Sulfur coordination modulates the orbital coupling of ZnCo dual-atomic for efficient one-step H2O2 scission into dual ·OH

Dual-atom catalysts (DACs) possess outstanding catalytic properties arising from unique intermetallic synergistic effects and electronic coupling, yet the precise construction of cooperative reaction centers remains a critical challenge. In this study, a synergistic electrostatic modulation strategy is employed to anchor Zn Co dual-atomic sites onto an S/N co-doped carbon substrate (Zn,Co-DAC/SNC), in which Zn and Co are cooperatively distributed at an interatomic distance of 2.59 Å within an N3 Zn Co N/C/S coordination environment, forming stable reactive centers. Sulfur doping induces Zn-p/Co-d orbital coupling, which strengthens electronic synergy and promotes efficient ·OH generation, endowing the catalyst with excellent ibuprofen (IBP) degradation activity (>98 %). In this system, Co serves as the primary active center responsible for O O bond cleavage, Zn modulates the electronic structure to enhance ·OH yield, and sulfur atoms stabilize metal coordination while regulating interfacial charge. Under sulfur regulation, the Zn Co bimetallic centers induce electron redistribution and an upshift of the d-band center, thereby lowering the O O bond cleavage barrier (−3.79 eV) and preferentially driving one-step bond scission to yield dual ·OH. This work elucidates the Zn/Co/S ternary synergy in H 2 O 2 activation and provides theoretical guidance for the structure-activity design of multimetal-heteroatom catalysts.