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dc.contributor.author
Sad, Maria Eugenia
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dc.contributor.author
Neurock, Matthew
dc.contributor.author
Iglesia, Enrique
dc.date.available
2018-07-23T18:57:47Z
dc.date.issued
2011-12
dc.identifier.citation
Sad, Maria Eugenia; Neurock, Matthew; Iglesia, Enrique; Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts; American Chemical Society; Journal of the American Chemical Society; 133; 50; 12-2011; 20384-20398
dc.identifier.issn
0002-7863
dc.identifier.uri
http://hdl.handle.net/11336/52868
dc.description.abstract
This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H 2 and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO 2 through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H 2O using H 2 added or formed in situ from CO/H 2O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H 2 equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H 2, propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
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dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Deoxigenation
dc.subject
Alkanediols
dc.subject
Alkanols
dc.subject
Copper Catalysts
dc.subject.classification
Otras Ingeniería Química
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dc.subject.classification
Ingeniería Química
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dc.subject.classification
INGENIERÍAS Y TECNOLOGÍAS
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dc.title
Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2018-07-20T14:18:22Z
dc.journal.volume
133
dc.journal.number
50
dc.journal.pagination
20384-20398
dc.journal.pais
Estados Unidos
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dc.description.fil
Fil: Sad, Maria Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentina. University of California at Berkeley; Estados Unidos
dc.description.fil
Fil: Neurock, Matthew. University of Virginia; Estados Unidos
dc.description.fil
Fil: Iglesia, Enrique. University of California at Berkeley; Estados Unidos
dc.journal.title
Journal of the American Chemical Society
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dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/ja207551f
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/ja207551f
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