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Effect of Temperature and Water Content on the Properties of Solid Protic Electrolyte of Tetra Calixarene Sulfonic Acid: NMR Study

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Abstract

The methods of 1H NMR and pulsed field gradient NMR are used to study the protic solid electrolyte of calix[4]arene-para-sulfonic acid in the temperature range of –15 to 24°C and water content λ of 1.6 to 5.7 H2O molecules per SO3H. Analysis of the 1H signal intensity in NMR spectra showed that no ice phase is formed in the whole studied temperature and water content range. The hydration numbers of H+(H2O)h complexes are calculated on the basis of the temperature dependences of chemical shift values. The pulsed field gradient NMR technique is used to determine self-diffusion coefficients. Activation energies Eact are calculated on the basis of the temperature dependences of self-diffusion coefficients. Good agreement of the data on diffusion Eact and protic conductivity are shown. A corollary of the Nernst–Einstein equation is used to calculate the values of protic conductivity on the basis of self-diffusion data. The calculated values of protic conductivity in the water content λ range of 1.6 to 5.7 agree with the data obtained experimentally.

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REFERENCES

  1. Pisareva, A.V., Pisarev, R.V., Karelin, A.I., Shmygleva, L.V., Antipin, I.S., Konovalov, A.I., Solovieva, S.E., Dobrovolsky, Y.A., and Aldoshin, S.M., Proton conductivity of calix[n]arene-para-sulfonic acids (n = 4, 8), Russ. Chem. Bull., 2012, vol. 61, p. 1892.

    Article  CAS  Google Scholar 

  2. Shmygleva, L.V., Pisareva, A.V., Pisarev, R.V., Ukshe, A.E., and Dobrovol’skii Y.A., Proton conductivity of calix[4]arene-para-sulfonic acids, Russ. J. Electrochem., 2013, vol. 49, p. 801.

    Article  CAS  Google Scholar 

  3. Shmygleva, L.V., Sanginov, E.A., Kayumov, R.R., Ukshe, A.E., and Dobrovol’skii, Y.A., Effect of the structure of calix[4]arene-para-sulfonic acid on its transport properties, Russ. J. Electrochem., 2015, vol. 51, p. 468.

    Article  CAS  Google Scholar 

  4. Shmygleva, L.V., Sanginov, E.A., Slesarenko, N.A., Chernyak, A.V., Karelin, A.I., and Dobrovolsky, Y.A., Aspects of proton transport in calix[6]arene sulfonic acid, Ionics, 2017, vol. 23, p. 1793.

    Article  CAS  Google Scholar 

  5. Shmygleva, L.V., Slesarenko, N.A., Chernyak, A.V., Sanginov, E.A., Karelin, A.I., Pisareva, A.V., Pisarev, R.V., and Dobrovolsky, Y.A., Effect of Calixarene Sulfonic Acids Hydration on Their Proton Transport Properties, Int. J. Electrochem. Sci., 2017, vol. 12, p. 4056.

    Article  CAS  Google Scholar 

  6. Atwood, J.L., Hamada, F., Robinson, K.D., Orr, G.W., and Vincent, R.L., X-ray diffraction evidence for aromatic π hydrogen bonding to water, Nature, 1991, vol. 349, p. 683.

    Article  CAS  Google Scholar 

  7. Coleman, A.W., Bott, S.G., Morley, S.D., Means, C.M., Robinson, K.D., Zhang, H., and Atwood, J.L., Novel Layer Structure of Sodium Calix[4]arenesulfonate Complexes—a Class of Organic Clay Mimics?, Angew. Chem. Int. Ed. Engl., 1988, vol. 10, p. 1361.

    Article  Google Scholar 

  8. Dalgarno, S.J. and Raston, C.L., Rapid capture of 4,13-diaza-18-crown-6 molecules by p-sulfonatocalix[4]arene in the presence of trivalent lanthanide ions, Dalton Trans., 2003, no. 3, p. 287.

  9. Martin, A.D. and Raston, C.L., Multifunctional pрphosphonated calixarenes, Chem. Commun., 2011, vol. 47, p. 9764.

    Article  CAS  Google Scholar 

  10. Dalgarno, S.J., Atwood, J.L., and Raston, C.L., Structural Versatility in Praseodymium Complexes of p-Sulfonatocalix[4]arene, Cryst. Growth Des., 2007, vol. 7, no. 9, p. 1762.

    Article  CAS  Google Scholar 

  11. Tauran, Y., Brioude, A., Shahgaldian, P., Cumbo, A., Kim, B., Perret, F., Coleman, A.W., and Montasserf, I., Calix-arene silver nanoparticles interactions with surfactants are charge, size and critical micellar concentration dependent, Chem. Commun., 2012, vol. 48, p. 9483.

    Article  CAS  Google Scholar 

  12. Scharff, J.-P. and Mahjoubi, M., Synthesis and acid-base properties of calix[4], calix[6] and calix[8]arene p‑Sulfonic Acids, New. J. Chem., 1991, vol. 15, p. 883.

    CAS  Google Scholar 

  13. Suh, K.J., Hong, Y.S., Skirda, V.D., Volkov, V.I., Lee, C.Y.J., and Lee, C.H., Water self-diffusion behavior in yeast cells studied by pulsed field gradient NMR. Biophys. Chem., 2003, vol. 104, p. 121.

    Article  CAS  PubMed  Google Scholar 

  14. Maklakov, A.I., Skirda, V.D., and Fatkullin, N.F., Self-Diffusion in Polymer Solutions and Melts. (in Russian), Kazan: State University Press. Kazan, 1987.

    Google Scholar 

  15. Volkov, V.I., Korotchkova, S.A., Ohya, H., and Guo Q., Self-diffusion of water-ethanol mixtures in polyacrylic acid-polysulfone composite membranes obtained by pulsed-field gradient nuclear magnetic resonance spectroscopy, J. Membr Sci., 1995, vol. 100, p. 273.

    Article  CAS  Google Scholar 

  16. Creekmore, R.W. and Reilley, C.N., Nuclear magnetic resonance determination of hydration numbers of electrolytes in concentrated aqueous solutions, J. Phys. Chem., 1969, vol. 73, p. 1564.

    Article  Google Scholar 

  17. Malinowski, E.R., Knapp, P.S., and Feuer, B., NMR studies of aqueous electrolyte solutions. I. Hydration number of NaCI determined from temperature effects on proton shift, J. Chem. Phys., 1966, vol. 45, p. 4276.

    Article  Google Scholar 

  18. Hucishvili, V.G., Bogachev, Yu.S., and Volkov, V.I., The study of the state of water in the phase of sulphocathionite KU-2 by the method of proton magnetic resonance, Zh. Fiz. Khim., 1983, vol. 57, no. 10, p. 2524.

    Google Scholar 

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Correspondence to A. V. Chernyak or N. A. Slesarenko.

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Translated by M. Ehrenburg

Based on the paper presented at the XIV Meeting “Fundamental Problems of Solid State Ionics,” Chernogolovka (Russia), September 9–13, 2018.

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Chernyak, A.V., Slesarenko, N.A. Effect of Temperature and Water Content on the Properties of Solid Protic Electrolyte of Tetra Calixarene Sulfonic Acid: NMR Study. Russ J Electrochem 55, 537–543 (2019). https://doi.org/10.1134/S1023193519060077

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  • DOI: https://doi.org/10.1134/S1023193519060077

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