Photocorrosion of WO3 Photoanodes in Different Electrolytes

Abstract

Photocorrosion of an n-type semiconductor is anticipated to be unfavorable if its decomposition potential is situated below its valence band-edge position. Tungsten trioxide (WO3) is generally considered as a stable photoanode for different photoelectrochemical (PEC) applications. Such oversimplified considerations ignore reactions with electrolytes added to the solvent. Moreover, kinetic effects are neglected. The fallacy of such approaches has been demonstrated in our previous study dealing with WO3 instability in H2SO4. In this work, in order to understand parameters influencing WO3 photocorrosion and to identify more suitable reaction environments, H2SO4, HClO4, HNO3, CH3O3SH, as electrolytes are considered. Model WO3 thin films are fabricated with a spray-coating process. Photoactivity of the samples is determined with a photoelectrochemical scanning flow cell. Photostability is measured in real time by coupling an inductively coupled plasma mass spectrometer to the scanning flow cell to determine the photoanode dissolution products. It is found that the photoactivity of the WO3 films increases as HNO3 < HClO4 ≈ H2SO4