L. Gomathi Devi

Review on Modified TiO2 Photocatalysis under UV/Visible Light: Selected Results and Related Mechanisms on Interfacial Charge Carrier Transfer Dynamics

Titania is one of the most widely used benchmark standard photocatalysts in the field of environmental applications. However, the large band gap of titania and massive recombination of photogenerated charge carriers limit its overall photocatalytic efficiency. The former can be overcome by modifying the electronic band structure of titania including various strategies like coupling with a narrow band gap semiconductor, metal ion/nonmetal ion doping, codoping with two or more foreign ions, surface sensitization by organic dyes or metal complexes, and noble metal deposition. The latter can be corrected by changing the surface properties of titania by fluorination or sulfation or by the addition of suitable electron acceptors besides molecular oxygen in the reaction medium. This review encompasses several advancements made in these aspects, and also some of the new physical insights related to the charge transfer events like charge carrier generation, trapping, detrapping, and their transfer to surface are discussed for each strategy of the modified titania to support the conclusions derived. The synergistic effects in the mixed polymorphs of titania and also the theories proposed for their enhanced activity are reported. A recent venture on the synthesis and applications of anatase titania with a large percentage of reactive {001} facets and their band gap extension to the visible region via nonmetal ion doping which is a current hot topic is briefly outlined.

Photo degradation of Methyl Orange an azo dye by Advanced Fenton Process using zero valent metallic iron: influence of various reaction parameters and its degradation mechanism.

Advanced Fenton process (AFP) using zero valent metallic iron (ZVMI) is studied as a potential technique to degrade the azo dye in the aqueous medium. The influence of various reaction parameters like effect of iron dosage, concentration of H(2)O(2)/ammonium per sulfate (APS), initial dye concentration, effect of pH and the influence of radical scavenger are studied and optimum conditions are reported. The degradation rate decreased at higher iron dosages and also at higher oxidant concentrations due to the surface precipitation which deactivates the iron surface. The rate constant for the processes Fe(0)/UV and Fe(0)/APS/UV is twice compared to their respective Fe(0)/dark and Fe(0)/APS/dark processes. The rate constant for Fe(0)/H(2)O(2)/UV process is four times higher than Fe(0)/H(2)O(2)/dark process. The increase in the efficiency of Fe(0)/UV process is attributed to the cleavage of stable iron complexes which produces Fe(2+) ions that participates in cyclic Fenton mechanism for the generation of hydroxyl radicals. The increase in the efficiency of Fe(0)/APS/UV or H(2)O(2) compared to dark process is due to continuous generation of hydroxyl radicals and also due to the frequent photo reduction of Fe(3+) ions to Fe(2+) ions. Though H(2)O(2) is a better oxidant than APS in all respects, but it is more susceptible to deactivation by hydroxyl radical scavengers. The decrease in the rate constant in the presence of hydroxyl radical scavenger is more for H(2)O(2) than APS. Iron powder retains its recycling efficiency better in the presence of H(2)O(2) than APS. The decrease in the degradation rate in the presence of APS as an oxidant is due to the fact that generation of free radicals on iron surface is slower compared to H(2)O(2). Also, the excess acidity provided by APS retards the degradation rate as excess H(+) ions acts as hydroxyl radical scavenger. The degradation of Methyl Orange (MO) using Fe(0) is an acid driven process shows higher efficiency at pH 3. The efficiency of various processes for the de colorization of MO dye is of the following order: Fe(0)/H(2)O(2)/UV>Fe(0)/H(2)O(2)/dark>Fe(0)/APS/UV>Fe(0)/UV>Fe(0)/APS/dark>H(2)O(2)/UV approximately Fe(0)/dark>APS/UV. Dye resisted to degradation in the presence of oxidizing agent in dark. The degradation process was followed by UV-vis and GC-MS spectroscopic techniques. Based on the intermediates obtained probable degradation mechanism has been proposed. The result suggests that complete degradation of the dye was achieved in the presence of oxidizing agent when the system was amended with iron powder under UV light illumination. The concentration of Fe(2+) ions leached at the end of the optimized degradation experiment is found to be 2.78 x 10(-3)M. With optimization, the degradation using Fe(0) can be effective way to treat azo dyes in aqueous solution.

Characterization of Mo Doped TiO2 and its Enhanced Photo Catalytic Activity Under Visible Light

Transition metal doping into the TiO2 lattice can expand the response of these metal oxide nano particles to the visible region. In view of this, Mo6+ ion is doped into the TiO2 lattice in order to understand the mechanism of its photo response. The prepared photocatalysts were characterized by X-ray diffraction, UV–Visible absorption spectroscopy, UV–Visible diffuse reflectance spectroscopy, SEM, EDX, FTIR and BET specific surface area techniques. The characterization results have confirmed the incorporation of metal ions into TiO2 lattice. XRD analysis shows no change in crystal structure except a slight variation in crystallite size and elongation along the c-axis with increase in the concentration of the dopant. Diffuse reflectance measurements showed a shift in the band edge position to longer wavelengths and an extension of the absorption to the visible region. The photo degradation efficiencies of these catalysts were studied with Tebuconazole pesticide as model pollutant. Under UV light, undoped catalyst showed higher activity than doped catalyst. But in the case of visible light irradiation Mo doped TiO2 with intermediate dopant concentration of 0.06 atom % had the highest photocatalytic reactivity. This may be due to the narrowing of band gap so that it could effectively absorb the light of longer wavelength. The degradation path way was followed by UV–Visible spectroscopy.

Review on modified N–TiO2 for green energy applications under UV/visible light: selected results and reaction mechanisms

Titanium dioxide photocatalyst has witnessed considerable interest for use in water and air cleanup owing to its fascinating properties like non-toxicity, ease of preparation, favorable band edge positions, water insolubility, multifaceted electronic properties, surface acid–base properties, and super hydrophilicity. Although it possesses much functionality, large bandgap and massive charge carrier recombination limits its wide utility under natural solar light. These drawbacks were overcome through nitrogen doping in titania matrix (N–TiO2), which alters the surface-bulk structure for visible light absorption with high quantum efficiency. In this review, we highlight the recent progress of N–TiO2 towards pollutant degradation, hydrogen evolution and its use in organic synthesis under ambient conditions. The preparation of N–TiO2 via different methods (physical and chemical methods) with diverse morphologies, nature of chemical dopants, induced defects and fundamental reaction parameters governing efficient photoinduced reactions are explored in this review. Further improvements in the photoefficiency of N–TiO2 were achieved through co-doping with foreign ions, heterostructuring with other semiconductors, metal deposition and the tuning of N–TiO2 with reactive exposed facets. The resultant improvement from each of the modification is discussed in the light of charge carrier generation–separation–transfer–recombination dynamics together with pollutant adsorption and their reactions with reactive oxygenated species in the liquid or gaseous regime. This review attempts to give an overview of the research highlights concerned with N–TiO2. Although it is impossible to cover all of the research articles in the literature, several milestones in the pathway towards highly applicable N–TiO2 are explored. It is hoped that this review article will trigger further research in synthesizing N–TiO2 with multifunctional features to enhance its capacity for green energy applications.

Heterogeneous photo catalytic degradation of anionic and cationic dyes over TiO2 and TiO2 doped with MO6+ ions under solar light: Correlation of dye structure and its adsorptive tendency on the degradation rate

Degradation of synthetic dyes like Methyl Orange (MO), p-amino azo benzene (PAAB), Congo Red (CR), Brilliant Yellow (BY), Rhodamine-B (RB) and Methylene Blue (MB) under solar light were carried out using TiO(2) doped with Mo(6+) ions. The rate constant for the degradation of anionic dyes MO, PAAB, CR and BY was high at pH 5.6, while for cationic dyes the highest rate constant was obtained in the alkaline pH 8.0. These differences can be accounted to their adsorption capacity on the catalyst surface at different pH conditions. Among the photocatalyst used, Mo(6+) (0.06%)-TiO(2) showed enhanced activity due to the effective separation of charge carriers.

Preparation, characterization and enhanced photocatalytic activity of Ni2+ doped titania under solar light.

Anatase TiO2 was prepared by sol-gel method through the hydrolysis of TiCl4. Ni2+ was doped into the TiO2 matrix in the concentration range of 0.02 to 0.1 at.% and characterized by various analytical techniques. Powder X-ray diffraction revealed only anatase phase for all the samples, while diffuse reflectance spectral studies indicated a red shift in the band gap absorption to the visible region. The photocatalytic activities of these photocatalysts were probed for the degradation of methyl orange under natural solar light. The photocatalyst with optimum doping of 0.08 at.% Ni2+, showed enhanced activity, which is attributed to: (i) effective separation of charge carriers and (ii) large red shift in the band gap to visible region. The influence of crystallite size and dopant concentration on the charge carrier trapping — recombination dynamics is investigated.

TiO2/BaTiO3-assisted photocatalytic mineralization of diclofop-methyl on UV-light irradiation in the presence of oxidizing agents

Gas chromatograph-mass spectroscopic identification of intermediate products in the degradation of diclofop-methyl and the kinetics of the reaction has been investigated. Formation of 4-[(2,4-dichlorophenoxy) phenoxy] ethane and (2,4-dichlorophenoxy) phenol was investigated. The other intermediate products are 2,4-dichlorophenol, 2,4-dichlorobenzene, phenol and acetic acid have been ascertained. The decrease in the concentration of the parent/intermediate compounds is followed by UV-vis spectral study and the supportive information on the functional groups in the intermediates has been obtained from IR-spectroscopy. Degradation process proceeds with oxidation-reduction reaction by the attack of OH*, H*, O(2)*(-) free radicals, which are photogenerated on the UV-light illuminated TiO(2)/BaTiO(3) photocatalysts particles in aqueous medium. In this presentation another wide band gap semiconductor BaTiO(3) is shown to have comparable photocatalytic efficiency. The oxidizing agents are added to accelerate the rate of the reaction by enhancing the formation of free radicals. Based on the intermediates formed in the process of degradation, a suitable mechanism has been proposed.

Strategies developed on the modification of titania for visible light response with enhanced interfacial charge transfer process: an overview

The modification of titania by metal / non metal ion doping, coupling with narrow band gap sensitizer, surface flourination, metal deposition, and together with recent ventures on application of {001} facets of anatase titania for visible light response with enhanced charge carrier separation are briefly overviewed.

Photo-Fenton and photo-Fenton-like processes for the degradation of methyl orange in aqueous medium: Influence of oxidation states of iron

Degradation of methyl orange (MO) was carried out by the photo-Fenton process (Fe2+/H2O2/UV) and photo-Fenton-like processes (Fe3+/H2O2/UV, Fe2+/S2O82−/UV, and Fe3+/S2O82−/UV) at the acidic pH of 3 using hydrogen peroxide and ammonium persulfate (APS) as oxidants. Oxidation state of iron had a significant influence on the efficiency of photo-Fenton/photo-Fenton-like processes. It was found that a process with a source of Fe3+ ions as the catalyst showed higher efficiency compared to a process with the Fe2+ ion as the catalyst. H2O2 served as a better oxidant for both oxidation states of iron compared to APS. The lower efficiency of APS is attributed to the generation of excess protons which scavenges the hydroxyl radicals necessary for degradation. Further, the sulfate ions produced from S2O82− form a complex with Fe2+/Fe3+ ions thereby reducing the concentration of free iron ions in the solution. This process can also reduce the concentration of hydroxyl radicals in the solution. Efficiency of the various MO degradation processes follows the order: Fe3+/H2O2/UV, Fe3+/APS/UV, Fe2+/H2O2/UV, Fe2+/APS/UV.

Structural characterization of Th-doped TiO2 photocatalyst and its extension of response to solar light for photocatalytic oxidation of oryzalin pesticide: a comparative study.

The degradation efficiency of Th-doped TiO2 / TiO2 photocatalysts were investigated under UV and solar light illumination. The model compound chosen for the study was Oryzalin (OZ). Doping of inner transition metal ion Th was intended to modify the electronic properties of TiO2. The Th-doped TiO2 were synthesized by incorporating 0.02, 0.04, 0.06, and 0.1 atom percentage of Th into the TiO2 lattice by solid-state reaction. The stochiometry of the prepared samples is Ti1−xThxO2, where ‘x’ is the percentage of Th. The samples were characterized by UV-Visible absorption, UV-Visible -Diffused reflectance spectra, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX) and X-ray Diffraction (XRD). The pore size and surface area of these samples were studied by Brunauer, Emmett and Teller (BET) adsorption method. It was found that metal ion doping at various percentage compositions enables a large shift in the absorption band of the TiO2 towards visible light region. This is due to the formation of various mid band gaps at 2.84 eV, 2.804 eV, 2.66 eV, and 2.55 eV. The extent of degradation of the pesticide was followed by UV-Visible spectroscopy and GC-MS methods. Based on the spectral analysis, the probable degradation reaction mechanism for OZ is proposed. These results indicate that Th-doped TiO2 with the modified electronic properties is a good catalyst under solar light irradiation. But these particles show marginal variation in rates under UV-illumination. All the photodegradation reactions follow the first order kinetics.