Photoinduced Biphasic Hydrogen Evolution: Decamethylosmocene as a Light‐Driven Electron Donor

Ge, Peiyu; Olaya, Astrid J.; Scanlon, Micheál D.; Patır, İmren Hatay; Vrubel, Heron

doi:10.1002/cphc.201300122

Cited by 35 publications

(38 citation statements)

References 103 publications

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“…However, the trend shown in Figure 4b demonstrates that recombination is not negligible under the experimental conditions. A second limiting case can be defined in terms of , resulting in a square root dependence of the j photo with I 0 as described by Equation 10. This relationship appears more consistent with the experimental trends in Figure 4.…”

Section: Equationsupporting

confidence: 59%

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Photoelectrochemical activity of colloidal TiO 2 nanostructures assembled at polarisable liquid/liquid interfaces

Plana

Fermı́n

2016

Journal of Electroanalytical Chemistry

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Photoelectrochemical responses arising from the heterogeneous hole-transfer from colloidal TiO 2 nanoparticles to ferrocene species across the polarizable water/1,2-dichloroethane (DCE) interface are investigated as a function of the formal redox potential of the electron donor. The interfacial assembly of electrostatically stabilized 5 nm TiO 2 colloids was monitored by impedance measurements at various Galvani potential difference across the liquid/liquid interface. The onset potential of the photocurrent responses is close to the potential at which the excess interfacial charge increases due to the assembly of the TiO 2 nanoparticles. However, a closer examination of the potential dependence of these two parameters show that the interfacial excess charge is not solely dependent on the adsorption of charged nanoparticles at the interface.We also provide strong evidence that the photoelectrochemical responses are determined by the relationship between rate of electron capture at the nanoparticle surface and surface A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT2 recombination processes, rather than the interfacial oxidation of the ferrocene derivatives.Second order surface recombination constants of the order of 10 -3 cm 2 s -1 were estimated, which are consistent with a ~0.6 quantum yield for the heterogenous hole-transfer. Highlights Photoelectrochemical study of colloidal TiO 2 at polarisable liquid/liquid interfaces. Kinetic study of hole-transfer and electron capture involving titania at the ITIES. Incident-photon-to-current efficiency independent of hole-acceptor redox potential. Electron removal (oxygen reduction) is the rate determining step.

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Section: Equationsupporting

confidence: 59%

“…Recent investigations have looked at a variety of complex multi-electron transfer reactions at the ITIES employing fully molecular redox active species [9][10][11]. In this sense, it could be argued that introducing colloidal nanomaterials (e.g.…”

Section: Introductionmentioning

confidence: 99%

Photoelectrochemical activity of colloidal TiO 2 nanostructures assembled at polarisable liquid/liquid interfaces

Plana

Fermı́n

2016

Journal of Electroanalytical Chemistry

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“…A burgeoning area of research is concerned with the biphasic electrocatalysis of redox reactions of interest for energy research, including the oxygen (O 2 ) reduction reaction (ORR) [9][10][11][12][13][14][15][16][17][18][19] and the hydrogen (H 2 ) evolution reaction (HER) [20][21][22][23][24][25][26][27][28], using soft interfaces functionalized with molecular species, metallic NPs or inorganic non-precious metal-based materials. The use of adsorbed solid particulate electrocatalysts at electrochemically polarisable soft interfaces has recently been reviewed by Dryfe and co-workers [29].…”

Section: Introductionmentioning

confidence: 99%

Gold Nanofilm Redox Catalysis for Oxygen Reduction at Soft Interfaces

Smirnov

Peljo

Scanlon

et al. 2016

Electrochimica Acta

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A B S T R A C TFunctionalization of a soft or liquid-liquid interface by a one gold nanoparticle thick "nanofilm" provides a conductive pathway to facilitate interfacial electron transfer from a lipophilic electron donor to a hydrophilic electron acceptor in a process known as interfacial redox catalysis. The gold nanoparticles in the nanofilm are charged by Fermi level equilibration with the lipophilic electron donor and act as an interfacial reservoir of electrons. Additional thermodynamic driving force can be provided by electrochemically polarising the interface. Using these principles, the biphasic reduction of oxygen by a lipophilic electron donor, decamethylferrocene, dissolved in a,a,a-trifluorotoluene was catalysed at a gold nanoparticle nanofilm modified water-oil interface. A recently developed microinjection technique was utilised to modify the interface reproducibly with the mirror-like gold nanoparticle nanofilm, while the oxidised electron donor species and the reduction product, hydrogen peroxide, were detected by ion transfer voltammetry and UV/vis spectroscopy, respectively. Metallization of the soft interface allowed the biphasic oxygen reduction reaction to proceed via an alternative mechanism with enhanced kinetics and at a significantly lower overpotential in comparison to a bare soft interface. Weaker lipophilic reductants, such as ferrocene, were capable of charging the interfacial gold nanoparticle nanofilm but did not have sufficient thermodynamic driving force to significantly elicit biphasic oxygen reduction.

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“…Indeed, both reactions are spontaneous in DCE and DCB when using either of the two commonly used lipophilic reducing agents, dimethylferrocene (DiMFc) and decamethylferrocene (DcMFc) . In the absence of any catalyst, the homogeneous mechanism is believed to dominate for both the HER and ORR, with the transfer of aqueous protons into the organic phase assisted by complexation with the organic reducing agent …”

Section: Introductionmentioning

confidence: 99%

Oxygen Reduction at the Liquid–Liquid Interface: Bipolar Electrochemistry through Adsorbed Graphene Layers

Rodgers

Dryfe

2015

ChemElectroChem

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The reduction of oxygen and protons at the interface between two immiscible electrolyte solutions (ITIES) has received a great deal of interest over the last decade, with various materials being used to catalyse these reactions. Probing the mechanisms through which these reactions proceed when using interfacial catalysts is important from both from the perspective of fundamental understanding and for catalyst optimisation. Herein, we have used interfacial‐assembled graphene to probe the importance of simple electron conductivity towards the catalysis of the oxygen reduction reaction (ORR) at the ITIES, and a bipolar setup to probe the homogeneous/heterogeneous nature of the ORR proceeding through interfacial graphene. We found that interfacial graphene provides a catalytic effect towards the reduction of oxygen at the ITIES, proceeding via the heterogeneous mechanism when using a strong reducing agent.

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Photoinduced Biphasic Hydrogen Evolution: Decamethylosmocene as a Light‐Driven Electron Donor

Cited by 35 publications

References 103 publications

Photoelectrochemical activity of colloidal TiO 2 nanostructures assembled at polarisable liquid/liquid interfaces

Photoelectrochemical activity of colloidal TiO 2 nanostructures assembled at polarisable liquid/liquid interfaces

Gold Nanofilm Redox Catalysis for Oxygen Reduction at Soft Interfaces

Oxygen Reduction at the Liquid–Liquid Interface: Bipolar Electrochemistry through Adsorbed Graphene Layers

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