4.6 Article

Tuning Strong Metal-Support Interaction Kinetics on Pt-Loaded TiO2 (110) by Choosing the Pressure: A Combined Ultrahigh Vacuum/ Near-Ambient Pressure XPS Study

Journal

JOURNAL OF PHYSICAL CHEMISTRY C
Volume 126, Issue 38, Pages 16127-16139

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.2c03851

Keywords

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Funding

  1. Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) [EXC 2089/1-390776260, CRC1441, 426888090]
  2. European Research Council (ERC) under the European Union [850764]
  3. Office of Science of the U.S. DOE [DE-AC0205CH11231]
  4. Young Academy of Sciences and Humanities
  5. Kekule Scholarship of the Fonds der Chemischen Industrie
  6. Condensed Phase and Interfacial Molecular Science Program in the Chemical Sciences Geosciences and Biosciences Division of the Office of Basic Energy Sciences of the U.S. Department of Energy [DE-AC02-05CH11231]

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The study shows that O-2 and H-2 have a significant impact on the SMSI state of Pt/TiO2 catalysts, with encapsulating oxide layer forming more rapidly at low O-2 pressures, but less effectively at higher pressures. The oxidation/reduction of Pt particles is reversible, but once encapsulated, they remain embedded in the support.
Pt catalyst particles on reducible oxide supports often change their activity significantly at elevated temperatures due to the strong metal-support interaction (SMSI), which induces the formation of an encapsulation layer around the noble metal particles. However, the impact of oxidizing and reducing treatments at elevated pressures on this encapsulation layer remains controversial, partly due to the pressure gap between surface science studies and applied catalysis. In the present work, we employ synchrotron-based near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) to study the effect of O-2 and H-2 on the SMSI-state of well-defined Pt/TiO2(110) catalysts at pressures of up to 0.1 Torr. By tuning the O-2 pressure, we can either selectively oxidize the TiO2 support or both the support and the Pt particles. Catalyzed by metallic Pt, the encapsulating oxide overlayer grows rapidly in 1 x 10(-5) Torr O-2, but orders of magnitude less effectively at higher O-2 pressures, where Pt is in an oxidic state. While the oxidation/reduction of Pt particles is reversible, they remain embedded in the support once encapsulation has occurred.

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