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

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 V_RHE reached 5.1 mA cm^-2, and a steady photocurrent of 3.0 mA cm^-2 at 0.8 V_RHE 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.