First-row transition metal/N-doped boron phosphide monolayer as single-atom catalysts for electrochemical reduction of CO2 towards CO: A density functional theory study

In this research, a two-dimensional (2D) single-atom system of first-row transition metal/N-doped hexagonal Boron Phosphide monolayer (MN3-BP-ML) was proposed for electrochemical CO2 reduction (ECR) to CO. The corresponding ten models were constructed to calculate the adsorption free energies of the reaction intermediates and overpotentials. The density functional theory (DFT) calculation results well support that the CrN3-BP-ML is beneficial for ECR and exhibits excellent catalytic activity and selectivity. More importantly, the research reveals the catalytic activity highly correlates with the interaction effect between the transition-metal atom and the absorbed COOH intermediate for the rate determining step. The computational strategy and methodology in this research enlighten an effective way of design BP based single-atom active catalysts for ECR application at atomic level.