Dual-Function Synergy in Boron-Doped Fe-N-C: Enhanced Site Density and Intrinsic Activity

Abstract

Atomically dispersed transition metal, nitrogen co-doped carbon (M-N-C) is hailed as the most promising platinum alternative for oxygen reduction reaction (ORR), while their practical deployment is bottlenecked by the inferior intrinsic activity and insufficient site density. Herein, we report a sodium borohydride (NaBH₄) assisted synthesis strategy to achieve dual enhancement of active site density and intrinsic activity. This strategy endows the B-doped catalyst (denoted as Fe-sZ8-N-C) with high active site density of 2.26 × 10²⁰ sites g^-1, a two-fold enhancement over the conventional Fe-N-C. Besides, the intrinsic activity of the catalyst is improved from 0.96 e site^-1 s^-1 to 1.5 e site^-1 s^-1. Density functional theory (DFT) calculations reveal boron-modulated coordination structure switches ORR pathway from associative OOH dissociation to direct O₂ cleavage while weakening intermediate adsorption strength, thereby boosting intrinsic activity. When assembled in practical PEMFC devices, the optimized Fe-sZ8-N-C catalyst delivers an exceptional peak power density of 1.3 W cm^-2 under H₂-O₂ conditions at 80℃, demonstrating its potential for fuel cell applications.