Electronic Structure Reconfiguration of Zn‐N <i> _x </i> B _4‐ <i> _x </i> Sites for Enhanced Fenton‐Like Catalysis

Abstract

Abstract Despite growing interest in single‐atom catalysts (SACs) for Fenton‐like reactions, zinc (Zn)‐based SACs remain unexplored due to the inherent inertness of Zn 2+ , whose fully occupied 3d 10 electronic configuration limits redox activity. Here, we overcome this limitation by introducing boron (B) atoms to reconfigure the electronic structure of Zn‐N 4 coordination sites, yielding an activated catalyst denoted as Zn‐NBC. This electronic modulation transforms inert Zn‐N 4 sites into catalytically active centers (Zn‐N x B 4‐ x ), enabling significantly enhanced Fenton‐like activity. Compared to the unmodified Zn‐N 4 catalyst (Zn‐N 4 C), Zn‐NBC exhibits a 26‐fold increase in the rate of organic pollutant degradation. Density functional theory (DFT) calculations and experimental results reveal that Zn‐N 4 C and Zn‐NBC exhibit distinct PDS adsorption behaviors, with B incorporation tuning both adsorption strength and electronic interactions at the Zn center. Crystal orbital Hamilton population (COHP) analysis further demonstrates that the Zn‐NBC facilitates the activation of the S─O bonds in peroxydisulfate (PDS), promoting the generation of reactive oxygen species, including peroxide radicals and singlet oxygen. These findings establish a new paradigm for activating electronically inert metal centers and position Zn‐NBC as a promising platform for efficient and sustainable environmental remediation.