Noble metals supported on reducible oxides, like CoOxand TiOx, exhibit superior activity in many chemical reactions, but the origin of the increased activity is not well understood. To answer this question we studied thin films of CoOxsupported on an Au(111) single crystal surface as a model for the CO oxidation reaction. We show that three reaction regimes exist in response to chemical and topographic restructuring of the CoOxcatalyst as a function of reactant gas phase CO/O2stoichiometry and temperature. Under oxygen-lean conditions and moderate temperatures (≤150 °C), partially oxidized films (CoOx<1) containing Co0were found to be efficient catalysts. In contrast, stoichiometric CoO films containing only Co2+form carbonates in the presence of CO that poison the reaction below 300 °C. Under oxygen-rich conditions a more oxidized catalyst phase (CoOx>1) forms containing Co3+species that are effective in a wide temperature range. Resonant photoemission spectroscopy (ResPES) revealed the unique role of Co3+sites in catalyzing the CO oxidation. Density function theory (DFT) calculations provided deeper insights into the pathway and free energy barriers for the reactions on these oxide phases. These findings in this work highlight the versatility of catalysts and their evolution to form different active phases, both topological and chemically, in response to reaction conditions exposing a new paradigm in the catalyst structure during operation.
Density functional theory (DFT) and microkinetic modeling are used to examine the water‐gas shift (WGS) reaction on TiO2(110)‐supported single Pt atoms. A CO‐adsorbed Pt atom supported on a TiO2surface exhibits a lower activity for the WGS than the Pt2+ion supported on a doped TiO2surface, although DFT predicts the CO‐adsorbed Pt on an undoped TiO2surface to be thermodynamically more stable. Trends observed in WGS activity for different active sites of TiO2‐supported Pt catalysts can be explained in terms of CO adsorption strength and the ability to form an oxygen vacancy on the oxide support.
more » « less- NSF-PAR ID:
- 10040302
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Chemie Ingenieur Technik
- Volume:
- 89
- Issue:
- 10
- ISSN:
- 0009-286X
- Page Range / eLocation ID:
- p. 1343-1349
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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