One‐Step Doping of P and S Elements to Fe‐ZIF‐8 Derivatives for Enhanced ROS Generation and Antibacterial Application

Artificial enzymes have been rapidly developed in recent years. However, the homogenous charge distribution of active sites hinders the enhancement of the substrate affinity and catalytic efficiency. Herein, a dual‐heteroatom doping strategy is developed for the design and modulation of MOF‐derived carbon hybrids (ZFPS: ZnS/FeP/Fe 4 P 6 N 12 S). By introducing electronegative P and S atoms, the coordination environment of the metal sites is tuned, leading to the formation of narrow bandgap materials with asymmetric charge distribution and electron‐rich active sites. This structural optimization enhances both substrate adsorption–desorption capacity and electron transfer efficiency. Density functional theory calculations confirm that P, S co‐doping modulates the D‐band electronic structure of Fe sites, thereby enhancing the affinity between the substrates and the active sites. Compared to its counterpart without P, S doping, ZFPS exhibits a 33.3‐fold increase in peroxidase‐like activity (K cat /K m ), as well as superior halogen peroxidase‐like and glutathione depletion capability. The multiple catalytic activities synergistically facilitate the rapid generation of highly toxic reactive oxygen species at low H 2 O 2 concentrations, enabling effective eradication of bacterial biofilms, which is verified in anti‐oral‐biofilm application. This work establishes a facile strategy for improving the catalytic activities of artificial enzymes, which will promote the development of antimicrobial biomaterials.