Synergistic Catalysis for Advanced Water Treatment Enabled by Precisely Constructed Ag–O–Bi Asymmetric Active Sites

ABSTRACT The escalating challenges of environmental pollution and antimicrobial resistance demand innovative materials capable of simultaneous pollutant degradation and pathogen inactivation. To address the common limitations of conventional photocatalysts, such as inefficient charge separation and a lack of multifunctional active sites, this work introduces an interfacial engineering strategy to create Ag–O–Bi asymmetric active centers in Ag‐doped BiOI. These sites act as integrated catalytic hubs, synergistically enhancing light absorption, charge carrier dynamics, and surface reactions. The optimized catalyst exhibits exceptional photocatalytic performance, degrading tetracycline (49.67%) and rhodamine B (58.46%) within 45 min under light, alongside potent antibacterial activity against Staphylococcus aureus (99.75% inactivation) and Escherichia coli (77.42%). Mechanistic studies reveal that the Ag–O–Bi unit operates as a bifunctional platform: it thermodynamically promotes O 2 adsorption on I site for ·O 2 − generation, while localizing H 2 O on the Ag site to boost ·OH production via hole oxidation. This spatial and energetic differentiation of adsorption pathways, driven by the tailored electronic structure of the Ag–O–Bi interface, enables parallel and synergistic generation of reactive oxygen species. By elucidating the critical role of asymmetric Ag–O–Bi centers, this study provides a generalizable blueprint for designing high‐performance, dual‐functional photocatalysts for environmental and biomedical applications.