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Unravelling the pH-dependence of a molecular photocatalytic system for hydrogen production

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Title: Unravelling the pH-dependence of a molecular photocatalytic system for hydrogen production
Authors: Reynal, A
Pastor, E
Gross, MA
Selim, S
Reisner, E
Durrant, JR
Item Type: Journal Article
Abstract: Photocatalytic systems for the reduction of aqueous protons are strongly pH-dependent, but the origin of this dependency is still not fully understood. We have studied the effect of different degrees of acidity on the electron transfer dynamics and catalysis taking place in a homogeneous photocatalytic system composed of a phosphonated ruthenium tris(bipyridine) dye (RuP) and a nickel bis(diphosphine) electrocatalyst (NiP) in an aqueous ascorbic acid solution. Our approach is based on transient absorption spectroscopy studies of the efficiency of photo-reduction of RuP and NiP correlated with pH-dependent photocatalytic H2 production and the degree of catalyst protonation. The influence of these factors results in an observed optimum photoactivity at pH 4.5 for the RuP–NiP system. The electron transfer from photo-reduced RuP to NiP is efficient and independent of the pH value of the medium. At pH <4.5, the efficiency of the system is limited by the yield of RuP photo-reduction by the sacrificial electron donor, ascorbic acid. At pH >4.5, the efficiency of the system is limited by the poor protonation of NiP, which inhibits its ability to reduce protons to hydrogen. We have therefore developed a rational strategy utilising transient absorption spectroscopy combined with bulk pH titration, electrocatalytic and photocatalytic experiments to disentangle the complex pH-dependent activity of the homogenous RuP–NiP photocatalytic system, which can be widely applied to other photocatalytic systems.
Issue Date: 28-May-2015
Date of Acceptance: 27-May-2015
URI: http://hdl.handle.net/10044/1/41775
DOI: http://dx.doi.org/10.1039/c5sc01349f
ISSN: 2041-6539
Publisher: Royal Society of Chemistry
Start Page: 4855
End Page: 4859
Journal / Book Title: Chemical Science
Volume: 6
Issue: 8
Copyright Statement: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Sponsor/Funder: Engineering & Physical Science Research Council (EPSRC)
Funder's Grant Number: EP/K039946/1
Keywords: Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
ELECTRON-TRANSFER REACTIONS
AQUEOUS-SOLUTION
NICKEL-CATALYST
H-2 PRODUCTION
COBALT CATALYST
WATER
REDUCTION
ELECTROCATALYSTS
COMPLEXES
EVOLUTION
Publication Status: Published
Appears in Collections:Chemistry
Faculty of Natural Sciences



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