Selective Hydrogenation of CO 2 to CH 3 OH on a Dynamically Magic Single-Cluster Catalyst: Cu 3 /MoS 2 /Ag(111)
2022; American Chemical Society; Volume: 13; Issue: 1 Linguagem: Inglês
10.1021/acscatal.2c05072
ISSN2155-5435
AutoresYawan Wang, Yandi Zhu, Xiaowen Zhu, Jinlei Shi, Xiaoyan Ren, Lili Zhang, Shunfang Li,
Tópico(s)Catalytic Processes in Materials Science
ResumoSelective 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.
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