Enhanced CO2 electrochemical reduction on single-atom catalysts with optimized environmental, central and axial chemical ambient

Single-atom catalysts (SACs) have received significant research interests for electrocatalytic CO 2 reduction reaction (CO 2 RR) to produce valuable chemicals. Designing optimal SACs for CO 2 RR is a great challenge because of the strong scaling relationship among the many carbon-containing intermediates. In this study, we designed high-performance SACs, breaking the scaling relationship through changing environmental nonmetals, central atoms and axial nonmetals together via a series of density functional theory (DFT) calculations. After screening through configuration stabilities, CO and CO 2 adsorption energy , limiting potential of H 2 , product adsorption energy , limiting potential of products, energy barrier of C–C coupling process and AIMD simulations , we finally observed ten optimal SACs (Ti-N4-B, Ti-N4-Si, Ti-CN3-Si, Ti-CN2O(1)-S, Sc-C2NO(1)-B, Sc-C2NO(1)-Si, Ti-BCN2(2)-N, Sc-CN2O(3)-Si, Ru-C2NO(3)-C and Ti-BONC-C) after considering 4311 possible configurations with high activity and selectivity for HCOOH, CH 4 and C 2 H 6 O formation. Among them, Ti-N4-B, Ru-C2NO(3)-C, and Sc-C2NO(1)-B have the lowest overpotentials for producing HCOOH, CH 4 , and C 2 H 6 O with U L of −0.2 V, −0.29 V, and −0.51 V, respectively. Subsequently, electronic analysis is implemented to provide a more comprehensive explanation at the electronic level for the enhanced CO 2 RR performance of the discovered SACs. Our research demonstrates that the performance of SACs on CO 2 RR can be significantly enhanced and altered by the combination of environmental nonmetals, central atoms, and axial nonmetals in a rational design. Importantly, it also establishes a design principle for the rapid screening of prospective catalysts for CO 2 RR with high activity and selectivity.