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

Yin Xiong, Yao Yang, Howie Joress, Elliot Padgett, Unmukt Gupta, Venkata Yarlagadda, David N. Agyeman-Budu, Xin Huang, Thomas E. Moylan, Rui Zeng, Anusorn Kongkanand, Fernando A. Escobedo, Joel D. Brock, Francis J. DiSalvo, David A. Muller, and Héctor D. Abruña
PNAS February 5, 2019 116 (6) 1974-1983; published ahead of print February 5, 2019 https://doi.org/10.1073/pnas.1815643116
Yin Xiong
aDepartment of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853;
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Yao Yang
aDepartment of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853;
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Howie Joress
bCornell High Energy Synchrotron Source, Cornell University, Ithaca, NY 14850;cDepartment of Materials Science and Engineering, Cornell University, Ithaca, NY 14850;
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Elliot Padgett
dSchool of Applied and Engineering Physics, Cornell University, Ithaca, NY 14853;
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Unmukt Gupta
eRobert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, NY 14853;
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Venkata Yarlagadda
fFuel Cell R&D, General Motors Global Propulsion Systems, Pontiac, MI 48340;
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David N. Agyeman-Budu
bCornell High Energy Synchrotron Source, Cornell University, Ithaca, NY 14850;cDepartment of Materials Science and Engineering, Cornell University, Ithaca, NY 14850;
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Xin Huang
bCornell High Energy Synchrotron Source, Cornell University, Ithaca, NY 14850;
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Thomas E. Moylan
fFuel Cell R&D, General Motors Global Propulsion Systems, Pontiac, MI 48340;
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Rui Zeng
aDepartment of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853;
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Anusorn Kongkanand
fFuel Cell R&D, General Motors Global Propulsion Systems, Pontiac, MI 48340;
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Fernando A. Escobedo
eRobert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, NY 14853;
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Joel D. Brock
bCornell High Energy Synchrotron Source, Cornell University, Ithaca, NY 14850;dSchool of Applied and Engineering Physics, Cornell University, Ithaca, NY 14853;
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Francis J. DiSalvo
aDepartment of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853;
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  • For correspondence: hda1@cornell.edudm24@cornell.edufjd3@cornell.edu
David A. Muller
dSchool of Applied and Engineering Physics, Cornell University, Ithaca, NY 14853;gKavli Institute at Cornell for Nanoscale Science, Cornell University, Ithaca, NY 14853
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  • For correspondence: hda1@cornell.edudm24@cornell.edufjd3@cornell.edu
Héctor D. Abruña
aDepartment of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853;
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  • For correspondence: hda1@cornell.edudm24@cornell.edufjd3@cornell.edu
  1. Contributed by Héctor D. Abruña, December 14, 2018 (sent for review September 10, 2018; reviewed by Plamen Atanassov, Marc Koper, and Eugene S. Smotkin)

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Significance

We present a comprehensive quantitative study of the dynamic order–disorder phase transition of Pt3Co nanoparticles, binary intermetallic oxygen-reduction reaction fuel cell electrocatalysts, during postsynthesis annealing. We employed in situ synchrotron-based X-ray diffraction (XRD) and in situ scanning transmission EM (STEM) to study the phase transition and morphological and structural changes during real-time annealing. In situ XRD revealed the impact of annealing/cooling conditions on the degree of ordering, particle size and lattice strain. In situ heating STEM enabled visualization of nanoparticle migration and growth. We find that a higher degree of ordering leads to more active and durable electrocatalysts. Our findings represent a groundbreaking advance in electrocatalyst development/design with a broad impact on energy materials, in general, and fuel cells, in particular.

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. Here, 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.

  • in situ heating TEM
  • in situ heating XRD
  • ordered intermetallics
  • order–disorder phase transition
  • oxygen reduction reaction

Footnotes

  • ↵1Y.X., Y.Y., and H.J. contributed equally to this work.

  • ↵2To whom correspondence may be addressed. Email: hda1{at}cornell.edu, dm24{at}cornell.edu, or fjd3{at}cornell.edu.
  • Author contributions: Y.X., Y.Y., A.K., F.A.E., J.D.B., F.J.D., D.A.M., and H.D.A. designed research; H.J. designed the in situ heating setup; Y.X., Y.Y., H.J., E.P., U.G., V.Y., D.N.A.-B., X.H., T.E.M., and R.Z. performed research; Y.X., Y.Y., and H.J. performed the in situ heating XRD experiment; Y.Y. and E.P. performed the in situ heating TEM experiment; U.G. performed the Monte Carlo simulation; Y.X., Y.Y., H.J., and E.P. analyzed data; and Y.X., Y.Y., H.J., and E.P. wrote the paper.

  • Reviewers: P.A., University of California, Irvine; M.K., Leiden University; and E.S.S., Northeastern University.

  • The authors declare no conflict of interest.

  • This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1815643116/-/DCSupplemental.

Published under the PNAS license.

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Revealing the atomic ordering of binary intermetallics using in situ heating techniques at multilength scales
Yin Xiong, Yao Yang, Howie Joress, Elliot Padgett, Unmukt Gupta, Venkata Yarlagadda, David N. Agyeman-Budu, Xin Huang, Thomas E. Moylan, Rui Zeng, Anusorn Kongkanand, Fernando A. Escobedo, Joel D. Brock, Francis J. DiSalvo, David A. Muller, Héctor D. Abruña
Proceedings of the National Academy of Sciences Feb 2019, 116 (6) 1974-1983; DOI: 10.1073/pnas.1815643116

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Revealing the atomic ordering of binary intermetallics using in situ heating techniques at multilength scales
Yin Xiong, Yao Yang, Howie Joress, Elliot Padgett, Unmukt Gupta, Venkata Yarlagadda, David N. Agyeman-Budu, Xin Huang, Thomas E. Moylan, Rui Zeng, Anusorn Kongkanand, Fernando A. Escobedo, Joel D. Brock, Francis J. DiSalvo, David A. Muller, Héctor D. Abruña
Proceedings of the National Academy of Sciences Feb 2019, 116 (6) 1974-1983; DOI: 10.1073/pnas.1815643116
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