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Title: Au 130− x Ag x Nanoclusters with Non‐Metallicity: A Drum of Silver‐Rich Sites Enclosed in a Marks‐Decahedral Cage of Gold‐Rich Sites

Abstract

Abstract The synthesis and structure of atomically precise Au 130− x Ag x (average x= 98) alloy nanoclusters protected by 55 ligands of 4‐ tert ‐butylbenzenethiolate are reported. This large alloy structure has a decahedral M 54 (M=Au/Ag) core. The Au atoms are localized in the truncated Marks decahedron. In the core, a drum of Ag‐rich sites is found, which is enclosed by a Marks decahedral cage of Au‐rich sites. The surface is exclusively Ag−SR; X‐ray absorption fine structure analysis supports the absence of Au−S bonds. The optical absorption spectrum shows a strong peak at 523 nm, seemingly a plasmon peak, but fs spectroscopic analysis indicates its non‐plasmon nature. The non‐metallicity of the Au 130− x Ag x nanocluster has set up a benchmark to study the transition to metallic state in the size evolution of bimetallic nanoclusters. The localized Au/Ag binary architecture in such a large alloy nanocluster provides atomic‐level insights into the Au−Ag bonds in bimetallic nanoclusters.

Authors:
 [1];  [2];  [3];  [4];  [2];  [5];  [3];  [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Department of Chemistry Carnegie Mellon University Pittsburgh PA 15213 USA
  2. Department of Chemistry University of Pittsburgh Pittsburgh PA 15260 USA
  3. Department of Chemistry Dalhousie University Halifax Nova Scotia B3H 4R2 Canada
  4. Center for Functional Nanomaterials Brookhaven National Laboratory Upton NY 11973 USA
  5. Center for Functional Nanomaterials Brookhaven National Laboratory Upton NY 11973 USA, Present address: Department of Physics Graduate Center City University of New York New York NY 10016 USA, Photonics Initiative Advanced Science Research Center City University of New York New York NY 10031 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1573510
Grant/Contract Number:  
SC0012704
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition) Journal Volume: 58 Journal Issue: 52; Journal ID: ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Higaki, Tatsuya, Liu, Chong, Morris, David J., He, Guiying, Luo, Tian‐Yi, Sfeir, Matthew Y., Zhang, Peng, Rosi, Nathaniel L., and Jin, Rongchao. Au 130− x Ag x Nanoclusters with Non‐Metallicity: A Drum of Silver‐Rich Sites Enclosed in a Marks‐Decahedral Cage of Gold‐Rich Sites. Germany: N. p., 2019. Web. doi:10.1002/anie.201908694.
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Higaki, Tatsuya, Liu, Chong, Morris, David J., He, Guiying, Luo, Tian‐Yi, Sfeir, Matthew Y., Zhang, Peng, Rosi, Nathaniel L., & Jin, Rongchao. Au 130− x Ag x Nanoclusters with Non‐Metallicity: A Drum of Silver‐Rich Sites Enclosed in a Marks‐Decahedral Cage of Gold‐Rich Sites. Germany. https://doi.org/10.1002/anie.201908694
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Higaki, Tatsuya, Liu, Chong, Morris, David J., He, Guiying, Luo, Tian‐Yi, Sfeir, Matthew Y., Zhang, Peng, Rosi, Nathaniel L., and Jin, Rongchao. Fri . "Au 130− x Ag x Nanoclusters with Non‐Metallicity: A Drum of Silver‐Rich Sites Enclosed in a Marks‐Decahedral Cage of Gold‐Rich Sites". Germany. https://doi.org/10.1002/anie.201908694.
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@article{osti_1573510,
title = {Au 130− x Ag x Nanoclusters with Non‐Metallicity: A Drum of Silver‐Rich Sites Enclosed in a Marks‐Decahedral Cage of Gold‐Rich Sites},
author = {Higaki, Tatsuya and Liu, Chong and Morris, David J. and He, Guiying and Luo, Tian‐Yi and Sfeir, Matthew Y. and Zhang, Peng and Rosi, Nathaniel L. and Jin, Rongchao},
abstractNote = {Abstract The synthesis and structure of atomically precise Au 130− x Ag x (average x= 98) alloy nanoclusters protected by 55 ligands of 4‐ tert ‐butylbenzenethiolate are reported. This large alloy structure has a decahedral M 54 (M=Au/Ag) core. The Au atoms are localized in the truncated Marks decahedron. In the core, a drum of Ag‐rich sites is found, which is enclosed by a Marks decahedral cage of Au‐rich sites. The surface is exclusively Ag−SR; X‐ray absorption fine structure analysis supports the absence of Au−S bonds. The optical absorption spectrum shows a strong peak at 523 nm, seemingly a plasmon peak, but fs spectroscopic analysis indicates its non‐plasmon nature. The non‐metallicity of the Au 130− x Ag x nanocluster has set up a benchmark to study the transition to metallic state in the size evolution of bimetallic nanoclusters. The localized Au/Ag binary architecture in such a large alloy nanocluster provides atomic‐level insights into the Au−Ag bonds in bimetallic nanoclusters.},
doi = {10.1002/anie.201908694},
journal = {Angewandte Chemie (International Edition)},
number = 52,
volume = 58,
place = {Germany},
year = {Fri Nov 08 00:00:00 EST 2019},
month = {Fri Nov 08 00:00:00 EST 2019}
}
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https://doi.org/10.1002/anie.201908694
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