Fermi Level Equilibration and Charge Transfer at the Exsolved Metal-Oxide Interface

Wang, Jiayue; Yang, Jing; Wardini, Jenna L.; Waluyo, Iradwikanari; Hunt, Adrian; Crumlin, Ethan J.; Fairley, Neal; Bowman, William J.; Hwang, Harold Y.; Yildiz, Bilge

doi:10.1021/jacs.4c14695

Fermi Level Equilibration and Charge Transfer at the Exsolved Metal-Oxide Interface

Journal Article · Thu Jan 16 00:00:00 EST 2025 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c14695· OSTI ID:2569474

^[1]; ^[2]; Wardini, Jenna L. ^[3]; ^[4]; ^[4]; ^[5]; Fairley, Neal ^[6]; ^[3]; Hwang, Harold Y. ^[7]; ^[8]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Max Planck Institute for Sustainable Materials, Düsseldorf (Germany)
Univ. of California, Irvine, CA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Casa Software Ltd, Teignmouth, Devon (United Kingdom)
Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Exsolution is a promising approach for fabricating oxide-supported metal nanocatalysts through redox-driven metal precipitation. A defining feature of exsolved nanocatalysts is their anchored metal-oxide interface, which exhibits exceptional structural stability in (electro)catalysis. However, the electronic interactions at this unique interface remain unclear, despite their known impact on catalytic performance. In this study, we confirm charge transfer between the host oxide and the exsolved metal by demonstrating a two-stage Fermi level (E_F) evolution on SrTi_0.65Fe_0.35O_3−δ (STF) during metallic iron (Fe⁰) exsolution. Combining ambient pressure X-ray photoelectron spectroscopy with theoretical analysis, we show that E_F initially rises due to electron doping from oxygen vacancy formation in STF. Subsequently, upon Fe⁰ precipitation, E_F stabilizes and becomes insensitive to further oxygen release in STF, driven by E_F equilibration and charge transfer between STF and the exsolved Fe⁰. In conclusion, these findings highlight the importance of considering electronic metal–support interactions when optimizing exsolved nanocatalysts.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Organization:: Gordon and Betty Moore Foundation; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; SC0012704

OSTI ID:: 2569474

Report Number(s):: BNL--228287-2025-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 4 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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