Electronic and reactivity changes in epitaxially grown Ce1-xZrxO2-δ (111) thin films

Mishra, Ashutosh; Robinson, Allison M.; Perkins, Craig L.; Karp, Eric M.; Medlin, J. Will

doi:10.1016/j.susc.2025.122739

Electronic and reactivity changes in epitaxially grown Ce_1-xZr_xO_2-δ (111) thin films

Journal Article · Mon Mar 17 00:00:00 EDT 2025 · Surface Science

DOI:https://doi.org/10.1016/j.susc.2025.122739· OSTI ID:2558982

Mishra, Ashutosh ^[1]; Robinson, Allison M. ^[2]; Perkins, Craig L. ^[3]; Karp, Eric M. ^[4]; ^[1]

Univ. of Colorado, Boulder, CO (United States)
US Department of Energy (USDOE), Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Crysalis BioSciences Inc., Louisville, CO (United States)

Ceria composite catalysts have long been used for ketonization reactions, which is a valuable chemistry for the upgrading of biomass-derived carboxylates. To better understand the interaction of zirconia with ceria in the context of ketonization, thin epitaxial films of ceria-zirconia mixed metal oxide Ce_1-xZr_xO_2-δ (x = 0-1) were grown on a Pt(111) substrate in ultrahigh vacuum conditions and studied with X-ray photoelectron spectroscopy (XPS). Core level and valence band XPS results suggest a strong interaction between ceria and zirconia cations, possibly due to increased filling of unoccupied 4f⁰ orbitals of ceria from neighboring Zr cations in the lattice structure. This leads to a partial reduction of ceria from Ce⁴⁺ to Ce³⁺, with Zr remaining predominantly in the 4+ oxidation state. Ketonization of acetic acid was studied using temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). These results found ketonization over mixed Ce-Zr composite oxides exhibited lower activation energies than for pure CeO₂ and ZrO₂, with Ce_0.38Zr_0.62O_2-δ exhibiting the highest yield of acetone among the studied surfaces. In conclusion, these results suggest the high activity of Ce-Zr catalysts appears to be a result of oxygen vacancy formation, stabilized by electron donation from Zr cations.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 2558982

Report Number(s):: NREL/JA--5K00-94363

Journal Information:: Surface Science, Journal Name: Surface Science Vol. 757; ISSN 0039-6028

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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