Synergy of Nickel Single-Atom and Heteroatoms Co-Doping in Carbon for Efficient Hydrogen Peroxide Electrosynthesis

Single-atom catalysts have emerged as cost-effective alternatives to noble metals for the two-electron oxygen reduction reaction (2e^- ORR); however, their practical application in hydrogen peroxide (H₂O₂) electrosynthesis remains limited by persistent trade-offs among activity, selectivity, and stability. Herein, we demonstrate that synergistic integration of atomically dispersed Ni and B, N co-dopants within a carbon matrix (Ni-BNC) effectively regulates the 2e^- ORR for efficient H₂O₂ production. The Ni-BNC catalyst delivers >90% Faradaic efficiency for H₂O₂ at current densities up to ∼-400 mA cm^-2 and critically maintains this high selectivity for over 50 h at -100 mA cm^-2 in a flow cell, achieving a maximum production rate of 31.13 mol g^-1 h^-1. In situ infrared spectroscopy and kinetic analysis revealed that B, N-coordination facilitates electron transfer from adjacent single Ni atoms, electronically modulating the *OOH adsorption energy and lowering the kinetic barrier. The practical viability is further demonstrated in a porous solid electrolyte reactor, which continuously produces pure, salt-free H₂O₂ (>1,400 ppm) for 100 h. This work highlights the effectiveness of atomic-level synergy for designing advanced electrocatalysts beyond sole active-site engineering.