Boosting the Proton‐coupled Electron Transfer via Fe−P Atomic Pair for Enhanced Electrochemical CO2 Reduction

Abstract Single‐atom catalysts exhibit superior CO 2 ‐to‐CO catalytic activity, but poor kinetics of proton‐coupled electron transfer (PCET) steps still limit the overall performance toward the industrial scale. Here, we constructed a Fe−P atom paired catalyst onto nitrogen doped graphitic layer (Fe 1 /PNG) to accelerate PCET step. Fe 1 /PNG delivers an industrial CO current of 1 A with FE CO over 90 % at 2.5 V in a membrane‐electrode assembly, overperforming the CO current of Fe 1 /NG by more than 300 %. We also decrypted the synergistic effects of the P atom in the Fe−P atom pair using operando techniques and density functional theory, revealing that the P atom provides additional adsorption sites for accelerating water dissociation, boosting the hydrogenation of CO 2 , and enhancing the activity of CO 2 reduction. This atom‐pair catalytic strategy can modulate multiple reactants and intermediates to break through the inherent limitations of single‐atom catalysts.