The partial oxidation of propene to acrolein over single-crystal Cu₂O

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dc.contributor.authorSchulz, Kirk H.en
dc.contributor.committeechairCox, Daviden
dc.contributor.committeememberMerola, Joseph S.en
dc.contributor.committeememberDillard, John G.en
dc.contributor.committeememberDavis, Mark E.en
dc.contributor.committeememberAnderson, Mark R.en
dc.contributor.departmentChemical Engineeringen
dc.date.accessioned2014-03-14T21:09:42Zen
dc.date.adate2007-02-26en
dc.date.available2014-03-14T21:09:42Zen
dc.date.issued1991en
dc.date.rdate2007-02-26en
dc.date.sdate2007-02-26en
dc.description.abstractThe partial oxidation of propene (CH₂=CHCH3) to acrolein (CH₂=CHCHO) has been studied over Cu₂0(100) and (111) single crystal surfaces. Propene adsorption under ultrahigh vacuum conditions yields no significant oxidation products, but the propene desorption temperatures are sensitive to the structural differences in the surfaces. Propene adsorption at atmospheric pressure followed by thermal desorption in ultrahigh vacuum demonstrates that propene may be activated at higher pressures. Over the nonpolar Cu₂0(111) surface, lattice oxygen insertion occurs at 300 K and 1 atm. with the formation of the σ-bonded allyl intermediate. Once formed, this specie is stable in ultrahigh vacuum and produces acrolein during TDS via a reaction-limited process. A comparison of these data with studies of allyl alcohol decomposition over Cu₂O surfaces indicate that the σ-bonded intermediate is surface allyloxy (CH₂=CH-CH₂0-) which dehydrogenates to acrolein via hydride elimination on the carbon α to the oxygen. Thus, oxygen insertion precedes the final hydrogen abstraction in the partial oxidation pathway. Propene is also observed during allyl alcohol decomposition indicating that the transformation of the π-allyl to the σ-allyl (allyloxy) during propene oxidation is reversible. The structure sensitivity of the propene oxidation reaction is demonstrated by the lack of acrolein production from the Cu-terminated, Cu₂0(100) surface following 1 atm. propene exposures. The origin of the structure sensitivity is related to the absence of coordinately-unsaturated lattice oxygen anions on the (100) surface.en
dc.description.degreePh. D.en
dc.format.extentxii, 180 leavesen
dc.format.mediumBTDen
dc.format.mimetypeapplication/pdfen
dc.identifier.otheretd-02262007-095951en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-02262007-095951/en
dc.identifier.urihttp://hdl.handle.net/10919/37413en
dc.language.isoenen
dc.publisherVirginia Techen
dc.relation.haspartLD5655.V856_1991.S348.pdfen
dc.relation.isformatofOCLC# 25651227en
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subject.lccLD5655.V856 1991.S348en
dc.subject.lcshCopper catalystsen
dc.subject.lcshPropene -- Oxidationen
dc.titleThe partial oxidation of propene to acrolein over single-crystal Cu₂Oen
dc.typeDissertationen
dc.type.dcmitypeTexten
thesis.degree.disciplineChemical Engineeringen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

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