Double couche electrochimique et cinetique des reactions d'electrode. Elucidation du mode d'action des cations tetraalkylammonium

Gierst, Lucien; Tondeur, J. J.; Nicolas, Edgard

doi:10.1016/0022-0728(65)80042-0

Cited by 28 publications

(11 citation statements)

References 16 publications

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“…Particularly, the benzyltrimethylammonium cation that is prevalently used in AAEM electrolytes leads to a drastic loss of methanol oxidation activity. This observation is consistent with previous literature that showed a higher surface inhibition with the longer alkyl length on the ammonium group …”

Section: Effect Of Ammonium Cation Poisoning On Interfacial Charge Tr...supporting

confidence: 94%

“…This observation is consistent with previous literature that showed a higher surface inhibition with the longer alkyl length on the ammonium group. 321 These results with different quaternary ammonium cations in aqueous electrolytes show that quaternary ammonium ion adsorption on Pt surfaces lowers the rate of methanol oxidation by blockage of the active catalyst surface area. As depicted in Figure 10d,e, Kohl et al 51 have recently proposed that the effect of methanol oxidation by the quaternary ammonium cation is likely to be 2-fold: one arising from the loss of active surface due to the cation and side chain adsorption.…”

Section: Effect Of Ammonium Cation Poisoning On Interfacial Charge Tr...mentioning

confidence: 94%

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Alkaline Anion-Exchange Membrane Fuel Cells: Challenges in Electrocatalysis and Interfacial Charge Transfer

2019

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Alkaline anion-exchange membrane (AAEM) fuel cells have attracted significant interest in the past decade, thanks to the recent developments in hydroxideanion conductive membranes. In this article, we compare the performance of current state of the art AAEM fuel cells to proton-exchange membrane (PEM) fuel cells and elucidate the sources of various overpotentials. While the continued development of highly conductive and thermally stable anion-exchange membranes is unambiguously a principal requirement, we attempt to put the focus on the challenges in electrocatalysis and interfacial charge transfer at an alkaline electrode/electrolyte interface. Specifically, a critical analysis presented here details the (i) fundamental causes for higher overpotential in hydrogen oxidation reaction, (ii) mechanistic aspects of oxygen reduction reaction, (iii) carbonate anion poisoning, (iv) unique challenges arising from the specific adsorption of alkaline ionomer cation-exchange head groups on electrocatalysts surfaces, and (v) the potential of alternative small molecule fuel oxidation. This review and analysis encompasses both the precious and nonprecious group metal based electrocatalysts from the perspective of various interfacial charge-transfer phenomena and reaction mechanisms. Finally, a research roadmap for further improvement in AAEM fuel cell performance is delineated here within the purview of electrocatalysis and interfacial charge transfer.

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Section: Effect Of Ammonium Cation Poisoning On Interfacial Charge Tr...supporting

confidence: 94%

Section: Effect Of Ammonium Cation Poisoning On Interfacial Charge Tr...mentioning

confidence: 94%

Alkaline Anion-Exchange Membrane Fuel Cells: Challenges in Electrocatalysis and Interfacial Charge Transfer

2019

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“…This observation is consistent with previous literature that showed a higher surface inhibition with the longer alkyl length on the ammonium group. 48 These results with different quaternary ammonium cations in aqueous electrolytes show that quaternary ammonium ion adsorption on Pt surfaces lowers the rate of methanol oxidation by blockage of the active catalyst surface area. However, the solid polymer electrolyte, ion-conducting medium in a polymer-based fuel cell is different from that of free ions in an aqueous solution.…”

Section: Resultsmentioning

confidence: 94%

Analysis of Double Layer and Adsorption Effects at the Alkaline Polymer Electrolyte-Electrode Interface

Ünlü

Abbott

Ramaswamy

et al. 2011

J. Electrochem. Soc.

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In this study, the performance of the anionic electrodes in polymer-based alkaline fuel cells is analyzed. Direct alcohol, alkaline fuel cells suffer from a rapid decrease in cell potential at low discharge currents. Several effects are described to account for this drop in cell potential. Quaternary ammonium ions can specifically adsorb on the catalyst surface decreasing the active surface area and lowering the rate of methanol oxidation. In addition, the tethering of the quaternary ammonium cations on the polymer electrolyte inhibits the cation mobility causing a diffuse double layer to be formed. The diffuse double layer electrostatically inhibits the migration of hydroxide to the surface of the electrode which is needed for alcohol oxidation.

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“…This indicates that Na + , Cu 2+ , and K + do not selectively adsorb on various faces whereas this is observed for several ammonium derivatives. 41,42 From this, it is expected that CTA + plays a role in nanocrystal growth. Note that the kinetic growth of nanorods is the same as that observed for the other chloride ions (Figure 4) with a smaller aspect ratio.…”

Section: Resultsmentioning

confidence: 96%

Is the Anion the Major Parameter in the Shape Control of Nanocrystals?

et al. 2003

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In this paper, copper nanocrystals are produced by using Cu(AOT)2−isooctane−water solution as a template. Even if the template does not change with various salt additions, the nanocrystal growth markedly depends on the salt used. It is demonstrated that chloride ions enable the growth of nanorods with an aspect ratio varying with chloride concentration. Conversely, only a slight amount of bromide ion is needed to increase the nanorod aspect ratio from 3 to 5 without any changes when increasing the bromide ion concentration. A rather large number of cubes are produced. Formations of nanorods and cubes are explained in terms of anion adsorption on (111) and (100) faces, respectively. By replacing chloride by other ions, the morphology of copper nanocrystals drastically changes. In all cases, the nanocrystals formed are fcc single crystals with a polyhedral shape or crystals composed of fcc tetrahedra (deformed or not) bounded by (111) faces. Some cylinders are formed by the connection of 2 different crystals with different 5-fold axes and/or with additional planes. This gives rise to various particle shapes.

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Double couche electrochimique et cinetique des reactions d'electrode. Elucidation du mode d'action des cations tetraalkylammonium

Cited by 28 publications

References 16 publications

Alkaline Anion-Exchange Membrane Fuel Cells: Challenges in Electrocatalysis and Interfacial Charge Transfer

Alkaline Anion-Exchange Membrane Fuel Cells: Challenges in Electrocatalysis and Interfacial Charge Transfer

Analysis of Double Layer and Adsorption Effects at the Alkaline Polymer Electrolyte-Electrode Interface

Is the Anion the Major Parameter in the Shape Control of Nanocrystals?

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