Boosting Electrochemical Nitrogen Fixation via Regulating Surface Electronic Structure by CeO2 Hybridization

Abstract Electrocatalytic nitrogen reduction reaction (NRR) paves a sustainable way to produce NH 3 but suffering from the relatively low NH 3 yield and poor selectivity. High‐performance NRR catalysts and a deep insight into the structure‐performance relationship are higher desired. Herein, a molten‐salt approach is developed to synthesize tiny CeO 2 nanoparticles anchored by ultra‐thin MoN nanosheets as advanced catalysts for NRR. Specifically, a considerably high NH 3 yield rate of 27.5 µg h −1 mg −1 with 17.2% Faradaic efficiency (FE) can be achieved at ‐0.3 V vs (RHE) under ambient conditions. Experimental and density functional theory (DFT) calculations further point out that the incorporation of MoN with CeO 2 can promotes the enlargement of the electron deficient area of nitrogen vacancy site. The enlarged electron deficient area contributes to the accommodation of lone pair electrons of N 2 , which dramatically improves the N 2 adsorption/activation and the key intermediates (*NNH and *NH 3 ) generation, thus boosting the NRR performance.