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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, providemore » important atomic-scale mechanistic details regarding the role of kinetics and chemical driving force in dictating shape transformations at the nanometer length scale.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1];  [3];  [2]; ORCiD logo [4]
  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:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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

Citation Formats

Hauwiller, Matthew R., Frechette, Layne B., Jones, Matthew R., Ondry, Justin C., Rotskoff, Grant M., Geissler, Phillip, and Alivisatos, A. Paul. Unraveling Kinetically-Driven Mechanisms of Gold Nanocrystal Shape Transformations Using Graphene Liquid Cell Electron Microscopy. United States: N. p., 2018. Web. doi:10.1021/acs.nanolett.8b02337.
Hauwiller, Matthew R., Frechette, Layne B., Jones, Matthew R., Ondry, Justin C., Rotskoff, Grant M., Geissler, Phillip, & Alivisatos, A. Paul. Unraveling Kinetically-Driven Mechanisms of Gold Nanocrystal Shape Transformations Using Graphene Liquid Cell Electron Microscopy. United States. doi:10.1021/acs.nanolett.8b02337.
Hauwiller, Matthew R., Frechette, Layne B., Jones, Matthew R., Ondry, Justin C., Rotskoff, Grant M., Geissler, Phillip, and Alivisatos, A. Paul. Thu . "Unraveling Kinetically-Driven Mechanisms of Gold Nanocrystal Shape Transformations Using Graphene Liquid Cell Electron Microscopy". United States. doi:10.1021/acs.nanolett.8b02337. https://www.osti.gov/servlets/purl/1532337.
@article{osti_1532337,
title = {Unraveling Kinetically-Driven Mechanisms of Gold Nanocrystal Shape Transformations Using Graphene Liquid Cell Electron Microscopy},
author = {Hauwiller, Matthew R. and Frechette, Layne B. and Jones, Matthew R. and Ondry, Justin C. and Rotskoff, Grant M. and Geissler, Phillip and Alivisatos, A. Paul},
abstractNote = {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 important atomic-scale mechanistic details regarding the role of kinetics and chemical driving force in dictating shape transformations at the nanometer length scale.},
doi = {10.1021/acs.nanolett.8b02337},
journal = {Nano Letters},
number = 9,
volume = 18,
place = {United States},
year = {2018},
month = {8}
}

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Works referenced in this record:

Videos of Etching Gold Nanocubes and Nanorhombic Dodecahedra in Graphene Liquid Cell Transmission Electron Microscopy
dataset, January 2018

  • Hauwiller, Matthew; Ondry, Justin; Alivisatos, A. Paul
  • UC Berkeley
  • DOI: 10.6078/d14h46

    Works referencing / citing this record:

    Videos of Etching Gold Nanocubes and Nanorhombic Dodecahedra in Graphene Liquid Cell Transmission Electron Microscopy
    dataset, January 2018

    • Hauwiller, Matthew; Ondry, Justin; Alivisatos, A. Paul
    • UC Berkeley
    • DOI: 10.6078/d14h46