Mobility of protons in 12-phosphotungstic acid and its acid and neutral salts

Chikin, A. I.; Chernyak, Alexander V.; Jin, Zhao; Naumova, Yulia Sergeevna; Ukshe, A. E.; Smirnova, N. V.; Volkov, V. I.; Dobrovolsky, Yu. A.

doi:10.1007/s10008-012-1687-6

Cited by 30 publications

(10 citation statements)

References 22 publications

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“…The material that we report is a salt consisting in Keggin anions (WP 3– ) and imidazolium cations (Imid + ); it has never been reported before and is a material that bridges the gap between proton conducting solid acids and ion conducting salt hydrates. Related materials to this new salt are proton conducting salts formed by proton transfer from a carboxylic acid to imidazole and those obtained by substituting the acidic protons in 12-tungstophosphoric acid hydrate with metal cations. ,, Compared to previously proposed, related materials, the Imid 3 WP hydrate shows superior proton conducting properties despite the lower degree of hydration as well as an improved thermochemical stability. This behavior is rationalized by the crystalline structure adopted, the nature of hydrogen bonds established within the ionic network, and the rotational dynamics of the charge carrying molecules.…”

Section: Introductionmentioning

confidence: 99%

“…As an example, proton conductivity decays of four or five decades have been regularly reported when the number of coordinating water molecules decreases from 21 to 6 . To circumvent these limitations, novel structures based on the (partial) substitution of the acidic protons with metal cations, − or on the incorporation of the heteropolyacid in mesoporous membranes, have been investigated as alternative, more stable solid-state proton conductors. Moreover, the degree of hydration in these solid acids influences the mechanism of proton transport, which varies from mainly vehicular for a high number of water molecules to Grotthuss for the pseudoanhydrous or totally anhydrous state .…”

Section: Introductionmentioning

confidence: 99%

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A New Solid-State Proton Conductor: The Salt Hydrate Based on Imidazolium and 12-Tungstophosphate

et al. 2021

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We report the structure and charge transport properties of a novel solid-state proton conductor obtained by acid–base chemistry via proton transfer from 12-tungstophosphoric acid to imidazole. The resulting material (henceforth named Imid3WP) is a solid salt hydrate that, at room temperature, includes four water molecules per structural unit. To our knowledge, this is the first attempt to tune the properties of a heteropolyacid-based solid-state proton conductor by means of a mixture of water and imidazole, interpolating between water-based and ionic liquid-based proton conductors of high thermal and electrochemical stability. The proton conductivity of Imid3WP·4H2O measured at truly anhydrous conditions reads 0.8 × 10–6 S cm–1 at 322 K, which is higher than the conductivity reported for any other related salt hydrate, despite the lower hydration. In the pseudoanhydrous state, that is, for Imid3WP·2H2O, the proton conductivity is still remarkable and, judging from the low activation energy (E a = 0.26 eV), attributed to structural diffusion of protons. From complementary X-ray diffraction data, vibrational spectroscopy, and solid-state NMR experiments, the local structure of this salt hydrate was resolved, with imidazolium cations preferably orienting flat on the surface of the tungstophosphate anions, thus achieving a densely packed solid material, and water molecules of hydration that establish extremely strong hydrogen bonds. Computational results confirm these structural details and also evidence that the path of lowest energy for the proton transfer involves primarily imidazole and water molecules, while the proximate Keggin anion contributes with reducing the energy barrier for this particular pathway.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A New Solid-State Proton Conductor: The Salt Hydrate Based on Imidazolium and 12-Tungstophosphate

et al. 2021

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“…[22][23][24][25] On the other hand, keggin-type polyoxometalate (POM), particularly phosphotungstic acid (PTA) has been demonstrated for many applications including supercapacitor, sensor, catalyst, fuel cells, proton memory devices, molecular conductors, and solid-state electronic devices because of its excellent solubility, thermal stability, high proton conductivity, high electronic density, strong acidity, and reversible multielectron redox activity of electrochemistry and photochemistry. 26,27 [28][29][30][31][32][33][34][35][36] High supercapacitance was achieved due to its faradaic involvement and homogeneous distribution of POM ions that directs to higher charge delocalization and enhanced conductivity. 37 Yet, articles on the judicious utilization of PDPA/PTA/PANI copolymer combination for supercapacitor applications are scanty.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, keggin‐type polyoxometalate (POM), particularly phosphotungstic acid (PTA) has been demonstrated for many applications including supercapacitor, sensor, catalyst, fuel cells, proton memory devices, molecular conductors, and solid‐state electronic devices because of its excellent solubility, thermal stability, high proton conductivity, high electronic density, strong acidity, and reversible multielectron redox activity of electrochemistry and photochemistry 26,27 . Importantly, POMs, including phosphomolybdic acid (H 3 PMo 12 O 40 ·xH 2 O), PTA (H 3 PW 12 O 40 ) exhibits superior capacitive performances 28‐36 .…”

Section: Introductionmentioning

confidence: 99%

Improved cyclic retention and high‐performance supercapacitive behavior of poly(diphenylamine‐co‐aniline)/phosphotungstic acid nanohybrid electrode

et al. 2020

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In this study, a simple and facile electrochemical deposition technique was employed to fabricate fluorine-doped tin oxide-based polydiphenylamine-polyaniline/phosphotungstic acid copolymer nanocomposite modified electrode (FTO/PDPA-PANI/PTA) for high-performance supercapacitors application.Crystalline and morphological structure and coating thickness of PDPA-PANI/ PTA nanocomposite on FTO were characterized using X-ray diffraction, scanning electron microscope, and atomic force microscope. The fabricated nanohybrid electrode exhibits superior specific capacitance of 360 Fg −1 at

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“…HPAs are nanosized polynuclear metal‐oxygen clusters with interesting conductivity, catalytic, and many other properties . They are one of the best proton conductive materials among the inorganic solid electrolytes.…”

Section: Introductionmentioning

confidence: 99%

Proton‐conductive membranes based on vanadium substituted heteropoly acids with Keggin structure and polymers

Tian

Yang

et al. 2015

J of Applied Polymer Sci

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In this article, novel proton-conducting composite membranes SPEEK/PW 11 V and PVA/SiW 11 V were synthesized from vanadium substituted heteropoly acids (H 4 PW 11 VO 40 Á8H 2 O and H 5 SiW 11 VO 40 Á15H 2 O, abbreviated as PW 11 V and SiW 11 V) and polymers (SPEEK or PVA) at the weight ratio 70 : 30. The membranes were characterized by the infrared spectroscopy, X-ray powder diffraction, and scanning electron microscopy, which confirmed the maintenance of the Keggin framework and dispersion homogeneously in the polymer matrix without long-range ordering. Their proton-conducting properties were investigated with electrochemical impedance spectroscopy. The results show that the respective proton conductivities of SPEEK/PW 11 V and PVA/SiW 11 V membranes were in the order of 10 22 and 10 24 S cm 21 at ambient temperature. The temperature dependence of the two composite membrane electrolytes exhibit Arrhenius behavior, and the observed activation energies to be 15.82 kJ mol 21 for SPEEK/PW 11 V and 14.40 kJ mol 21 for PVA/SiW 11 V, which indicates that the proton conduction complies with the Grotthuss mechanism. V C 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42204.

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Mobility of protons in 12-phosphotungstic acid and its acid and neutral salts

Cited by 30 publications

References 22 publications

A New Solid-State Proton Conductor: The Salt Hydrate Based on Imidazolium and 12-Tungstophosphate

A New Solid-State Proton Conductor: The Salt Hydrate Based on Imidazolium and 12-Tungstophosphate

Improved cyclic retention and high‐performance supercapacitive behavior of poly(diphenylamine‐co‐aniline)/phosphotungstic acid nanohybrid electrode

Proton‐conductive membranes based on vanadium substituted heteropoly acids with Keggin structure and polymers

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