High-Temperature Growth of CeOx on Au(111) and Behavior under Reducing and Oxidizing Conditions

Tschammer, Rudi; Buß, Lars; Pożarowska, Emilia; Morales, Carlos; Senanayake, Sanjaya D.; Prieto, Mauricio J.; Tănase, Liviu C.; de Souza Caldas, Lucas; Tiwari, Aarti; Schmidt, Thomas; Niño, Miguel A.; Foerster, Michael; Falta, Jens; Flege, Jan Ingo

doi:10.1021/acs.jpcc.4c08072

Title: High-Temperature Growth of CeO_x on Au(111) and Behavior under Reducing and Oxidizing Conditions

Journal Article · 11 February 2025 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.4c08072 · OSTI ID:2514551

Tschammer, Rudi ^[1]; Buß, Lars ^[2]; Pożarowska, Emilia ^[1]; Morales, Carlos ^[1];

^[3];

^[4];

^[4]; Niño, Miguel A. ^[5]; Foerster, Michael ^[5]; Falta, Jens ^[6];

^[1]

Brandenburg University of Technology, Cottbus (Germany)
Brandenburg University of Technology, Cottbus (Germany); University of Bremen (Germany)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Fritz-Haber-Institute of the Max-Planck Society, Berlin (Germany)
ALBA Synchrotron Light Facility, Cerdanyola del Valles (Spain)
University of Bremen (Germany)

Inverse oxide–metal model catalysts can show superior activity and selectivity compared with the traditional supported metal–oxide architecture, commonly attributed to the synergistic overlayer–support interaction. We have investigated the growth and redox properties of ceria nanoislands grown on Au(111) between 700 and 890 °C, which yields the CeO₂–Au(111) model catalyst system. We have observed a distinct correlation between deposition temperature, structural order, and oxide composition through low-energy electron microscopy, low-energy electron diffraction, intensity–voltage curves, and X-ray absorption spectroscopy. Improved structural order and thermal stability of the oxide have been achieved by increasing the oxygen chemical potential at the substrate surface using reactive oxygen (O/O₂) instead of molecular O₂ during growth. In situ characterization under reducing (H₂) and oxidizing atmospheres (O₂, CO₂) indicates an irreversible loss of structural order and redox activity at high reduction temperatures, while moderate temperatures result in partial decomposition of the ceria nanoislands (Ce³⁺/Ce⁴⁺) to metallic cerium (Ce⁰). The weak interaction between Au(111) and CeO_x would facilitate its reduction to the Ce⁰ metallic state, especially considering the comparatively strong interaction between Ce⁰ and Au⁰. Besides, the higher reactivity of atomic oxygen promotes a stronger interaction between the gold and oxide islands during the nucleation process, explaining the improved stability. Thus, we propose that by driving the nucleation and growth of the ceria/Au system in a highly oxidizing regime, novel chemical properties can be obtained.

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Research Organization:: Brandenburg University of Technology, Cottbus-Senftenberg (Germany); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: German Federal Ministry of Education and Research (BMBF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0012704

OSTI ID:: 2514551

Report Number(s):: BNL--227643-2025-JAAM

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 7 Vol. 129; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: High-Temperature Growth of CeOx on Au(111) and Behavior under Reducing and Oxidizing Conditions

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Title: High-Temperature Growth of CeO_x on Au(111) and Behavior under Reducing and Oxidizing Conditions