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dc.contributor.authorWindle, Christopher D
dc.contributor.authorPastor, Ernest
dc.contributor.authorReynal, Anna
dc.contributor.authorWhitwood, Adrian C
dc.contributor.authorVaynzof, Yana
dc.contributor.authorDurrant, James R
dc.contributor.authorPerutz, Robin N
dc.contributor.authorReisner, Erwin
dc.date.accessioned2015-03-23T12:05:13Z
dc.date.available2015-03-23T12:05:13Z
dc.date.issued2015-02-23
dc.identifier.citationChemistry - a European Journal, 2015, 21, 3746 – 3754, DOI: 10.1002/chem.201405041
dc.identifier.issn0947-6539
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/247139
dc.description.abstractThe photocatalytic activity of phosphonated Re complexes, [Re(2,2'-bipyridine-4,4'-bisphosphonic acid) (CO)3(L)] (ReP; L = 3-picoline or bromide) immobilised on TiO2 nanoparticles is reported. The heterogenised Re catalyst on the semiconductor, ReP-TiO2 hybrid, displays an improvement in CO2 reduction photocatalysis. A high turnover number (TON) of 48 molCO molRe(-1) is observed in DMF with the electron donor triethanolamine at λ>420 nm. ReP-TiO2 compares favourably to previously reported homogeneous systems and is the highest TON reported to date for a CO2-reducing Re photocatalyst under visible light irradiation. Photocatalytic CO2 reduction is even observed with ReP-TiO2 at wavelengths of λ>495 nm. Infrared and X-ray photoelectron spectroscopies confirm that an intact ReP catalyst is present on the TiO2 surface before and during catalysis. Transient absorption spectroscopy suggests that the high activity upon heterogenisation is due to an increase in the lifetime of the immobilised anionic Re intermediate (t50% >1 s for ReP-TiO2 compared with t50% = 60 ms for ReP in solution) and immobilisation might also reduce the formation of inactive Re dimers. This study demonstrates that the activity of a homogeneous photocatalyst can be improved through immobilisation on a metal oxide surface by favourably modifying its photochemical kinetics.
dc.description.sponsorshipFinancial support from the EPSRC (EP/H00338X/2 to E.R.; studentship and Doctoral Prize to C.D.W.; DTP scholarship to E.P.), the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and the 28 National Foundation for Research, Technology and Development) and the OMV Group (to E.R.), the ERC (project Intersolar to J.D.) and the European Commission Marie Curie CIG (PCIG10-GA-2011-303650 to A.R.) is gratefully acknowledged.
dc.languageEnglish
dc.language.isoen
dc.publisherWiley
dc.rightsAttribution 2.0 UK: England & Wales
dc.rightsCreative Commons Attribution License 2.0 UK
dc.rights.urihttp://creativecommons.org/licenses/by/2.0/uk/
dc.titleImproving the photocatalytic reduction of CO2 to CO through immobilisation of a molecular Re catalyst on TiO2.
dc.typeArticle
dc.description.versionThis is the final published version. It first appeared in Chemistry - a European Journal, 2015, 21, 3746 – 3754, DOI: 10.1002/chem.201405041
prism.endingPage3754
prism.publicationDate2015
prism.publicationNameChemistry
prism.startingPage3746
prism.volume21
dc.rioxxterms.funderEPSRC
dc.rioxxterms.funderERC
dc.rioxxterms.projectidEP/H00338X/2
rioxxterms.versionofrecord10.1002/chem.201405041
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserved
rioxxterms.licenseref.startdate2015-01-29
dc.contributor.orcidReisner, Erwin [0000-0002-7781-1616]
dc.identifier.eissn1521-3765
rioxxterms.typeJournal Article/Review
pubs.funder-project-idEngineering and Physical Sciences Research Council (EP/H00338X/2)
cam.issuedOnline2015-01-29


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Attribution 2.0 UK: England & Wales
Except where otherwise noted, this item's licence is described as Attribution 2.0 UK: England & Wales