SECM study of hydrogen photogeneration in a 1,2-dichloroethane | water biphasic system with decamethylruthenocene electron donor regeneration

Jedraszko, Justyna; Adamiak, Wojciech; Nogala, Wojciech; Girault, Hubert H.; Opałło, Marcin

doi:10.1016/j.jelechem.2017.09.026

Cited by 15 publications

(14 citation statements)

References 30 publications

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“…Interfacial reaction and mass transport processes have been disentangled by placing an microdisk electrode as a sensor close to any liquid|liquid interfaces and using the instrumentation for scanning electrochemical microscopy (SECM) . Reaction products that were detected by SECM include H 2 O 2 , O 2 , H 2 in the substrate‐generation/tip collection (SG/TG) mode. Recently, the feedback mode of SECM was used to study chemically polarized liquid|liquid interfaces, that is, systems in which a Galvani potential difference

Δ_{o}^{normalw} φ

between the two immiscible electrolyte solutions was formed by partitioning of a common ion.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Activity of Alkali Metal Cations for the Chemical Oxygen Reduction Reaction in a Biphasic Liquid System Probed by Scanning Electrochemical Microscopy

Rastgar

Santos

Angelucci

2020

Chemistry A European J

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Chemical reduction of dioxygen in organic solvents for the production of reactive oxygen species or the concomitant oxidation of organic substrates can be enhanced by the separation of products and educts in biphasic liquid systems. Here, the coupled electron and ion transfer processes is studied as well as reagent fluxes across the liquid|liquid interface for the chemical reduction of dioxygen by decamethylferrocene (DMFc) in a dichloroethane‐based organic electrolyte forming an interface with an aqueous electrolyte containing alkali metal ions. This interface is stabilized at the orifice of a pipette, across which a Galvani potential difference is externally applied and precisely adjusted to enforce the transfer of different alkali metal ions from the aqueous to the organic electrolyte. The oxygen reduction is followed by H2O2 detection in the aqueous phase close to the interface by a microelectrode of a scanning electrochemical microscope (SECM). The results prove a strong catalytic effect of hydrated alkali metal ions on the formation rate of H2O2, which varies systematically with the acidity of the transferred alkali metal ions in the organic phase.

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Δ_{o}^{normalw} φ

between the two immiscible electrolyte solutions was formed by partitioning of a common ion.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Activity of Alkali Metal Cations for the Chemical Oxygen Reduction Reaction in a Biphasic Liquid System Probed by Scanning Electrochemical Microscopy

Rastgar

Santos

Angelucci

2020

Chemistry A European J

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“…We have previously described the photoproduction of hydrogen by [Cp* 2 Ru II ]w ith electrochemical recycling of the oxidized [Cp* 2 Ru III ] + product. [18,28,39] Herein,w es ignificantly advance our earlier work by investigating the photoreduction of organic protons in as ingle organic phase. The multistep photomechanism leadingt oH 2 evolution with [Cp* 2 Ru II ]w as fully elucidated by using electrochemical, GC, and spectroscopic (UV/Vis, 1 Ha nd 13 CNMR) experimental approaches, with corroboration by DFT calculations.…”

Section: Introductionmentioning

confidence: 81%

“…We have previously described the photoproduction of hydrogen by [Cp* 2 Ru II ] with electrochemical recycling of the oxidized [Cp* 2 Ru III ] + product . Herein, we significantly advance our earlier work by investigating the photoreduction of organic protons in a single organic phase.…”

Section: Introductionmentioning

confidence: 86%

Mechanistic Study on the Photogeneration of Hydrogen by Decamethylruthenocene

Rivier

Peljo

Maye

et al. 2019

Chemistry A European J

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Detailed studies on hydrogen evolution by decamethylruthenocene ([Cp* 2 Ru II ]) highlighted that metallocenes are capable of photoreducing hydrogen without the need for an additionals ensitizer.E lectrochemical, gas chromatographic, and spectroscopic (UV/Vis, 1 Ha nd 13 CNMR) measurements corroborated by DFTc alculations indicated that the production of hydrogen occurs by at wo-stepp rocess. First, decamethylruthenocene hydride [Cp* 2 Ru IV (H)] + is formed in the presence of an organic acid. Subsequently, [Cp* 2 Ru IV (H)] + is reversibly reduced in ah eterolytic reaction with one-photon excitation leadingt oafirst releaseo fh y-drogen. Thereafter,t he resultant decamethylruthenocenium ion [Cp* 2 Ru III ] + is further reduced with as econd releaseo f hydrogenb yd eprotonation of am ethyl group of [Cp* 2 Ru III ] + .E xperimental and computational data show spontaneous conversion of [Cp* 2 Ru II ]t o[ Cp* 2 Ru IV (H)] + in the presence of protons. Calculations highlight that the first reductioni se ndergonic (DG 0 = 108 kJ mol À1 )a nd needs an input of energy by light for the reactiont oo ccur.T he hydricityo ft he methylp rotons of [Cp* 2 Ru II ]w as also considered.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

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“…215 The same electrocatalyst exhibited good activity towards the OER as well and this performance is attributed to the karst landform structure, which seems to ease the mass diffusion and to provide sufficient catalytic sites. 215 SECM was employed as well for the investigation of photogenerated hydrogen at a 1,2-dichloroethane/water (DCE/W) interface by Jedraszko et al 216 During the HER, decamethylruthenocene (DMRc) is formed as a by-product during the hydrogen evolution, and then serves as an electron donor, which permits a continuous HER. 216 The SECM setup consisted of two Pt electrodes separated by only 50 mm from each other through a liquid/liquid interface, in order to ensure an efficient generation of DMRc by DMRc + reduction.…”

Section: Hydrogen Evolution Reaction (Her)mentioning

confidence: 99%