Activation of CO2 at chromia-nanocluster-modified rutile and anatase TiO2

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dc.contributor.author Nolan, Michael
dc.contributor.author Fronzi, Marco
dc.date.accessioned 2018-12-03T09:36:03Z
dc.date.available 2018-12-03T09:36:03Z
dc.date.issued 2018-11-27
dc.identifier.citation Nolan, M. and Fronzi, M. (2018) 'Activation of CO2 at chromia-nanocluster-modified rutile and anatase TiO2', Catalysis Today. doi:10.1016/j.cattod.2018.11.062 en
dc.identifier.issn 0920-5861
dc.identifier.uri http://hdl.handle.net/10468/7162
dc.identifier.doi 10.1016/j.cattod.2018.11.062
dc.description.abstract Converting CO2 to fuels is required to enable the production of sustainable fuels and to contribute to alleviating CO2 emissions. In considering conversion of CO2, the initial step of adsorption and activation by the catalyst is crucial. In addressing this difficult problem, we have examined how nanoclusters of reducible metal oxides supported on TiO2 can promote CO2 activation. In this paper we present density functional theory (DFT) simulations of CO2 activation on heterostructures composed of clean or hydroxylated extended rutile and anatase TiO2 surfaces modified with chromia nanoclusters. The heterostructures show non-bulk Cr and O sites in the nanoclusters and an upshifted valence band edge that is dominated by Cr 3d- O 2p interactions. We show that the supported chromia nanoclusters can adsorb and activate CO2 and that activation of CO2 is promoted whether the TiO2 support is oxidised or hydroxylated. Reduced heterostructures, formed by removal of oxygen from the chromia nanocluster, also promote CO2 activation. In the strong CO2 adsorption modes, the molecule bends giving OCO angles of 127 - 132° and elongation of CO distances up to 1.30 Å; no carbonates are formed. The electronic properties show a strong CO2CrO interaction that drives the interaction of CO2 with the nanocluster and induces the structural distortions. These results highlight that a metal oxide support modified with reducible metal oxide nanoclusters can activate CO2, thus helping to overcome difficulties associated with the difficult first step in CO2 conversion. en
dc.description.sponsorship Science Foundation Ireland (M-ERA.net co-fund program - Grant Number SFI 16/M-ERA/2918) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher Elsevier B.V. en
dc.rights © 2018, Elsevier B.V. All rights reserved. This manuscript version is made available under the CC-BY-NC-ND 4.0 license. en
dc.rights.uri https://creativecommons.org/licenses/by-nc-nd/4.0/ en
dc.subject DFT en
dc.subject CO2 Activation en
dc.subject Adsorption en
dc.subject Heterostructures en
dc.title Activation of CO2 at chromia-nanocluster-modified rutile and anatase TiO2 en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Michael Nolan, Tyndall Theory Modelling & Design Centre, University College Cork, Cork, Ireland. +353-21-490-3000 Email: michael.nolan@tyndall.ie en
dc.internal.availability Full text available en
dc.check.info Access to this article is restricted until 24 months after publication by request of the publisher. en
dc.check.date 2020-11-27
dc.date.updated 2018-12-03T09:17:22Z
dc.description.version Accepted Version en
dc.internal.rssid 464181895
dc.contributor.funder Science Foundation Ireland en
dc.contributor.funder Horizon 2020 en
dc.description.status Peer reviewed en
dc.identifier.journaltitle Catalysis Today en
dc.internal.copyrightchecked Yes en
dc.internal.licenseacceptance Yes en
dc.internal.IRISemailaddress michael.nolan@tyndall.ie en
dc.internal.bibliocheck In press. Add vol. / issue / page numbers. Amend citation as necessary.
dc.relation.project info:eu-repo/grantAgreement/SFI/SFI US Ireland R&D Partnership/14/US/E2915/IE/SusChEM: Using theory-driven design to tailor novel nanocomposite oxides for solar fuel production/ en
dc.relation.project info:eu-repo/grantAgreement/EC/H2020::ERA-NET-Cofund/685451/EU/ERA-NET for materials research and innovation/M-ERA.NET 2 en


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© 2018, Elsevier B.V. All rights reserved.  This manuscript version is made available under the CC-BY-NC-ND 4.0 license. Except where otherwise noted, this item's license is described as © 2018, Elsevier B.V. All rights reserved. This manuscript version is made available under the CC-BY-NC-ND 4.0 license.
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