Carbon and Oxygen Coordinating Atoms Adjust Transition Metal Single-Atom Catalysts Based On Boron Nitride Monolayers for Highly Efficient CO2 Electroreduction

Abstract

Although single-atom catalysts (SACs) with transition metal–nitrogen complexes have been studied widely, investigations that use light-element atoms to adjust the coordination environment of the central metal atoms in metal–nitrogen complexes are still rare but show enormous potential for various electrocatalytic reactions. Herein, we design novel SACs based on monolayer BN adjusted by B, C, or O coordinating atoms as catalysts for the CO₂ reduction reaction (CRR). These SACs are denoted as [email?protected]_D (BN = monolayer boron nitride; D = B, C, or O atom; M = Co, Cr, Fe, Mn, Mo, Pd, Pt, Ru, V, W, Ni, Zn, Zr, Ag, Au, Cu, or Ti atom) and are investigated as CRR catalysts using density functional theory calculations. Among these structures, we identified some promising candidate catalysts for CRR with impressive low limiting potential (U_L): [email?protected]_C with a U_L of ?0.18 for the product CH₄ and [email?protected]_C and [email?protected]_O with U_L of ?0.41 and ?0.37 V, respectively, for the product CH₃OH. In particular, [email?protected]_C shows a remarkable reduction in U_L for the product CH₄ compared to any existing catalysts, synthesized or predicted. In addition, the ultralow U_L for CRR on [email?protected]_C was derived from the unique bonding feature between the single metal atom and adsorbates and the modulation of ionic interactions induced by the coordination effect of the C atom.