10.1002/anie.201903853
Angewandte Chemie International Edition
COMMUNICATION
for intermediates, and transition states can be found in Supporting
Information.
In summary, our studies show that the alteration of a gold
nanocluster by one central atom can significantly change the
catalytic properties. The catalytic activity can be switched by one-
central-atom removal and addition. The work apparently impacts
one’s understanding of the contributions of individual atoms on
different sites in a catalyst to the catalytic performance and
provides design rules on how to control the catalytic properties of
a catalyst by one-atom removal and addition.
Acknowledgements
We acknowledge financial support from National Natural Science
Foundation of China (21773109, 91845104, and U1530401) and
Fundamental Research Funds for the Central Universities
.
We thank Prof. Rongchao Jin from Carnegie Mellon University for
helpful discussion.
Keywords: atom • vacancy • Au25 • Au24 • catalysis
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Figure 4. Proposed catalytic mechanism and predicted reaction enthalpy
profiles for the methane oxidation on (a, b) Au25 and (c, d) Au24 at the DFT
PBE/LANL2DZ level with [Au24/25(PH3)8(PPh3)2(SCH3)2(SC2H4Ph)3Cl2]+/2+
models using GAUSSIAN09 program. Reaction enthalpies are at 0 K in kcal/mol.
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Au24 complexes are denoted as 24N*. All of the corresponding optimized
geometries can be found in Figure S10. Black paths indicate the reaction
pathways for Au25 and Au24 without involving the central vacancy, whereas the
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More supplemental discussion about the structural and electronic
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