The Role of Cobalt‐Based Cocatalysts on BiVO4 for Photoelectrochemical Water Oxidation

Abstract Cocatalysts play a key role in enhancing activity of photoelectrodes while the study of their interaction remains a challenge. Here, we decoupled the relationship between oxygen evolution reaction (OER) performance and photoelectrochemical (PEC) water oxidation performance by modifying an identical BiVO 4 with different cobalt‐based OER catalysts including Co, CoO, Co 3 O 4 , and Co 4 N. The electrochemical OER activities of these cobalt specimens were quite similar. Their anodic photocurrent density followed an order of: Co 4 N>Co>Co 3 O 4 >CoO after loading on the BiVO 4 electrode. The kinetics process and energy band diagram were analyzed, revealing that the interface between different cobalt specimens and BiVO 4 electrode influenced the charge recombination and transfer. Accordingly, we propose a corresponding structural model, which shows that the cocatalysts consist of inner part for interface modulation and the outer layer for catalysis. The present work reveals the vital role of contact interface between cocatalysts and semiconductors, and more attention should be paid when selecting the cocatalysts.