Effect of d-metal hydroxides on water dissociation in bipolar membranes

Melnikov, Stanislav; Shapovalova, O. V.; Шельдешов, Н. В.; Заболоцкий, В. И.

doi:10.1134/s0965544111070097

Cited by 36 publications

(29 citation statements)

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“…The dried membrane samples were incinerated and then dissolved in concentrated nitric acid. Then, the amount of copper was determined by means of atomic absorption spectroscopy and the total fraction of ter nary, secondary, and primary amines was calculated in [15] 0.0032 [17] 0.045 9.10 [13] 3.65 × 10 -9 [13] MA 40M In the bulk -NH 2 (R) + on the surface 0.0032 [17] 0.045 2.5 × 10 -5 -MA 41 0.0013 [17] 0.045 0.40 [13] 7.17 × 10 -9 [13] Ralex AMH 0.0020 0.060 3.75 [14] 5.16 × 10 -9 [14] Note: Q is the exchange capacity of impregnated membrane; d m is the membrane thickness; k Σ is the effective rate constant of water dissociation in the absence of electric field; β is the entropy factor.…”

Section: Methodsmentioning

confidence: 99%

“…Then, we obtain (14) 0, We assume that the electric field strength beyond the SCR does not shift the equilibrium of reactions (2)- (4). Then, the current density with respect to Н + and ОН -ions is the same throughout the SCR thickness and equal to (15) where λ is the SCR thickness in the membrane.…”

Section: н о H Ohmentioning

confidence: 99%

“…According to the second Wien effect, for monopolar membranes, the acceleration of this reaction in response to electric field is insignificant [12]. Actually, in membranes with strongly basic quaternary amino groups, the rate con stant of water dissociation experimentally measured by the impedance frequency spectroscopy was 4-5 orders of magnitude higher [13,14].…”

Section: Transfer Of Electrolyte Ions and Water Dissociation In Anionmentioning

confidence: 99%

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Transfer of electrolyte ions and water dissociation in anion-exchange membranes under intense current conditions

et al. 2012

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Polarization characteristics of electromembrane systems (EMS) based on the Russian commer cial heterogeneous membranes MA 40 and MA 41, the anion exchange heterogeneous membrane AMH (Mega, Czech Republic), and the modified membrane MA 40M are studied by the method of rotating mem brane disk in dilute sodium chloride solutions. The effective transport numbers of ions are found; the partial voltammetric characteristics (VAC) with respect to chloride and hydroxyl ions are measured; the limiting cur rent densities are calculated as a function of the membrane disk rotation rate. In terms of the theory of the overlimiting state of EMS, based on experimental VAC and the dependences of the effective transport num bers on the current density, the following internal parameters of systems under study are calculated: the space charge and electric field strength distribution over the diffusion layer and the membrane. It is shown that water dissociation can be virtually completely eliminated by substituting chemically stable quaternary ammo nium groups inert with respect to water dissociation in the surface layer of a heterogeneous anion exchange membrane MA 40 for the active ternary and secondary functional amino groups. The maximum electric field strength values at the membrane/solution interface, which were found in the framework of the theory of over limiting state, turned out to be close for all anion exchange membranes studied, namely, (7-9) × 10 6 V/cm. This suggests that it is the nature of ionogenic groups in the surface layer rather than the field effect that plays the decisive role in the membrane ability to accelerate the water dissociation reaction. It is proved experimen tally that in highly intense current modes of the electrodialysis process, the thermal hydrolysis of quaternary ammonium bases occurs in strongly basic MA 41 and AMH membranes by the Hofmann reaction to form ternary amino groups catalytically active in water dissociation reaction. Based on the concept on the catalytic mechanism of water dissociation, the fraction of ternary amino groups formed by thermal hydrolysis in the surface layer (the space charge region) of monopolar anion exchange membranes MA 41 and AMH is assessed quantitatively as 0.7 and 6.5%, respectively.

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Section: Methodsmentioning

confidence: 99%

Section: н о H Ohmentioning

confidence: 99%

Section: Transfer Of Electrolyte Ions and Water Dissociation In Anionmentioning

confidence: 99%

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Transfer of electrolyte ions and water dissociation in anion-exchange membranes under intense current conditions

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“…Based on these reactions, the series of catalytic activity for the water dissociation of Table 4.11 was completed in Table 4.12 with the inclusion of the catalytic activity of transition metal compounds, which includes the precipitates of Ni(OH) 2 and Fe(OH) 3 formed during our chronopotentiometric experiments [97]. Table 4.12.…”

Section: Overlimiting Currents Originated By Water Splitting Productsmentioning

confidence: 99%

“…To explain the drastic increase in water splitting associated with the presence of precipitates at the membrane surface Mel'nikov developed a model based on the following cascade reactions of catalytic water dissociation [97]:…”

Section: Overlimiting Currents Originated By Water Splitting Productsmentioning

confidence: 99%

Determination of transport properties of Ni(II) through a Nafion cation-exchange membrane in chromic acid solutions

Martí-Calatayud

García-Gabaldón

Pérez-Herranz

et al. 2011

Journal of Membrane Science

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Acknowledgements / Agradecimientos / AgraïmentsEn primer lugar quisiera agradecer a Valentín y a Montse por haberme dado la oportunidad de investigar con ellos, por introducirme en un mundo que me ha fascinado, por haberme dirigido, por haberme ayudado en momentos de desasosiego; porque, en definitiva, creo que hemos formado un gran equipo.Quisiera agradecer a la Universitat Politècnica de València la financiación recibida para realizar la tesis. En general, he de agradecer al sistema de educación pública que ha permitido que un hijo de trabajadores como yo haya podido llegar hasta aquí. Además, quiero aprovechar para exigir un sistema de educación público, de calidad, e igualitario, que forme a personas con espíritu crítico y libre; puesto que sólo así se conseguirá que progresemos como sociedad.I would also like to thank to all the people from the group of Chemical Process Engineering of the RWTH Aachen University, especially to Matthias Wessling and Said Abdu, for accepting me in their research group. They have been very kind to me and I have learnt a lot from them and from this fruitful and unforgettable experience in Aachen.También quisiera agradecer a Daniella Buzzi por haberme dejado ser su "chefinho", por tantos momentos buenos y algún que otro momento crítico vividos juntos, porque es bonito saber que tengo una gran amiga al otro lado del charco.Gracias al Grupo IEC, en especial a mis compañeros, con los que he pasado más momentos juntos. Ellos han sido mi familia investigadora. Gracias a Isaac y Carlos, porque han sido para mí un referente, a Jordi y Ramón, porque han estado desde el principio, han sido como mis hermanos, y a Vir y Tepe, ellas han contribuido a que haya un ambiente de trabajo inmejorable! Quiero también dar las gracias al resto de componentes del grupo por su ayuda, en especial a Emma Ortega, a José Luis Guiñón por su ayuda con los equilibrios, y a Anna Igual porque con su energía consigue contagiar su pasión por la investigación.El fruto del trabajo de todos estos años tampoco sería posible sin los momentos vividos junto a mis amigos, el "Kanchy". Ellos son "los de toda la vida", los que siempre han estado, están y estarán ahí. Quisiera hacer mención especial a Lidia por su ayuda con la Tesis, y cómo no, a Sergio, porque juntos hemos arreglado el mundo un millón de veces… ¡para volverlo a destrozar otras tantas! No quiero olvidarme de ninguna de las personas con las que he coincidido y he pasado buenos momentos tanto en Valencia, como en Berlín o en Aachen… Maite, Laura, Guillaume… es imposible nombrarlos a todos… pero quiero agradecer en especial a Tania, porque con ella no existe el tiempo ni la distancia, sé que siempre está ahí a mi lado.Ha arribat el moment d'agrair a les quimixiques els grans moments viscuts. Amb elles hem format una gran família. Em sent molt afortunat d'haver caigut en un grup tan de "puça mare": gràcies a les Silvies, Elena, Gabriel·la, Angeleta, Rosa de Xeraco, Alicia, i en especial a Susana, la meua companya de batalles, i a Ingrid, una gran amiga.Per últim...

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Improving the Stability, Selectivity, and Cell Voltage of a Bipolar Membrane Zero‐Gap Electrolyzer for Low‐Loss CO₂ Reduction

Siritanaratkul

Sharma

et al. 2023

Adv Materials Inter

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Electrolyzers for CO2 reduction containing bipolar membranes (BPM) are promising due to low loss of CO2 as carbonates and low product crossover, but improvements in product selectivity, stability, and cell voltage are required. In particular, direct contact with the acidic cation exchange layer leads to high levels of H2 evolution with many common cathode catalysts. Here, Co phthalocyanine (CoPc) is reported as a suitable catalyst for a zero‐gap BPM device, reaching 53% Faradaic efficiency to CO at 100 mA cm−2 using only pure water and CO2 as the input feeds. It is also shown that the cell voltage can be lowered by constructing a customized BPM using TiO2 water dissociation catalyst, however this is at the cost of decreased selectivity. Switching the pure‐water anolyte to KOH improved both the cell voltage and CO selectivity (62% at 200 mA cm−2), but cation crossover could cause complications. The results demonstrate viable strategies for improving a BPM CO2 electrolyzer toward practical‐scale CO2‐to‐chemicals conversion.

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Effect of d-metal hydroxides on water dissociation in bipolar membranes

Cited by 36 publications

References 9 publications

Transfer of electrolyte ions and water dissociation in anion-exchange membranes under intense current conditions

Transfer of electrolyte ions and water dissociation in anion-exchange membranes under intense current conditions

Determination of transport properties of Ni(II) through a Nafion cation-exchange membrane in chromic acid solutions

Improving the Stability, Selectivity, and Cell Voltage of a Bipolar Membrane Zero‐Gap Electrolyzer for Low‐Loss CO₂ Reduction

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Effect of d-metal hydroxides on water dissociation in bipolar membranes

Cited by 36 publications

References 9 publications

Transfer of electrolyte ions and water dissociation in anion-exchange membranes under intense current conditions

Transfer of electrolyte ions and water dissociation in anion-exchange membranes under intense current conditions

Determination of transport properties of Ni(II) through a Nafion cation-exchange membrane in chromic acid solutions

Improving the Stability, Selectivity, and Cell Voltage of a Bipolar Membrane Zero‐Gap Electrolyzer for Low‐Loss CO2 Reduction

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Product

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Improving the Stability, Selectivity, and Cell Voltage of a Bipolar Membrane Zero‐Gap Electrolyzer for Low‐Loss CO₂ Reduction