Theoretical Screening of High-Performance Electrocatalysts for Nitrogen Fixation with Single Metal Atoms Anchored on CuO

NH3 is an efficient hydrogen carrier and a crucial chemical in various industrial various applications. In comparison to the traditional Haber–Bosch process, the nitrogen reduction reaction (NRR) is a promising green alternative technology. Therefore, exploring NRR electrocatalysts with excellent performance is of great significance for sustainable development. Herein, density functional theory calculations were employed to explore the potential of transition metal (TM) atoms anchored on defective CuO surface formation TM@CuO catalysts. The thermodynamic stability of TM@CuO structures was confirmed through binding energy calculations. The high catalytic activity of Nb@CuO, Mo@CuO, Ru@CuO, and Ta@CuO was successfully determined by screening the free energy of the potential-determining step and comparing with the competitive hydrogen evolution reaction. The simulation of the entire pathway showed that the limiting potentials of Mo@CuO and Ru@CuO were −0.358 and −0.540 V, respectively. Furthermore, the charge density difference, Bader charge, density of states, and crystal orbital Hamiltonian population of Mo@CuO and Ru@CuO were analyzed, and the reasons for their excellent catalytic activity were identified. The research result of this study is expected to provide theoretical guidance for the rational design of new NRR electrocatalysts.