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

Abstract 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 (H 2 O 2 ) 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 H 2 O 2 production. The Ni‐BNC catalyst delivers >90% Faradaic efficiency for H 2 O 2 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 H 2 O 2 (>1,400 ppm) for 100 h. This work highlights the effectiveness of atomic‐level synergy for designing advanced electrocatalysts beyond sole active‐site engineering.