Insight into the Transition‐Metal Hydroxide Cover Layer for Enhancing Photoelectrochemical Water Oxidation

Depositing a transition‐metal hydroxide (TMH) layer on a photoanode has been demonstrated to enhance photoelectrochemical (PEC) water oxidation. However, the controversial understanding for the improvement origin remains a key challenge to unlock the PEC performance. Herein, by taking BiVO 4 /iron‐nickel hydroxide (BVO/F x N 4− x ‐H) as a prototype, we decoupled the PEC process into two processes including charge transfer and surface catalytic reaction. The kinetic information at the BVO/F x N 4− x ‐H and F x N 4− x ‐H/electrolyte interfaces was systematically evaluated by employing scanning photoelectrochemical microscopy (SPECM), intensity modulated photocurrent spectroscopy (IMPS) and oxygen evolution reaction (OER) model. It was found that F x N 4− x ‐H acts as a charge transporter rather than a sole electrocatalyst. PEC performance improvement is mainly ascribed to the efficient suppression of charge recombination by fast hole transfer kinetics at BVO/F x N 4− x ‐H interface.