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Title: Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy

Abstract

Graphene liquid cell electron microscopy has the needed temporal and spatial resolution to enable the in situ observation of nanoscale dynamics in solution. Yet, the chemistry of the solution in the liquid cell during imaging is as yet poorly understood due to the generation of a complex mixture of radiolysis products by the electron beam. In this work, the etching trajectories of nanocrystals were used as a probe to determine the effect of the electron beam dose rate and preloaded etchant, FeCl 3, on the chemistry of the liquid cell. Initially, illuminating the sample at a low electron beam dose rate generates hydrogen bubbles, providing a reservoir of sacrificial reductant. Increasing the electron beam dose rate leads to a constant etching rate that varies linearly with the electron beam dose rate. Comparing these conclusions with the oxidation potentials of the species in solution, the electron beam likely controls the total concentration of oxidative species in solution and FeCl 3 likely controls the relative ratio of oxidative species, independently determining the etching rate and chemical potential of the reaction, respectively. Correlating these liquid cell etching results with the ex situ oxidative etching of gold nanocrystals using FeCl 3 provides further insightmore » into the liquid cell chemistry while corroborating the liquid cell dynamics with ex situ synthetic behavior. This understanding of the chemistry in the liquid cell will allow researchers to better control the liquid cell electron microscopy environment, enabling new nanoscale materials science experiments to be conducted systematically in a reproducible manner.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), 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). Materials Sciences & Engineering Division
OSTI Identifier:
1542379
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 10; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Hauwiller, Matthew R., Ondry, Justin C., Chan, Cindy M., Khandekar, Prachi, Yu, Jessica, and Alivisatos, A. Paul. Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy. United States: N. p., 2019. Web. doi:10.1021/jacs.9b00082.
Hauwiller, Matthew R., Ondry, Justin C., Chan, Cindy M., Khandekar, Prachi, Yu, Jessica, & Alivisatos, A. Paul. Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy. United States. doi:10.1021/jacs.9b00082.
Hauwiller, Matthew R., Ondry, Justin C., Chan, Cindy M., Khandekar, Prachi, Yu, Jessica, and Alivisatos, A. Paul. Tue . "Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy". United States. doi:10.1021/jacs.9b00082.
@article{osti_1542379,
title = {Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy},
author = {Hauwiller, Matthew R. and Ondry, Justin C. and Chan, Cindy M. and Khandekar, Prachi and Yu, Jessica and Alivisatos, A. Paul},
abstractNote = {Graphene liquid cell electron microscopy has the needed temporal and spatial resolution to enable the in situ observation of nanoscale dynamics in solution. Yet, the chemistry of the solution in the liquid cell during imaging is as yet poorly understood due to the generation of a complex mixture of radiolysis products by the electron beam. In this work, the etching trajectories of nanocrystals were used as a probe to determine the effect of the electron beam dose rate and preloaded etchant, FeCl3, on the chemistry of the liquid cell. Initially, illuminating the sample at a low electron beam dose rate generates hydrogen bubbles, providing a reservoir of sacrificial reductant. Increasing the electron beam dose rate leads to a constant etching rate that varies linearly with the electron beam dose rate. Comparing these conclusions with the oxidation potentials of the species in solution, the electron beam likely controls the total concentration of oxidative species in solution and FeCl3 likely controls the relative ratio of oxidative species, independently determining the etching rate and chemical potential of the reaction, respectively. Correlating these liquid cell etching results with the ex situ oxidative etching of gold nanocrystals using FeCl3 provides further insight into the liquid cell chemistry while corroborating the liquid cell dynamics with ex situ synthetic behavior. This understanding of the chemistry in the liquid cell will allow researchers to better control the liquid cell electron microscopy environment, enabling new nanoscale materials science experiments to be conducted systematically in a reproducible manner.},
doi = {10.1021/jacs.9b00082},
journal = {Journal of the American Chemical Society},
number = 10,
volume = 141,
place = {United States},
year = {2019},
month = {2}
}

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This content will become publicly available on February 19, 2020
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