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Mediated water electrolysis in biphasic systems

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dc.contributor.author Scanlon, Micheál D.
dc.contributor.author Peljo, Pekka
dc.contributor.author Rivier, Lucie
dc.contributor.author Vrubel, Heron
dc.contributor.author Girault, Hubert H.
dc.date.accessioned 2017-11-06T14:36:29Z
dc.date.issued 2017
dc.identifier.uri http://hdl.handle.net/10344/6234
dc.description peer-reviewed en_US
dc.description.abstract The concept of efficient electrolysis by linking photoelectrochemical biphasic H2 evolution and water oxidation processes in the cathodic and anodic compartments of an H-cell, respectively, is introduced. Overpotentials at the cathode and anode are minimised by incorporating light-driven elements into both biphasic reactions. The concepts viability is demonstrated by electrochemical H2 production from water splitting utilising a polarised water-organic interface in the cathodic compartment of a prototype H-cell. At the cathode the reduction of decamethylferrocenium cations ([Cp2*Fe(III)]+) to neutral decamethylferrocene (Cp2*Fe(II)) in 1,2-dichloroethane (DCE) solvent takes place at the solid electrode/oil interface. This electron transfer process induces the ion transfer of a proton across the immiscible water/oil interface to maintain electroneutrality in the oil phase. The oil-solubilised proton immediately reacts with Cp2*Fe(II) to form the corresponding hydride species, [Cp2*Fe(IV)(H)]+. Subsequently, [Cp2*Fe(IV)(H)]+ spontaneously undergoes a chemical reaction in the oil phase to evolve hydrogen gas (H2) and regenerate [Cp2*Fe(III)]+, whereupon this catalytic Electrochemical, Chemical, Chemical (ECC’) cycle is repeated. During biphasic electrolysis, the stability and recyclability of the [Cp2*Fe(III)]+/Cp2*Fe(II) redox couple were confirmed by chronoamperometric measurements and, furthermore, the steady-state concentration of [Cp2*Fe(III)]+ monitored in situ by UV/vis spectroscopy. Post-biphasic electrolysis, the presence of H2 in the headspace of the cathodic compartment was established by sampling with gas chromatography. The rate of the biphasic hydrogen evolution reaction (HER) was enhanced by redox catalysis in the presence of floating catalytic molybdenum carbide (Mo2C) microparticles at the immiscible water/oil interface. The use of a superhydrophobic organic electrolyte salt was critical to ensure proton transfer from water to oil, and not anion transfer from oil to water, in order to maintain electroneutrality after electron transfer. The design, testing and successful optimisation of the operation of the biphasic electrolysis cell under dark conditions with Cp2*Fe(II) lays the foundation for the achievement of photo-induced biphasic water electrolysis at low overpotentials using another metallocene, decamethylrutheneocene (Cp2*Ru(II)). Critically, Cp2*Ru(II) may be recycled at a potential more positive than that of proton reduction in DCE. en_US
dc.language.iso eng en_US
dc.publisher Royal Society of Chemistry en_US
dc.relation.ispartofseries Physical Chemistry Chemical Physics;19, pp. 22700-22710
dc.relation.uri http://dx.doi.org/10.1039/C7CP04601D
dc.subject chemistry en_US
dc.subject physics en_US
dc.title Mediated water electrolysis in biphasic systems en_US
dc.type info:eu-repo/semantics/article en_US
dc.type.supercollection all_ul_research en_US
dc.type.supercollection ul_published_reviewed en_US
dc.identifier.doi 10.1039/C7CP04601D
dc.contributor.sponsor SFI en_US
dc.contributor.sponsor Swiss National Science Foundation en_US
dc.relation.projectid 13/SIRG/2137 en_US
dc.relation.projectid 160553 en_US
dc.date.embargoEndDate 2018-08-12
dc.embargo.terms 2018-08-12 en_US
dc.rights.accessrights info:eu-repo/semantics/openAccess en_US
dc.internal.rssid 2736311


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