Evolution of metastable structures on bimetallic surfaces from microscopy and machine-learning molecular dynamics

ORAL

Abstract

Restructuring of interfaces plays a crucial role in materials science and heterogeneous catalysis. In particular, bimetallic surfaces often adopt very different composition and morphology compared to the bulk. For the first time, we reveal a detailed long-timescale restructuring of Pd deposited on Ag by combining microscopy, spectroscopy, and novel simulation methods. We develop and perform accelerated machine-learning molecular dynamics, followed by automated mechanistic characterization, to discover surface restructuring events in an unbiased fashion, including Pd-Ag place exchange and Ag pop-out. We find that encapsulation of Pd islands by Ag always precedes layer-by-layer dissolution of Pd into Ag, resulting in significant migration of Ag out of the surface and leaving behind extensive vacancy pits within microseconds. Because Ag-encapsulated Pd remains much more accessible to reactants than bulk-dissolved Pd, these metastable structures are of vital catalytic importance. Systematic investigation of other bimetallic systems (e.g. Pd/Au, Pt/Ag, Co/Pt) and adsorbate-induced restructuring (e.g. CO, H2) is underway.

*Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the US Department of Energy (Award No. DE-SC0012573)

Presenters

  • Jin Soo Lim

    • Chemistry and Chemical Biology, Harvard University
    • Chemistry & Chemical Biology, Harvard University
    • John A. Paulson School of Engineering and Applied Sciences, Harvard University
    • Harvard University

Authors

  • Jin Soo Lim

    • Chemistry and Chemical Biology, Harvard University
    • Chemistry & Chemical Biology, Harvard University
    • John A. Paulson School of Engineering and Applied Sciences, Harvard University
    • Harvard University
  • Jonathan Vandermause

    • Physics, Harvard University
    • Harvard University
    • John A. Paulson School of Engineering and Applied Sciences, Harvard University
  • Matthijs A. van Spronsen

    • Chemistry and Chemical Biology, Harvard University
  • Albert Musaelian

    • John A. Paulson School of Engineering and Applied Sciences, Harvard University
  • Yu Xie

    • Harvard University
    • John A. Paulson School of Engineering and Applied Sciences, Harvard University
    • School of Engineering & Applied Sciences, Harvard University
  • Lixin Sun

    • John A. Paulson School of Engineering and Applied Sciences, Harvard University
    • School of Engineering & Applied Sciences, Harvard University
    • Harvard University
  • Christopher O'Connor

    • Chemistry and Chemical Biology, Harvard University
    • Chemistry, Harvard University
  • Tobias Egle

    • John A. Paulson School of Engineering and Applied Sciences, Harvard University
  • Nicola Molinari

    • Harvard University
    • John A. Paulson School of Engineering and Applied Sciences, Harvard University
  • Jacob Florian

    • Chemistry and Chemical Biology, Harvard University
  • Kaining Duanmu

    • Chemical and Biomolecular Engineering, University of California Los Angeles
  • Robert J. Madix

    • John A. Paulson School of Engineering and Applied Sciences, Harvard University
  • Philippe Sautet

    • Chemical and Biomolecular Engineering, University of California Los Angeles
  • Cynthia Friend

    • Chemistry and Chemical Biology, Harvard University
    • Chemistry, Harvard University
  • Boris Kozinsky

    • Harvard University
    • John A. Paulson School of Engineering and Applied Sciences, Harvard University
    • School of Engineering & Applied Sciences, Harvard University