Ampere-Level Nitrate Electroreduction to Ammonia over Monodispersed Bi-Doped FeS2

Electrochemical conversion of NO3- into NH3 (NO3RR) holds an enormous prospect to simultaneously yield valuable NH3 and alleviate NO3- pollution. Herein, we report monodispersed Bi-doped FeS2 (Bi-FeS2) as a highly effective NO3RR catalyst. Atomic coordination characterizations of Bi-FeS2 disclose that the isolated Bi dopant coordinates with its adjacent Fe atom to create the unconventional p-d hybridized Bi-Fe dinuclear sites. Operando spectroscopic measurements combined with theoretical calculations disclose that Bi-Fe dinuclear sites can synergistically enhance the hydrogenation energetics of NO3--to-NH3 pathway, while suppressing the competitive hydrogen evolution, leading to a high NO3RR selectivity and activity. Consequently, the specially designed flow cell equipped with Bi-FeS2 exhibits a high NH3 yield rate of 83.7 mg h-1 cm-2 with a near-100% NO3--to-NH3 Faradaic efficiency at an ampere-level current density of 1023.2 mA cm-2, together with an excellent long-term stability for 100 h of electrolysis, ranking almost the highest performance among all reported NO3RR catalysts.