Title: Unraveling Kinetically-Driven Mechanisms of Gold Nanocrystal Shape Transformations Using Graphene Liquid Cell Electron Microscopy

Abstract

Mechanisms of kinetically driven nanocrystal shape transformations were elucidated by monitoring single particle etching of gold nanocrystals using in situ graphene liquid cell transmission electron microscopy (TEM). By systematically changing the chemical potential of the oxidative etching and then quantifying the facets of the nanocrystals, nonequilibrium processes of atom removal could be deduced. Etching at sufficiently high oxidation potentials, both cube and rhombic dodecahedra (RDD)-shaped gold nanocrystals transform into kinetically stable tetrahexahedra (THH)-shaped particles. Whereas {100}-faceted cubes adopt an {hko}-faceted THH intermediate where h/k depends on chemical potential, {110}-faceted RDD adopt a {210}-faceted THH intermediate regardless of driving force. For cube reactions, Monte Carlo simulations show that removing 6-coordinate edge atoms immediately reveals 7-coordinate interior atoms. The rate at which these 6- and 7-coordinate atoms are etched is sensitive to the chemical potential, resulting in different THH facet structures with varying driving force. Conversely, when RDD are etched to THH, removal of 6-coordinate edge atoms reveals 6-coordinate interior atoms. Thus, changing the driving force for oxidation does not change the probability of edge atom versus interior atom removal, leading to a negligible effect on the kinetically stabilized intermediate shape. These fundamental insights, facilitated by single-particle liquid-phase TEM imaging, provide importantmore » atomic-scale mechanistic details regarding the role of kinetics and chemical driving force in dictating shape transformations at the nanometer length scale.« less

Authors:

Hauwiller, Matthew R.  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-5448-6937"
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Frechette, Layne B.  ^[2];

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• Search DOE PAGES for ORCID "0000-0002-4263-6651"
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Jones, Matthew R.  ^[1];

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Ondry, Justin C.  ^[1];

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Rotskoff, Grant M. ^[3]; Geissler, Phillip ^[2]; Alivisatos, A. Paul  ^[4]

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• Search DOE PAGES for ORCID "0000-0001-6895-9048"
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+ Show Author Affiliations

1. Univ. of California, Berkeley, CA (United States)
2. Univ. of California, Berkeley, CA (United States); Univ. of Vienna (Austria)
3. New York Univ. (NYU), NY (United States)
4. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Inst., Berkeley, CA (United States)

Publication Date:

2018-08-02

Research Org.:

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1532337

Grant/Contract Number:  

AC02-05CH11231

Resource Type:

Accepted Manuscript

Journal Name:

Nano Letters

Additional Journal Information:

Journal Volume: 18; Journal Issue: 9; Journal ID: ISSN 1530-6984

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

77 NANOSCIENCE AND NANOTECHNOLOGY; Graphene liquid cell; TEM; nanocrystals; oxidative etching