Atomic Metal‒Nonmetal Catalytic Pair Cooperatively Drives Efficient Enzyme‐Mimetic Catalysis

Abstract

Abstract Single‐atom catalysts with maximum atom utilization and well‐defined coordination environments are promising alternatives to natural enzymes. However, their catalytic performance in enzymatic reactions is intrinsically restricted by the scaling relations, which impose an inherent trade‐off between substrate adsorption/activation and product desorption. Here we report atomically dispersed manganese‒sulfur (Mn─S) catalytic pairs with strong electronic coupling that integratively drive enzymatic catalysis, in which the S atom not only modulates the electronic structure of the adjacent Mn site to promote substrate adsorption and activation, but also functions as the secondary catalytic site for stabilizing oxygenated intermediates and facilitating product desorption. Consequently, this metal‒nonmetal dual‐site cooperation enables simultaneous optimization of both adsorption/activation and desorption processes, leading to remarkably enhanced catalytic activity. As a potential application, the Mn─S catalytic pairs with coupled catalase‐, peroxidase‐, and oxidase‐mimicking activities are successfully demonstrated for synergistic tumor catalytic therapy. This work establishes a paradigm for the rational design of highly efficient artificial enzymes through catalytic pair engineering.