Abstract
Selective two-electron (2e(-)) oxygen reduction reaction (ORR) offers great opportunities for hydrogen peroxide (H(2)O(2)) electrosynthesis and its widespread employment depends on identifying cost-effective catalysts with high activity and selectivity. Main-group metal and nitrogen coordinated carbons (M-N-Cs) are promising but remain largely underexplored due to the low metal-atom density and the lack of understanding in the structure-property correlation. Here, we report using a nanoarchitectured Sb(2)S(3) template to synthesize high-density (10.32 wt%) antimony (Sb) single atoms on nitrogen- and sulfur-codoped carbon nanofibers (Sb-NSCF), which exhibits both high selectivity (97.2%) and mass activity (114.9 A g(-1) at 0.65 V) toward the 2e(-) ORR in alkaline electrolyte. Further, when evaluated with a practical flow cell, Sb-NSCF shows a high production rate of 7.46 mol g(catalyst)(-1) h(-1) with negligible loss in activity and selectivity in a 75-h continuous electrolysis. Density functional theory calculations demonstrate that the coordination configuration and the S dopants synergistically contribute to the enhanced 2e(-) ORR activity and selectivity of the Sb-N(4) moieties.