Construction of dual sites on FeS2 surface for enhanced electrocatalytic reduction of nitrite to ammonia

[Display omitted] Cost-effective iron sulfides (FeS2) hold great potential as high-performance catalysts for NO2− electroreduction to NH3 (NO2ER), which is hindered by the weak NO2 activation. Herein, the design of nonmetal-doped FeS2 electrocatalysts was initially conducted by density functional theory (DFT) computations. We found that doping with different nonmetal atoms effectively not only regulates the electronic structures of the d-electrons of Fe atoms but also creates the unique p-d hybridized dual active sites, thereby boosting the efficient NO2 activation. Owing to the optimal NO2 adsorption strength, N–doped FeS2 demonstrates a low limiting potential for the NO2−–to–NH3 conversion, thus significantly improving NO2ER activity. Direct experimental evidence was provided afterward: an NH3 yield rate of 424.5 μmol/hcm−2 with a 92.4 % Faradaic efficiency was achieved. Our findings not only suggest a promising NO2ER catalyst through theoretical computations to guide experiments but also provide a comprehensive understanding of the structure-properties relationship.