▎ 摘　　要

Introduction of graphene-like heterostructures supported single-atom catalysts (SACs) has been considered as a promising strategy for generating sustainable energy sources. By using first-principles calculation, different kinds of single transition metal (TM = Mn, Fe, Co and Ni) atoms anchored boron phosphide (BP-TM) and the effects of added graphene substrate on its electronic property and sensitivity toward the gas reactants are comparably investigated. The graphene support can provide the transferred electron to BP sheet and then regulate the adsorption strength and electronic structure of TM atoms anchored systems (BP-gra-TM). Besides, the adsorption of N-2 molecule (parallel and end-on modes) on BP-gra-TM (including pristine and single vacancy (SV) within BP, i.e., BP-gra-SV-TM) are more stable than those on BP-TM and BP-SV-TM sheets, and then induce the change in electronic and magnetic properties of supported systems. Furthermore, the potential catalytic performances of four reactive substrates (BP-TM, BP-gra-TM, BP-SV-TM and BP-gra-SV-TM) are systematically explored for nitrogen reduction reaction (NRR). It is found that the NRR processes on BP-gra-Mn via enzymatic pathways and BP-gra-Fe via distal mechanism have lower limiting potential (0.52 V and 0.63 V) than other ones, indicating that the introduction of graphene can improve the surface activity of BP-TM sheets, which would provide useful guidance to design two-dimensional heterostructure-based SACs with high activity, efficiency and selectivity for the NRR.