posted on 2022-12-23, 13:12authored byYawan Wang, Yandi Zhu, Xiaowen Zhu, Jinlei Shi, Xiaoyan Ren, Lili Zhang, Shunfang Li
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 Cu2 and
Cu8 in the gas phase are well recognized as magic clusters
due to closed-shell electronic structures, Cu3 and Cu7 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 Cu3 species with an alkali-metal-like electronic
feature and the dz2 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 ∼1.10 eV. However, the deposited
Cu7 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.