High Selectivity and Abundant Active Sites in Atomically Dispersed M2c12 Monolayer for Co2 Reduction

Abstract

Developing highly efficient single-atom catalysts (SACs) for electrocatalytic carbon dioxide reduction reaction (CO2RR) is a promising approach to promoting carbon neutrality. However, challenges such as low activity, selectivity, and high costs hinder industrial scaling, attributed to the lack of innate activity or insufficient transition metal (TM) active site density in current catalysts. Therefore, the focus of CO2RR research remains on developing SACs with intrinsic catalytic activity, high TM coverage, and cost-effectiveness. This study presents the design of high TM coverage material M2C12 (M = Mo, Ru, Rh, W, Re, Os, and Ir) as electrocatalyst SACs  for CO2RR using density functional theory calculations. Among these materials, W2C12 demonstrates superior selectivity and catalytic activity for CO2RR to CO products with overpotentials of 0.45 V and a W coverage of up to 71.84 weight percent (wt%). To further enhance its catalytic activity, non-metallic coordination modification (NM = B, N, O, P doping, and C vacancy) was explored on W2C12. The results indicate that N-doped W2C12 (N-W2C12) can significantly improve selectivity and catalytic activity, achieving an extremely low overpotential of 0.34 V. This research offers valuable insights into designing SACs with high activity, selectivity, and stability for CO2RR and other catalytic reactions.

Keywords: High active site density, Intrinsic catalytic activity, single-atom catalysts (SACs), CO2 reduction reaction, Electrocatalysis