Flexible modulations on selectivity of syngas formation via CO2 reduction on atomic catalysts

Electrocatalysts with multi-active sites are significant to achieve the flexible selectivity modulation of syngas components to couple with different chemical productions. Compared to the complicated composite electrocatalyst to realize multi-active sites, Graphdiyne (GDY) based single atomic catalysts (SACs) have offered a simple approach through intrinsic electroactivity of the GDY and the variation of atomically dispersed metal. In this work, we have proposed a systematic investigation of syngas formation on the GDY-SACs. It is found that f and p orbitals of lanthanide and GDY are able to facilitate the adsorption of reactants CO2 and H2O, respectively, which flexibly control the CO: H-2 ratios in syngas formation. Machine learning results indicate that solely relying on the adsorption energies leads to deviated selectivity. This indicates that a comprehensive understanding of thermodynamic preference and electronic structures is needed to achieve the highly accurate prediction of selectivity. This work has supplied an innovative understanding of the selectivity control in syngas formation, which benefits the future rational design of atomic catalysts for efficient CO2 reduction.