Versatile photocatalytic systems for H2 generation in water based on an efficient Dubois-type nickel catalyst

Hdl Handle:
http://hdl.handle.net/10149/596106
Title:
Versatile photocatalytic systems for H2 generation in water based on an efficient Dubois-type nickel catalyst
Authors:
Gross, M. A. (Manuela); Reynal, A. (Anna); Durrant, J. R. (James); Reisner, E. (Erwin)
Affiliation:
Teesside University, School of Science & Engineering.
Citation:
Gross, M. A.; Reynal, A.; Durrant, J. R.; Reisner, E. (2014) 'Versatile photocatalytic systems for H2 generation in water based on an efficient Dubois-type nickel catalyst' Journal of the American Chemical Society; 136(1): 356–366.
Publisher:
American Chemical Society
Journal:
Journal of the American Chemical Society
Issue Date:
8-Jan-2014
URI:
http://hdl.handle.net/10149/596106
DOI:
10.1021/ja410592d
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/ja410592d
Abstract:
The generation of renewable H2 through an efficient photochemical route requires photoinduced electron transfer (ET) from a light harvester to an efficient electrocatalyst in water. Here, we report on a molecular H2 evolution catalyst (NiP) with a DuBois-type [Ni(P2R′N2R″)2]2+ core (P2R′N2R″ = bis(1,5-R′-diphospha-3,7-R″-diazacyclooctane), which contains an outer coordination sphere with phosphonic acid groups. The latter functionality allows for good solubility in water and immobilization on metal oxide semiconductors. Electrochemical studies confirm that NiP is a highly active electrocatalyst in aqueous electrolyte solution (overpotential of approximately 200 mV at pH 4.5 with a Faradaic yield of 85 ± 4%). Photocatalytic experiments and investigations on the ET kinetics were carried out in combination with a phosphonated Ru(II) tris(bipyridine) dye (RuP) in homogeneous and heterogeneous environments. Time-resolved luminescence and transient absorption spectroscopy studies confirmed that directed ET from RuP to NiP occurs efficiently in all systems on the nano- to microsecond time scale, through three distinct routes: reductive quenching of RuP in solution or on the surface of ZrO2 (“on particle” system) or oxidative quenching of RuP when the compounds were immobilized on TiO2 (“through particle” system). Our studies show that NiP can be used in a purely aqueous solution and on a semiconductor surface with a high degree of versatility. A high TOF of 460 ± 60 h–1 with a TON of 723 ± 171 for photocatalytic H2 generation with a molecular Ni catalyst in water and a photon-to-H2 quantum yield of approximately 10% were achieved for the homogeneous system.
Type:
Article
Language:
en
ISSN:
0002-7863; 1520-5126
Rights:
Author can archive post-print (ie final draft post-refereeing) after 12 month embargo from publication. For full details see http://www.sherpa.ac.uk/romeo [Accessed 12/02/2016]

Full metadata record

DC FieldValue Language
dc.contributor.authorGross, M. A. (Manuela)en
dc.contributor.authorReynal, A. (Anna)en
dc.contributor.authorDurrant, J. R. (James)en
dc.contributor.authorReisner, E. (Erwin)en
dc.date.accessioned2016-02-12T11:41:02Zen
dc.date.available2016-02-12T11:41:02Zen
dc.date.issued2014-01-08en
dc.identifier.citationJournal of the American Chemical Society; 136(1): 356–366.en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/ja410592den
dc.identifier.urihttp://hdl.handle.net/10149/596106en
dc.description.abstractThe generation of renewable H2 through an efficient photochemical route requires photoinduced electron transfer (ET) from a light harvester to an efficient electrocatalyst in water. Here, we report on a molecular H2 evolution catalyst (NiP) with a DuBois-type [Ni(P2R′N2R″)2]2+ core (P2R′N2R″ = bis(1,5-R′-diphospha-3,7-R″-diazacyclooctane), which contains an outer coordination sphere with phosphonic acid groups. The latter functionality allows for good solubility in water and immobilization on metal oxide semiconductors. Electrochemical studies confirm that NiP is a highly active electrocatalyst in aqueous electrolyte solution (overpotential of approximately 200 mV at pH 4.5 with a Faradaic yield of 85 ± 4%). Photocatalytic experiments and investigations on the ET kinetics were carried out in combination with a phosphonated Ru(II) tris(bipyridine) dye (RuP) in homogeneous and heterogeneous environments. Time-resolved luminescence and transient absorption spectroscopy studies confirmed that directed ET from RuP to NiP occurs efficiently in all systems on the nano- to microsecond time scale, through three distinct routes: reductive quenching of RuP in solution or on the surface of ZrO2 (“on particle” system) or oxidative quenching of RuP when the compounds were immobilized on TiO2 (“through particle” system). Our studies show that NiP can be used in a purely aqueous solution and on a semiconductor surface with a high degree of versatility. A high TOF of 460 ± 60 h–1 with a TON of 723 ± 171 for photocatalytic H2 generation with a molecular Ni catalyst in water and a photon-to-H2 quantum yield of approximately 10% were achieved for the homogeneous system.en
dc.language.isoenen
dc.publisherAmerican Chemical Societyen
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/ja410592den
dc.rightsAuthor can archive post-print (ie final draft post-refereeing) after 12 month embargo from publication. For full details see http://www.sherpa.ac.uk/romeo [Accessed 12/02/2016]en
dc.titleVersatile photocatalytic systems for H2 generation in water based on an efficient Dubois-type nickel catalysten
dc.typeArticleen
dc.contributor.departmentTeesside University, School of Science & Engineering.en
dc.identifier.journalJournal of the American Chemical Societyen
or.citation.harvardGross, M. A.; Reynal, A.; Durrant, J. R.; Reisner, E. (2014) 'Versatile photocatalytic systems for H2 generation in water based on an efficient Dubois-type nickel catalyst' Journal of the American Chemical Society; 136(1): 356–366.en
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