Surface Reconstruction and Passivation of BiVO4 Photoanodes Depending on the "Structure Breaker" Cs.

ABSTRACT

Monoclinic BiVO4 is one of the most promising photoanode materials for solar water splitting. The photoelectrochemical performance of a BiVO4 photoanode could be significantly influenced by the noncovalent interactions of redox-inert metal cations at the photoanode-electrolyte interfaces, but this point has not been well investigated. In this work, we studied the Cs+-dependent surface reconstruction and passivation of BiVO4 photoanodes. Owing to the "structure breaker" nature of Cs+, the Cs+ at the BiVO4 photoanode-electrolyte interfaces participated in BiVO4 surface photocorrosion to form a Cs+-doped bismuth vanadium oxide amorphous thin layer, which inhibited the continuous photocorrosion of BiVO4 and promoted surface charge transfer and water oxidation. The resulting cocatalyst-free BiVO4 photoanodes achieved 3.3 mA cm-2 photocurrent for water oxidation. With the modification of FeOOH catalysts, the photocurrent at 1.23 VRHE reached 5.1 mA cm-2, and a steady photocurrent of 3.0 mA cm-2 at 0.8 VRHE was maintained for 30 h. This work provides new insights into the understanding of Cs+ chemistry and the effects of redox-inert cations at the electrode-electrolyte interfaces.