Improving the Photocatalytic Reduction of CO2 to CO through Immobilisation of a Molecular Re Catalyst on TiO2

Hdl Handle:
http://hdl.handle.net/10149/595940
Title:
Improving the Photocatalytic Reduction of CO2 to CO through Immobilisation of a Molecular Re Catalyst on TiO2
Authors:
Windle, C. D. (Christopher); Pastor, E. (Ernest); Reynal, A. (Anna); Whitwood, A. C. (Adrian); Vaynzof, Y. (Yana); Durrant, J. R. (James); Perutz, R. N. (Robin); Reisner, E. (Erwin)
Affiliation:
Teesside University, School of Science & Engineering.
Citation:
Windle, C.D.; Pastor, E.; Reynal, A.; Whitwood, A. C.; Vaynzof, Y.; Durrant, J. R.; Perutz, R. N.; Reisner, E. 'Improving the photocatalytic reduction of CO2 to CO through immobilization of a molecular Re catalyst onto TiO2' Chemistry - A European Journal; 21(9): 3746–3754.
Publisher:
Wiley-VCH Verlag
Journal:
Chemistry - A European Journal
Issue Date:
23-Feb-2015
URI:
http://hdl.handle.net/10149/595940
DOI:
10.1002/chem.201405041
Additional Links:
http://doi.wiley.com/10.1002/chem.201405041
Abstract:
The 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
Type:
Article
Language:
en
Keywords:
CO2 reduction; heterogeneous catalysis; immobilisation; photocatalysis; time-resolved spectroscopy
ISSN:
0947-6539
EISSN:
1521-3765
Rights:
Does not support Open Access. For full details see http://www.sherpa.ac.uk/romeo [Accessed 09/02/2016]

Full metadata record

DC FieldValue Language
dc.contributor.authorWindle, C. D. (Christopher)en
dc.contributor.authorPastor, E. (Ernest)en
dc.contributor.authorReynal, A. (Anna)en
dc.contributor.authorWhitwood, A. C. (Adrian)en
dc.contributor.authorVaynzof, Y. (Yana)en
dc.contributor.authorDurrant, J. R. (James)en
dc.contributor.authorPerutz, R. N. (Robin)en
dc.contributor.authorReisner, E. (Erwin)en
dc.date.accessioned2016-02-09T11:53:51Zen
dc.date.available2016-02-09T11:53:51Zen
dc.date.issued2015-02-23en
dc.identifier.citationChemistry - A European Journal; 21(9): 3746–3754.en
dc.identifier.issn0947-6539en
dc.identifier.doi10.1002/chem.201405041en
dc.identifier.urihttp://hdl.handle.net/10149/595940en
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 kineticsen
dc.language.isoenen
dc.publisherWiley-VCH Verlagen
dc.relation.urlhttp://doi.wiley.com/10.1002/chem.201405041en
dc.rightsDoes not support Open Access. For full details see http://www.sherpa.ac.uk/romeo [Accessed 09/02/2016]en
dc.subjectCO2 reductionen
dc.subjectheterogeneous catalysisen
dc.subjectimmobilisationen
dc.subjectphotocatalysisen
dc.subjecttime-resolved spectroscopyen
dc.titleImproving the Photocatalytic Reduction of CO2 to CO through Immobilisation of a Molecular Re Catalyst on TiO2en
dc.typeArticleen
dc.identifier.eissn1521-3765en
dc.contributor.departmentTeesside University, School of Science & Engineering.en
dc.identifier.journalChemistry - A European Journalen
or.citation.harvardWindle, C.D.; Pastor, E.; Reynal, A.; Whitwood, A. C.; Vaynzof, Y.; Durrant, J. R.; Perutz, R. N.; Reisner, E. 'Improving the photocatalytic reduction of CO2 to CO through immobilization of a molecular Re catalyst onto TiO2' Chemistry - A European Journal; 21(9): 3746–3754.en
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