First-principles study on screening diatomic catalysts for electrocatalytic NO reduction on single-layer BAs

Abstract

Electrocatalytic NO reduction reaction (NORR) technology can not only synthesize a highly significant chemical compound, NH₃, but also provide a green and efficient method for removing the harmful NO gas. Based on density functional theory (DFT) calculations, diatomic catalysts (DACs) with TM₂C₄ coordination environment were constructed on the surface of BAs in this work. The catalytic performance and mechanism of NH₃ synthesis by NO reduction were investigated in detail, and the formation mechanisms of by-products under high concentration coverage and competitive reactions were compared. The results showed that Zn₂C₄@BAs exhibited excellent catalytic activity and high selectivity for NH₃ synthesis. Additionally, elementary reaction kinetics were investigated through microkinetic modeling. Furthermore, by studying the adsorption performance and the degree of NO activation on the catalyst surface, the descriptor for the NO activation degree was explored and predicted. It was found that the d-band center, the first ionization energy and the number of d electrons were strongly correlated with the parameters representing the activation degree of NO. This work provides an approach to construct a diatomic catalyst for the NORR.