Oxygen Vacancy‐Engineered S‐Scheme FeOOH/Ov‐BiVO 4 Heterojunction: Interfacial Charge Dynamics Optimization and Pathogenic Polypeptide Aggregates Degradation

The construction of heterostructures is crucial for achieving efficient photoelectrochemical (PEC) applications. However, composite photoanodes often suffer from inadequate interfacial contact and weak binding forces, which significantly impede charge transfer across the heterojunction. In this work, oxygen vacancies (OVs) are strategically introduced at the heterointerface to construct a novel S‐scheme FeOOH/Ov‐BiVO 4 photoelectrode. It is demonstrated that OVs mediate the formation of an intimate contact and robust chemical bonds at the FeOOH/Ov‐BiVO 4 interface, thereby facilitating highly efficient carrier transfer. Furthermore, the cone‐shaped FeOOH not only acts as a hole transport layer and cocatalyst but also induces a “tip effect” that significantly enhances the localized adsorption of reactant molecules on the electrode surface. These synergistic effects reduce charge transfer resistance while effectively suppressing the recombination of photogenerated carriers. As a result, the optimized FeOOH/Ov‐BiVO 4 achieves an outstanding photocurrent density, which is 3.4 and 8.5 times higher than that of FeOOH/BiVO 4 and pristine BiVO 4 , respectively. Consequently, the FeOOH/Ov‐BiVO 4 photoelectrode is successfully deployed to degrade stubborn amyloid β‐polypeptide aggregates (APAs), displaying a significant advantage in comparison with the FeOOH/BiVO 4 sample. This work provides a comprehensive dual‐strategy paradigm for improving interfacial charge dynamics and surface adsorption, thereby paving the way for the rational design of advanced S‐scheme heterojunctions.