4.8 Article

Thermally Stable and Regenerable Platinum-Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 56, Issue 31, Pages 8986-8991

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201701115

Keywords

catalyst regeneration; ceria; light alkane dehydrogenation; single atoms; subnanometer Pt-Sn catalysis

Funding

  1. US Department of Energy [DE-FG02-05ER15712]
  2. Center for Biorenewable Chemicals (CBiRC) - NSF [EEC-0813570]
  3. National Natural Science Foundation of China [21673040]
  4. Natural Science Foundation of Fujian Province [2016J01052]
  5. National Science Foundation [CHE-1462019]
  6. European Research Council (ERC) [321140]
  7. DOE's Office of Biological and Environmental Research

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Ceria (CeO2) supports are unique in their ability to trap ionic platinum (Pt), providing exceptional stability for isolated single atoms of Pt. The reactivity and stability of single-atom Pt species was explored for the industrially important light alkane dehydrogenation reaction. The single-atom Pt/CeO2 catalysts are stable during propane dehydrogenation, but are not selective for propylene. DFT calculations show strong adsorption of the olefin produced, leading to further unwanted reactions. In contrast, when tin (Sn) is added to CeO2, the single-atom Pt catalyst undergoes an activation phase where it transforms into Pt-Sn clusters under reaction conditions. Formation of small Pt-Sn clusters allows the catalyst to achieve high selectivity towards propylene because of facile desorption of the product. The CeO2-supported Pt-Sn clusters are very stable, even during extended reaction at 680 degrees C. Coke formation is almost completely suppressed by adding water vapor to the feed. Furthermore, upon oxidation the Pt-Sn clusters readily revert to the atomically dispersed species on CeO2, making Pt-Sn/CeO2 a fully regenerable catalyst.

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