Show simple item record

dc.contributor.authorBozal-Ginesta, Carlota
dc.contributor.authorRao, Reshma R
dc.contributor.authorMesa, Camilo A
dc.contributor.authorWang, Yuanxing
dc.contributor.authorZhao, Yanyan
dc.contributor.authorHu, Gongfang
dc.contributor.authorAntón-García, Daniel
dc.contributor.authorStephens, Ifan EL
dc.contributor.authorReisner, Erwin
dc.contributor.authorBrudvig, Gary W
dc.contributor.authorWang, Dunwei
dc.contributor.authorDurrant, James R
dc.date.accessioned2022-06-07T08:13:33Z
dc.date.available2022-06-07T08:13:33Z
dc.date.issued2022-05-18
dc.identifier.issn0002-7863
dc.identifier.other35511107
dc.identifier.otherPMC9121376
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/337795
dc.descriptionFunder: bp International Centre for Advanced Materials
dc.description.abstractWater oxidation is the step limiting the efficiency of electrocatalytic hydrogen production from water. Spectroelectrochemical analyses are employed to make a direct comparison of water oxidation reaction kinetics between a molecular catalyst, the dimeric iridium catalyst [Ir2(pyalc)2(H2O)4-(μ-O)]2+ (IrMolecular, pyalc = 2-(2'pyridinyl)-2-propanolate) immobilized on a mesoporous indium tin oxide (ITO) substrate, with that of an heterogeneous electrocatalyst, an amorphous hydrous iridium (IrOx) film. For both systems, four analogous redox states were detected, with the formation of Ir(4+)-Ir(5+) being the potential-determining step in both cases. However, the two systems exhibit distinct water oxidation reaction kinetics, with potential-independent first-order kinetics for IrMolecular contrasting with potential-dependent kinetics for IrOx. This is attributed to water oxidation on the heterogeneous catalyst requiring co-operative effects between neighboring oxidized Ir centers. The ability of IrMolecular to drive water oxidation without such co-operative effects is explained by the specific coordination environment around its Ir centers. These distinctions between molecular and heterogeneous reaction kinetics are shown to explain the differences observed in their water oxidation electrocatalytic performance under different potential conditions.
dc.languageeng
dc.publisherAmerican Chemical Society (ACS)
dc.rightsAttribution 4.0 International
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.sourcenlmid: 7503056
dc.sourceessn: 1520-5126
dc.titleSpectroelectrochemistry of Water Oxidation Kinetics in Molecular versus Heterogeneous Oxide Iridium Electrocatalysts.
dc.typeArticle
dc.date.updated2022-06-07T08:13:32Z
prism.endingPage8459
prism.issueIdentifier19
prism.publicationNameJ Am Chem Soc
prism.startingPage8454
prism.volume144
dc.identifier.doi10.17863/CAM.85204
rioxxterms.versionofrecord10.1021/jacs.2c02006
rioxxterms.versionVoR
rioxxterms.licenseref.urihttps://creativecommons.org/licenses/by/4.0/
dc.contributor.orcidBozal-Ginesta, Carlota [0000-0001-7299-5869]
dc.contributor.orcidRao, Reshma R [0000-0002-6655-3105]
dc.contributor.orcidMesa, Camilo A [0000-0002-8450-2563]
dc.contributor.orcidWang, Yuanxing [0000-0003-3742-7238]
dc.contributor.orcidZhao, Yanyan [0000-0002-1428-5022]
dc.contributor.orcidHu, Gongfang [0000-0002-0387-9079]
dc.contributor.orcidStephens, Ifan EL [0000-0003-2157-492X]
dc.contributor.orcidReisner, Erwin [0000-0002-7781-1616]
dc.contributor.orcidBrudvig, Gary W [0000-0002-7040-1892]
dc.contributor.orcidWang, Dunwei [0000-0001-5581-8799]
dc.contributor.orcidDurrant, James R [0000-0001-8353-7345]
dc.identifier.eissn1520-5126
pubs.funder-project-idEngineering and Physical Sciences Research Council (EP/M508007/1)
cam.issuedOnline2022-05-05


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record

Attribution 4.0 International
Except where otherwise noted, this item's licence is described as Attribution 4.0 International