Facet Engineering Modulates d‐π* Hybridization for Boosting Antimicrobial Activity

Abstract Reactive oxygen species (ROS) have been growing as an emerging “hot” topic in antimicrobial applications. However, optimizing antimicrobial activity by enhancing ROS generation remains a formidable challenge. Here, using bassanite as a proof of concept, the facet engineering of bassanite matrix can enhance the ROS generation efficiency via tuning the d ‐band center of Cu atom is proposed. Theoretical calculation and experimental investigations reveal that the d ‐band center of Cu atoms is significantly shifted upward when Cu doped into the (204) facet of bassanite compared to the (400) facet. A higher d ‐band center facilitates adsorption and activation between Cu and O 2 through the formation of stronger d ‐ π * orbital hybridization, resulting in increased ROS production. Through engineering, the material exhibits better antimicrobial activity when Cu doped into the (204) facet, which presents a clear potential in construction materials and personal protection. This work shed light on designing new materials with high antimicrobial activity and the application of facet engineering.