Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 9, Pages 3746-3754Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201405041
Keywords
CO2 reduction; heterogeneous catalysis; immobilisation; photocatalysis; time-resolved spectroscopy
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Funding
- EPSRC [EP/H00338X/2]
- EPSRC (DTP)
- Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy)
- Christian Doppler Research Association (National Foundation for Research, Technology and Development)
- OMV Group
- ERC [291482]
- European Commission Marie Curie CIG [PCIG10-GA-2011-303650]
- Engineering and Physical Sciences Research Council [EP/H00338X/2, 1230594, EP/K039946/1] Funding Source: researchfish
- EPSRC [EP/K039946/1, EP/H00338X/2, EP/F047770/1] Funding Source: UKRI
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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 48mol(CO)mol(Re)(-1) is observed in DMF with the electron donor triethanolamine at >420nm. 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 >495nm. 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 (t(50%)>1s for ReP-TiO2 compared with t(50%)=60ms 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.
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