Constructed Red Phosphorus/BiVO ₄ S‐Scheme Heterojunction for Efficient Photocatalytic Overall Water Splitting

Rapid electron‐hole recombination and low oxidative potential restrict red phosphorus (Red P) photocatalytic performance in water splitting. To address these limitations, integrating Red P with BiVO 4 through an S‐scheme heterojunction design enables synergistic optimization of their respective properties. Electrochemical characterization reveals that the interfacial built‐in electric field within this heterostructure significantly promotes charge separation and directional carrier migration, substantially prolonging the survival time of photoinduced charge carriers. Moreover, BiVO 4 serves as a proficient oxidation catalyst that markedly accelerates the oxygen evolution reaction kinetics. The optimized Red P/BiVO 4 composite demonstrates remarkable visible‐light‐driven photocatalytic activity, achieving a hydrogen production rate of 480.5 μmol h −1 g −1 in overall water splitting experiments—representing a 3.55‐fold enhancement compared to pristine Red P. This study provides mechanistic insights into the role of BiVO 4 as an effective performance enhancer for Red P‐based photocatalytic systems through rational heterojunction engineering.