Constructing Asymmetric Fe–Nb Diatomic Sites to Enhance ORR Activity and Durability

作者：Rui Sui, Bo Liu, Chang Chen, Chang Chen, Xin Tan, Chang He, Dongyue Xin, Bowen Chen, Zhiyuan Xu, Jiazhan Li, Wenxing Chen, Zhongbin Zhuang, Zhen‐Bo Wang, Chen Chen, Chen Chen · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.4c09642 · 被引用次数：211 · 研究领域：Electrocatalysts for Energy Conversion、Fuel Cells and Related Materials、Advanced Memory and Neural Computing

Iron–nitrogen–carbon (Fe–N–C) materials have been identified as a promising class of platinum (Pt)-free catalysts for the oxygen reduction reaction (ORR). However, the dissolution and oxidation of Fe atoms severely restrict their long-term stability and performance. Modulating the active microstructure of Fe–N–C is a feasible strategy to enhance the ORR activity and stability. Compared with common 3d transition metals (Co, Ni, etc.), the 4d transition metal atom Nb has fewer d electrons and more unoccupied orbitals, which could potentially forge a more robust interaction with the Fe site to optimize the binding energy of the oxygen-containing intermediates while maintaining stability. Herein, an asymmetric Fe–Nb diatomic site catalyst (FeNb/c-SNC) was synthesized, which exhibited superior ORR performance and stability compared with those of Fe single-atom catalysts (SACs). The strong interaction within the Fe–Nb diatomic sites optimized the desorption energy of key intermediates (*OH), so that the adsorption energy of Fe–*OH approaches the apex of the volcano plot, thus exhibiting optimal ORR activity. More importantly, introducing Nb atoms could effectively strengthen the Fe–N bonding and suppress Fe demetalation, causing an outstanding stability. The zinc–air battery (ZAB) and hydroxide exchange membrane fuel cell (HEMFC) equipped with our FeNb/c-SNC could deliver high peak power densities of 314 mW cm –2 and 1.18 W cm –2, respectively. Notably, the stable operation time fo...