New BiVO₄ Dual Photoanodes with Enriched Oxygen Vacancies for Efficient Solar‐Driven Water Splitting

Bismuth vanadate (BiVO₄ ) is a promising photoanode material for photoelectrochemical (PEC) water splitting. However, owing to the short carrier diffusion length, the trade-off between sufficient light absorption and efficient charge separation often leads to poor PEC performance. Herein, a new electrodeposition process is developed to prepare bismuth oxide precursor films, which can be converted to transparent BiVO₄ films with well-controlled oxygen vacancies via a mild thermal treatment process. The optimized BiVO₄ film exhibits an excellent back illumination charge separation efficiency mainly due to the presence of enriched oxygen vacancies which act as shallow donors. By loading FeOOH/NiOOH as the cocatalysts, the BiVO₄ dual photoanodes exhibit a remarkable and highly stable photocurrent density of 5.87 mA cm⁻² at 1.23 V versus the reversible hydrogen electrode under AM 1.5 G illumination. An artificial leaf composed of the BiVO₄ /FeOOH/NiOOH dual photoanodes and a single sealed perovskite solar cell delivers a solar-to-hydrogen conversion efficiency as high as 6.5% for unbiased water splitting.