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Stoichiometric and non-stoichiometric tungsten doping effect in bismuth vanadate based photoactive material for photoelectrochemical water splitting
摘要： In photoelectrochemical (PEC) water splitting, BiVO4 has attracted attention due to its favorable band gap but it suffers low PEC performance due to poor conductivity. The vast majority of publications on this system has examined doping of stoichiometric composition of tungsten (W) on this system to increase bulk and interfacial conductivity while managing the contaminant generation of crystallographic defects and recombination sites. In this paper, a deep investigation was carried out to examine the effect of non-stoichiometric W doping in BiVO4 system. Stoichiometric and non-stoichiometric W-doped monoclinic BiVO4 (i.e. Bi1-(xtd)V1-xWxtdO4; BiV1-xWxtdO4 and BiV1-yWyO4; x ? 0.008; y ? 0.03 and d ? 0.005) were prepared using a facile dip coating technique. The stoichiometric composition contains charge balanced Bi, V and W atoms whereas non-stoichiometric compositions contain excess Bi and excess Bi and W. The non-stoichiometric composition BiV1-xWxtdO4 has shown better photoelectrochemical water splitting performance with respect to other compositions at 1.23 V vs RHE, under one sun illumination of electrode. The XRD and XPS results shows that non-stoichiometric doping with excess Bi or with excess Bi and W can possibly create an environment where V5t ions are substitutional replaced by W6t ions without generating other defects. But there was no signi?cant difference in band gap of different compositional samples observed. Further electrochemical impedance technique was used to analyze change in bulk and surface charge mobility with W-doping in BiVO4. The electrochemical impedance analysis showed the presence of low interfacial resistance, lower charge transfer resistance and high charge donor/surface state density for non-stoichiometric composition BiV1-xWxtdO4 electrode. It is evident from and cyclic voltammetry that the addition of excess Bi and W from its stoichiometric quantity ef?ciently suppressed the formation of hole-electron pair recombination sites. The electrochemical analytical results lead us to believe that the particular non-stoichiometric composition of BiV1-xWxtdO4 can signi?cantly lower trap sites and enhances kinetics of charge transfer, leading to the better photoelectrochemical water splitting performance.
关键词： Oxygen evolution,Photoelectrochemical cell,Water splitting,Bismuth vanadate,Tungsten doping
更新于2025-09-23 15:23:52
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Acceleration of tungsten doping on vanadium dioxide (VO2) by alkali species
摘要： The monoclinic vanadium dioxide, VO2(M), undergoes reversible phase transition from monoclinic (semiconductor) to tetragonal (metal), which exhibits a good thermochromic property. VOSO4, as a vanadium source, is easy to handle produces VO2(M) under mild condition in the presence of alkali species. In this study, the effects of the additions of NH4HCO3, NH3·H2O, and NaOH on the VO2 crystal formation with/without tungsten doping for thermochromicity were investigated. NaOH, the strongest base of the three, provided the strongest and narrowest x-ray diffraction peak, while NH4HCO3, the weakest base, provided the opposite. Interestingly, for the tungsten doping to adjust the transition temperature, the use of NH4HCO3 was more suitable due to the possibility of a slow crystal frame formation as compared to the use of NaOH.
关键词： Sodium hydroxide,Vanadium dioxide,Ammonium hydrogen carbonate,Ammonium hydroxide,Tungsten doping
更新于2025-09-23 15:22:29