Real Time Monitoring of the Dynamic Intracluster Diffusion of Single Gold Atoms into Silver Nanoclusters

Zheng, Kaiyuan; Fung, Victor; Yuan, Xun; Jiang, De-en; Xie, Jianping

doi:10.1021/jacs.9b05776

Title: Real Time Monitoring of the Dynamic Intracluster Diffusion of Single Gold Atoms into Silver Nanoclusters

Full Record
Other Related Research

Abstract

Alloying metal materials with heterometal atoms is an efficient way to diversify the function of materials, but in-depth understanding of the dynamic heterometallic diffusion inside the alloying materials is rather limited, especially at the atomic level. Here, we report the real-time monitoring of the dynamic diffusion process of a single gold (Au) atom into an atomically precise silver nanocluster (Ag NC), Ag₂₅(MHA)₁₈ (MHA = 6-mercaptohexanoic acid), by using in situ UV–vis absorption spectroscopy in combination with mass and tandem mass spectrometry. We found that the Au heteroatom first replaces the Ag atom at the surface Ag₂(MHA)₃ motifs of Ag₂₅(MHA)₁₈. After that, the Au atom diffuses into the surface layer of the icosahedral Ag₁₃ kernel and finally occupies the center of the alloy NCs to form the thermodynamically stable [email protected]₂₄(MHA)₁₈ product. Density functional theory (DFT) calculations reveal that the key thermodynamic driving force is the preference of the Au heteroatom for the central site of alloy NCs. Furthermore, the real-time monitoring approach developed in this study could also be extended to other metal alloy systems to reveal the reaction dynamics of intracluster diffusion of heteroatoms, as well as the formation mechanisms of metal alloy nanomaterials.

Authors:

^[1]; Fung, Victor ^[2]; Yuan, Xun ^[3];

^[2];

^[4]

National Univ. of Singapore (Singapore)
Univ. of California, Riverside, CA (United States)
Qingdao Univ. of Science and Technology, Qingdao (China)
National Univ. of Singapore (Singapore); Joint School of National Univ. of Singapore and Tianjin Univ., Binhai New City (China)

Publication Date:: Mon Oct 14 00:00:00 EDT 2019

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Ministry of Education; Taishan Scholar Foundation; Young Talents Joint Fund of Shandong Province

OSTI Identifier:: 1712709

Grant/Contract Number:: AC05-00OR22725; R-279-000-538-114; ZR2019YQ07; tsqn201812074

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 141; Journal Issue: 48; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Alloying; alloys; gold; energy; collisions

Citation Formats


                    Zheng, Kaiyuan, Fung, Victor, Yuan, Xun, Jiang, De-en, and Xie, Jianping. Real Time Monitoring of the Dynamic Intracluster Diffusion of Single Gold Atoms into Silver Nanoclusters.  United States: N. p., 2019. 
Web.  doi:10.1021/jacs.9b05776.

Copy to clipboard


                    Zheng, Kaiyuan, Fung, Victor, Yuan, Xun, Jiang, De-en, & Xie, Jianping. Real Time Monitoring of the Dynamic Intracluster Diffusion of Single Gold Atoms into Silver Nanoclusters.  United States.  https://doi.org/10.1021/jacs.9b05776

Copy to clipboard


                    Zheng, Kaiyuan, Fung, Victor, Yuan, Xun, Jiang, De-en, and Xie, Jianping. Mon .  
"Real Time Monitoring of the Dynamic Intracluster Diffusion of Single Gold Atoms into Silver Nanoclusters".  United States.  https://doi.org/10.1021/jacs.9b05776.  https://www.osti.gov/servlets/purl/1712709.

Copy to clipboard


                    
@article{osti_1712709,

  title        = {Real Time Monitoring of the Dynamic Intracluster Diffusion of Single Gold Atoms into Silver Nanoclusters},

  author       = {Zheng, Kaiyuan and Fung, Victor and Yuan, Xun and Jiang, De-en and Xie, Jianping},

  abstractNote = {Alloying metal materials with heterometal atoms is an efficient way to diversify the function of materials, but in-depth understanding of the dynamic heterometallic diffusion inside the alloying materials is rather limited, especially at the atomic level. Here, we report the real-time monitoring of the dynamic diffusion process of a single gold (Au) atom into an atomically precise silver nanocluster (Ag NC), Ag25(MHA)18 (MHA = 6-mercaptohexanoic acid), by using in situ UV–vis absorption spectroscopy in combination with mass and tandem mass spectrometry. We found that the Au heteroatom first replaces the Ag atom at the surface Ag2(MHA)3 motifs of Ag25(MHA)18. After that, the Au atom diffuses into the surface layer of the icosahedral Ag13 kernel and finally occupies the center of the alloy NCs to form the thermodynamically stable [email protected]24(MHA)18 product. Density functional theory (DFT) calculations reveal that the key thermodynamic driving force is the preference of the Au heteroatom for the central site of alloy NCs. Furthermore, the real-time monitoring approach developed in this study could also be extended to other metal alloy systems to reveal the reaction dynamics of intracluster diffusion of heteroatoms, as well as the formation mechanisms of metal alloy nanomaterials.},

  doi          = {10.1021/jacs.9b05776},

  journal      = {Journal of the American Chemical Society},

  number       = 48,

  volume       = 141,

  place        = {United States},

  year         = {Mon Oct 14 00:00:00 EDT 2019},

  month        = {Mon Oct 14 00:00:00 EDT 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/jacs.9b05776

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Revealing the etching process of water-soluble Au₂₅ nanoclusters at the molecular level

Journal Article Cao, Yitao ; Liu, Tongyu ; Chen, Tiankai ; ... - Nature Communications

Etching (often considered as decomposition) is one of the key considerations in the synthesis, storage, and application of metal nanoparticles. However, the underlying chemistry of their etching process still remains elusive. Here, we use real-time electrospray ionization mass spectrometry to study the reaction dynamics and size/structure evolution of all the stable intermediates during the etching of water-soluble thiolate-protected gold nanoclusters (Au NCs), which reveal an unusual “recombination” process in the oxidative reaction environment after the initial decomposition process. Interestingly, the sizes of NC species grow larger and their ligand-to-metal ratios become higher during this recombination process, which are distinctly differentmore »« less
https://doi.org/10.1038/s41467-021-23568-0

Full Text Available
Control of single-ligand chemistry on thiolated Au₂₅ nanoclusters

Journal Article Cao, Yitao ; Fung, Victor ; Yao, Qiaofeng ; ... - Nature Communications

Diverse methods have been developed to tailor the number of metal atoms in metal nanoclusters, but control of surface ligand number at a given cluster size is rare. Here we demonstrate that reversible addition and elimination of a single surface thiolate ligand (-SR) on gold nanoclusters can be realized, opening the door to precision ligand engineering on atomically precise nanoclusters. We find that oxidative etching of [Au₂₅SR₁₈]^– nanoclusters adds an excess thiolate ligand and generates a new species, [Au₂₅SR₁₉]⁰. The addition reaction can be reversed by CO reduction of [Au₂₅SR₁₉]⁰, leading back to [Au₂₅SR₁₈]^– and eliminating precisely one surface ligand.more »« less
https://doi.org/10.1038/s41467-020-19327-2

Full Text Available
A Quantum Alloy: The Ligand-Protected Au{sub 25-x}Ag{sub x}(SR){sub 18} Cluster

Journal Article Kauffman, Douglas R ; Alfonso, Dominic ; Matranga, Christopher ; ... - JOURNAL OF PHYSICAL CHEMISTRY C

Recent synthetic advances have produced very small (sub-2 nm), ligand-protected mixed-metal clusters. Realization of such clusters allows the investigation of fundamental questions: (1) Will heteroatoms occupy specific sites within the cluster? (2) How will the inclusion of heteroatoms affect the electronic structure and chemical properties of the cluster? (3) How will these very small mixed-metal systems differ from larger, more traditional alloy materials? In this report we provide experimental and computational characterization of the ligand-protected mixed-metal Au{sub 25–x}Ag{sub x}(SC{sub 2}H{sub 4}Ph){sub 18} cluster (abbreviated as Au{sub 25–x}Ag{sub x}, where x = 0–5 Ag atoms) compared with the unsubstituted Au{sub 25}(SC{submore »« less
https://doi.org/10.1021/jp4013224
A Quantum Alloy: The Ligand-Protected Au{sub 25-x}Ag{sub x}(SR){sub 18} Cluster

Journal Article Kauffman, Douglas R ; Alfonso, Dominic ; Matranga, Christopher ; ... - Journal of Physical Chemistry C

Recent synthetic advances have produced very small (sub-2 nm), ligand-protected mixed-metal clusters. Realization of such clusters allows the investigation of fundamental questions: (1) Will heteroatoms occupy specific sites within the cluster? (2) How will the inclusion of heteroatoms affect the electronic structure and chemical properties of the cluster? (3) How will these very small mixed-metal systems differ from larger, more traditional alloy materials? In this report we provide experimental and computational characterization of the ligand-protected mixed-metal Au{sub 25–x}Ag{sub x}(SC{sub 2}H{sub 4}Ph){sub 18} cluster (abbreviated as Au{sub 25–x}Ag{sub x}, where x = 0–5 Ag atoms) compared with the unsubstituted Au{sub 25}(SC{submore »« less
https://doi.org/10.1021/jp4013224
Atomically-precise dopant-controlled single cluster catalysis for electrochemical nitrogen reduction

Journal Article Yao, Chuanhao ; Guo, Na ; Xi, Shibo ; ... - Nature Communications

The ability to precisely engineer the doping of sub-nanometer bimetallic clusters offers exciting opportunities for tailoring their catalytic performance with atomic accuracy. However, the fabrication of singly dispersed bimetallic cluster catalysts with atomic-level control of dopants has been a long-standing challenge. Herein, we report a strategy for the controllable synthesis of a precisely doped single cluster catalyst consisting of partially ligand-enveloped Au₄Pt₂ clusters supported on defective graphene. This creates a bimetal single cluster catalyst (Au₄Pt₂/G) with exceptional activity for electrochemical nitrogen (N₂) reduction. Our mechanistic study reveals that each N₂ molecule is activated in the confined region between cluster andmore »« less
https://doi.org/10.1038/s41467-020-18080-w

Similar Records