Search

Abstract: Co–M–B–P quaternary alloy catalyst powders (where M = Cr, Mo, W, and Cu) were synthesized by chemical reduction method to improve the catalytic performance of Co–B catalyst for hydrogen production by hydrolysis of Ammonia Borane (AB). The catalytic activity increases significantly due to the combined promoting effects induced by M and P in quaternary alloy as compared to binary Co–B catalyst. The promoting roles of each doping element in Co–B catalyst during AB hydrolysis were studied using XPS, XRD, SEM, and BET surface area analyses. Each transition element, present in the form of either oxides or metal, acts as an atomic barrier to prevent Co–B particle agglomeration to increase the effective surface area. At the same time these species also act as Lewis acid sites to improve the absorption of the reactants on to the surface. Inclusion of phosphorous, in addition, is able to create higher number of Co-active sites on the surface, which was inferred from XPS analysis. Among all the alloy catalysts, Co–Cr–B–P showed the highest H2 generation rate, which was mainly attributed to the collective effects of Cr and P in forming the catalyst surface having higher surface area and more Co-active sites. On the contrary, in the case of Cu doped Co–B catalyst, the inclusion of P considerably lowers the surface area, which decreases the catalytic activity. [Copyright &y& Elsevier]

Abstract: In order to sensitize TiO2 in visible light and to reduce photo-induced charge recombination, the multilayer films of Indium–Tin Oxide (ITO)/V-doped TiO2 were synthesized by radio-frequency magnetron sputtering. V-doped TiO2 thin films showed red shift in TiO2 absorption edge with increasing dopant concentration and, most importantly, the dopant energy levels are formed in the TiO2 band gap due to V5+/V4+ ions as confirmed by UV–Visible and XPS spectra. Multilayer films with different numbers of ITO/V-doped TiO2 (6 at.%) bilayers (namely, 2-, 3-, 4-, 5-, 6- and 7-bilayers) were deposited, in order to reduce the charge recombination rate, by keeping the total thickness of TiO2 constant in each multilayer film. In multilayer films, when exposed to visible light the photocurrent increases as function of the number of bilayers by reaching the maximum with 6-bilayers of ITO/V-doped TiO2. The measured enhanced photocurrent is attributed to: 1) ability of V-doped TiO2 to absorb visible light, 2) number of space-charge layers in form of ITO/TiO2 interfaces in multilayer films, and 3) generation of photoelectrons just in/or near to the space-charge layer by decreasing the V-doped TiO2 layer thickness. The reduced charge recombination rate in multilayer films was also confirmed by the photocurrent kinetic curves. The superior photocatalytic efficiency of the 6-bilayers film is also reflected in hydrogen production rate through water-splitting: we obtained indeed 31.2 μmol/h of H2 production rate. [Copyright &y& Elsevier]

Abstract: Cr-doped-TiO2 thin films, with three different Cr concentrations (2, 5.5, and 9 at.%), have been synthesized by radio-frequency magnetron sputtering in order to sensitize TiO2 in visible light. UV–visible spectra showed that maximum narrowing (2.1 eV) of the TiO2 band gap is obtained for the highest Cr concentration. However, negligible photocurrent was measured with Indium Tin Oxide (ITO)/Cr-doped-TiO2 (9 at.%) single bilayer sample due to the increased recombination rate of the photo-generated charges on the defects associated to the Cr3+ ions. To lower the charge recombination rate in the Cr-doped-TiO2, multilayer films with different numbers of ITO/Cr-doped-TiO2 (9 at.%) bilayers (namely, 3-, 4-, 5-, 6- and 7-bilayers) were deposited by keeping the total thickness of TiO2 constant in each multilayer film. When the multilayer films were exposed to visible light, we observed that the photocurrent increases as function of the number of bilayers by reaching the maximum with 6-bilayers of ITO/Cr-doped-TiO2. The enhanced photocurrent is attributed to: 1) higher absorption of visible light by Cr-doped-TiO2, 2) number of space charge layers in form of ITO/TiO2 interfaces in multilayer films, and 3) generation of photoelectrons just in/or near to the space charge layer by decreasing the Cr-doped-TiO2 layer thickness. The reduced charge recombination rate in multilayer films was also confirmed by studying the photocurrent kinetic curve. The superior photocatalytic efficiency of the 6-bilayers film implies higher hydrogen production rate through water-splitting: we obtained indeed 24.4 μmol/h of H2 production rate, a value about two times higher than that of pure TiO2 (12.5 μmol/h). [Copyright &y& Elsevier]

Abstract: Cr- or Fe-ion-doped TiO2 thin films have been synthesized by radio-frequency magnetron sputtering and a sol–gel method to study hydrogen generation by photocatalytic water-splitting under visible light irradiation. The doping method, dopant concentration, charge transfer from metal dopants to TiO2, and type of dopants used for modification of TiO2 were investigated for their ability to enhance photocatalytic activity. UV–Visible spectra show that the metal-doped-TiO2 obtained by sputtering is much more efficient than that obtained by the sol–gel technique at inducing a red shift of the absorption edge in the visible light range. Low concentration metal ion doping must be done near the conducting indium tin oxide (ITO) – TiO2 interface to avoid the formation of recombination centers for photo-generated electron–hole pairs. H2 production rate (μmol/h) is higher for Fe-doped TiO2 (15.5μmol/h) than for Cr-doped TiO2 (5.3μmol/h) due to the ability of Fe ions to trap both electrons and holes, thus avoiding recombination, while Cr can only trap one type of charge carrier. A constant H2 generation rate is obtained for long periods of time by all the investigated TiO2 films because of the separate evolution of H2 and O2 gases, thus eliminating the back-reaction effect. [Copyright &y& Elsevier]

Abstract: TiO2 thin films have been synthesized by radio-frequency magnetron sputtering and sol–gel method to study the hydrogen generation by photocatalytic water splitting under visible light irradiation. Photoelectrochemical cell with chemical bias, involving photo-anode in form of TiO2 film deposited on conducting indium tin oxide (ITO) film and Pt as cathode, is developed. The effect of conducting ITO layer on photo-voltage is studied by varying the thickness of ITO films. Constant H2 generation rate is obtained for long period of time by both the TiO2 films because of the separated evolution of H2 and O2 gas, thus eliminating the back-reaction effect. Sputter-deposited film as compared to sol–gel-synthesized film showed better H2 generation rate, mainly explained in terms of the higher visible light absorption achieved by oxygen vacancies created in the TiO2 film by the energetic target ions during deposition in pure Ar gas pressure. [Copyright &y& Elsevier]