Fast Surface Oxygen Release Kinetics Accelerate Nanoparticle Exsolution in Perovskite Oxides
Name
jiayue_JACS_2023.pdf
Description
Accepted version
Size
4.61 MB
Format
Adobe PDF
Checksum (MD5)
84ad8175ac021946a3548c2db8aee06a
Author(s)
Wang, Jiayue
Kalaev, Dmitri
Yang, Jing
Waluyo, Iradwikanari
Hunt, Adrian
Sadowski, Jerzy T
Tuller, Harry L
Yildiz, Bilge
Date Issued
January 10, 2023
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Wang, Jiayue, Kalaev, Dmitri, Yang, Jing, Waluyo, Iradwikanari, Hunt, Adrian et al. 2023. "Fast Surface Oxygen Release Kinetics Accelerate Nanoparticle Exsolution in Perovskite Oxides." Journal of the American Chemical Society.
Version
Author's final manuscript
Abstract
Exsolution is a recent advancement for fabricating oxide-supported metal nanoparticle catalysts via phase precipitation out of a host oxide. A fundamental understanding and control of the exsolution kinetics are needed to engineer exsolved nanoparticles to obtain higher catalytic activity toward clean energy and fuel conversion. Since oxygen release via oxygen vacancy formation in the host oxide is behind oxide reduction and metal exsolution, we hypothesize that the kinetics of metal exsolution should depend on the kinetics of oxygen release, in addition to the kinetics of metal cation diffusion. Here, we probe the surface exsolution kinetics both experimentally and theoretically using thin-film perovskite SrTi0.65Fe0.35O3 (STF) as a model system. We quantitatively demonstrated that in this system the surface oxygen release governs the metal nanoparticle exsolution kinetics. As a result, by increasing the oxygen release rate in STF, either by reducing the sample thickness or by increasing the surface reactivity, one can effectively accelerate the Fe0 exsolution kinetics. Fast oxygen release kinetics in STF not only shortened the prereduction time prior to the exsolution onset, but also increased the total quantity of exsolved Fe0 over time, which agrees well with the predictions from our analytical kinetic modeling. The consistency between the results obtained from in situ experiments and analytical modeling provides a predictive capability for tailoring exsolution, and highlights the importance of engineering host oxide surface oxygen release kinetics in designing exsolved nanocatalysts.
MIT Department
Massachusetts Institute of Technology. Department of Nuclear Science and Engineering
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Creative Commons Attribution-Noncommercial-Share Alike
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DOI of Published Version
https://doi.org/10.1021/jacs.2c10256
