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Nano Research 2023, 16(8): 11383-11388 https://doi.org/10.1007/s12274-023-5862-0
Research Article | Issue | Published: 21 June 2023

The modification toward excited-state dynamics and catalytic activity by isomeric Au44 clusters

Show Author's Information Tongxin Song1,§,  Jie Kong2,§,  Shisi Tang1,  Xiao Cai1,  Xu Liu1,  Meng Zhou2( ),  Wen Wu Xu3( ),  Weiping Ding1,  Yan Zhu1( )
School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China
Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
School of Physical Science and Technology, Ningbo University, Ningbo 315211, China

§ Tongxin Song and Jie Kong contributed equally to this work.

Keywords:
catalysis, surface ligand, excited-state dynamics, cluster, metal core
Topics:
Gold nanoclusters
Cite this article:
Song T, Kong J, Tang S, et al. The modification toward excited-state dynamics and catalytic activity by isomeric Au44 clusters. Nano Research, 2023, 16(8): 11383-11388. https://doi.org/10.1007/s12274-023-5862-0
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Abstract Full text Electronic supplementary material About this article

The structure determination of metal nanoclusters protected by ligands is critical in understanding their physical and chemical properties, yet it remains elusive how the metal core and ligand of metal clusters cooperatively contribute to the observed performances. Here, with the successful synthesis of Au44TBPA22Cl2 cluster (TBPA = 4-tert-butylphenylacetylene), the structural isomer of previously reported Au44L28 clusters (L denoted as ligand) is filled, thereby providing an opportunity to explore the property evolution rules imparted by different metal core structures or different surface ligands. Time-resolved transient absorption spectroscopy reveals that the difference in the core structure between Au44TBPA22Cl2 and Au44L28 can bring nearly 360 times variation of excited-state lifetime, while only 3–24 times differences in excited-state lifetimes of the three Au44L28 nanoclusters with identical metal core but different ligands are observed, which is due to much stronger impact of the metal core than the surface ligands in the electronic energy bands of the clusters. In addition, the Au44 clusters protected by alkyne ligands are shown to be highly effective toward the electrochemical oxidation of ethanol, compared to the Au44 clusters capped by thiolates, which is ascribed to smaller charge transfer impedance of the former clusters. We anticipate that the study will enhance the process in controlling the nanomaterial properties by precisely tailoring metal core or surface patterns.


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Electronic supplementary material
About this article

The modification toward excited-state dynamics and catalytic activity by isomeric Au44 clusters

Show Author's information Tongxin Song1,§, Jie Kong2,§, Shisi Tang1, Xiao Cai1, Xu Liu1, Meng Zhou2( ), Wen Wu Xu3( ), Weiping Ding1, Yan Zhu1( )
School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China
Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
School of Physical Science and Technology, Ningbo University, Ningbo 315211, China

§ Tongxin Song and Jie Kong contributed equally to this work.

Abstract

The structure determination of metal nanoclusters protected by ligands is critical in understanding their physical and chemical properties, yet it remains elusive how the metal core and ligand of metal clusters cooperatively contribute to the observed performances. Here, with the successful synthesis of Au44TBPA22Cl2 cluster (TBPA = 4-tert-butylphenylacetylene), the structural isomer of previously reported Au44L28 clusters (L denoted as ligand) is filled, thereby providing an opportunity to explore the property evolution rules imparted by different metal core structures or different surface ligands. Time-resolved transient absorption spectroscopy reveals that the difference in the core structure between Au44TBPA22Cl2 and Au44L28 can bring nearly 360 times variation of excited-state lifetime, while only 3–24 times differences in excited-state lifetimes of the three Au44L28 nanoclusters with identical metal core but different ligands are observed, which is due to much stronger impact of the metal core than the surface ligands in the electronic energy bands of the clusters. In addition, the Au44 clusters protected by alkyne ligands are shown to be highly effective toward the electrochemical oxidation of ethanol, compared to the Au44 clusters capped by thiolates, which is ascribed to smaller charge transfer impedance of the former clusters. We anticipate that the study will enhance the process in controlling the nanomaterial properties by precisely tailoring metal core or surface patterns.

Keywords: catalysis, surface ligand, excited-state dynamics, cluster, metal core

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Publication history
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Acknowledgements

Publication history

Received: 27 April 2023
Revised: 17 May 2023
Accepted: 18 May 2023
Published: 21 June 2023
Issue date: August 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

We acknowledge financial support from the National Natural Science Foundation of China (Nos. 22125202, 22273095, and 22101128), Programs for high-level entrepreneurial and innovative talents introduction of Jiangsu Province, the Fundamental Research Funds for the Central Universities, Chinese Academy of Sciences (No. YSBR-007), and China Postdoctoral Science Foundation (No. 2022M721551).

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