Rapid Synthesis of Ultrathin Ni:FeOOH with In Situ-Induced Oxygen Vacancies for Enhanced Water Oxidation Activity and Stability of BiVO₄ Photoanodes

The coupling of oxygen evolution reaction (OER) catalysts with photoanodes is a promising strategy for enhancing the photoelectrochemical (PEC) performance by passivating photoanode’s surface defect states and facilitating charge transfer at the photoanode/electrolyte interface. However, a serious interface recombination issue caused by poor interface and OER catalysts coating quality often limits further performance improvement of photoanodes. Herein, a rapid Fenton-like reaction method is demonstrated to produce ultrathin amorphous Ni:FeOOH catalysts with in situ-induced oxygen vacancies (Vo) to improve the water oxidation activity and stability of BiVO 4 photoanodes. The combined physical characterizations, PEC studies, and density functional theory calculations revealed that the reductive environment in a Fenton-like reaction in situ produces abundant Vo in Ni:FeOOH catalysts, which significantly improves charge separation and charge transfer efficiency of BiVO 4 while also offering abundant active sites and a reduced energy barrier for OER. As a result, Ni:FeOOH-Vo catalysts yielded a more than 2-fold increased photocurrent density in the BiVO 4 photoanode (from 1.54 to 4.15 mA cm –2 at 1.23 V RHE ), accompanied by high stability for 5 h. This work not only highlights the significance of abundant Vo in catalysts but also provides new insights into the rational design and fabrication of efficient and stable solar water-splitting systems.