Ordered and Isolated Pd Sites Endow Antiperovskite‐Type PdFe3N with High CO‐Tolerance for Formic Acid Electrooxidation

Abstract The fundamental understanding and precise control of catalytic sites are challenging yet essential to explore advanced electrocatalysts for the formic acid oxidation reaction (FAOR). Herein, this work demonstrates a new and promising catalyst prototype of antiperovskite‐type PdFe 3 N which possesses ordered and isolated Pd sites. The as‐synthesized PdFe 3 N/N‐rGO exhibits significant enhancement in catalytic activity, robust stability, and Fe anti‐dissolution properties when compared with PdFe 3 /rGO and Pd/C. Density functional theory (DFT) calculations reveal that isolated and ordered Pd sites are beneficial for high formate coverage and thus suppressing CO formation/poisoning. Moreover, the strong Fe–N covalent bonds improve the vacancy formation energy of Fe, which ensures superior Fe anti‐dissolution properties. Beyond offering a promising candidate for catalyzing FAOR, these findings provide deeper insights into the structure of CO tolerance relationships and benefit the theory‐guided design of highly efficient catalysts.