Pt Particles on a Dynamic TiO2 Support in Near-Ambient Conditions−Disentangling Size, Pressure, and Support Effects

Kraushofer, Florian; Krinninger, Matthias; de la Higuera-Domingo, Marina; Falling, Lorenz; Strauss, Lukas; Kaiser, Sebastian; Salehi, Mohammad; Anand, Gaurav; Dieste, Virginia Pérez; Blum, Monika; Lechner, Barbara A. J.

doi:10.1021/jacs.5c14353

Pt Particles on a Dynamic TiO₂ Support in Near-Ambient Conditions−Disentangling Size, Pressure, and Support Effects

Journal Article · Fri Oct 17 00:00:00 EDT 2025 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5c14353· OSTI ID:3000753

^[1]; ^[1]; de la Higuera-Domingo, Marina ^[1]; Falling, Lorenz ^[1]; Strauss, Lukas ^[1]; ^[1]; ^[1]; Anand, Gaurav ^[1]; Dieste, Virginia Pérez ^[2]; ^[3]; ^[1]

Technical Univ. of Munich (Germany)
ALBA Synchrotron Light Source, Cerdanyola del Valles (Spain)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Platinum particles on reducible oxides are known to form complex and highly dynamic catalyst systems at elevated pressures and temperatures, often adopting active structures that differ from those found at room temperature and under ultrahigh vacuum (UHV). Here, we study the oxidation and structural evolution of subnanometer Pt clusters and nanoparticles supported on rutile TiO₂(110) across an oxygen pressure range from UHV to 0.1 mbar, using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), scanning tunneling microscopy (STM) under UHV and NAP conditions, and low-energy ion scattering (LEIS). Our results reveal distinct differences in oxidation behavior and thermal stability between Pt nanoparticles and clusters, which are further modulated by the support stoichiometry and oxygen pressure. Small Pt clusters become oxidized even at room temperature but are susceptible to accelerated sintering in 0.1 mbar O₂ at elevated temperatures. In contrast, well-crystallized Pt nanoparticles on near-stoichiometric TiO₂ show weaker oxidation. On a reduced, defective TiO₂ support, Pt instead quickly becomes deeply buried by new titania layers, which are formed during support reoxidation. This process appears to result primarily from interactions of the support with the gas phase, unlike the classical, selflimited encapsulation that is induced by the strong metal−support interaction (SMSI). Finally, we address the full complexity of real catalysts in a direct side-by-side comparison of the single-crystalline model system with a Pt-loaded TiO₂ powder catalyst (P25). We conclude that the stoichiometry of the model supports must be carefully chosen and controlled to accurately reproduce the expected state of powder supports during redox reactions.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 3000753

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 43 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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Pt Particles on a Dynamic TiO2 Support in Near-Ambient Conditions−Disentangling Size, Pressure, and Support Effects

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