absorber in nuclear reactors. 9: Effect of pH on the photoreduction activity.Materials Science Forum Vol. insecticides. hence the thermodynamic driving force for the photocatalytic reduction is small. 10: SEM image of the catalyst (a) before reaction. [163] when TiO2 was modified with thiolactic acid. 734 199 80 Photoreduction (mol%) 70 60 50 40 30 20 10 0 0.2 Lead and cadmium Photoreduction of Pb(II). . ethanol and citric acid used. Cadmium reduction is only feasible in presence of selective hole scavengers. It is highly toxic and can enter the human body through food.2.5 4. the presence of formate ions enhances both adsorption and photoreduction of cadmium [160]. alloys. 159]. the degradation of the organic pollutant and PbO2 deposition has taken place simultaneously [156]. The reductive process is enhanced on pure TiO2 in presence of strong hole scavenger such as 2-propanol [157]. Photoreduction of cadmium to its metallic form is possible in presence of formate whereas there is no reduction with methanol [161]. In particular. [155] have found efficient reduction of Pb(II) under the illumination of Pt–TiO2 suspensions. The redox potential of cadmium is -0. They have identified PbO2 as the product on use of Pt-TiO2 photocatalyst while PbO is formed on use of pure TiO2. is very difficult using TiO2 photocatalyst. Further study shows that formic acid and 2propanol exhibit highest effects on lead reduction among other hole scavengers such as methanol. paints.

2. Spherical binary oxide photocatalysts showed high surface area and catalytic activity towards lead reduction even after calcinations above 700 °C as shown in Fig-11. Mercury is toxic at concentrations higher than 0. Pt-TiO2. addition of hole scavenger increases the activity many folds and complete removal of Pb2+ and Cd2+ was possible in 60 minutes of reaction using synthesized catalysts. Fe(III) [168] etc. Chen et al. Among all the organic hole scavengers used.3 Mercury and chromium Mercury is regarded as serious pollutant. 3. inhibits the photocatalytic reduction of Hg(II) due to their more positive reduction potential and better adsorption behaviour on catalyst surface while the presence of hole scavengers increases the Hg(II) photoreduction. both in laboratory scale and large scale. 166]. as it can not be degraded either biologically or chemically.005 mg/l and included in the list of priority pollutants [164]. thiolactic acid adsorbed TiO2 has detrimental effect on photoreduction of Hg(II) [170]. sodium formate is found to be the most active one. On the other hand. CdS and WO3 has been widely studied. It has been seen that initial formation of elemental mercury by the photoreduction process increases the activity of TiO2 and thereafter decreases with time [165. for technological . In the mixed metal solution comparatively lead is reduced at a faster rate than that of cadmium which is correlated to the reduction potential of the corresponding metal ion. 45]. [168] has shown that the presence of EDTA enhances the photoreduction of Hg(II) more than the 4-nitrophenol. methanol and salicylic acid. The photocatalytic reduction of toxic Cr(VI) species with semiconductors such as TiO2. Thus the above study indicates that the presence of certain oxides like silica and zirconia in low quantity with titania can facilitates the photocatalytic process selectively in UV as well as visible light. ZnO.200 Photocatalytic Materials & Surfaces for Environmental Cleanup-II It is reported that mixing of 10wt% silica with titania not only increases the surface area of the material but also increases the photocatalytic activity in UV light [44. In particular mixing of zirconia with titania proved to be beneficial for visible light reaction. High affinity of sulphur for mercury and probable formation of HgS are the main reasons for this inhibition. Arginine modification of TiO2 enhances the adsorption of Hg(II). 100 Photoreduction of lead (mol%) 80 60 40 20 0 Ti TiSi-10 TiSi-20 TiZr-10 TiZr-20 Photocatalysts 500C 700C 900C Fig. Presence of other metal ions such as Cr(VI) [167]. Interestingly quite high metal removal (89 %) is also observed in presence of visible light within 60minutes of reaction. facilitate charge transfer and also prevent charge recombination [169].11: Effect of calcinations temperature on photocatalytic removal of lead after 60 min of reaction in visible light. However.

succinic acid and citric acid increases the reduction rates. complete As(V) removal in the presence of methanol under N2 at pH ~ 3 indicates the participation of an indirect reductive mechanism [176]. For example. SnO2 and SrTiO3 substrates under inert atmosphere which can be recovered quantitatively from the catalyst. the optimum pH for the adsorption of Cr(VI) has been found to be in the range 3-6. 100 100 80 60 40 20 0 0 10 20 30 40 50 60 NO2NH4+ N2 60 40 20 0 Reaction Time (min) Fig. Process involves photocatalytic oxidation of As(III) to As(V) in a fast step followed by a slow adsorption of arsenate. In the presence of EDTA and other reducing agents. In another study [173]. low molecular weight acids. In fact the reduction of Cr(VI) is dependent on the type of organic compound added. environmental friendly mixture of TiO2 and slag-iron oxide for As(III) removal.12: Correlation of nitrate photoreduction and product selectivity with reaction time over WN co-doped TiO2 photocatalyst Nitrate (NO3-) a major component of fertilizers is toxic to human as per WHO recommendation with a maximum allowed concentration of 10 mg/l in drinking water. indicating that oxygen did not affect the rate of deposition. 172]. 3. 183] show the deposition of Pt from its aqueous acetate solution over TiO2. while easily oxidizable organics such as EDTA. 734 201 applications. the Cr(VI) reduction is relatively more than that occurs in neutral or basic pH [171. In acidic pH. Zhang et al. WO3. However. Au clusters (d < 3. Air and argon purging yielded the same results. some essential aspects of the photodeposition process are yet to be well understood. Other reports by the same group [182. However. However. Though photocatalysis under visible or solar light is a green process but limited studies were carried out on the photocatalytic nitrate reduction [187-189]. [178] has reported the rapid photochemical deposition of Au(III) from its aqueous chloride solution in the presence of TiO2 (UV light) or WO3 (visible light) at pH ~ 3.Materials Science Forum Vol. 175].0 nm) can be formed rapidly on TiO2 by using physisorbed H2O as a reductant [180]. Addition of H2PtCl6 to degassed aqueous suspensions of TiO2 results in irreversible Pt0 deposition on the particles with no reoxidation of the metal [181]. Borgarello et al. Synthesis of gold having different morphology on TiO2 surface by photoreduction method is of immense potential in modulating the catalytic processes [179].2. 186]. It is not possible to reduce Cr(VI) to Cr(0) but can be converted to less toxic Cr(III) through photocatalytic process. Metal doped titania is found to reduce nitrate selectively NO3 conversion (%) Selectivity (%) 80 . [177] has described a low-cost. noble metal loading is reported to increase the nitrate reduction [184]. Cr(VI) reduction is greatly accelerated [174. Role of reductants such as humic acid and oxalic acid on nitrate reduction have been found encouraging for further research [185.4 Other inorganic ions As(V) or As(III) transformation by a direct reductive pathway is not thermodynamically possible.1. Photocatalytic reduction of nitrate on bare TiO2 has been reported to be negligible. alcohols and aldehydes do not cause any effect on reduction of Cr(VI).

The change in the product selectivity with reaction time and surface area is presented in the Fig. porosity and photocatalytic activity. surface hydroxyl group and mesoporosity. High nitrate reduction with formic acid is attributed to the formation of CO2•– species having high reduction potential. Recently Mishra et al reported selective nitrate reduction under visible light over WN codoped titania photocatalyst [27]. Particulary through doping of another metal oxide brookite or anatase phase can be stabilized. Formation of copper selenide instead of pure copper and selenium metal during simultaneous reduction of copper and selenium indicates the possibility of depositing different alloys on oxide surface through photocatalytic reduction of multicomponent systems.6%.12. Amount of hole scavenger also controls the reaction efficiency and product selectivity. presence of oxygen vacancy and substantial N-doping. This can be looked into seriously keeping the energy level of different oxides so as to develop more efficient photocatalyst for specific reactions. Rapid development of material science and technique in the past few years has resulted in the creation of various advanced photocatalytic materials. Conclusion and future prospect This review concludes that mixing of another oxide with titania can improve the phase stabilisation. This confirms that nitrate reduction to nitrogen gas proceed via nitrite formation. In addition these mixed oxides can be efficiently used in the development of Z scheme photocatalyst which is of present importance. formic acid is found to be the best one with 94. As such. It is observed that chloride ion can not be used as a hole scavenger but in combination with the formic acid. Mostly silver doped titania is reported to be the better catalyst for nitrate reduction. Few researchers emphasized that the synergistic N/F codoping is better than the pure N doped binary oxides. However. it can enhance the rate of the reduction process. Enhanced photocatalytic reduction activity of nitrogen doped titania based mixed oxides under visible light can be attributed to the synergistic effect of high surface area. .202 Photocatalytic Materials & Surfaces for Environmental Cleanup-II and efficiently under UV light [188]. Overall the increased nitrate removal with high nitrogen gas selectivity over WN co-doped titania can be attributed to the synergistic effect of tungsten and nitrogen co-doping. Among the studied hole scavengers. the enhanced visible light photocatalysis of the synthesized materials may generate significant interest for waste-water treatment under visible/solar light. Zinc doped WO3 is reported as a potential photocatalyst under visible light [190]. Further study is warrant to see the comparative effect of anatase and brookite phase on different the photocatalytic reactions. Acknowledgement Authors acknowledge the encouragements of IPSG members and Director of CSIR-NML throughout the work. tungsten oxide and zirconia mixed titania than titania alone justifies the need to study the effect of other oxides on titania. Interesting properties may be explored by combining these novel mixed oxide photocatalysts with graphene or graphene oxide sheets.6 % nitrogen gas selectivity. Ammonia selectivity nearly remains constant throughout the reaction. This could open up an interesting way for material development. One of the authors NA acknowledges the CSIR for providing SRF fellowship to carry out the Ph. Overall the improvement of photocatalytic activity of silica. So it is important to study further the beneficial effect of binary oxides for future development of solar photocatalyst. D work. Initial few minutes of reaction shows the high nitrite selectivity and low N2 selectivity. 4. Again in all the cases it is well observed that nonmetal doped binary oxides are better photocatalyst than that of doped titania. Among all the materials N doped 2% W containing titania shows the highest surface area and nitrate photoconversion. after 20 min of reaction nitrogen selectivity approaches 90 % and thereafter slowly increases to 94. In future these techniques can be utilized to produce more size and shape controlled composite photocatalytic materials. ceria.

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