10.1002/anie.201805319
Angewandte Chemie International Edition
COMMUNICATION
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922-926.
CO2 carboxylation reaction. In contrast, the M@Ag24 catalysts
serve as the temporary hosts for the active [CH3C≡C]- species,
and facilitate the formation of [CH3C≡C-COO]-. In addition, due
to the excessively strong bonding of [CH3C≡C]- and [CH3C≡C-
COO]- to the cations, the dissociations of the Cs and PPh4
propiolates are highly endothermic, which inhibits the formation
of the propiolic acid. Overall, the M@Ag24 catalysts show unique
mechanism in catalyzing the coupling reactions in the presence
of bases in the solution.
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In summary, we report for the first time the influence of the
central doping of a foreign atom into Ag25 clusters on the
catalytic carboxylation of CO2 with terminal alkyne through C-C
bond formation to produce propiolic acid. The foreign core atom
of clusters indeed contributes to the catalytic properties, even
though the foreign atom is surrounded by the external atoms
and away from active sites. Our results provide fundamental
understanding of how to tune the catalysis of clusters by
removal and addition of a single atom of a cluster and also shed
light on the strategy for controlling the doping position to tune
the catalytic properties.
Acknowledgements
Y.Z. acknowledges financial support from Nanjing University,
Fundamental Research Funds for the Central Universities,
and National Natural Science Fundation of China (21773109).
M.C. acknowledges funding from National Natural Science
Foundation of China (U1530401).
Keywords: central doping • core atom • cluster • catalysis • CO2
conversion
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