Phosphorus Induced Electron Localization of Single Iron Sites for Boosted CO₂ Electroreduction Reaction

Electrochemical reduction of carbon dioxide (CO 2 ) into chemicals and fuels has recently attracted much interest, but normally suffers from a high overpotential and low selectivity. In this work, single P atoms were introduced into a N‐doped carbon supported single Fe atom catalyst (Fe‐SAC/NPC) mainly in the form of P−C bonds for CO 2 electroreduction to CO in an aqueous solution. This catalyst exhibited a CO Faradaic efficiency of ≈97 % at a low overpotential of 320 mV, and a Tafel slope of only 59 mV dec −1 , comparable to state‐of‐the‐art gold catalysts. Experimental analysis combined with DFT calculations suggested that single P atom in high coordination shells ( n ≥3), in particular the third coordination shell of Fe center enhanced the electronic localization of Fe, which improved the stabilization of the key *COOH intermediate on Fe, leading to superior CO 2 electrochemical reduction performance at low overpotentials.