An Electrochemical Method for the Determination of the Saturation Pressure and Heat of Solution of Hydrogen in a Two-phase Pd-H Alloy

Ratchford, Robert J.; Castellan, Gilbert W.

doi:10.1021/j150567a025

Cited by 24 publications

(15 citation statements)

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“…• C. [54][55][56][57][58] However, these results were obtained with diluted aqueous electrolytes, the measurements at T > 100…”

Section: F28mentioning

confidence: 99%

“…[54][55][56][57][58] For the 3-electrode measurements using the Pd-H wire as a reference electrode, the potential of the Pt working electrode vs. RHE was obtained by simply adding the measured potentials and values listed in Table I. The latter were also used to calculate the initial and final potentials used in the cyclic voltammograms and polarization curves for each temperature.…”

Section: F28mentioning

confidence: 99%

See 1 more Smart Citation

2-Sulfoethylammonium Trifluoromethanesulfonate as an Ionic Liquid for High Temperature PEM Fuel Cells

Wippermann

Wackerl

Lehnert

et al. 2015

J. Electrochem. Soc.

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Tafel Oxygen reduction reaction (ORR) in polymer electrolyte fuel cells (PEFC).-High temperature polymer electrolyte fuel cells (HT-PEFCs) are currently based on phosphoric acid-doped polybenzimidazole-type membranes (PBI) and are operated in a temperature range of 120-180• C. HT-PEFCs have several advantages over low temperature PEFCs, such as: easier water and heat management, the possibility of recovering high-grade waste heat, a more compact cooling system and a higher CO tolerance by the anode catalyst.However, a major drawback of HT-PEFCs is the sluggish oxygen reduction reaction (ORR) kinetics in the presence of phosphoric acid. This is primarily caused by three effects: (i) The inhibition effect of phosphoric acid on the ORR because of the poisoning of the Pt catalyst due to the adsorption of the H 3 PO 4 species onto active catalyst sites. (ii) The low solubility of oxygen in phosphoric acid. (iii) The slow diffusion of oxygen through the film of phosphoric acid which covers the platinum catalyst.The adsorption of phosphate by platinum has been studied for more than 30 years 1-15 by means of cyclic voltammetry (CV), [2][3][4][5]9,[11][12][13][14][16][17][18][19][20][21] rotating disc electrode measurements (RDE), [2][3][4][5]8,9,11,13,14 electrochemical impedance spectroscopy (EIS), 13,16,22 transient measurements, 9,23,24 Fourier transform infrared spectroscopy (FTIR), 20,25-27 electrochemical quartz crystal microbalance (QCM), 18 radio tracer experiments, 28 X-ray photoelectron spectroscopy (XPS) 17 and X-ray absorption spectroscopy (XAS). 14,15 The in-operando XAS measurements recently published by Kaserer et al. show the adsorption behavior of H 3 PO 4 species on Pt/C fuel cell cathode catalysts in the temperature range of 50-170• C under the operating conditions of an HT-PEFC. 15In diluted aqueous solutions and at moderate temperatures, sulphuric acid and sulfonic acids like methanesulfonic acid (MSA) or trifluoromethanesulfonic acid (triflic acid, TFMSA) have been found to be less poisonous than phosphoric acid because sulfonate groups are less strongly adsorbed on Pt. 3,29,30 For example, Zelenay et al.,29 in a comparative study of phosphoric acid and TFMSA, showed that * Electrochemical Society Active Member. z E-mail: k.wippermann@fz-juelich.de 0.02 M TFMSA is indeed less strongly adsorbed by comparison to 0.02 M phosphoric acid at room temperature. However, the free space available for oxygen reduction is found to be similar at elevated temperatures and for concentrated solutions. 29 Under these conditions, the advantage of TFMSA lies in its higher oxygen solubility and diffusivity rather than its poisoning effect. 29 Although this result cannot be generalized, it still indicates the importance of oxygen solubility and the diffusion coefficient of oxygen in the electrolyte being used. Proton conducting ionic liquids (PIL).-With respect to alternative electrolytes for HT-PEFCs, proton-conducting ionic liquids (PILs) appear to be suitable, as they do not rely on solvents like water. Moreover...

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“…• C. [54][55][56][57][58] However, these results were obtained with diluted aqueous electrolytes, the measurements at T > 100…”

Section: F28mentioning

confidence: 99%

Section: F28mentioning

confidence: 99%

2-Sulfoethylammonium Trifluoromethanesulfonate as an Ionic Liquid for High Temperature PEM Fuel Cells

Wippermann

Wackerl

Lehnert

et al. 2015

J. Electrochem. Soc.

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“…The working electrodes were polyfacetted platinum single crystal spheres prepared following a slightly modified version of the melting procedure described earlier in the literature [26,27]. A Pd/H, reference electrode ending with a Luggin-Haber capillary tip [28] and a Pt cylindrical counterelectrode (3 mm radius), surrounding the working electrode, were used. The working electrode and the tip of the Luggin were placed on the axis of the Pt cylinder and separated by a 1 mm gap.…”

mentioning

confidence: 99%

“…Two types of working electrodes were used, namely, polyfacetted platinum, Pt(pc) and preferred crystalline oriented platinum, Pt(pco). The latter was obtained by using the electrochemical facetting technique already described elsewhere [29-311. In the text, potential values are referred to the RHE scale temperature after correction by using the temperature coefficient taken from the literature [28]. The temperature was monitored by two precision thermistors (YSI 44OOlA), one of which was placed in the bulk of the solution while the other was adjacent to the working electrode surface, avoiding as much as possible shielding effects.…”

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confidence: 99%

Comparative voltammetric behaviour of H- and O-atoms on a Pt electrode in sulphuric acid solutions within the 293 K to 233 K range

Florit¹,

Martins²,

Arvía³

1989

Journal of Electroanalytical Chemistry and Interfacial Electroc

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“…It can be mentioned the pioneering works of S. Schuldiner 17 and G.W. Castellan 18 as well as the more recent studies due to A. Lasia, [19][20][21][22][23] where the mechanisms of hydrogen insertion in the Pd matrix starting from the proton electroreduction were discussed. [19][20][21][22][23][24][25][26] The indirect mechanism postulates that proton is reduced to adsorbed hydrogen (H ad ) through the Volmer step and then it is absorbed in palladium.…”

mentioning

confidence: 99%

Unexpected Behavior of the Hydrogen Oxidation Reaction on Palladium in Alkaline Solution: A Feasible Kinetic Explanation

Montero¹,

Gennero²,

Chialvo³

2018

J. Electrochem. Soc.

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The hydrogen oxidation reaction was studied on a thin film palladium electrode supported on a gold substrate in alkaline solution. The hydrogen absorption process was analyzed by open circuit potential transient and the current -overpotential dependences were obtained by chronoamperometry at different rotation rates in a solution saturated with hydrogen. The results obtained show an unexpected profile at low overpotentials, where current decreases as rotation rate increases. A kinetic mechanism was proposed to interpret this behavior and the corresponding equations were derived. They were used to correlate the results, with a good agreement between the experimental and fitted curves.

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An Electrochemical Method for the Determination of the Saturation Pressure and Heat of Solution of Hydrogen in a Two-phase Pd-H Alloy

Abstract: Heat of Solution of Hydrogen in a Two-phase Pd-H Alloy 1123 in the introduction depended on the observed first power dependence of the uranium extraction coefficients, [U] Show more

Cited by 24 publications

References 0 publications

2-Sulfoethylammonium Trifluoromethanesulfonate as an Ionic Liquid for High Temperature PEM Fuel Cells

2-Sulfoethylammonium Trifluoromethanesulfonate as an Ionic Liquid for High Temperature PEM Fuel Cells

Comparative voltammetric behaviour of H- and O-atoms on a Pt electrode in sulphuric acid solutions within the 293 K to 233 K range

Unexpected Behavior of the Hydrogen Oxidation Reaction on Palladium in Alkaline Solution: A Feasible Kinetic Explanation

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