Regulating the Coordination Geometry and Oxidation State of Single‐Atom Fe Sites for Enhanced Oxygen Reduction Electrocatalysis
Minjie Wang, Li Wang, Qing-Bin Li, Dan Wang, Yang Liu, Yong-Jun Han, Yuan Ren, Gang Tian, Xiaoyang Zheng, Muwei Ji, Caizhen Zhu, Lishan Peng, Geoffrey I. N. Waterhouse
Abstract
Abstract FeNC catalysts demonstrate remarkable activity and stability for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells and Zn–air batteries (ZABs). The local coordination of Fe single atoms in FeNC catalysts strongly impacts ORR activity. Herein, FeNC catalysts containing Fe single atoms sites with FeN 3 , FeN 4 , and FeN 5 coordinations are synthesized by carbonization of Fe‐rich polypyrrole precursors. The FeN 5 sites possess a higher Fe oxidation state (+2.62) than the FeN 3 (+2.23) and FeN 4 (+2.47) sites, and higher ORR activity. Density functional theory calculations verify that the FeN 5 coordination optimizes the adsorption and desorption of ORR intermediates, dramatically lowering the energy barrier for OH − desorption in the rate‐limiting ORR step. A primary ZAB constructed using the FeNC catalyst with FeN 5 sites demonstrates state‐of‐the‐art performance (an open circuit potential of 1.629 V, power density of 159 mW cm −2 ). Results confirm an intimate structure‐activity relationship between Fe coordination, Fe oxidation state, and ORR activity in FeNC catalysts.