Nitrogen‐Doped NiO Nanosheet Array for Boosted Electrocatalytic N2 Reduction

Abstract Electrocatalytic N 2 reduction reaction (NRR) provides a sustainable approach for ambient N 2 fixation. Non‐noble transition metal‐based electrocatalysts (TMEs) are emerging as the most promising NRR catalysts, but commonly exhibited limited NRR activity. Heteroatom doping is an effective method to improve the electrocatalytic activity of TMEs by finely modulating the electronic structures. Herein, as a proof‐of‐concept, nitrogen‐doped NiO nanosheet array on carbon cloth (N‐NiO/CC) was investigated as model heteroatom‐doped TMEs for NRR. The N‐NiO/CC exhibited the considerably enhanced NRR performance with a NH 3 yield of 22.7 μg h −1 mg −1 and an FE of 7.3 % in 0.1 M LiClO 4 at −0.5 V (vs. RHE), far superior to those of undoped counterpart. Density functional theory (DFT) calculations revealed that the N‐doping could induce the enhanced surface conductivity and upraised d‐band center, leading to promoted *NNH stabilization, reduced reaction energy barrier and thus improved NRR performance.