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

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Title: Mechanism of Atmospheric CO2 Fixation in the Cavities of a Dinuclear Cryptate
Authors: El-Hendawy, Morad M.English, Niall J.Mooney, Damian A.
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Date: 7-May-2012
Online since: 2012-08-17T13:47:03Z
Abstract: Using 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.
Funding Details: Science Foundation Ireland
Other funder
metadata.dc.description.othersponsorship: Irish Centre for High End Computing
Type of material: Journal Article
Publisher: ACS Publications
Journal: Inorganic Chemistry
Volume: 51
Issue: 9
Start page: 5282
End page: 5288
Copyright (published version): 2012 American Chemical Society
Keywords: DFTCO2 fixationDinuclear cryptateTransition state
Subject LCSH: Density functionals
Atmospheric carbon dioxide
Carbon cycle (Biogeochemistry)
DOI: 10.1021/ic300224w
Language: en
Status of Item: Peer reviewed
Appears in Collections:Solar Energy Conversion (SEC) Cluster Research Collection
Chemical and Bioprocess Engineering Research Collection
CSCB Research Collection

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