Neighboring effects of active sites for CO₂ transition to C₁ products on atomic catalysts

Abstract

The metal sites of single atomic catalysts (SAC) have usually been considered as the only active sites while the neighboring effects are rarely discussed. To enhance our understanding of the reaction mechanisms and the contributions of active sites, we have carried out a detailed investigation to reveal the correlations between the neighboring effects and the thermodynamic reaction trend of CO2 reduction reactions (CO2RR). In particular, the CO2 adsorptions on graphdiyne (GDY) based SACs are strongly correlated with the electronic configurations of the anchoring metals, especially for 3d and 4d transition metals. Owing to the neighboring effect, the initial adsorption of CO2 and further reduction process show different preferred active sites, supporting the migration of intermediates during CO2RR. More importantly, it is found that GDY-lanthanide SACs are able to effectively suppress the neighboring effects to promote the formation of the CH3OH and CH4 via the metal sites. This work has supplied in-depth insights into the neighboring effects to facilitate the design of efficient atomic catalysts in future works.