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dc.contributor.author
Zhao, Chuanlin
dc.contributor.author
Watt, Charles
dc.contributor.author
Kent, Paul R.
dc.contributor.author
Overbury, Steven H.
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Mullins, David R.
dc.contributor.author
Calaza, Florencia Carolina
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dc.contributor.author
Savara, Aditya
dc.contributor.author
Xu, Ye
dc.date.available
2019-08-18T21:15:12Z
dc.date.issued
2019-04
dc.identifier.citation
Zhao, Chuanlin; Watt, Charles; Kent, Paul R.; Overbury, Steven H.; Mullins, David R.; et al.; Coupling of Acetaldehyde to Crotonaldehyde on CeO 2-x (111): Bifunctional Mechanism and Role of Oxygen Vacancies; American Chemical Society; Journal of Physical Chemistry C; 123; 13; 4-2019; 8273-8286
dc.identifier.issn
1932-7447
dc.identifier.uri
http://hdl.handle.net/11336/81777
dc.description.abstract
Selective C-C coupling of oxygenates is pertinent to the manufacture of fuel and chemical products from biomass and from derivatives of C 1 compounds (i.e., oxygenates produced from methane and CO 2 ). Here we report a combined experimental and theoretical study on the temperature-programmed reaction (TPR) of acetaldehyde (AcH) on a partially reduced CeO 2-x (111) thin film surface. The experiments have been carried out under ultra-high-vacuum conditions without continuous gas exposure, allowing better isolation of active sites and reactive intermediates than in flow reaction conditions. AcH does not undergo aldol condensation in a typical TPR procedure, even though the enolate form of AcH (CH 2 CHO) is readily produced on CeO 2-x (111) with oxygen vacancies. We find however that a tailored "double-ramp" TPR procedure is able to successfully produce an aldol adduct, crotonaldehyde (CrA). Using density functional theory calculations and microkinetic modeling we explore several possible C-C coupling pathways. We conclude that the double-ramp procedure allows surface oxygen vacancy dimers, stabilized by adsorbate occupation, to form dynamically during the TPR. The vacancy dimers in turn enable C-C coupling to occur between an enolate and an adjacent AcH molecule via a bifunctional enolate-keto mechanism that is distinct from conventional acid-or base-catalyzed aldol condensation reactions. The proposed mechanism indicates that CrA desorption is rate-limiting while C-C coupling is facile.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
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dc.rights
info:eu-repo/semantics/restrictedAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Crotonaldehyde
dc.subject
Ceo2
dc.subject
Oxygen Vacancies
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C-C Coupling
dc.subject.classification
Físico-Química, Ciencia de los Polímeros, Electroquímica
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dc.subject.classification
Ciencias Químicas
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dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
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dc.title
Coupling of Acetaldehyde to Crotonaldehyde on CeO 2-x (111): Bifunctional Mechanism and Role of Oxygen Vacancies
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2019-08-01T19:59:14Z
dc.journal.volume
123
dc.journal.number
13
dc.journal.pagination
8273-8286
dc.journal.pais
Estados Unidos
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dc.description.fil
Fil: Zhao, Chuanlin. Louisiana State University;
dc.description.fil
Fil: Watt, Charles. University of Princeton; Estados Unidos. Oak Ridge National Laboratory;
dc.description.fil
Fil: Kent, Paul R.. Oak Ridge National Laboratory;
dc.description.fil
Fil: Overbury, Steven H.. Oak Ridge National Laboratory;
dc.description.fil
Fil: Mullins, David R.. Oak Ridge National Laboratory;
dc.description.fil
Fil: Calaza, Florencia Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
dc.description.fil
Fil: Savara, Aditya. Oak Ridge National Laboratory;
dc.description.fil
Fil: Xu, Ye. Louisiana State University;
dc.journal.title
Journal of Physical Chemistry C
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dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/acs.jpcc.8b08535
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