Selective Hydrogenation of CO₂ to CH₃OH on a Dynamically Magic Single-Cluster Catalyst: Cu₃/MoS₂/Ag(111)

Selective hydrogenation of carbon dioxide (CO2) into value-added chemicals via highly efficient catalysts is of great significance in CO2 conversion and utilization. Here, taking CuN/ MoS2/Ag(111) heterostructures (N = 1-8) as prototypical examples, we theoretically establish a concept of a dynamically magic single-cluster catalyst (DMSCC) for high-efficient selective hydrogenation of CO2 to CH3OH. It is found that, though Cu-2 and Cu-8 in the gas phase are well recognized as magic clusters due to closed-shell electronic structures, Cu-3 and Cu-7 become new magic clusters when deposited on MoS2/Ag(111) due to their high-symmetric structures and strong Cu-S ionic bonding. Moreover, the dynamic evolution of the geometric structure of the Cu-3 species with an alkali-metal-like electronic feature and the d(z)(2) frontier orbital accounts for its highly selective catalytic activity for CO2 reduction to CH3OH rather than HCOO with a low rate-limiting reaction barrier of similar to 1.10 eV. However, the deposited Cu-7 is relatively highly inert toward CO2 activation because of its halogen-element-like electronic characteristics. The present findings on DMSCC are expected to be constructive in design and fabrication of highly efficient single-atomic-scale catalysts for CO2 activation and conversion.