Fast Surface Oxygen Release Kinetics Accelerate Nanoparticle Exsolution in Perovskite Oxides

Wang, Jiayue; Kalaev, Dmitri; Yang, Jing; Waluyo, Iradwikanari; Hunt, Adrian; Sadowski, Jerzy T.; Tuller, Harry L.; Yildiz, Bilge

doi:10.1021/jacs.2c10256

Fast Surface Oxygen Release Kinetics Accelerate Nanoparticle Exsolution in Perovskite Oxides

Journal Article · Tue Jan 10 00:00:00 EST 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c10256· OSTI ID:1924197

^[1]; Kalaev, Dmitri ^[1]; ^[1]; ^[2]; ^[2]; ^[3]; Tuller, Harry L. ^[1]; ^[1]

Massachusetts Institute of Technology (MIT), Cambridge, MA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

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. In this report we probe the surface exsolution kinetics both experimentally and theoretically using thin-film perovskite SrTi_0.65Fe_0.35O₃ (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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1924197

Report Number(s):: BNL-224042-2023-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 3 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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