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Slesarenko, N. Ion Exchange Membranes by NMR. Encyclopedia. Available online: (accessed on 14 June 2024).
Slesarenko N. Ion Exchange Membranes by NMR. Encyclopedia. Available at: Accessed June 14, 2024.
Slesarenko, Nikita. "Ion Exchange Membranes by NMR" Encyclopedia, (accessed June 14, 2024).
Slesarenko, N. (2021, June 08). Ion Exchange Membranes by NMR. In Encyclopedia.
Slesarenko, Nikita. "Ion Exchange Membranes by NMR." Encyclopedia. Web. 08 June, 2021.
Ion Exchange Membranes by NMR

An ion-exchange membrane lets pass certain ions while blocking other ions or neutral molecules. Nuclear Magnetic Resonance (NMR) spectroscopy is a technique for determining the content, purity, and molecular structure of a sample. NMR methods provide the unique possibility of acquiring detailed information on the state of molecules and ions, the local molecular and ionic mobility, and the diffusion on the spatial scale from several tenths of nanometer to several millimeters.

ion exchange membranes hydration protein association red blood cells chemical shift spin–relaxation pulsed field gradient NMR

1. Overview

The results of NMR, and especially pulsed field gradient NMR (PFG NMR) investigations, are summarized. Pulsed field gradient NMR technique makes it possible to investigate directly the partial self-diffusion processes in spatial scales from tenth micron to millimeters. Modern NMR spectrometer diffusive units enable to measure self-diffusion coefficients from 10−13 m2/s to 10−8 m2/s in different materials on 1 H, 2 H, 7 Li, 13 C, 19 F, 23 Na, 31 P, 133 Cs nuclei. PFG NMR became the method of choice for reveals of transport mechanism in polymeric electrolytes for lithium batteries and fuel cells. Second wide field of application this technique is the exchange processes and lateral diffusion in biological cells as well as molecular association of proteins. In this case a permeability, cell size, and associate lifetime could be estimated. The authors have presented the review of their research carried out in Karpov Institute of Physical Chemistry, Moscow, Russia; Institute of Problems of Chemical Physics RAS, Chernogolovka, Russia; Kazan Federal University, Kazan, Russia; Korea University, Seoul, South Korea; Yokohama National University, Yokohama, Japan. The results of water molecule and Li+, Na+, Cs+ cation self-diffusion in Nafion membranes and membranes based on sulfonated polystyrene, water (and water soluble) fullerene derivative permeability in RBC, casein molecule association have being discussed.

2. Cation-Exchange Membranes. Structure, Hydration, Ionic, and Molecular Mobility

Ion-exchange membranes are widely applied for modern electrochemical technologies and separation processes. New materials design requires an electro mass transfer investigation. This research is mainly concerned about macroscopic transport processes [1][2][3][4][5][6][7]. However, ion and molecular translation microscopic mobilities have to be investigated for membrane selectivity mechanism understanding.
Of most interest is the relationship between the following fundamentally important characteristics that determine the ion and molecular transport:
  • The nanoscale structure of ion transport channels. The structure and dynamics of polymer matrix at the submicro level from several tenths of nanometer (sizes of solvated ions and molecules) to several nanometers or several tens of nanometers (characteristic lateral dimensions and lengths of ionic channels), determine the selective ion transport because these structural units form transport path for ion transfer by macroscopic distances. Studying the nanostructure opens up the prospects for targeted synthesis of ion exchange polymer, insofar as their preparation is accompanied by the formation of the nanostructure.
  • The type of interaction of mobile ions and hydration water molecules with functional groups. Data on the structure of ionic complexes and on the mechanisms of interaction of ions and water molecules with the polymer matrix are necessary for understanding the mechanisms of selectivity of ion-exchange membranes and elementary steps of the diffusion transport of ions.
  • The elementary steps of diffusion of ions and molecules, which can be characterized by the lifetime of a species on functional group, the time of translational displacement, the partial diffusion coefficient on various spatial scales (if diffusion occurs in a heterogeneous medium).
The problem of elementary diffusion jumps logically follows from the aforesaid. Evidently, the time of elementary jump and the height of the potential barrier overcome by a moving species are largely determined by the geometry of diffusion channels and the structure of hydrate ionic complexes. This information is necessary for both the elaboration of adequate transport models and the targeted synthesis of high-performance ion exchange polymers.
The knowledge of structure and dynamics in a different spatial scale and in a broad band of molecular motion frequencies may be obtained by NMR directly.
NMR spectroscopy The most popular method is 1H NMR, which was used to study Dowex 50 W, CU-2 sulfonate cation exchanger resin and the corresponding membranes MC-40, cation exchange membranes based on polyethylene and sulfonated grafted polystyrene MSC [8][9][10][11][12][13][14][15][16][17] and perfluorinated cation-exchange membranes [18][19][20][21][22][23][24][25][26]. To date, techniques have been developed for recording high-resolution NMR spectra and the main factors that determine the chemical shift of water protons in granulated sulfonate cation-exchangers and ion-exchange membranes have been elucidated. The required information can also be obtained from the solid-state high-resolution NMR spectroscopy data [23][24]. Information on hydration of ionic channels in membranes is of fundamental importance for understanding the mechanism of migration of cations and water molecules.
Alkaline metal cations of lithium, sodium, and cesium were studied by NMR on 7 Li, 23 Na and 133 Cs nuclei in cation-exchange membranes [16][17][20][21][27][28][29][30][31][32] and in sulfonated polystyrene salts [33][34]. Some qualitative data about ionogenic group-cation interaction and cation motion were obtained.
Pulse NMR methods NMR relaxation techniques were for the first time applied for local cationic and water molecules mobility characterization in polymeric electrolytes more than 50 years ago [10]. Spin–lattice and spin–spin relaxation times measurements on 1 H, 7 Li, 19 F NMR nuclei were performed in Nafion and MF-4SC (Russian Nafion type membrane) membranes [35][36][37][38][39][40][41]. Unfortunately, the numerical calculation of correlation times is hard work because of wide molecular motion frequency distribution.
The study of the metal ion mobility is associated with even more serious complications. The most serious obstacle is the absence of theoretical works to serve as the base for studying the region of diffusion motion with the characteristic correlation times longer than ωo−1 (where ω0 is the NMR frequency, usually, ~109 Hz). To date, 7 Li and 23 Na NMR relaxation works have been performed dealing with the mobilities of lithium and sodium cations in the CU-2 type sulfonate cation exchangers and the corresponding membranes, perfluorinated sulfonate cation-exchange membranes [31][32][33][34][39][40][41].
The pulsed field gradient NMR method, [42][43] which makes it possible to directly measure the diffusion coefficients of protons and other ions in heterogeneous media, is free from these drawbacks. The number of studies of this type substantially increased in recent decades, [5][6][19][38][39][40][41][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][78][79][80][81][82][83] which was associated with the increased interest in the problems of ionic mobility in polyelectrolytes.
To summarize the foregoing, the following points should be underlined. The magnetic resonance techniques and, especially, NMR methods provide the unique possibility of acquiring detailed information on the state of molecules and ions, the local molecular and ionic mobility, and the diffusion on the spatial scale from several tenths of nanometer to several millimeters. The advantages of NMR spectroscopy also involve the possibility of studying one and the same sample under conditions resembling the service conditions by several methods simultaneously, which makes it possible to compare the results of different measurements and unambiguously interpret them. For these studies to be performed the experimental procedures should be worked out and the problems associated with theoretical quantitative description of data should be solved.
The NMR methods are especially attractive for acquiring detailed information on the ion and molecular transport in polymer electrolytes. The modern level of experimental research instruments allows one to study both elementary processes and macroscopic transfer under the service conditions of electrochemical systems. The successful introduction of NMR methods into the research and technological practice is limited by the lack of publications devoted, first of all, to demonstration of the potential of experimental NMR techniques in this research field.
Despite the considerable number of NMR studies of polymer electrolytes, the reviews on this subject are scarce. In the present review, the experimental results obtained by NMR methods on the ion and water molecular transport in polymer ion exchangers carried out in Russia and abroad are analyzed and generalized. From our point of view, such an analysis will demonstrate the potential of modern NMR methods and help to reveal some fundamental features of ion and molecular transport in ion exchange membranes at the molecular level.
The main results of NMR studies in ion-exchange membranes are discussed. Attention is focused on the potential of NMR techniques in solving particular problems in relation to the most widely known ion exchangers. The most thorough studies were carried out for perfluorinated membranes. Using these membranes as examples, an attempt is made to find the relationship between the polymer matrix structure, the ion hydration details, and the diffusion mobility of ions and molecules on different spatial scales and then to apply this information for revealing details of the ion transport mechanism in ion-exchange membranes.

3. Conclusions

Nowadays, chemical power sources, based on sulfocation exchange membranes find wide application. The principal part of these systems is formed by a polymer ion exchange membrane that should have high ionic conductivity. The problem of revealing the mechanism of ion transport in these membranes becomes quite challenging. The last decade was characterized by active studies of the state and mobility of cations and molecules in ion-exchange membranes of various types by using the methods of NMR and pulsed field gradient NMR on various nuclei.
Therefore, the review of NMR technique applications is a problem of today. In this review paper the results of cation-exchange membrane investigation obtained by hetero nuclear high resolution NMR spectroscopy, NMR relaxation, pulsed field gradient NMR are discussed.
The main attention is given to interconnection of membrane diffusion channel nanostructure, cation hydration and water molecule and cation mobility in different spatial scales. NMR self-diffusion data are compared with ionic conductivity measurements.
The main parts of NMR investigations were carried out in Nafion (or Russian Nafion analog) MF-4SC sulfonate perfluorinated membranes. These membranes are most studied by different physical techniques and could be a model system for a wide set of ion-exchangers.
The comparison of local water molecule and Li+ cation mobility calculated from 1 H and 7 Li spin relaxation data with water and lithium cation self-diffusion coefficients measured by PFG NMR shows that macroscopic transfer is controlled by ion and molecular jumping near sulfonate groups. This result is conformed to Nafion channel structure model in Figure 3. Therefore, a cation hydration governs by ionic motion.
Hydration numbers of alkaline and alkaline–earth metal cations were calculated from water molecule 1H chemical shift temperature dependences. For Li+, Na+, Cs+ counter ions, the relative part of contact pairs cation-charge group dependently on humidity was measured by 7 Li, 23 Na,133 Cs NMR. Some conclusions about membrane selectivity mechanism to these ions were proposed.
It was definitely shown that in sulfonate cation–exchangers in acid ionic form the least hydration number is equal two and at low water content hydrated cation [H5O2]+ is formed.
In opposite to conception based on DSC data about water freezing in membranes below 0 °C it was shown that amount of mobile water molecules does not change at temperature variation in spite of DSC peak observing. On the basic of 1 H spin–relaxation data it was supposed that at freezing temperature water molecules form mobile associates, but not ice phase. This assumption explains water and cation self-diffusion and ion conductivity temperature dependences.
A comparison of ion conductivity calculated from cation self-diffusion coefficients with experimental values confirms the cluster-channel structural model for membranes based on sulfonated polystyrene and channel structural model for Nafion membranes.
From our opinion these NMR results give opportunity to understand mechanism of ionic and molecular transport in ion-exchange membranes more deeply.
Funding: NMR measurements were performed using equipment of the Multi-User Analytical Center of the Institute of Problems of Chemical Physics RAS and Science Center in Chernogolovka RAS with the support of State Assignment of the Institute of Problems of Chemical Physics RAS (state registration No 0089-2019-0010/AAAA-A19-119071190044-3).


  1. Hwang, S.-T.; Kemmermeyer, K. Membranes in Separations; John Wiley & Sons: Hoboken, NJ, USA, 1975; p. 654.
  2. Chalykh, A.E. Diffuziya v Polimernykh Sistemakh (Diffusion in Polymer Systems); Khimiya: Moscow, Russia, 1987; p. 276.
  3. Shaposhnik, V.A. Kinetika Elektrodializa (Kinetics of Electro- dialysis); Voronezh State University: Voronezh, Russia, 1989; p. 187.
  4. Nikolaev, N.I. Diffuziya v Membranakh (Diffusion in Membranes); Khimiya: Moscow, Russia, 1980; p. 221.
  5. Timashev, S.F. Physical Chemistry of Membrane Processes; Ellis Horwood Series in Physical Chemistry Series; Ellis Horwood: New York, NY, USA; London, UK; Toronto, ON, Canada; Sydney, Australia; Tokyo, Japan; Singapore, 1991; p. 246.
  6. Yaroslavtsev, A.B. Khimiya Tverdogo Tela (The Chemistry of Solid); Nauchnyi Mir: Moscow, Russia, 2009; p. 312.
  7. Zabolotskii, V.I.; Nikonenko, V.V. Perenos Ionov v Membranakh (Ion Transfer in Membranes); Nauka: Moscow, Russia, 1996; p. 342.
  8. Creekmore, R.W.; Reilley, C.N. Nuclear Magnetic Resonance Study of Ion-Exchange Resins. Anal. Chem. 1970, 42, 570–575.
  9. Gough, T.E.; Sharma, H.D.; Subramanian, N. Proton magnetic resonance studies of ionic solvation in ion-exchange resins. Part I. Sulfonated cation-exchange resins. Can. J. Chem. 1970, 48, 917–923.
  10. Bystrov, G.S.; Grigor’eva, G.A.; Nikovaev, N.I. Nuclear Magnetic Resonance Study of Ion-exchange Resin-Solvent Systems. Russ. Chem. Rev. 1976, 45, 823–846.
  11. Mank, V.V.; Kurilenko, O.D. Issledovanie Mezhmolekulyarnykh Vzaimodeistvii v Ionoobmennykh Smolakh Metodom YaMR (Investigation of Intermolecular Interactions in Ion-Exchange Resins by NMR); Naukova Dumka: Kiev, Ukraine, 1976; p. 79.
  12. Mank, V.V.; Lebovka, N.I. Voda v Dispersnykh Sistemakh (Water in Dispersion Systems); Khimiya: Moscow, Russia, 1989; p. 203.
  13. Khutsishvili, V.G.; Bogachev, Y.S.; Volkov, V.I.; Serebryanskaya, A.I.; Shapet’ko, N.N.; Timashev, S.F.; Orman, M.L. Water state investigation in sulfocationite CU-2 phase by proton magnetic resonance technique. Russ. J. Phys. Chem. 1983, 57, 2524–2527.
  14. Saldadze, G.K.; Tagirova, R.I.; Volkov, V.I.; Chizhanov, S.A. The structure of one charge cation and water mass transfer in sulfocationexchangers on NMR data. Russ. J. Phys. Chem. 1993, 67, 1818–1823.
  15. Volkov, V.I.; Saldadze, G.K.; Tagirova, R.I.; Kropotov, L.V.; Khutsishvili, V.G.; Shapet’ko, N.N. Water state and diffusion mobility in ion exchange membrane MC-40 studied by NMR. Russ. J. Phys. Chem. 1989, 63, 1005–1009.
  16. Volkov, V.I.; Chernyak, A.V.; Golubenko, D.V.; Shevlyakova, N.V.; Tverskoy, V.A.; Yaroslavtsev, A.B. Mobility of cations and water molecules in sulfocation-exchange membranes based on polyethylene and sulfonated grafted polystyrene. Membr. Membr. Technol. 2020, 1, 54–62.
  17. Volkov, V.I.; Chernyak, A.V.; Golubenko, D.V.; Tverskoy, V.A.; Lochin, G.A.; Odjigaeva, E.S.; Yaroslavtsev, A.B. Hydration and diffusion of H+, Li+, Na+, Cs+ ions in cation-exchange membranes based on polyethylene and sulfonated-grafted polystyrene studied by NMR technique and ionic conductivity measurements. Membranes 2020, 10, 272.
  18. Khutsishvili, V.G.; Bogachev, Y.S.; Volkov, V.I.; Tarasova, B.V.; Dreiman, N.A.; Shapetko, N.N.; Timashev, S.F. Water state investigation in perfluorinated sulfo cation exchange membranes by proton magnetic resonance technique. Russ. J. Phys. Chem. 1984, 58, 2633.
  19. Volkov, V.I.; Sidorenkova, E.A.; Timashev, S.F.; Lakeev, S.G. State and diffusive mobility of water in perfluorinated sulfocationite membranes according to proton magnetic resonance data. Russ. J. Phys. Chem. 1993, 67, 914–918.
  20. Skirda, V.D.; Volkov, V.I. Pulsed field gradient NMR for the molecular system physical-chemistry processes investigations. Russ. J. Phys. Chem. 1999, 73, 323–342.
  21. Volkov, V.I.; Volkov, E.V.; Sanginov, E.A.; Pavlov, A.A.; Timofeev, S.V.; Safronova, E.Y.; Stenina, I.A.; Yaroslavtsev, A.B. Diffusion mobility of alkali metals in perfluorinated sulfocationic and carboxylic membranes as probed by 1H, 7Li, 23Na, and 133Cs NMR spectroscopy. Russ. J. Inorg. Chem. 2010, 55, 318–324.
  22. Bunce, N.J.; Sondheimer, S.J.; Fyle, C.A. Proton NMR Method for the Quantitative Determination of the Water Content of the Polymeric Fluorosulfonic Acid Nafion-H. Macromolecules 1986, 19, 333–339.
  23. Ye, G.; Janzen, N.; Goward, G.R. Solid-State NMR Study of Two Classic Proton Conducting Polymers: Nafion and Sulfonated Poly(ether ether ketone)s. Macromolecules 2006, 39, 3283–3290.
  24. Shestakov, S.L.; Pavlov, A.A.; Maksimychev, A.V.; Chernyak, A.V.; Volkov, V.I.; Timofeev, S.V. A NMR study of the hydration of sulfo and carboxyl groups in perfluorinated cation exchange membranes. Russ. J. Phys. Chem. B 2010, 4, 1005–1013.
  25. Chernyak, A.V.; Vasiliev, S.G.; Avilova, I.A.; Volkov, V.I. Hydration and Water Molecules Mobility in Acid Form of Nafion Membrane Studied by 1H NMR Techniques. Appl. Magn. Reson. 2019, 5, 677–693.
  26. Hammer, R.; Schönhoff, M.; Hansen, M.R. Comprehensive Picture of Water Dynamics in Nafion Membranes at Different Levels of Hydration. J. Phys. Chem. B 2019, 123, 8313–8324.
  27. Komoroski, R.A.; Mauritz, K.A. A sodium-23 nuclear magnetic resonance study of ionic mobility and contact ion pairing in a perfluorosulfonate ionomer. J. Am. Chem. Soc. 1978, 100, 7487–7489.
  28. Komoroski, R.A. A Multinuclear Fourier Transform NMR Study of Perfluorosulfonate Ionomers. Adv. Chem. Ser. 1980, 187, 155–168.
  29. Volkov, V.I.; Sidorenkova, E.A.; Korochkova, S.A.; Novikov, N.A.; Sokol’skaya, I.B.; Timashev, S.F. The nature of selectivity of perfluorinated sulfocation exchanger membranes to alkiline metal ions on 7Li, 23Na, 133Cs NMR. Russ. J. Phys. Chem. 1994, 68, 309–316.
  30. Volkov, V.I.; Sidorenkova, E.A.; Korochkova, S.A.; Novikov, N.A.; Sokol’skaya, I.B.; Timashev, S.F. Effect of electrolyte sorbed by nonion-exchange mechanism on the state and diffusive mobility of water and alkali metal ions in perfluorinated sulfocationic membranes from NMR data. Russ. J. Phys. Chem. 1994, 68, 559–564.
  31. Nesterov, I.A.; Volkov, V.I.; Pukhov, K.K.; Timashev, S.F. Magnetic-relaxation of 7Li+ nuclei and dynamics of movements of lithium counter-ions and water-molecules in perfluorinated sulfocationite membranes. Russ. J. Chem. Phys. 1990, 10, 1155–1162.
  32. Tromp, R.H.; Van der Maarel, J.R.C.; De Bleijser, J.; Leyte, J.C. Counter-ion dynamics in crosslinked poly( styrene sulfonate) systems studied by NMR. Biophys. Chem. 1991, 41, 81–100.
  33. Halle, B.; Bratko, D.; Piculell, L. Interpretetion of Counterion Spin Relaxation in Polyelectrolyte Solutions. II. Effects of Finite Polyion Lenght. Ber. Bunsenges. Phys. Chem. 1985, 89, 1254–1260.
  34. Halle, B.; Wennerstrom, H.; Piculell, L. Interpretation of Counterion Spin Relaxation in Polyelectrolyte Solutions. J. Phys. Chem. 1984, 88, 2482–2494.
  35. Boyle, N.G.; McBrierty, V.J.; Douglass, D.C. The behavior of water in Nafion membranes. Macromolecules 1983, 16, 75–80.
  36. Volkov, V.I.; Nesterov, I.A.; Chichagov, A.V.; Muromtsev, V.I.; Timashev, S.F. NMR methods for studying ion and molecular transport in polymer electrolytes. Russ. J. Chem. Phys. 1985, 4, 644–650.
  37. Volkov, V.I.; Nesterov, I.A.; Sundukov, V.I.; Kropotov, L.V.; Timashev, S.F. The diffusion transfer of water in perfluorinated sulfocation exchange membranes as studied by pulse NMR. Russ. J. Chem. Phys. 1989, 8, 209.
  38. Volkov, V.I.; Vasilyak, S.L.; Park, I.-W.; Kim, H.J.; Ju, H.; Volkov, E.V.; Choh, S.H. Water Behavior in Perfluorinated Ion-Exchange Membranes. Appl. Magn. Reson. 2003, 25, 43–53.
  39. Volkov, V.I.; Volkov, E.V.; Timashev, S.F. The Mechanism for Ionic and Water Transport in Nafion Membranes from Resonance Data. In Magnetic Resonance in Colloid and Interface Science; Kluwer Academic Publishers: Amsterdam, The Netherlands, 2002; p. 267.
  40. Volkov, V.I.; Volkov, E.V.; Vasilyak, S.L.; Hong, Y.S.; Lee, C.H. The Ionic and Molecular Transport in Polymeric and Biological Membranes on Magnetic Resonance Data. In Fluid Transport in Nanoporous Materials; Springer: New York, NY, USA, 2006; p. 48.
  41. Volkov, V.I.; Eliseev, Y.G.; Kirsh, Y.E.; Fedotov, Y.A.; Timashev, S.F. Water and lithium self-diffusion in bi-sulfocontaining aromatic polyamides. Russ. J. Phys. Chem. 1992, 66, 1618–1622.
  42. Stejskal, E.O.; Tanner, J.E. Spin Diffusion Measurements: Spin Echoes in the Presence of a Time Dependent Field Gradient. J. Chem. Phys. 1965, 42, 288.
  43. Maklakov, A.; Skirda, V.; Fatkullin, N. Selfdiffusion in Polymer Solutions and Melts (Samodiffisia v Rastvorakh i Rasplavakh Polymerov); Soloviev, U., Chalykh, A., Eds.; Kazan University Press: Kazan, USSR, 1987; p. 224. (In Russian)
  44. Saldadze, G.K.; Tagirova, R.I.; Volkov, V.I.; Chizhanov, S.A. Self-Diffusion Of Li+ Counter-ions And Water Molecules In CU-23 Macroporous Sulfocationites According To Pulse Nuclear-Magnetic-Resonance. Russ. J. Phys. Chem. 1993, 67, 1941–1943.
  45. Saldadze, G.K.; Volkov, V.I.; Tagirova, R.I.; Chizhanov, S.A. Water Diffusion in Heterogeneous Sulfocationite Systems According to Proton Magnetic-Resonance. Russ. J. Phys. Chem. 1993, 67, 773–776.
  46. Volkov, V.I.; Korochtkova, S.A.; Nesterov, I.A.; Kirsh, Y.E.; Timashev, S.F. Diffusion Mobility Of Water-Molecules In Cation-Exchange Membranes Based On Sulfonate-Containing Polyphenylenephthalamides. Russ. J. Phys. Chem. 1994, 68, 1310–1316.
  47. Volkov, V.I.; Korochtkova, S.A.; Timashev, S.F. Characteristics of Self-Diffusion of Aliphatic Monoatomic Alcohols in Perfluorinated Sulfocationite Membranes. Russ. J. Phys. Chem. 1995, 69, 1124–1129.
  48. Volkov, V.I.; Korotchkova, S.A.; Ohya, H.; 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, 100, 273–286.
  49. Sokolova, S.A.; Djakonova, O.V.; Kotov, V.V.; Hong, Y.S.; Volkov, V.I.; Lee, C.H. The self-diffusion of water and membrane structure in the new type of cation-exchange polyamide-acid membrane. Magn. Res. Imag. 2001, 19, 588–589.
  50. Volkov, V.I.; Korotchkova, S.A.; Nesterov, I.A.; Ohya, H.; Guo, Q.; Huang, J.; Chen, J. The self-diffusion of water and ethanol in cellulose derivative membranes and particles with the pulsed field gradient NMR data. J. Membr. Sci. 1996, 110, 1–11.
  51. Volkov, V.I.; Pavlov, A.A.; Sanginov, E.A. Ionic transport mechanism in cation-exchange membranes studied by NMR technique. Solid State Ion. 2011, 188, 124–128.
  52. Volkov, V.I.; Popkov, Y.M.; Timashev, S.F.; Bessarabov, D.G.; Sanderson, R.D.; Twardowski, Z. Self-diffusion of water and fluorine ions in anion-exchange polymeric materials (membranes and resin) as determined by pulsed-field gradient nuclear magnetic resonance spectroscopy. J. Membr. Sci. 2000, 180, 1–13.
  53. Kotov, V.V.; Dyakonova, O.V.; Sokolova, S.A.; Volkov, V.I. Struktura i elektrokhimicheskie svoistva kationoobmennykh membran na osnove chastichno imidizirovannoi poliamidokisloty [Structure and electrochemical properties of cation exchange membranes based on partially imidizated polyamide acid. Elektrokhimiya 2002, 38, 994–997.
  54. Volkov, V.I.; Kotov, V.V.; Netesova, G.A. The self-diffusion of water and saturated aliphatic alcohols in cation-exchange membranes. Russ. J. Phys. Chem. 2008, 82, 1184–1188.
  55. Ponomarev, A.N.; Dobrovol’skii, Y.A.; Abdrashitov, E.F.; Bokun, V.C.; Sanginov, E.A.; Volkov, E.V.; Volkov, V.I. The new approach to the modification of the per fluorinated ion-ex changing membranes promising in hydrogen energy. Bull. RAS Energetika 2008, 3, 124–134.
  56. Volkov, V.I.; Dobrovolsky, Y.A.; Nurmiev, M.S.; Sanginov, E.A.; Volkov, E.V.; Pisareva, A.V. Charge and mass transport in the phenol-2,4-disulfonic acid-polyvinyl alcohol ion exchange membranes studied by pulsed field gradient NMR and impedance spectroscopy. Solid State Ion. 2008, 179, 148–153.
  57. Volkov, V.I.; Ponomarev, A.N.; Yaroslavtsev, A.B.; Sanginov, E.A.; Pavlov, A.A. NMR investigation of proton conductive ion-exchange membranes transport behaviour. ISJAEE 2008, 2, 101–106.
  58. Voropaeva, E.Y.; Sanginov, E.A.; Volkov, V.I.; Pavlov, A.A.; Shalimov, A.S.; Stenina, I.A.; Yaroslavtsev, A.B. Transport Properties of MF-4SC Membranes Modified with Inorganic Dopants. Russ. J. Inorg. Chem. 2008, 53, 1536–1541.
  59. Volkov, V.I.; Pavlov, A.A.; Fedotov, Y.A.; Marinin, A.A. Self-diffusion of water and alkaline cations in bisulfur-containing aromatic polyamides-water systems. Russ. J. Phys. Chem. 2010, 84, 1705–1711.
  60. Volkov, V.I.; Volkov, E.V.; Timofeev, S.V.; Sanginov, E.A.; Pavlov, A.A.; Safronova, E.Y.; Stenina, I.A.; Yaroslavtsev, A.B. Water self-diffusion and ionic conductivity in perfluorinated sulfocationic membranes MF4SK. Russ. J. Inorg. Chem. 2010, 55, 355–360.
  61. Safronova, E.Y.; Volkov, V.I.; Yaroslavtsev, A.B. Ion mobility and conductivity of hybrid ion-exchange membranes incorporating inorganic nanoparticles. Solid State Ion. 2011, 188, 129–131.
  62. Volkov, V.I.; Volkov, E.V. Ionic and molecular Self-Diffusion in Ion-Exchange materials for fuel energetics studied by pulsed field gradient NMR. Appl. Magn. Reson. 2005, 29, 495–501.
  63. Tsushima, S.; Teranishi, K.; Hirai, S. Water diffusion measurement in fuel-cell SPE membrane by NMR. Energy 2005, 30, 235–245.
  64. Baglio, V.; Arico, A.S.; Antonucci, V.; Nicotera, I.; Oliviero, C.; Coppola, L.; Antonucci, P.L. An NMR spectroscopic study of water and methanol transport properties in DMFC composite membranes: Influence on the electrochemical behaviour. J. Power Sources 2006, 163, 52–55.
  65. Edmondson, C.A.; Stallworth, P.E.; Chapman, M.E.; Fontanella, J.J.; Wintersgill, M.C.; Chung, S.H.; Greenbaum, S.G. Complex impedance studies of proton-conducting membranes. Solid State Ion. 2000, 135, 419–423.
  66. Every, H.A.; Hickner, M.A.; McGrath, J.E.; Zawodzinski, T.A., Jr. An NMR study of methanol diffusion in polymer electrolyte fuel cell membranes. J. Membr. Sci. 2005, 250, 183–188.
  67. Jayakody, J.R.P.; Khalfan, A.; Mananga, E.S.; Greenbaum, S.G.; Dang, T.D.; Mantz, R. NMR investigation of water and methanol transport in sulfonated polyareylenethioethersulfones for fuel cell applications. J. Power Sources 2006, 156, 195–199.
  68. Freger, V.; Korin, E.; Wisniak, J.; Korngold, E.; Ise, M.; Kreuer, K.D. Diffusion of water and ethanol in ion-exchange membranes: Limits of the geometric approach. J. Membr. Sci. 1999, 160, 213–224.
  69. Gong, X.; Bandis, A.; Tao, A.; Meresi, G.; Wang, Y.; Inglefield, P.T.; Jones, A.A.; Wen, W.-Y. Self-diffusion of water, ethanol and decafluropentane in perfluorosulfonate ionomer by pulse field gradient NMR. Polymer 2001, 42, 6485–6492.
  70. Khalfan, A.N.; Sanchez, L.M.; Kodiweera, C.; Greenbaum, S.G.; Bai, Z.; Dang, T.D. Water and proton transport properties of hexafluorinated sulfonated poly(arylenethioethersulfone) copolymers for applications to proton exchange membrane fuel cells. J. Power Sources 2007, 173, 853–859.
  71. Huang, Y.F.; Chuang, L.C.; Kannan, A.M.; Lin, C.W. Proton-conducting membranes with high selectivity from cross-linked poly (vinyl alcohol) and poly (vinyl pyrrolidone) for direct methanol fuel cell applications. J. Power Sources 2009, 186, 22–28.
  72. Hallberg, F.; Vernersson, T.; Pettersson, E.T.; Dvinskikh, S.V.; Lindbergh, G.; Furo, I. Electrokinetic transport of water and methanol in Nafion membranes as observed by NMR spectroscopy. Electrochim. Acta 2010, 55, 3542–3549.
  73. Kritskaya, D.A.; Abdrashidov, E.F.; Bokun, V.C.; Ponomarev, A.N.; Chernyak, A.V.; Vasil’ev, S.G.; Volkov, V.I. An NMR Study of Sorption-Diffusion Properties of MF-4SK-Carbon Composite Membranes in Aqueous Methanol Solutions. Pet. Chem. 2011, 1, 266–272.
  74. Guillermo, A.; Gebel, G.; Mendil-Jakani, H.; Pinton, E. NMR and pulsed field gradient NMR approach of water sorption properties in Nafion at low temperature. J. Phys. Chem. B 2009, 113, 6710–6717.
  75. Ma, Z.; Jiang, R.; Myers, M.E.; Thompson, E.L.; Gittleman, C.S. NMR studies of proton transport in fuel cell membranes at sub-freezing conditions. J. Mater. Chem. 2011, 21, 9302–9311.
  76. Kusoglu, A.; Weber, A.Z. New Insights into Perfluorinated Sulfonic-Acid Ionomers. Chem. Rev. 2017, 117, 987–1104.
  77. Zhao, Q.; Majsztrik, P.; Benziger, J. Diffusion and Interfacial Transport of Water in Nafion. J. Phys. Chem. B 2011, 115, 2717–2727.
  78. Zawodzinski, T.A.; Derouin, C.; Radzinski, S.; Sherman, R.J.; Smith, V.T.; Springer, T.E.; Gottesfeld, S. Water Uptake by and Transport Through Nafion 117 Membranes. J. Electrochem. Soc. 1993, 140, 1041–1047.
  79. Zawodzinski, T.A.; Springer, T.E.; Davey, J.; Jestel, R.; Lopez, C.; Valerio, J.; Gottesfeld, S. A Comparative Study of Water Uptake by and Transport through Ionomeric Fuel Cell Membranes. J. Electrochem. Soc. 1993, 140, 1981–1985.
  80. Cappadonia, M.; Erning, J.W.; Niaki, S.M.S.; Stimming, U. Conductance of Nafion 117 membranes as a function of temperature and water content. Solid State Ion. 1995, 77, 65–69.
  81. Nicotera, I.; Coppola, L.; Rossi, C.O.; Youssry, M.; Ranieri, G.A. NMR Investigation of the Dynamics of Confined Water in Nafion-Based Electrolyte Membranes at Subfreezing Temperatures. J. Phys. Chem. B 2009, 113, 13935–13941.
  82. Suh, K.-J.; Hong, Y.-S.; Skirda, V.D.; Volkov, V.I.; Lee, C.-Y.; Lee, C.-H. Water self-diffusion behavior in yeast cells studied by pulsed field gradient NMR. Biophys. Chem. 2003, 104, 121–130.
  83. Cho, C.-H.; Hong, Y.-S.; Kang, K.; Volkov, V.I.; Skirda, V.D.; Lee, C.-Y.J.; Lee, C.H. Water self-diffusion in Chlorella sp. studied by pulse field gradient NMR. Magn. Reson. Imaging 2003, 21, 1009–1017.
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