Photoelectrocatalytic degradation of oxalic acid using WO3 and stratified WO3/TiO2 photocatalysts under sunlight illumination.

The WO3 and stratified WO3/TiO2 thin films are successfully prepared by the spray pyrolysis method. The structural, morphological, compositional and photoelectrocatalytic properties of WO3 and stratified WO3/TiO2 thin films are studied. XRD analysis confirms that films are polycrystalline with monoclinic and tetragonal crystal structures for WO3 and TiO2 respectively. The SEM images clearly show 3D sheeted porous structure of the as-prepared TiO2 forms on WO3 in stratified WO3/TiO2 samples. The synthesized photoelectrodes was used as catalyst for photoelectrocatalytic degradation of oxalic acid in aqueous medium. The rate constant (k) was evaluated as a function of the initial concentration of species. A significant decrease in concentrations of organic species was observed from COD analysis. The photoelectrocatalytic degradation effect is relatively higher in the case of the stratified WO3/TiO2 than WO3 thin film photoelectrode in the degradation of oxalic acid and 83% removal efficiency of oxalic acid is obtained after 180min. Based on the obtained experimental data, the possible photoelectrocatalytic reaction mechanism was proposed. The photoelectrocatalytic experimental results indicate that stratified WO3/TiO2 photoelectrode is the promising material for removing of water pollutants.

Photoelectrocatalytic degradation of benzoic acid using Au doped TiO2 thin films.

Highly transparent pure and Au doped TiO2 thin films are successfully deposited by using simple chemical spray pyrolysis technique. The effect of Au doping onto the structural and physicochemical properties has been investigated. The PEC study shows that, both short circuit current (Isc) and open circuit voltage (Voc) are (Isc=1.81mA and Voc=890mV) relatively higher at 3at.% Au doping percentage. XRD study shows that the films are nanocrystalline in nature with tetragonal crystal structure. FESEM images show that the film surface covered with a smooth, uniform, compact and rice shaped nanoparticles. The Au doped thin films exhibit indirect band gap, decreases from 3.23 to 3.09eV with increase in Au doping. The chemical composition and valence states of pure and Au doped TiO2 films are studied by using X-ray photoelectron spectroscopy. The photocatalytic degradation effect is 49% higher in case 3at.% Au doped TiO2 than the pure TiO2 thin film photoelectrodes in the degradation of benzoic acid. It is revealed that Au doped TiO2 can be reused for five cycles of experiments without a requirement of post-treatment while the degradation efficiency was retained.

Fabrication of ZnFe2O4 films and its application in photoelectrocatalytic degradation of salicylic acid.

ZnFe2O4 thin films are successfully deposited onto bare and fluorine doped tin oxide (FTO) coated quartz substrate using the spray pyrolysis method. The structure and morphology of ZnFe2O4 photoelectrodes were studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). The X-ray diffraction pattern confirms the polycrystalline nature of films with a spinel cubic crystal structure. The AFM micrographs shows the granular nature of the films. The dielectric constant and dielectric loss shows dispersion behavior as a function of frequency measured in the range from 20Hz to 1MHz. Photoelectrocatalysis degradation of salicylic acid using ZnFe2O4 photoelectrode under sunlight illumination has been investigated. The result shows that the degradation percentage of salicylic acid on ZnFe2O4 photoelectrodes is reached 49% under neutral conditions after 320min illumination. The decrease in values of COD from 19.4mg/L to 6.4mg/L indicates there is mineralization of salicylic acid with time.

Enhanced photocatalytic activity of sprayed Au doped ferric oxide thin films for salicylic acid degradation in aqueous medium.

Various doping percentage of Au were successfully introduced into the Fe2O3 photocatalysts via a spray pyrolysis method different. The effect of Au doping on photoelectrochemical, structural, optical and morphological properties of these deposited thin films is studied. The PEC characterization shows that, the photocurrent increases gradually with increasing Au content initially up to 2at.% indicating the maximum values of short circuit current (Isc) and open circuit voltage (Voc) are (Isc=90µA and Voc=220.5mV) and then decreases after exceeding the optimal Au doping content. Therefore, the photocurrent of Au doped Fe2O3 photocatalysts can be adjusted by the Au content. Deposited films are polycrystalline with a rhombohedral crystal structure having (104) preferred orientation. SEM and AFM images show deposited thin films are compact and uniform. The photocatalytic activities of the Fe2O3 and Au:Fe2O3 photocatalyst were evaluated by photoelectrocatalytic degradation of salicylic acid under sunlight irradiation. The results show that the Au:Fe2O3 thin film photocatalyst exhibited about 45% more degradation of pollutants than the pure Fe2O3. Thus, in Au doped Fe2O3 photocatalysts, the interaction between Au and Fe2O3 reduces the recombination of photogenerated charge carriers and improve the photocatalytic activity.

Photodegradation of organic pollutants using N-titanium oxide catalyst.

Photoelectrocatalytic degradation of typical aromatic compounds with persistent reaction rate is studied using thin layers of N-titanium dioxide deposited on transparent and conducting glass substrates. Backside illuminated flow-through parallel plate photoelectrochemical reactors is used and electrical bias for suppressing charge carrier recombination is applied externally. The degradation experiments are performed under solar irradiation with the conditions aimed at reducing contaminant concentrations to maximal tolerated levels as specified under environmental regulations. From the observed COD-time relations, rate constants normalized to unit volume and photocurrent (kinetic parameters), characterizing the efficiency of the electrochemical oxidation process involving photogenerated valence band holes or their immediate reaction products, are calculated and compared to the decrease of optical extinction of the solutions. The parameters for salicylic acid, 4-chlorophenol, benzoic acid and oxalic acid are found to decrease as the main absorption peaks of these substances diminish in due course of degradation reaction. In order to realize a complete mineralization of such compounds, which should be an ultimate aim of water purification, COD and TOC is analyzed.

Remediation of wastewater: role of hydroxyl radicals.

The photocatalytic oxidation of wastewater with TiO2 and coupling effect of different advanced oxidation processes onto the oxidation of wastewater has been studied. A basic mechanism involved during oxidation has been reported. The role of hydroxyl radical in the breakdown of the wastewater is elucidated through determining the degradation rates, kinetics, analyzing transformation intermediates and studies using computational chemistry methods. In order to realize a complete mineralization of wastewater COD, BOD and TOC analysis has been carried out.

Oxidative degradation of industrial wastewater using spray deposited TiO2/Au:Fe2O3 bilayered thin films.

The Fe2O3, Au:Fe2O3, TiO2/Fe2O3 and TiO2/Au:Fe2O3 thin films are successfully prepared by the spray pyrolysis technique at an optimised substrate temperature of 400 °C and 470 °C, respectively onto amorphous and F:SnO2 coated glass substrates. The effect of TiO2 layer onto photoelectrochemical (PEC), structural, optical and morphological properties of Fe2O3, Au:Fe2O3, TiO2/Fe2O3 and TiO2/Au:Fe2O3 thin films is studied. The PEC characterization shows that, maximum values of short circuit current (Isc) and open circuit voltage (Voc) are (Isc = 185 µA and Voc = 450 mV) are at 38 nm thickness of TiO2. Deposited films are polycrystalline with a rhombohedral and anatase crystal structure having (104) preferred orientation. SEM and AFM images show deposited thin films are compact and uniform with seed like grains. The photocatalytic activities of the large surface area (64 cm(2)) TiO2/Au:Fe2O3 thin film photocatalysts were evaluated by photoelectrocatalytic degradation of industrial wastewater under sunlight light irradiation. The results show that the TiO2/Au:Fe2O3 thin film photocatalyst exhibited about 87% and 94% degradation of pollutant in sugarcane and textile industrial wastewater, respectively. The significant reduction in COD and BOD values from 95 mg/L to 13 mg/L and 75 mg/L to 11 mg/L, respectively was also observed.

Visible light catalysis of rhodamine B using nanostructured Fe(2)O(3), TiO(2) and TiO(2)/Fe(2)O(3) thin films.

The Fe(2)O(3), TiO(2) and TiO(2)/Fe(2)O(3) composite films are deposited using spray pyrolysis method onto glass and FTO coated substrates. The structural, morphological, optical and photocatalytic properties of Fe(2)O(3), TiO(2) and TiO(2)/Fe(2)O(3) thin films are studied. XRD analysis confirms that films are polycrystalline with rhombohedral and tetragonal crystal structures for Fe2O3 and TiO(2) respectively. The photocatalytic activity was tested for the degradation of Rhrodamine B (Rh B) in aqueous medium. The rate constant (-k) was evaluated as a function of the initial concentration of species. Substantial reduction in concentrations of organic species was observed from COD and TOC analysis. Photocatalytic degradation effect is relatively higher in case of the TiO(2)/Fe(2)O(3) than TiO(2) and Fe(2)O(3) thin film photoelectrodes in the degradation of Rh B and 98% removal efficiency of Rh B is obtained after 20min. The photocatalytic experimental results indicate that TiO(2)/α-Fe(2)O(3) photoelectrode is promising material for removing of water pollutants.

Photoelectrochemical properties of highly mobilized Li-doped ZnO thin films.

Li-doped ZnO thin films with preferred (002) orientation have been prepared by spray pyrolysis technique in aqueous medium on to the corning glass substrates. The effect of Li-doping on to the photoelectrochemical, structural, morphological, optical, luminescence, electrical and thermal properties has been investigated. XRD and Raman study indicates that the films have hexagonal crystal structure. The transmittance, reflectance, refractive index, extinction coefficient and bandgap have been analyzed by optical study. PL spectra consist of a near band edge and visible emission due to the electronic defects, which are related to deep level emissions, such as oxide antisite (OZn), interstitial zinc (Zni), interstitial oxygen (Oi) and zinc vacancy (VZn). The Li-doped ZnO films prepared for 1at% doping possesses the highest electron mobility of 102cm(2)/Vs and carrier concentration of 3.62×10(19)cm(-3). Finally, degradation of 2,4,6-Trinitrotoluene using Li-doped ZnO thin films has been reported.

Oxidative degradation of acid orange 7 using Ag-doped zinc oxide thin films.

Ag-doped ZnO thin films with preferred c-axis orientation along (002) have been prepared by spray pyrolysis technique in aqueous medium on to the corning glass substrates. The effect of Ag-doping on to the photoelectrochemical, structural, morphological, optical, luminescence, electrical and thermal properties has been investigated. XRD and Raman study indicates that the films have hexagonal (wurtzite) crystal structure. The effect of Ag loading on the photocatalytic activity of Ag-doped ZnO in the degradation of azo dye is studied and results are compared with pure ZnO. The results show that the rate of degradation of azo dye over Ag-doped ZnO is much higher as compared to pure ZnO. Ag doping in ZnO is highly effective and can significantly enhance the photocatalytic degradation and mineralization of azo dye. The enhancement of photocatalytic activity of Ag-doped ZnO thin films is mainly due to their smaller crystallite size and capability for reducing the electron-hole pair recombination. Kinetic parameters have been investigated in terms of a first order rate equation. The rate constant (-k) for this heterogeneous photocatalysis is evaluated as a function of the initial concentration of original species. Substantial reduction in azo dye is achieved as analyzed from COD and TOC studies.

Size dependent electron-phonon coupling in N, Li, In, Ga, F and Ag doped ZnO thin films.

Polarized micro-Raman measurements are performed to study the phonon modes of N, Li, In, Ga, F and Ag doped ZnO thin films, grown by spray pyrolysis on corning glass substrates. The E(2)(high) mode displays a visible asymmetric line shape. The size and dopant dependence onto coupling strength between electron and LO phonon is experimentally estimated.

Hydroxyl radical's role in the remediation of wastewater.

The photocatalytic degradation of wastewater with ZnO based photocatalysts under solar illumination has been investigated. Advanced oxidation processes such as photoelectrocatalysis, sonolysis and H(2)O(2) treatment show promise in eliminating the dangers of exposure to wastewater and the products of their natural breakdown. A basic understanding of the mechanistic details involved in the oxidative transformations remains the key for improving the effectiveness of the advanced oxidation processes. The role of hydroxyl radical in the breakdown of the wastewater is elucidated through determining the degradation rates, analyzing transformation intermediates and studies using computational chemistry methods. In order to realize a complete mineralization of wastewater COD, BOD and TOC analysis has been carried out.

Photocatalytic degradation of toluene using sprayed N-doped ZnO thin films in aqueous suspension.

Thin films of N-doped ZnO are synthesized via spray pyrolysis technique in aqueous medium using zinc acetate and ammonium acetate as precursors. Influence of N doping onto photochemical, structural, morphological, optical and thermal properties have been investigated. Structural analysis depicts hexagonal (wurtzite) crystal structure. The effect of N doping on the photocatalytic activity of N-doped ZnO in the degradation of toluene is studied and results are compared with pure ZnO. The results show that the rate of degradation of toluene over N-doped ZnO is higher as compared to that of pure ZnO and increases with increasing N doping up to 10 at.% and then decreases. The enhancement of photocatalytic activity of N-doped ZnO thin films is mainly due to their capability for reducing the electron hole pair recombination. The photocatalytic mineralization of toluene in aqueous solution has been studied by measuring COD and TOC. Possible reaction mechanism pathways during toluene degradation over N-doped ZnO has been proposed.

Photoelectrocatalytic decolorization and degradation of textile effluent using ZnO thin films.

Zinc oxide (ZnO) thin films have been successfully deposited onto fluorine doped tin oxide coated glass at substrate temperature of 400 °C and used as electrode in photoelectrocatalytic reactor. The untreated textile effluent was circulated through photoelectrocatalytic reactor under UVA illumination for the decolorization and degradation. Textile effluent was decolorized by 93% within 3h at room temperature with significant reduction in COD (69%). High performance liquid chromatography (HPLC) and Fourier transform infrared spectroscopy (FTIR) analysis of samples before and after decolorization confirmed the degradation of dyes molecules from textile effluent into simpler oxidizable products. Phytotoxicity study revealed reduction in toxic nature of textile effluent after treatment.

Photo-corrosion inhibition and photoactivity enhancement with tailored zinc oxide thin films.

The nanocrystalline ZnO, TiO(2) and ZnO/TiO(2) films are deposited onto FTO-coated glass substrates by using spray pyrolysis technique. The structural, morphological, optical and photoelectrochemical properties of the ZnO, TiO(2) and ZnO/TiO(2) are investigated by X-ray diffraction, scanning electron microscopy, UV-Vis spectroscopy and photoelectrochemical techniques. XRD analysis shows that films are polycrystalline and having hexagonal and tetragonal crystal structure for pure ZnO and TiO(2). The photocatalytic degradation of methylene blue has been investigated with ZnO, TiO(2) and ZnO/TiO(2) photocatalysts. ZnO/TiO(2) thin films have proved quite effective mineralization of methylene blue, while pure ZnO and TiO(2) do not lead complete mineralization of methylene blue. The metabolites produced during degradation are analyzed by HPLC and Fourier transforms infrared spectroscopy. The by-products detected during degradation have been identified by GCMS technique.

Zinc oxide mediated heterogeneous photocatalytic degradation of organic species under solar radiation.

The photocatalytic decomposition of eco-persistent toluene, salicylic acid and 4-chlorophenol with sun light in an oxygenated aqueous suspension has been studied under nanocrystalline hexagonal ZnO photocatalyst. The effect of substrate temperature onto the structural, morphological and photoactive properties has been investigated. The degradation of toluene, salicylic acid and 4-chlorophenol were achieved using a photoelectrochemical reactor module equipped with synthesized ZnO electrodes. Kinetic parameters have been investigated in terms of a first order rate equation. The rate constant (-k) for this heterogeneous photocatalysis was evaluated as a function of the initial concentration of original species. Substantial reduction in concentrations of toluene, salicylic acid and 4-chlorophenol was achieved as analyzed from COD and TOC studies. The mechanism for the degradation of toluene, salicylic acid and 4-chlorophenol could be explained on the basis of Langmuir-Hinshelwood mechanism.

Photocatalytic activity of sea water using TiO2 catalyst under solar light.

Wastewater is generally released into the rivers and streams in developing countries. Industrial wastewater usually contains highly toxic pollutants, cyanides, chlorinated compounds. Ultraviolet (UV) radiation from sunlight also decomposes organic compounds by oxidation process. However, the process is less effective due to large amount of toxic effluent entering in the main stream of water. The solar radiation can effectively be applied to accelerate the process by using suitable catalyst for economically cleaning the water sources. This paper describes the photocatalytic degradation of the sea water using novel approach of photoelectrochemical (PEC) reactor module consisting of nine photoelectrochemical cells equipped with spray deposited TiO2 catalysts under solar light. The resulted water samples were studied for physicochemical and bacteriological analysis. The complete mineralization of degraded sample was confirmed by total organic carbon (TOC) analysis, COD measurement and estimation of the formation of inorganic ions such as NH4(+), NO3⁻, Cl⁻ and SO²â»4. Microbiological examinations are performed to determine the bacterial analysis. This implies that photoelectrocatalysis could be a promising way for improving water quality in developing countries with low cost and clean energy reliable resource.

Chemical vapor deposited carbon nanotubes for aqueous H2-Cl2 fuel cells.

Carbon nanotubes having large surface area is an interesting material to develop H2-Cl2 fuel cell electrodes. The attempts were made to deposit carbon nanotubes on porous substrates by chemical vapour deposition. Turpentine oil (C10H16) was used as a precursor, decomposed at 1100 degrees C reactor temperature. Nickel, platinum, tin, Ni-Pt, Ni-Sn, Pt-Sn, Ni-Pt-Sn catalysts were used to grow carbon nanotubes. Nickel was deposited with electrodeposition, platinum with sputter coater and tin with vacuum deposition technique. The developed electrodes were characterized by XRD, SEM, TEM, FTIR, and resistivity by van-der Pauw method. Carbon nanotubes have been formed for 0.25 N nickel deposited for 45 and 60 min; 0.5 N, 0.75 N and 1 N nickel deposited for 15 to 60 min, at the interval of 15. Ni-Pt, Ni-Sn, Pt-Sn and Ni-Pt-Sn activated carbon also shows the well grown CNTs. Aqueous H2-Cl2 fuel cell performance was tested with these grown carbon nanotubes. 40% KCl with 1067 mohm(-1) cm(-1) conductivity was used as electrolyte. Linear sweep voltametry shows reduction potential for hydrogen gas. Chronoamperometry results show better half cell performance for nickel, deposited with 1 N, 45 min deposition time period; and combination of Ni-Pt-Sn with 140, and 110-100 mA/cm2 stable current density respectively.