Proton conductivity of calix[4]arene-para-sulfonic acids

Shmygleva, L. V.; Pisareva, A. V.; Pisarev, R. V.; Ukshe, A. E.; Dobrovol’skii, Yu. A.

doi:10.1134/s1023193513080181

Cited by 20 publications

(5 citation statements)

References 16 publications

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“…The frequency dependences of the resistance of the sam ples were obtained on a Z 3000 (Elins, Russia) imped ance meter in the frequency range 1 Hz-3 MHz with the amplitude of the measurement signal 10-70 mV. The proton conductivity of the samples was calcu lated by approximating the spectra of the experimental cell according to the equivalent circuit described in detail in [2].…”

Section: Methodsmentioning

confidence: 99%

“…A detailed description of proton conductivity was given in [2,3]. The temperature dependences of con ductivity of the calixarene compounds at different moisture contents showed that they conform with the Arrhenius equation (Fig.…”

Section: Proton Conductivitymentioning

confidence: 96%

“…Earlier, we showed [2][3][4] that effective ionic transport appears in these compounds, leading to the production of substances with record breaking proton conductivity. Therefore, here we studied the influence of the morphology of calixarene sulfonic acids on their transport properties.…”

Section: Introductionmentioning

confidence: 94%

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Effect of the structure of calix[4]arene-para-sulfonic acid on its transport properties

et al. 2015

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The effect of a change in the ambient temperature and humidity on the behavior of calix(4)arene para sulfonic acid was studied. For the calixarene under study, at least two stable hydrates were observed: tetra and octahydrate. The number of water molecules in the crystalline hydrate of the acid was confirmed by simultaneous thermal analysis data and the shape of the IR spectra and diffraction patterns. The change in the composition of the hydrate from n = 4 to n = 20 affected the conductivity but slightly; in the region of phase transitions between the hydrates, the activation energy of conductivity changed abruptly.

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Section: Methodsmentioning

confidence: 99%

Section: Proton Conductivitymentioning

confidence: 96%

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Effect of the structure of calix[4]arene-para-sulfonic acid on its transport properties

et al. 2015

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“…Previous investigations have found that SC[n]A exhibited high proton conductivity up to 10 −1 S cm −1 at room temperature, 80%−85% RH, 39,40 close to or even higher than that of heteropolyacids H 3 PW 12 O 40 •xH 2 O or Nafion, 41,42 and increased in the order of SC [4]A < SC [6]A < SC [8]A. 37,43 Thus, SC[n]As hold great promise in incorporating sufficient proton donors within GO nanosheets, while firmly supporting adjacent GO nanosheets with less space occupancy.…”

Section: Introductionmentioning

confidence: 96%

“…p -Sulfonato calix[ n ]arenes ( p -SC[ n ]A, n = 4–8), an emerging family of hydrophilic supramolecular substances, have been extensively explored in molecular or ionic recognition and sensing, enzyme assays, and biological/medical chemistry et al − From the standpoint of proton conductivity, SC[ n ]A should be a preferred choice owing to its unique properties: a rigid fragment of an organic core, layers comprised of proton donors (−SO 3 H) that was surrounded by a large amount of bound water molecules, , an ultrahigh theoretical ion exchange capacity (IEC w ) of 5.37 mmol g –1 and easy modifiability. Previous investigations have found that SC[ n ]A exhibited high proton conductivity up to 10 –1 S cm –1 at room temperature, 80%–85% RH, , close to or even higher than that of heteropolyacids H 3 PW 12 O 40 · x H 2 O or Nafion, , and increased in the order of SC[4]A < SC[6]A < SC[8]A. , Thus, SC[ n ]As hold great promise in incorporating sufficient proton donors within GO nanosheets, while firmly supporting adjacent GO nanosheets with less space occupancy.…”

Section: Introductionmentioning

confidence: 98%

Supramolecular Calix[n]arenes-Intercalated Graphene Oxide Membranes for Efficient Proton Conduction

Mao

et al. 2019

ACS Appl. Mater. Interfaces

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Graphene oxide (GO) membranes with 2D interlaminar channels have triggered intensive interest as ion conductors. Incorporating abundant ion-conducting sites into GO interlayers is recognized as an effective strategy to facilitate ion conduction. Herein, we designed supramolecular compounds, para-sulphonato-calix[n]arenes (p-SC[n]As), as versatile intercalators to acquire highly conductive and robust GO membranes. The SC[n]A with ultrahigh ionic exchange capacity (IEC w , 5.37 mmol g −1 ) imparts sufficient proton donors, and its rigid framework imparts strong support of adjacent nanosheets. We designed three kinds of SC [n]As with the same IEC w but different sizes as intercalators, endowing the GO/ SC[n]A membranes with increasing ion concentration and d-spacing in the order of GO/SC[4]A < GO/SC[6]A < GO/SC[8]A. Therefore, the interlayers of GO/SC[8]A membranes afforded higher density of proton donors and could accommodate more water molecules to construct more continuous H-bond networks for proton transfer. Accordingly, the proton conductivities exhibited the same increasing trend, up to 327.0 mS cm −1 of GO/ SC[8]A-30% at 80 °C, 100% RH, which was 2.80 times higher than that of the GO membrane. Moreover, the GO/SC[n]A membranes remained stable in wet state, along with a 66% elevation in mechanical performance compared to the GO membrane.

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Solvated proton as the main reagent and a catalyst in the single-stage aromatic sulfonation and protodesulfonation of sulfonic acids

2017

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This review is devoted to the critical analysis of the existing contradictory ideas about kinetic description and the mechanisms of electrophilic aromatic substitution (EAS), ie, reversible arene sulfonation and hydrolysis (protodesulfonation) of arenesulfonic acids. Contemporary scientific and educational literature contains prevailing, widespread points of view on the multistage nature processes of the EAS that proceed via πand σ-complexes and are accompanied by arenium ion formation. This interpretation does not account for determining influence of the medium, and the process accompanies the loss of aromaticity. The review presents an alternative point of view: These processes proceed via singlestage and the same transition state. To substantiate this position, we reviewed in detail the contemporary ideas on the solvated proton structure, the limits of applicability of acidity function Н о and excess acidity Х scales, and the experimental solubility data of arenesulfonic acid hydrates in sulfuric acid. This solubility depends on the medium acidity (h o ), which provides the formation of 3 conjugated types of hydrates: anionic (АrSO 3 − ·H 2 O), hydroxonium-arene sulfonated (АrSO 3 − ·H 3 O + ), and the hydroxonium complex with the H-form of АrSO 3 Н·H 3 O + acid. In sulfuric acid solutions with an excess of water, irreversible hydrolysis proceeds with the participation of ArSO 3 − ·H 3 O + . However, protodesulfonation becomes reversible and proceeds with the participation of ArSO 3 Н·H 3 O + in solutions with an excess of sulfuric acid. A conclusion has been made about determining the role of the hydrated proton environment by means the formation of a cyclic transition state. An alternative 2-stage mechanism of EAS is logically and energetically unsubstantiated and, therefore, should be rejected.

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Proton conductivity of calix[4]arene-para-sulfonic acids

Cited by 20 publications

References 16 publications

Effect of the structure of calix[4]arene-para-sulfonic acid on its transport properties

Effect of the structure of calix[4]arene-para-sulfonic acid on its transport properties

Supramolecular Calix[n]arenes-Intercalated Graphene Oxide Membranes for Efficient Proton Conduction

Solvated proton as the main reagent and a catalyst in the single-stage aromatic sulfonation and protodesulfonation of sulfonic acids

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