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

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.

doi:10.1073/pnas.1815643116

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

Journal Article · 21 January 2019 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.1815643116 · OSTI ID:1491622

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.

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.

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Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0007271

OSTI ID:: 1491622

Alternate ID(s):: OSTI ID: 1613422

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 6 Vol. 116; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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