Different photostability of BiVO₄ in near-pH-neutral electrolytes

Photoelectrochemical water splitting is a promising route to produce hydrogen from solar energy. However, corrosion of photoelectrodes remains a fundamental challenge for their implementation. Here, we reveal different dissolution behaviors of BiVO4 photoanode in pH-buffered borate, phosphate, and citrate (hole-scavenger) electrolytes, studied in operando employing an illuminated scanning flow cell. We demonstrate that decrease in photocurrents alone does not reflect the degradation of photoelectrodes. Changes in dissolution rates correlate to the evolution of surface chemistry and morphology. The correlative measurements on both sides of the liquid-semiconductor junction provide quantitative comparison and mechanistic insights into the degradation processes.