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

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 M@BN_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 (UL): Pt@BN_C with a UL of −0.18 for the product CH4 and Co@BN_C and Au@BN_O with UL of −0.41 and −0.37 V, respectively, for the product CH3OH. In particular, Pt@BN_C shows a remarkable reduction in UL for the product CH4 compared to any existing catalysts, synthesized or predicted. In addition, the ultralow UL for CRR on Pt@BN_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.