Stand for high pressure electrochemical measurements

Górecki, J.; Gołaś, Janusz

doi:10.1002/elan.1140080705

Cited by 5 publications

(11 citation statements)

References 5 publications

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“…Detailed accounts of these results have been produced previously and readers are pointed to the following articles for a more thorough overview of these early experiments [3, 4, 12, 22 ± 29]. However, it has since been observed that these early studies often lacked reproducibility and accuracy [23], which can be attributed to the practical difficulties and the complicated experimental apparatus [30] required to record accurate measurements at high pressure.…”

Section: Introductionmentioning

confidence: 93%

“…Golas and co-workers [30] have recently described a complete apparatus for voltammetric measurements at high pressure (up to 0.8 GPa, or ca. 8 kbar) and provided practical advice on how to prepare and maintain the electrodes used in such experiments [30,31,55].…”

Section: Three Electrode Cellsmentioning

confidence: 99%

“…8 kbar) and provided practical advice on how to prepare and maintain the electrodes used in such experiments [30,31,55]. The apparatus for high pressure (up to 0.8 GPa) electrochemical measurements consists of four components: a high pressure chamber with pressure control system, a press, an electrochemical analyzer and, finally, an electrochemical cell with a set of electrodes.…”

Section: Three Electrode Cellsmentioning

confidence: 99%

“…Other technical obstacles related to properties of the working electrode material, preparation of its surface, construction of the cell and availability of suitable reference electrodes have also been observed [30,31]. In addition it has been found that some electrochemically active couples are not sufficiently stable over the time required to complete a cycle of measurements at various pressures (experiments at high pressure require a full working day, placing stringent demands on the chemical stability of the couple being studied) [2,30]. In view of these difficulties in high pressure work it is not surprising that few early experimentalists took up the challenge of undertaking such measurements!…”

Section: Introductionmentioning

confidence: 97%

“…In view of these difficulties in high pressure work it is not surprising that few early experimentalists took up the challenge of undertaking such measurements! However, most of these limitations have been overcome over the last 15 years as standard items of high pressure equipment have become readily available and as such removed much of the experimental difficulty [1,2,30,32]. A range of high pressure vessels, pumps, gauges, etc., can be obtained from engineering companies specializing in high pressure equipment and assembled without special tools or facilities.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Electrochemistry at High Pressures: A Review

2004

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High pressure electrochemical studies are potentially dangerous and less immediately implemented than conventional investigations. Technical obstacles related to properties of the working electrode material, preparation of its surface, availability of suitable reference electrodes, and the need for specially designed high pressure equipment and cells may account for the relative lack of experimental data on electrochemistry at high pressures. However, despite the stringent requirements for system and equipment stability, significant developments have been made in recent years and the combination of electrochemical methods with high hydrostatic pressure has provided useful insights into the thermodynamics, kinetics, and other physico-chemical characteristics of a wide range of redox reactions. In addition to fundamental information, high pressure electrochemistry has also lead to a better understanding of a variety of processes under non-classical conditions with potential applications in today×s industrial environment from extraction and electrosynthesis in supercritical fluids to measurement of the pH at the bottom of the ocean. The purpose of this article is to detail the experimental pressurizing apparatus for electroanalytical measurements at high pressures and to review the relevant literature on the effect of pressure on electrode processes and on the properties of aqueous electrolyte solutions.

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Section: Introductionmentioning

confidence: 93%

Section: Three Electrode Cellsmentioning

confidence: 99%

Section: Three Electrode Cellsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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Electrochemistry at High Pressures: A Review

2004

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Dynamic Electrochemistry: Methodology and Application

1998

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Redox Behavior of a Dinuclear Ruthenium(II) Complex Bearing an Uncommon Bridging Ligand: Insights from High-Pressure Electrochemistry

Dürr¹,

Klein

Kahnt³

et al. 2017

Inorg. Chem.

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A dinuclear ruthenium complex bridged by 2,3,5,6-pyrazinetetracarboxylic acid (μ-LH) was synthesized and characterized by X-ray crystallography, cyclic voltammetry under ambient and elevated pressures, electron paramagnetic resonance (EPR) and UV/vis-NIR (NIR = near-infrared) spectroelectrochemistry, pulse radiolysis, and computational methods. We probed for the first time in the field of mixed-valency the use of high-pressure electrochemical methods. The investigations were directed toward the influence of the protonation state of the bridging ligand on the electronic communication between the ruthenium ions, since such behavior is interesting in terms of modulating redox chemistry by pH. Starting from the [Ru(μ-LH)Ru] configuration, which shows an intense metal-to-ligand charge transfer absorption band at 600 nm, cyclic voltammetry revealed a pH-independent, reversible one-electron reduction and a protonation-state-dependent (proton coupled electron transfer, PCET) reversible oxidation. Deeper insight into the electrode reactions was provided by pressure-dependent cyclic voltammetry up to 150 MPa, providing insight into the conformational changes, the protonation state, and the environment of the molecule during the redox processes. Spectroelectrochemical investigations (EPR, UV/vis-NIR) of the respective redox reactions suggest a ligand-centered radical anion [Ru(μ-LH)Ru] upon reduction (EPR Δg = 0.042) and an ambiguous, EPR-silent one-electron oxidized state. In both cases, the absence of the otherwise typical broad intervalence charge transfer bands in the NIR region for mixed-valent complexes support the formulation as radical anionic bridged compound. However, on the basis of high-pressure electrochemical data and density functional theory calculations the one-electron oxidized form could be assigned as a charge-delocalized [Ru(μ-LH)Ru] valence tautomer rather than [Ru(μ-LH)Ru]. Deprotonation of the bridging ligand causes a severe shift of the redox potential for the metal-based oxidation toward lower potentials, yielding the charge-localized [Ru(μ-LH)Ru] complex. This PCET process is accompanied by large intrinsic volume changes. All findings are supported by computational methods (geometry optimization, spin population analysis). For all redox processes, valence alternatives are discussed.

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Stand for high pressure electrochemical measurements

Cited by 5 publications

References 5 publications

Electrochemistry at High Pressures: A Review

Electrochemistry at High Pressures: A Review

Dynamic Electrochemistry: Methodology and Application

Redox Behavior of a Dinuclear Ruthenium(II) Complex Bearing an Uncommon Bridging Ligand: Insights from High-Pressure Electrochemistry

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