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Origin of the High CO Oxidation Activity on CeO 2 Supported Pt Nanoparticles: Weaker Binding of CO or Facile Oxygen Transfer from the Support?
Author(s) -
Lu Yubing,
Thompson Coogan,
Kunwar Deepak,
Datye Abhaya K.,
Karim Ayman M.
Publication year - 2020
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201901848
Subject(s) - reactivity (psychology) , catalysis , oxygen , kinetics , chemistry , isothermal microcalorimetry , adsorption , metal , reaction mechanism , infrared spectroscopy , nanoparticle , photochemistry , inorganic chemistry , materials science , nanotechnology , organic chemistry , enthalpy , medicine , physics , alternative medicine , pathology , quantum mechanics
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.