Origin of the High CO Oxidation Activity on CeO2 Supported Pt Nanoparticles: Weaker Binding of CO or Facile Oxygen Transfer from the Support?
Abstract
Abstract Pt clusters supported on CeO 2 are highly active for low temperature CO oxidation. The enhanced reactivity could be caused by weakening of the CO binding on Pt, allowing adsorbed oxygen to more effectively compete for sites. An alternative explanation is that interfacial sites allow adsorbed CO on Pt to react with lattice oxygen in the ceria. Here we explore the origins of enhanced CO oxidation reactivity on Pt/CeO 2 using in‐situ/operando infrared and x‐ray spectroscopies, microcalorimetry, and reaction kinetics. We show that CO adsorbs strongly (∼110–120 kJ/mol) on Pt clusters (∼1.5 nm) and Pt is almost fully covered by CO during reaction, indicating that the high activity can be related to reactive interfacial O* species. Using in‐situ infrared spectroscopy we show that when the reaction mixture of CO and O 2 stops flowing over the catalyst, the adsorbed CO on Pt is lost since it reacts with interfacial O*, but if this O* is depleted, the CO band does not disappear. The role of CeO 2 is not to alter the binding of CO, but rather to enhance the reactivity of the interfacial metal‐support lattice oxygens. The reaction mechanism involving the interfacial Pt−CeO 2 sites (two‐site mechanism) is further confirmedmore »
- Authors:
-
[1]
- Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
- Univ. of New Mexico, Albuquerque, NM (United States)
- Publication Date:
- Research Org.:
- Univ. of New Mexico, Albuquerque, NM (United States); Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Sponsoring Org.:
- US Army Research Office (ARO); US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1800255
- Alternate Identifier(s):
- OSTI ID: 1598399
- Grant/Contract Number:
- FG02-05ER15712; AC02-76SF00515; W911NF-16-1-0400; FA9550-18-1-0413
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemCatChem
- Additional Journal Information:
- Journal Volume: 12; Journal Issue: 6; Journal ID: ISSN 1867-3880
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; Pt/CeO2; CO oxidation; reaction kinetics; spectroscopy; calorimetry
Citation Formats
Lu, Yubing, Thompson, Coogan, Kunwar, Deepak, Datye, Abhaya K., and Karim, Ayman M. Origin of the High CO Oxidation Activity on CeO2 Supported Pt Nanoparticles: Weaker Binding of CO or Facile Oxygen Transfer from the Support?. United States: N. p., 2019.
Web. doi:10.1002/cctc.201901848.
Lu, Yubing, Thompson, Coogan, Kunwar, Deepak, Datye, Abhaya K., & Karim, Ayman M. Origin of the High CO Oxidation Activity on CeO2 Supported Pt Nanoparticles: Weaker Binding of CO or Facile Oxygen Transfer from the Support?. United States. https://doi.org/10.1002/cctc.201901848
Lu, Yubing, Thompson, Coogan, Kunwar, Deepak, Datye, Abhaya K., and Karim, Ayman M. Fri .
"Origin of the High CO Oxidation Activity on CeO2 Supported Pt Nanoparticles: Weaker Binding of CO or Facile Oxygen Transfer from the Support?". United States. https://doi.org/10.1002/cctc.201901848. https://www.osti.gov/servlets/purl/1800255.
@article{osti_1800255,
title = {Origin of the High CO Oxidation Activity on CeO2 Supported Pt Nanoparticles: Weaker Binding of CO or Facile Oxygen Transfer from the Support?},
author = {Lu, Yubing and Thompson, Coogan and Kunwar, Deepak and Datye, Abhaya K. and Karim, Ayman M.},
abstractNote = {Abstract Pt clusters supported on CeO 2 are highly active for low temperature CO oxidation. The enhanced reactivity could be caused by weakening of the CO binding on Pt, allowing adsorbed oxygen to more effectively compete for sites. An alternative explanation is that interfacial sites allow adsorbed CO on Pt to react with lattice oxygen in the ceria. Here we explore the origins of enhanced CO oxidation reactivity on Pt/CeO 2 using in‐situ/operando infrared and x‐ray spectroscopies, microcalorimetry, and reaction kinetics. We show that CO adsorbs strongly (∼110–120 kJ/mol) on Pt clusters (∼1.5 nm) and Pt is almost fully covered by CO during reaction, indicating that the high activity can be related to reactive interfacial O* species. Using in‐situ infrared spectroscopy we show that when the reaction mixture of CO and O 2 stops flowing over the catalyst, the adsorbed CO on Pt is lost since it reacts with interfacial O*, but if this O* is depleted, the CO band does not disappear. The role of CeO 2 is not to alter the binding of CO, but rather to enhance the reactivity of the interfacial metal‐support lattice oxygens. The reaction mechanism involving the interfacial Pt−CeO 2 sites (two‐site mechanism) is further confirmed by kinetic measurements which show near zero order dependence on CO and O 2 partial pressures.},
doi = {10.1002/cctc.201901848},
journal = {ChemCatChem},
number = 6,
volume = 12,
place = {United States},
year = {Fri Dec 27 00:00:00 EST 2019},
month = {Fri Dec 27 00:00:00 EST 2019}
}
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