Exsolution-Driven Surface Transformation in the Host Oxide

Wang, Jiayue; Kumar, Abinash; Wardini, Jenna L.; Zhang, Zhan; Zhou, Hua; Crumlin, Ethan J.; Sadowski, Jerzy T.; Woller, Kevin B.; Bowman, William J.; LeBeau, James M.; Yildiz, Bilge

doi:10.1021/acs.nanolett.2c01439

Exsolution-Driven Surface Transformation in the Host Oxide

Journal Article · Thu Jun 30 00:00:00 EDT 2022 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.2c01439· OSTI ID:1875471

^[1]; Kumar, Abinash ^[1]; Wardini, Jenna L. ^[2]; Zhang, Zhan ^[3]; ^[3]; ^[4]; ^[5]; Woller, Kevin B. ^[1]; ^[2]; LeBeau, James M. ^[1]; ^[1]

Massachusetts Institute of Technology (MIT), Cambridge, MA (United States)
University of California, Irvine, CA (United States)
Argonne National Laboratory (ANL), Lemont, IL (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

Exsolution synthesizes self-assembled metal nanoparticle catalysts via phase precipitation. An overlooked aspect in this method thus far is how exsolution affects the host oxide surface chemistry and structure. Such information is critical as the oxide itself can also contribute to the overall catalytic activity. Here, combining X-ray and electron probes, we investigated the surface transformation of thin-film SrTi_0.65Fe_0.35O₃ during Fe⁰ exsolution. We found that exsolution generates a highly Fe-deficient near-surface layer of about 2 nm thick. Moreover, the originally single-crystalline oxide near-surface region became partially polycrystalline after exsolution. Such drastic transformations at the surface of the oxide are important because the exsolution-induced nonstoichiometry and grain boundaries can alter the oxide ion transport and oxygen exchange kinetics and, hence, the catalytic activity toward water splitting or hydrogen oxidation reactions. These findings highlight the need to consider the exsolved oxide surface, in addition to the metal nanoparticles, in designing the exsolved nanocatalysts.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Lemont, IL (United States); 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:: AC02-05CH11231; AC02-06CH11357; SC0012704

OSTI ID:: 1875471

Alternate ID(s):: OSTI ID: 1970705

Report Number(s):: BNL-223126-2022-JAAM

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 13 Vol. 22; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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