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

Abstract

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 different from that observed in the reductive growth of Au NCs (e.g., lower ligand-to-metal ratios with increasing sizes). The etching chemistry revealed in this study provides molecular-level understandings on how metal nanoparticles transform under the oxidative reaction environment, providing efficient synthetic strategies for new NC species through the etching reactions.

Authors:

Cao, Yitao ^[1]; Liu, Tongyu ^[2]; Chen, Tiankai ^[1]; Zhang, Bihan ^[3]; Jiang, De-en  ^[2];

• Search DOE PAGES for author "Jiang, De-en"
• Search DOE PAGES for ORCID "0000-0001-5167-0731"

Xie, Jianping  ^[3]

• Search DOE PAGES for author "Xie, Jianping"
• Search DOE PAGES for ORCID "0000-0002-3254-5799"

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+ Show Author Affiliations

1. National Univ. of Singapore (Singapore)
2. Univ. of California, Riverside, CA (United States)
3. National Univ. of Singapore (Singapore); Joint School of National University of Singapore and Tianjin University (China)

Publication Date:

Fri May 28 00:00:00 EDT 2021

Research Org.:

Univ. of California, Riverside, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Ministry of Education, Singapore

OSTI Identifier:

1816714

Grant/Contract Number:  

R-279-000-580-112; R-279-000-538-114; R-279-000-634-114

Resource Type:

Accepted Manuscript

Journal Name:

Nature Communications

Additional Journal Information:

Journal Volume: 12; Journal Issue: 1; Journal ID: ISSN 2041-1723

Publisher:

Nature Publishing Group

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nanoparticles; synthesis and processing