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

作者：Liang, Lecheng; Li, Meng; Zhang, Bentian; Liang, Jinhui; Zeng, Binwen; Wang, Liming; Tang, Yawen; Fu, Gengtao^*; Cui, Zhiming^*

来源：Advanced Energy Materials, 2023, 13(10).

DOI：10.1002/aenm.202203803

• catalytic mechanisms
• CO resistance
• FAOR
• intermetallic nitrides
• stability

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 PdFe3N which possesses ordered and isolated Pd sites. The as-synthesized PdFe3N/N-rGO exhibits significant enhancement in catalytic activity, robust stability, and Fe anti-dissolution properties when compared with PdFe3/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.