Microenvironment-coordinated P1CoN3 single-atom sites for selective photocatalytic CO2 reduction to C2 products

Abstract

Gaining a comprehensive understanding of the C–C coupling process involving metal active sites and their local coordination environments remains a significant challenge. In this study, we developed a Co_sacP-CN/MA photocatalyst by incorporating the nonmetal p-block element phosphorus (P) to precisely tailor the coordination environment of individual cobalt (Co) atoms, followed by hybridization with MgAl-LDH. The resulting single-atom catalyst, characterized by a P₁CoN₃ coordination structure, demonstrates remarkable performance for C₂H₆ production with nearly 60% selectivity. The asymmetric P₁CoN₃ single-atom site significantly enhances CO₂ activation, stabilizes CO intermediates, and improves the utilization of photogenerated electrons, offering both thermodynamic and kinetic advantages for the deep reduction of CO₂. This work offers valuable insights into the precise engineering of the coordination environment of single-atom metal centers to optimize the selective production of C₂ products.