Mechanism of Atmospheric CO2 Fixation in the Cavities of a Dinuclear Cryptate

DC FieldValueLanguage
dc.contributor.authorEl-Hendawy, Morad M.
dc.contributor.authorEnglish, Niall J.
dc.contributor.authorMooney, Damian A.
dc.date.accessioned2012-08-17T13:47:03Z
dc.date.available2012-08-17T13:47:03Z
dc.date.copyright2012 American Chemical Societyen
dc.date.issued2012-05-07
dc.identifier.citationInorganic Chemistryen
dc.identifier.urihttp://hdl.handle.net/10197/3743
dc.description.abstractUsing density functional theory (DFT) methods, we have investigated two possible mechanisms for atmospheric CO2 fixation in the cavity of the dinuclear zinc (II) octaazacryptate, and the subsequent reaction with methanol whereby this latter reaction transforms the (essentially) chemically inert CO2 into useful products. The first mechanism (I) was proposed by Chen et al. [Chem. Asian J. 2007, 2, 710], and involves the attachment of one CO2 molecule onto the hydroxyl-cryptate form, resulting in the formation of a bicarbonate-cryptate species and subsequent reaction with one methanol molecule. In addition, we suggest another mechanism that is initiated via the attachment of a methanol molecule onto one of the Zn-centres, yielding a methoxy-cryptate species. The product is used to activate a CO2 molecule and generate a methoxycarbonate-cryptate. The energy profiles of both mechanisms were determined and we conclude that, while both mechanisms are energetically feasible, free energy profiles suggest that the scheme proposed by Chen et al. is most likely.en
dc.description.sponsorshipScience Foundation Irelanden
dc.description.sponsorshipOther funderen
dc.format.extent5925789 bytes
dc.format.mimetypeapplication/pdf
dc.language.isoenen
dc.publisherACS Publicationsen
dc.relation.requiresChemical and Bioprocess Engineering Research Collectionen
dc.relation.requiresCSCB Research Collectionen
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/ic300224w.en
dc.subjectDFTen
dc.subjectCO2 fixationen
dc.subjectDinuclear cryptateen
dc.subjectTransition stateen
dc.subject.lcshDensity functionalsen
dc.subject.lcshAtmospheric carbon dioxideen
dc.subject.lcshCarbon cycle (Biogeochemistry)en
dc.titleMechanism of Atmospheric CO2 Fixation in the Cavities of a Dinuclear Cryptateen
dc.typeJournal Articleen
dc.internal.availabilityFull text availableen
dc.statusPeer revieweden
dc.identifier.volume51en
dc.identifier.issue9en
dc.identifier.startpage5282en
dc.identifier.endpage5288en
dc.identifier.doi10.1021/ic300224w-
dc.neeo.contributorEl-Hendawy|Morad M.|aut|-
dc.neeo.contributorEnglish|Niall J.|aut|-
dc.neeo.contributorMooney|Damian A.|aut|-
dc.description.othersponsorshipIrish Centre for High End Computingen
dc.description.adminEmbargo 12 monthen
item.grantfulltextopen-
item.fulltextWith Fulltext-
Appears in Collections:Solar Energy Conversion (SEC) Cluster Research Collection
Chemical and Bioprocess Engineering Research Collection
CSCB Research Collection
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