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Title: Revealing the atomic ordering of binary intermetallics using in situ heating techniques at multilength scales

Abstract

Ordered intermetallic nanoparticles are promising electrocatalysts with enhanced activity and durability for the oxygen-reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). The ordered phase is generally identified based on the existence of superlattice ordering peaks in powder X-ray diffraction (PXRD). However, after employing a widely used postsynthesis annealing treatment, we have found that claims of “ordered” catalysts were possibly/likely mixed phases of ordered intermetallics and disordered solid solutions. In this work, we employed in situ heating, synchrotron-based, X-ray diffraction to quantitatively investigate the impact of a variety of annealing conditions on the degree of ordering of large ensembles of Pt3Co nanoparticles. Monte Carlo simulations suggest that Pt3Co nanoparticles have a lower order–disorder phase transition (ODPT) temperature relative to the bulk counterpart. Furthermore, we employed microscopic-level in situ heating electron microscopy to directly visualize the morphological changes and the formation of both fully and partially ordered nanoparticles at the atomic scale. In general, a higher degree of ordering leads to more active and durable electrocatalysts. The annealed Pt3Co/C with an optimal degree of ordering exhibited significantly enhanced durability, relative to the disordered counterpart, in practical membrane electrode assembly (MEA) measurements. The results highlight the importance of understanding the annealing processmore » to maximize the degree of ordering in intermetallics to optimize electrocatalytic activity.« less

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
General Motors LLC, Detroit, MI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Science Foundation (NSF)
OSTI Identifier:
1491622
Alternate Identifier(s):
OSTI ID: 1613422
Grant/Contract Number:  
EE0007271; DMR-1429155; DMR-1719875; DMR-1332208
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 6; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; science & technology - other topics; in situ heating TEM; in situ heating XRD; ordered intermetallics; order–disorder phase transition; oxygen reduction reaction

Citation Formats

Xiong, Yin, Yang, Yao, Joress, Howie, Padgett, Elliot, Gupta, Unmukt, Yarlagadda, Venkata, Agyeman-Budu, David N., Huang, Xin, Moylan, Thomas E., Zeng, Rui, Kongkanand, Anusorn, Escobedo, Fernando A., Brock, Joel D., DiSalvo, Francis J., Muller, David A., and Abruña, Héctor D. Revealing the atomic ordering of binary intermetallics using in situ heating techniques at multilength scales. United States: N. p., 2019. Web. doi:10.1073/pnas.1815643116.
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Xiong, Yin, Yang, Yao, Joress, Howie, Padgett, Elliot, Gupta, Unmukt, Yarlagadda, Venkata, Agyeman-Budu, David N., Huang, Xin, Moylan, Thomas E., Zeng, Rui, Kongkanand, Anusorn, Escobedo, Fernando A., Brock, Joel D., DiSalvo, Francis J., Muller, David A., & Abruña, Héctor D. Revealing the atomic ordering of binary intermetallics using in situ heating techniques at multilength scales. United States. https://doi.org/10.1073/pnas.1815643116
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Xiong, Yin, Yang, Yao, Joress, Howie, Padgett, Elliot, Gupta, Unmukt, Yarlagadda, Venkata, Agyeman-Budu, David N., Huang, Xin, Moylan, Thomas E., Zeng, Rui, Kongkanand, Anusorn, Escobedo, Fernando A., Brock, Joel D., DiSalvo, Francis J., Muller, David A., and Abruña, Héctor D. Tue . "Revealing the atomic ordering of binary intermetallics using in situ heating techniques at multilength scales". United States. https://doi.org/10.1073/pnas.1815643116.
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@article{osti_1491622,
title = {Revealing the atomic ordering of binary intermetallics using in situ heating techniques at multilength scales},
author = {Xiong, Yin and Yang, Yao and Joress, Howie and Padgett, Elliot and Gupta, Unmukt and Yarlagadda, Venkata and Agyeman-Budu, David N. and Huang, Xin and Moylan, Thomas E. and Zeng, Rui and Kongkanand, Anusorn and Escobedo, Fernando A. and Brock, Joel D. and DiSalvo, Francis J. and Muller, David A. and Abruña, Héctor D.},
abstractNote = {Ordered intermetallic nanoparticles are promising electrocatalysts with enhanced activity and durability for the oxygen-reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). The ordered phase is generally identified based on the existence of superlattice ordering peaks in powder X-ray diffraction (PXRD). However, after employing a widely used postsynthesis annealing treatment, we have found that claims of “ordered” catalysts were possibly/likely mixed phases of ordered intermetallics and disordered solid solutions. In this work, we employed in situ heating, synchrotron-based, X-ray diffraction to quantitatively investigate the impact of a variety of annealing conditions on the degree of ordering of large ensembles of Pt3Co nanoparticles. Monte Carlo simulations suggest that Pt3Co nanoparticles have a lower order–disorder phase transition (ODPT) temperature relative to the bulk counterpart. Furthermore, we employed microscopic-level in situ heating electron microscopy to directly visualize the morphological changes and the formation of both fully and partially ordered nanoparticles at the atomic scale. In general, a higher degree of ordering leads to more active and durable electrocatalysts. The annealed Pt3Co/C with an optimal degree of ordering exhibited significantly enhanced durability, relative to the disordered counterpart, in practical membrane electrode assembly (MEA) measurements. The results highlight the importance of understanding the annealing process to maximize the degree of ordering in intermetallics to optimize electrocatalytic activity.},
doi = {10.1073/pnas.1815643116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 6,
volume = 116,
place = {United States},
year = {2019},
month = {1}
}
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https://doi.org/10.1073/pnas.1815643116
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