Surface modification of conductive oxide glass (F‐SnO2: FTO) anode substrates using 10 oxides was investigated for efficiently producing oxidative hydrogen peroxide (H2O2) from water with hydrogen (H2) production at a Pt cathode. Bismuth vanadate (BiVO4) or titanium oxide modification significantly facilitated oxidative H2O2 production in an aqueous solution of bicarbonate (HCO3−) on the anode substrate in the dark. The BiVO4‐supported FTO anode (BiVO4/FTO) achieved not only approximately twice the H2O2 generation performance compared with a bare FTO substrate but also high H2O2 accumulation, and the maximum selectivity (η(H2O2)) and accumulation reached ca. 35 % and 5 mM, respectively.
The photoelectrochemical production and degradation properties of hydrogen peroxide (H O ) were investigated on a WO /BiVO photoanode in an aqueous electrolyte of hydrogen carbonate (HCO ). High concentrations of HCO species rather than CO species inhibited the oxidative degradation of H O on the WO /BiVO photoanode, resulting in effective oxidative H O generation and accumulation from water (H O). Moreover, the Au cathode facilitated two-electron reduction of oxygen (O ), resulting in reductive H O production with high current efficiency. Combining the WO /BiVO photoanode with a HCO electrolyte and an Au cathode also produced a clean and promising design for a photoelectrode system specializing in H O production (η (H O )≈50 %, η (H O )≈90 %) even without applied voltage between the photoanode and cathode under simulated solar light through a two-photon process; this achieved effective H O production when using an Au-supported porous BiVO photocatalyst sheet.
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