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

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. © 2022 Elsevier Ltd.