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Title: Stability limits and defect dynamics in Ag nanoparticles probed by Bragg coherent diffractive imaging

Abstract

Dissolution is critical to nanomaterial stability, especially for partially dealloyed nanoparticle catalysts. Unfortunately, highly active catalysts are often not stable in their reactive environments, preventing widespread application. Thus, focusing on the structure–stability relationship at the nanoscale is crucial and will likely play an important role in meeting grand challenges. Recent advances in imaging capability have come from electron, X-ray, and other techniques but tend to be limited to specific sample environments and/or two-dimensional images. Here, we report investigations into the defect-stability relationship of silver nanoparticles to voltage-induced electrochemical dissolution imaged in situ in three dimensional detail by Bragg coherent diffractive imaging. We first determine the average dissolution kinetics by stationary probe rotating disk electrode in combination with inductively coupled plasma mass spectrometry, which allows in situ measurement of Ag+ ion formation. We then observe the dissolution and redeposition processes in single nanocrystals, providing unique insight about the role of surface strain, defects, and their coupling to the dissolution chemistry. Finally, the methods developed and the knowledge gained go well beyond a “simple” silver electrochemistry and are applicable to all electrocatalytic reactions where functional links between activity and stability are controlled by structure and defect dynamics.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences and Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1346723
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 17; Journal Issue: 3; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Y., Lopes, P. P., Cha, W., Harder, R., Maser, J., Maxey, E., Highland, M. J., Markovic, N. M., Hruszkewycz, S. O., Stephenson, G. B., You, H., and Ulvestad, A. Stability limits and defect dynamics in Ag nanoparticles probed by Bragg coherent diffractive imaging. United States: N. p., 2017. Web. doi:10.1021/acs.nanolett.6b04760.
Liu, Y., Lopes, P. P., Cha, W., Harder, R., Maser, J., Maxey, E., Highland, M. J., Markovic, N. M., Hruszkewycz, S. O., Stephenson, G. B., You, H., & Ulvestad, A. Stability limits and defect dynamics in Ag nanoparticles probed by Bragg coherent diffractive imaging. United States. doi:10.1021/acs.nanolett.6b04760.
Liu, Y., Lopes, P. P., Cha, W., Harder, R., Maser, J., Maxey, E., Highland, M. J., Markovic, N. M., Hruszkewycz, S. O., Stephenson, G. B., You, H., and Ulvestad, A. Fri . "Stability limits and defect dynamics in Ag nanoparticles probed by Bragg coherent diffractive imaging". United States. doi:10.1021/acs.nanolett.6b04760. https://www.osti.gov/servlets/purl/1346723.
@article{osti_1346723,
title = {Stability limits and defect dynamics in Ag nanoparticles probed by Bragg coherent diffractive imaging},
author = {Liu, Y. and Lopes, P. P. and Cha, W. and Harder, R. and Maser, J. and Maxey, E. and Highland, M. J. and Markovic, N. M. and Hruszkewycz, S. O. and Stephenson, G. B. and You, H. and Ulvestad, A.},
abstractNote = {Dissolution is critical to nanomaterial stability, especially for partially dealloyed nanoparticle catalysts. Unfortunately, highly active catalysts are often not stable in their reactive environments, preventing widespread application. Thus, focusing on the structure–stability relationship at the nanoscale is crucial and will likely play an important role in meeting grand challenges. Recent advances in imaging capability have come from electron, X-ray, and other techniques but tend to be limited to specific sample environments and/or two-dimensional images. Here, we report investigations into the defect-stability relationship of silver nanoparticles to voltage-induced electrochemical dissolution imaged in situ in three dimensional detail by Bragg coherent diffractive imaging. We first determine the average dissolution kinetics by stationary probe rotating disk electrode in combination with inductively coupled plasma mass spectrometry, which allows in situ measurement of Ag+ ion formation. We then observe the dissolution and redeposition processes in single nanocrystals, providing unique insight about the role of surface strain, defects, and their coupling to the dissolution chemistry. Finally, the methods developed and the knowledge gained go well beyond a “simple” silver electrochemistry and are applicable to all electrocatalytic reactions where functional links between activity and stability are controlled by structure and defect dynamics.},
doi = {10.1021/acs.nanolett.6b04760},
journal = {Nano Letters},
number = 3,
volume = 17,
place = {United States},
year = {Fri Feb 10 00:00:00 EST 2017},
month = {Fri Feb 10 00:00:00 EST 2017}
}

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  • Polycrystalline material properties depend on the distribution and interactions of their crystalline grains. In particular, grain boundaries and defects are crucial in determining their response to external stimuli. A long-standing challenge is thus to observe individual grains, defects, and strain dynamics inside functional materials. Here we report a technique capable of revealing grain heterogeneity, including strain fields and individual dislocations, that can be used under operando conditions in reactive environments: grain Bragg coherent diffractive imaging (gBCDI). Using a polycrystalline gold thin film subjected to heating, we show how gBCDI resolves grain boundary and dislocation dynamics in individual grains in three-dimensionalmore » detail with 10-nanometer spatial and subangstrom displacement field resolution. Finally, these results pave the way for understanding polycrystalline material response under external stimuli and, ideally, engineering particular functions.« less
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