najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2024-15-5-716-725najo-171Research ArticleCHEMISTRY AND MATERIAL SCIENCEХИМИЯ И МАТЕРИАЛОВЕДЕНИЕIonic channel structure in perfluorinated membranes studied by small angle X-ray scattering, optical and Mossbauer spectroscopyСтруктура ионных каналов в перфторированных мембранах, исследованная методами малоуглового рентгеновского рассеяния, оптической и мессбауэровской спектроскопииhttps://orcid.org/0000-0003-4894-0862LebedevVasily T.

Vasily T. Lebedev

188300, Gatchina

KozlovValery S.

Valery S. Kozlov

188300, Gatchina

kozlovvs1@pnpi.nrcki.ruRemizovMikhail V.

Mikhail V. Remizov

188300, Gatchina

m.remizov97@gmail.comhttps://orcid.org/0000-0002-3228-3039KulvelisYury V.

Yury V. Kulvelis

188300, Gatchina

kulvelisyv@pnpi.nrcki.ruhttps://orcid.org/0000-0003-1637-8537PrimachenkoOleg N.

Oleg N. Primachenko

199004, St. Petersburg

alex-prima@mail.ruhttps://orcid.org/0000-0003-2160-2003MarinenkoElena A.

Elena A. Marinenko

199004, St. Petersburg

emarinenkospb@gmail.comhttps://orcid.org/0000-0003-3597-9370PetersGeorgy S.

Georgy S. Peters

123182, Moscow

georgspeters@gmail.comPetersburg Nuclear Physics Institute named by B. P. Konstantinov of National Research Center “Kurchatov Institute”Russian FederationInstitute of Macromolecular Compounds, Russian Academy of SciencesRussian FederationNational Research Center “Kurchatov Institute”Russian Federation202403062025155716725Copyright © Lebedev V.T., Kozlov V.S., Remizov M.V., Kulvelis Y.V., Primachenko O.N., Marinenko E.A., Peters G.S., 20252025Lebedev V.T., Kozlov V.S., Remizov M.V., Kulvelis Y.V., Primachenko O.N., Marinenko E.A., Peters G.S.Lebedev V.T., Kozlov V.S., Remizov M.V., Kulvelis Y.V., Primachenko O.N., Marinenko E.A., Peters G.S.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/171

Small angle X-ray scattering optical and Mossbauer spectroscopy has been used to study ionic ¨ channels in perfluorinated Nafion® -type membranes. X-ray scattering data have revealed the ordering of ionic groups of polymer chains at nanoscales into extended fine channels for proton conductivity. Then the membranes were saturated with Fe3+ ions to probe their interaction with sulfonic groups. This remarkably changed electron properties of copolymer in which the energy of optical gap has decreased. The Mossbauer spectra ¨ have confirmed that even at ambient temperature in membrane, Fe3+ ions are assembled into antiferromagnetic dimers with water shells and associated with sulfonic groups at the channel surfaces. The applied complementary methods allowed us to examine a short-range order of ionic groups forming a network of channels in membranes that provide their functional properties in hydrogen fuel cells.

Методом малоуглового рентгеновского рассеяния, оптической и мессбауэровской спектроскопией исследованы ионные каналы в перфторированных мембранах типа Нафион®. Данные рентгеновского рассеяния выявили упорядочение ионных групп полимерных цепей на наномасштабах в протяженные тонкие каналы протонной проводимости. Затем мембраны насыщались ионами Fe3+ для исследования их взаимодействия с сульфоновыми группами. Это заметно изменило электронные свойства сополимера, у которого уменьшилась энергия оптической щели. Мессбауэровские спектры подтвердили, что даже при комнатной температуре в мембране ионы Fe3+ организуются в антиферромагнитные димеры с водными оболочками и связываются с сульфоновыми группами на поверхности каналов. Примененные комплементарные методы позволили изучить ближний порядок ионных групп, образующих сеть каналов в мембранах, обеспечивающих их функциональные свойства в водородных топливных ячейках.

 

 

 

 

ионканалмембранаструктурагамма-спектроскопияionchannelmembranestructuregamma-spectroscopyThe work was supported by the Russian Science Foundation under Grant No. 23- 23-00129. The authors thank Professor V. G. Semenov for methodological help, Engineers I. N. Ivanova, L. I. Lisovskaya for technical assistance.ReferencesAhmad S., Nawaz T., Ali A., Orhan M.F., Samreen A., Kannan A.M. An overview of proton-exchange membranes for fuel cells: Materials and manufacturing. Int. J. of Hydrogen Energy, 2022, 47 (44), P. 19086–19131.Ahmad S., Nawaz T., Ali A., Orhan M.F., Samreen A., Kannan A.M. An overview of proton-exchange membranes for fuel cells: Materials and manufacturing. Int. J. of Hydrogen Energy, 2022, 47 (44), P. 19086–19131.Pan M., Pan C., Li C., Zhao J. A review of membranes in proton exchange membrane fuel cells: Transport phenomena, performance and durability. Renewable and Sustainable Energy Reviews, 2021, 141 (25), 110771.Pan M., Pan C., Li C., Zhao J. A review of membranes in proton exchange membrane fuel cells: Transport phenomena, performance and durability. Renewable and Sustainable Energy Reviews, 2021, 141 (25), 110771.Yaroslavtsev A.B., Stenina I.A. Current progress in membranes for fuel cells and reverse electrodialysis. Mendeleev Commun., 2021, 31, P. 423– 432.Yaroslavtsev A.B., Stenina I.A. Current progress in membranes for fuel cells and reverse electrodialysis. Mendeleev Commun., 2021, 31, P. 423– 432.Yaroslavtsev A.B., Stenina I.A., Golubenko D.V. Membrane materials for energy production and storage. Pure Appl. Chem., 2020, 92 (7), P. 1147– 1157.Yaroslavtsev A.B., Stenina I.A., Golubenko D.V. Membrane materials for energy production and storage. Pure Appl. Chem., 2020, 92 (7), P. 1147– 1157.Li T., Shen J., Chen G., Guo S., Xie G. Performance Comparison of Proton Exchange Membrane Fuel Cells with Nafion and Aquivion Perfluorosulfonic Acids with Different Equivalent Weights as the Electrode Binders. ACS Omega, 2020, 5 (28), P. 17628–17636.Li T., Shen J., Chen G., Guo S., Xie G. Performance Comparison of Proton Exchange Membrane Fuel Cells with Nafion and Aquivion Perfluorosulfonic Acids with Different Equivalent Weights as the Electrode Binders. ACS Omega, 2020, 5 (28), P. 17628–17636.Mugtasimova K.R., Melnikov A.P., Galitskaya E.A., Kashin A.M., Dobrovolskiy A., Don G.M., Likhomanov V.S., Sivak A.V., Sinitsyn V.V. Fabrication of Aquivion-type membranes and optimization of their elastic and transport characteristics. Ionics, 2018, 24, P. 3897–3903.Mugtasimova K.R., Melnikov A.P., Galitskaya E.A., Kashin A.M., Dobrovolskiy A., Don G.M., Likhomanov V.S., Sivak A.V., Sinitsyn V.V. Fabrication of Aquivion-type membranes and optimization of their elastic and transport characteristics. Ionics, 2018, 24, P. 3897–3903.Dombaycıoglu S¸, G ˘ unsel H., Aydın A.O. Nafion/Aquivion-Based Composite Lithium Ion Exchange Membranes for High Capacity Li–S Batteries. ¨ Chemistry Select, 2022, 7 (39), e202202910.Dombaycıoglu S¸, G ˘ unsel H., Aydın A.O. Nafion/Aquivion-Based Composite Lithium Ion Exchange Membranes for High Capacity Li–S Batteries. ¨ Chemistry Select, 2022, 7 (39), e202202910.Hsu W.Y., Gierke T.D. Ion transport and clustering in Nafion perfluorinated membranes. J. of Membrane Science, 1983, 13 (3), P. 307–326.Hsu W.Y., Gierke T.D. Ion transport and clustering in Nafion perfluorinated membranes. J. of Membrane Science, 1983, 13 (3), P. 307–326.Gebel G., Diat O. Neutron and X-ray scattering: Suitable tools for studying ionomer membranes. Fuel Cells, 2005, 5, P. 261–276.Gebel G., Diat O. Neutron and X-ray scattering: Suitable tools for studying ionomer membranes. Fuel Cells, 2005, 5, P. 261–276.Schmidt-Rohr K., Chen Q. Parallel cylindrical water nanochannels in Nafion fuel-cell membranes. Nature Mater., 2008, 7, P. 75–83.Schmidt-Rohr K., Chen Q. Parallel cylindrical water nanochannels in Nafion fuel-cell membranes. Nature Mater., 2008, 7, P. 75–83.Fernandez Bord´ın S.P., Andrada H.E., Carreras A.C., Castellano G.E., Oliveira R.G., Galvan Josa V.M. Nafion membrane channel structure studied ´ by small-angle X-ray scattering and Monte Carlo simulations. Polymer, 2018, 155, P. 58–63.Fernandez Bord´ın S.P., Andrada H.E., Carreras A.C., Castellano G.E., Oliveira R.G., Galvan Josa V.M. Nafion membrane channel structure studied ´ by small-angle X-ray scattering and Monte Carlo simulations. Polymer, 2018, 155, P. 58–63.Bazaid M., Huang Y., Goddard W.A., Jang S.S. Proton transport through interfaces in nanophase-separation of hydrated aquivion membrane: Molecular dynamics simulation approach. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 676, Part A, 132187.Bazaid M., Huang Y., Goddard W.A., Jang S.S. Proton transport through interfaces in nanophase-separation of hydrated aquivion membrane: Molecular dynamics simulation approach. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 676, Part A, 132187.Petrov A.V., Murin I.V. Electronic Structure of SO3H Functional Groups and Proton Mobility in Nafion and Aquivion Ionomer Membranes. Russian J. of General Chemistry, 2019, 89 (3), P. 553–555.Petrov A.V., Murin I.V. Electronic Structure of SO3H Functional Groups and Proton Mobility in Nafion and Aquivion Ionomer Membranes. Russian J. of General Chemistry, 2019, 89 (3), P. 553–555.Agarwal T., Prasad A.K., Advani S.G., Babu S.K., Borup R.L. Infrared spectroscopy for understanding the structure of Nafion and its associated properties. J. Mater. Chem. A, 2024, 12, P. 14229–14244.Agarwal T., Prasad A.K., Advani S.G., Babu S.K., Borup R.L. Infrared spectroscopy for understanding the structure of Nafion and its associated properties. J. Mater. Chem. A, 2024, 12, P. 14229–14244.Mbarek S., El Kissi N., Baccouch Z., Iojoiu C. Extrusion of Nafion and Aquivion membranes: environmentally friendly procedure and good conductivities. Polymer Bulletin, 2019, 76, P. 1151–1166.Mbarek S., El Kissi N., Baccouch Z., Iojoiu C. Extrusion of Nafion and Aquivion membranes: environmentally friendly procedure and good conductivities. Polymer Bulletin, 2019, 76, P. 1151–1166.Haubold H.-G., Vad T., Jungbluth H., Hiller P. Nano structure of NAFION: a SAXS study. Electrochimica Acta, 2001, 46 (10), P. 1559–1563.Haubold H.-G., Vad T., Jungbluth H., Hiller P. Nano structure of NAFION: a SAXS study. Electrochimica Acta, 2001, 46 (10), P. 1559–1563.Barbi V., Funari S.S., Gehrke R., Scharnagl N., Stribeck N. Nanostructure of Nafion membrane material as a function of mechanical load studied by SAXS. Polymer, 2003, 44, P. 4853–4861.Barbi V., Funari S.S., Gehrke R., Scharnagl N., Stribeck N. Nanostructure of Nafion membrane material as a function of mechanical load studied by SAXS. Polymer, 2003, 44, P. 4853–4861.Elliott J.A., Wu D.S., Paddison S.J., Moore R.B. A unified morphological description of Nafion membranes from SAXS and mesoscale simulations. Soft Matter, 2011, 7 (15), P. 6820–6827.Elliott J.A., Wu D.S., Paddison S.J., Moore R.B. A unified morphological description of Nafion membranes from SAXS and mesoscale simulations. Soft Matter, 2011, 7 (15), P. 6820–6827.Xue T., Trent J.S., Osseo-Asare K. Characterization of Nafion® membranes by transmission electron microscopy. J. of Membrane Science, 1989, 45 (3), P. 261–271.Xue T., Trent J.S., Osseo-Asare K. Characterization of Nafion® membranes by transmission electron microscopy. J. of Membrane Science, 1989, 45 (3), P. 261–271.Yakovlev S., Balsara N.P., Downing K.H. Insights on the Study of Nafion Nanoscale Morphology by Transmission Electron Microscopy. Membranes, 2013, 3, P. 424–439.Yakovlev S., Balsara N.P., Downing K.H. Insights on the Study of Nafion Nanoscale Morphology by Transmission Electron Microscopy. Membranes, 2013, 3, P. 424–439.Yakovlev S., Downing K., Balsara N. Electron Microscopy of Nafion Membrane. Microscopy and Microanalysis, 2013, 19 (S2), P. 1652–1653.Yakovlev S., Downing K., Balsara N. Electron Microscopy of Nafion Membrane. Microscopy and Microanalysis, 2013, 19 (S2), P. 1652–1653.Aleksandrova E., Hink S., Hiesgen R., Roduner E. Spatial distribution and dynamics of proton conductivity in fuel cell membranes: Potential and limitations of electrochemical atomic force microscopy measurements. J. of Physics: Condensed Matter, 2011, 23 (23), 234109.Aleksandrova E., Hink S., Hiesgen R., Roduner E. Spatial distribution and dynamics of proton conductivity in fuel cell membranes: Potential and limitations of electrochemical atomic force microscopy measurements. J. of Physics: Condensed Matter, 2011, 23 (23), 234109.Hiesgen R., Aleksandrova E., Meichsner G., Andreas Friedrich K. High-resolution imaging of ion conductivity of Nafion (R) membranes with electrochemical atomic force microscopy. Electrochimica Acta, 2009, 55, P. 423–429.Hiesgen R., Aleksandrova E., Meichsner G., Andreas Friedrich K. High-resolution imaging of ion conductivity of Nafion (R) membranes with electrochemical atomic force microscopy. Electrochimica Acta, 2009, 55, P. 423–429.Tsimbal T.Yu., Chibirova F.Kh., Kostyuchenko I.G. Magnetic relaxation and submicrostructure of iron hydroxide precipitates in ionomer membrane. J. of Magnetism and Magnetic Materials, 1994, 136, P. 197–203.Tsimbal T.Yu., Chibirova F.Kh., Kostyuchenko I.G. Magnetic relaxation and submicrostructure of iron hydroxide precipitates in ionomer membrane. J. of Magnetism and Magnetic Materials, 1994, 136, P. 197–203.Maksimichev A.V., Kostyuchenko I.G., Chibirova F.Kh., Zhilinskaya E.A., Chakulaeva L.N., Timashev S.F. Binding of Fe3+ ions to halobacterial purple membranes as studied by Mossbauer spectroscopy. ¨ Membrane & Cell Biology, 1997, 10 (5), P. 487–501.Maksimichev A.V., Kostyuchenko I.G., Chibirova F.Kh., Zhilinskaya E.A., Chakulaeva L.N., Timashev S.F. Binding of Fe3+ ions to halobacterial purple membranes as studied by Mossbauer spectroscopy. ¨ Membrane & Cell Biology, 1997, 10 (5), P. 487–501.Chibirova F.Kh., Kostyuchenko I.G., Kirsh Yu.E. Specific features of the structure of polymer ion-exchange membranes prepared from sulfocationic aromatic polyamides as studied by Mossbauer spectroscopy. ¨ Russian J. of Physical Chemistry, 1999, 73 (1), P. 111–116.Chibirova F.Kh., Kostyuchenko I.G., Kirsh Yu.E. Specific features of the structure of polymer ion-exchange membranes prepared from sulfocationic aromatic polyamides as studied by Mossbauer spectroscopy. ¨ Russian J. of Physical Chemistry, 1999, 73 (1), P. 111–116.Cui Z., Drioli E., Lee, Y.M. Recent progress in fluoropolymers for membranes. Progress in Polymer Science, 2014, 39 (1), P. 164–198.Cui Z., Drioli E., Lee, Y.M. Recent progress in fluoropolymers for membranes. Progress in Polymer Science, 2014, 39 (1), P. 164–198.Ivanchev S.S., Myakin S.V. Polymer membranes for fuel cells: manufacture, structure, modification, properties. Russ. Chem. Rev., 2010, 79 (2), P. 101–117.Ivanchev S.S., Myakin S.V. Polymer membranes for fuel cells: manufacture, structure, modification, properties. Russ. Chem. Rev., 2010, 79 (2), P. 101–117.Primachenko O.N., Marinenko E.A., Odinokov A.S., Kononova S.V., Kulvelis Yu.V., Lebedev V.T. State of the art and prospects in the development of proton?conducting perfluorinated membranes with short side chains: A review. Polymers for Advanced Technologies, 2021, 32 (4), P. 1386– 1408.Primachenko O.N., Marinenko E.A., Odinokov A.S., Kononova S.V., Kulvelis Yu.V., Lebedev V.T. State of the art and prospects in the development of proton?conducting perfluorinated membranes with short side chains: A review. Polymers for Advanced Technologies, 2021, 32 (4), P. 1386– 1408.Pan H.K., Yarusso D.J., Knapp G.S., Pineri M., Meagher A., Coey J.M.D., Cooper S.L. EXAFS and Mossbauer studies of iron neutralized Nafion ¨ ionomers. J. Chem. Phys., 1983, 79 (10), P. 4736–4745.Pan H.K., Yarusso D.J., Knapp G.S., Pineri M., Meagher A., Coey J.M.D., Cooper S.L. EXAFS and Mossbauer studies of iron neutralized Nafion ¨ ionomers. J. Chem. Phys., 1983, 79 (10), P. 4736–4745.Chen N., Lee Y.M. Anion exchange polyelectrolytes for membranes and ionomers. Progress in Polymer Science, 2021, 113, 101345.Chen N., Lee Y.M. Anion exchange polyelectrolytes for membranes and ionomers. Progress in Polymer Science, 2021, 113, 101345.Eisenberg A., Hird B., Moore R.B. A new multiplet-cluster model for the morphology of random ionomers. Macromolecules, 1990, 23 (18), P. 4098–4107.Eisenberg A., Hird B., Moore R.B. A new multiplet-cluster model for the morphology of random ionomers. Macromolecules, 1990, 23 (18), P. 4098–4107.Page K.A., Cable K.M., Moore R.B. Molecular Origins of the Thermal Transitions and Dynamic Mechanical Relaxations In Perfluorosulfonate Ionomers. Macromolecules, 2005, 38 (15), P. 6472–6484.Page K.A., Cable K.M., Moore R.B. Molecular Origins of the Thermal Transitions and Dynamic Mechanical Relaxations In Perfluorosulfonate Ionomers. Macromolecules, 2005, 38 (15), P. 6472–6484.Wakabayashi K., Register R.A. Morphological origin of the multistep relaxation behavior in semicrystalline ethylene/methacrylic acid ionomers. Macromolecules, 2006, 39 (3), P. 1079–1086.Wakabayashi K., Register R.A. Morphological origin of the multistep relaxation behavior in semicrystalline ethylene/methacrylic acid ionomers. Macromolecules, 2006, 39 (3), P. 1079–1086.Weiss R.A., Yu W.C. Viscoelastic Behavior of Very Lightly Sulfonated Polystyrene Ionomers. Macromolecules, 2007, 40 (10), P. 3640–3643.Weiss R.A., Yu W.C. Viscoelastic Behavior of Very Lightly Sulfonated Polystyrene Ionomers. Macromolecules, 2007, 40 (10), P. 3640–3643.Mohamed H.F.M., Kobayashi Y., Kuroda C.S., Ohira A. Effects of Ion Exchange on the Free Volume and Oxygen Permeation in Nafion for Fuel Cells. J. Phys. Chem. B, 2009, 113 (8), P. 2247–2252.Mohamed H.F.M., Kobayashi Y., Kuroda C.S., Ohira A. Effects of Ion Exchange on the Free Volume and Oxygen Permeation in Nafion for Fuel Cells. J. Phys. Chem. B, 2009, 113 (8), P. 2247–2252.Mohamed H.F M., Kobayashi Y., Kuroda C.S., Ohira A. Free volume and gas permeation in ion-exchanged forms of the Nafion® membrane. J. Phys. Conf. Ser., 2010, 225, 012038.Mohamed H.F M., Kobayashi Y., Kuroda C.S., Ohira A. Free volume and gas permeation in ion-exchanged forms of the Nafion® membrane. J. Phys. Conf. Ser., 2010, 225, 012038.Ruan D., Simmons D.S. Roles of Chain Stiffness and Segmental Rattling in Ionomer Glass Formation. J. Polym. Sci., Part B: Polym. Phys., 2015, 53, P. 1458–1469.Ruan D., Simmons D.S. Roles of Chain Stiffness and Segmental Rattling in Ionomer Glass Formation. J. Polym. Sci., Part B: Polym. Phys., 2015, 53, P. 1458–1469.Park H.B., Nam S.Y., Rhim J.W., Lee J.M., Kim S.E., Kim J.R., Lee Y.M. Gas-transport properties through cation-exchanged sulfonatedpolysulfone membranes. J. Appl. Polym. Sci., 2002, 86 (10), P. 2611–2617.Park H.B., Nam S.Y., Rhim J.W., Lee J.M., Kim S.E., Kim J.R., Lee Y.M. Gas-transport properties through cation-exchanged sulfonatedpolysulfone membranes. J. Appl. Polym. Sci., 2002, 86 (10), P. 2611–2617.Mukaddam M., Wang Y., Pinnau I. Structural, Thermal, and Gas-Transport Properties of Fe3+ Ion-Exchanged Nafion Membranes. ACS Omega, 2018, 3 (7), P. 7474–7482.Mukaddam M., Wang Y., Pinnau I. Structural, Thermal, and Gas-Transport Properties of Fe3+ Ion-Exchanged Nafion Membranes. ACS Omega, 2018, 3 (7), P. 7474–7482.Heitner-Wirguin C. Infra-red spectra of perfluorinated cation-exchanged membranes. Polymer, 1979, 20 (3), P. 371–374.Heitner-Wirguin C. Infra-red spectra of perfluorinated cation-exchanged membranes. Polymer, 1979, 20 (3), P. 371–374.Chen M., Ma J., Wang Z., Zhang X., Wu Z. Insights into iron induced fouling of ion-exchange membranes revealed by a quartz crystal microbalance with dissipation monitoring. RSC Adv., 2017, 7, P. 36555–36561.Chen M., Ma J., Wang Z., Zhang X., Wu Z. Insights into iron induced fouling of ion-exchange membranes revealed by a quartz crystal microbalance with dissipation monitoring. RSC Adv., 2017, 7, P. 36555–36561.Odinokov A.S., Bazanova O.S., Sokolov L.F., Barabanov V.G., Timofeev S.V.Kinetics of copolymerization of tetrafluoroethylene with perfluoro(3,6-dioxa-4-methyl-7-octen)sulfonyl fluoride. Russian J. of Applied Chemistry, 2009, 82 (1), P. 112–115.Odinokov A.S., Bazanova O.S., Sokolov L.F., Barabanov V.G., Timofeev S.V.Kinetics of copolymerization of tetrafluoroethylene with perfluoro(3,6-dioxa-4-methyl-7-octen)sulfonyl fluoride. Russian J. of Applied Chemistry, 2009, 82 (1), P. 112–115.Ivanchev S.S., Myakin S.V. Polymer membranes for fuel cells: manufacture, structure, modification, properties. Russian Chemical Reviews, 2010, 79 (2), P. 101–117.Ivanchev S.S., Myakin S.V. Polymer membranes for fuel cells: manufacture, structure, modification, properties. Russian Chemical Reviews, 2010, 79 (2), P. 101–117.Primachenko O.N., Odinokov A.S., Barabanov V.G., Tyulmankov V.P., Marinenko E.A., Gofman I.V., Ivanchev S.S. Relationship between the Morphology, Nanostructure, and Strength Properties of Aquivion® Type Perfluorinated Proton-Conducting Membranes Prepared by Casting from Solution. Russ. J. Appl. Chem., 2018, 91, P. 101–104.Primachenko O.N., Odinokov A.S., Barabanov V.G., Tyulmankov V.P., Marinenko E.A., Gofman I.V., Ivanchev S.S. Relationship between the Morphology, Nanostructure, and Strength Properties of Aquivion® Type Perfluorinated Proton-Conducting Membranes Prepared by Casting from Solution. Russ. J. Appl. Chem., 2018, 91, P. 101–104.Peters G.S., Gaponov Yu.A., Konarev P.V., Marchenkova M., Ilina K., Volkov V.V., Pisarevsky Yu.V., Kovalchuk M.V. Upgrade of the BioMUR beamline at the Kurchatov synchrotron radiation source for serial small-angle X-ray scattering experiments in solutions. Nuclear Instruments and Methods in Physics Research Section A Accelerators Spectrometers Detectors and Associated Equipment, 2021, 1025, 166170.Peters G.S., Gaponov Yu.A., Konarev P.V., Marchenkova M., Ilina K., Volkov V.V., Pisarevsky Yu.V., Kovalchuk M.V. Upgrade of the BioMUR beamline at the Kurchatov synchrotron radiation source for serial small-angle X-ray scattering experiments in solutions. Nuclear Instruments and Methods in Physics Research Section A Accelerators Spectrometers Detectors and Associated Equipment, 2021, 1025, 166170.Svergun D.I., Feigin L.A. Structure Analysis by Small-Angle X-ray and Neutron Scattering. Plenum Press, New York, USA; London, UK, 1987, 335 p.Svergun D.I., Feigin L.A. Structure Analysis by Small-Angle X-ray and Neutron Scattering. Plenum Press, New York, USA; London, UK, 1987, 335 p.Primachenko O.N., Kulvelis Yu.V., Odinokov A.S., Glebova N.V., Krasnova A.O., Antokolskiy L.A., Nechitailov A.A., Shvidchenko A.V., Gofman I.V., Marinenko E.A., Yevlampieva N.P., Lebedev V.T., Kuklin A.I. New Generation of Compositional Aquivion®-Type Membranes with Nanodiamonds for Hydrogen Fuel Cells: Design and Performance. Membranes, 2022, 12 (9), 827.Primachenko O.N., Kulvelis Yu.V., Odinokov A.S., Glebova N.V., Krasnova A.O., Antokolskiy L.A., Nechitailov A.A., Shvidchenko A.V., Gofman I.V., Marinenko E.A., Yevlampieva N.P., Lebedev V.T., Kuklin A.I. New Generation of Compositional Aquivion®-Type Membranes with Nanodiamonds for Hydrogen Fuel Cells: Design and Performance. Membranes, 2022, 12 (9), 827.Semenov V.G., Moskvin L.N., Ufimov A.A. Analytical potential of Mossbauer spectroscopy. ¨ Russ. Chem. Rev., 2006, 75 (4), P. 317–327.Semenov V.G., Moskvin L.N., Ufimov A.A. Analytical potential of Mossbauer spectroscopy. ¨ Russ. Chem. Rev., 2006, 75 (4), P. 317–327.Kamzin A.S., Obaidat I.M., Kozlov V.S., Voronina E.V., Narayanaswamy V., Al-Omari I.A. Graphene Oxide/Iron Oxide (GrO/FeOx) Nanocomposites for Biomedicine: Synthesis and Study. Physics of the Solid State, 2021, 63 (6), P. 856–865.Kamzin A.S., Obaidat I.M., Kozlov V.S., Voronina E.V., Narayanaswamy V., Al-Omari I.A. Graphene Oxide/Iron Oxide (GrO/FeOx) Nanocomposites for Biomedicine: Synthesis and Study. Physics of the Solid State, 2021, 63 (6), P. 856–865.Kamzin A.S., Obaidat I.M., Kozlov V.S., Voronina E.V., Narayanaswamy V., Al-Omari I.A. Magnetic Nanocomposites Graphene Oxide/Magnetite + Cobalt Ferrite (GrO/Fe3O4 + CoFe2O4) for Magnetic Hyperthermia. Physics of the Solid State, 2021, 63, P. 998–1008.Kamzin A.S., Obaidat I.M., Kozlov V.S., Voronina E.V., Narayanaswamy V., Al-Omari I.A. Magnetic Nanocomposites Graphene Oxide/Magnetite + Cobalt Ferrite (GrO/Fe3O4 + CoFe2O4) for Magnetic Hyperthermia. Physics of the Solid State, 2021, 63, P. 998–1008.Lebedev V.T., Kulvelis Yu.V., Tor¨ ok Gy., Ivankov O.I., Polotskaya G.A., Vinogradova L.V., Vul A.Ya., Primachenko O.N., Marinenko E.A., ¨ Odinokov A.S. Structure of diffusive polymer membranes for molecular and ionic transport. J. of Surface Investigation: X-ray, Synchrotron and Neutron Techniques, 2021, 15 (5), P. 939–946. ©Pleiades Publishing, Ltd., 2021. ISSN 1027-4510.Lebedev V.T., Kulvelis Yu.V., Tor¨ ok Gy., Ivankov O.I., Polotskaya G.A., Vinogradova L.V., Vul A.Ya., Primachenko O.N., Marinenko E.A., ¨ Odinokov A.S. Structure of diffusive polymer membranes for molecular and ionic transport. J. of Surface Investigation: X-ray, Synchrotron and Neutron Techniques, 2021, 15 (5), P. 939–946. ©Pleiades Publishing, Ltd., 2021. ISSN 1027-4510.Popov I., Zhu Z., Young-Gonzales A.R., Sacci R.L., Mamontov E., Gainaru C., Paddison S.J., Sokolov A.P. Search for a Grotthuss mechanism through the observation of proton transfer. Commun. Chem., 2023, 6, 77.Popov I., Zhu Z., Young-Gonzales A.R., Sacci R.L., Mamontov E., Gainaru C., Paddison S.J., Sokolov A.P. Search for a Grotthuss mechanism through the observation of proton transfer. Commun. Chem., 2023, 6, 77.Tauc J., Menth A., Wood D. Optical and Magnetic Investigations of the Localized States in Semiconducting Glasses. Phys. Rev. Lett., 1970, 25, P. 749–752.Tauc J., Menth A., Wood D. Optical and Magnetic Investigations of the Localized States in Semiconducting Glasses. Phys. Rev. Lett., 1970, 25, P. 749–752.Dorranian D., Abedini Z., Hojabri A., Ghoranneviss M. Structural and optical characterization of PMMA surface treated in low power nitrogen and oxygen RF plasmas. J. of Non-Oxide Glasses, 2009, 1 (3), P. 217–229.Dorranian D., Abedini Z., Hojabri A., Ghoranneviss M. Structural and optical characterization of PMMA surface treated in low power nitrogen and oxygen RF plasmas. J. of Non-Oxide Glasses, 2009, 1 (3), P. 217–229.Mishjil K.A., Chiad S.S., Abass K., Habubi N.F. Effect of Al doping on structural and optical parameters of ZnO thin films. Materials Focus, 2016, 5 (5), P. 471–475.Mishjil K.A., Chiad S.S., Abass K., Habubi N.F. Effect of Al doping on structural and optical parameters of ZnO thin films. Materials Focus, 2016, 5 (5), P. 471–475.Latif D.M.A., Chiad S.S., Erhayief M.S., Abass K.H., Habubi N.F., Hussin H.A. Effects of FeCl3 additives on optical parameters of PVA. IOP Conf. Series: J. of Physics: Conf. Series, 2018, 1003, 012108.Latif D.M.A., Chiad S.S., Erhayief M.S., Abass K.H., Habubi N.F., Hussin H.A. Effects of FeCl3 additives on optical parameters of PVA. IOP Conf. Series: J. of Physics: Conf. Series, 2018, 1003, 012108.Reichmanis E., Donnel J.O. Irradiation of Polymeric Materials, and the Effect of Radiation on High Technology Polymers. ACS Symposium Series, 1993, 381 (527), 108.Reichmanis E., Donnel J.O. Irradiation of Polymeric Materials, and the Effect of Radiation on High Technology Polymers. ACS Symposium Series, 1993, 381 (527), 108.Omer M.A.A., Gar-elnabi M.E.M., Ahmed A.H., Eidam G.A., Khidir N.A.N. Radiochemical Properties of Irradiated PVAAgNO3 Film by Electron Beam. Int. J. of Science and Research, 2013, 2 (9), P. 361–364.Omer M.A.A., Gar-elnabi M.E.M., Ahmed A.H., Eidam G.A., Khidir N.A.N. Radiochemical Properties of Irradiated PVA\AgNO3 Film by Electron Beam. Int. J. of Science and Research, 2013, 2 (9), P. 361–364.Bauminger E.R., Levy A., Labenski de Kanter F., Ofer S., Heitner-Wirquin C. Mossbauer spectra of iron containing Nafion membranes. ¨ J. de Physique. Colloque C1, 1980, 41 (1), 329.Bauminger E.R., Levy A., Labenski de Kanter F., Ofer S., Heitner-Wirquin C. Mossbauer spectra of iron containing Nafion membranes. ¨ J. de Physique. Colloque C1, 1980, 41 (1), 329.Lechan R., Nicolini C., Abeledo C.R., Frankel R.B. Hyperfine Interactions in the Intramolecular Antiferromagnet (Fe salen C1)2. J. Chem. Phys., 1973, 59 (6), P. 3138–3142.Lechan R., Nicolini C., Abeledo C.R., Frankel R.B. Hyperfine Interactions in the Intramolecular Antiferromagnet (Fe salen C1)2. J. Chem. Phys., 1973, 59 (6), P. 3138–3142.Rodmacq B., Pineri M., Coey J.M.D., Meagher A. Moussbauer spectroscopy of Nafion polymer membranes exchanged with Fe ¨ 2+, Fe3+, and Eu3+. J. Polym. Sci. Polym. Phys. Ed., 1982, 20 (4), P. 603–619.Rodmacq B., Pineri M., Coey J.M.D., Meagher A. Moussbauer spectroscopy of Nafion polymer membranes exchanged with Fe ¨ 2+, Fe3+, and Eu3+. J. Polym. Sci. Polym. Phys. Ed., 1982, 20 (4), P. 603–619.Freitknecht W., Giovanoli R., Michaelis W., Miiller M. Uber die Hydrolyse von Eisen(III)Salzl ¨ osungen. I. Die Hydrolyse der L ¨ osungen von ¨ Eisen(III)chlorid. Helv. Chim. Acta, 1973, 56 (8), P. 2847–2856.Freitknecht W., Giovanoli R., Michaelis W., Miiller M. Uber die Hydrolyse von Eisen(III)Salzl ¨ osungen. I. Die Hydrolyse der L ¨ osungen von ¨ Eisen(III)chlorid. Helv. Chim. Acta, 1973, 56 (8), P. 2847–2856.Knudsen L.M., Larsen E., Moreira J.E., Nielsen O.F. Characterization of Decaaqua-mu-oxodi-iron(III) by Mossbauer and Vibrational Spec- ¨ troscopy. Acta. Chem. Scand. Sect. A, 1975, 29 (9), P. 833–839.Knudsen L.M., Larsen E., Moreira J.E., Nielsen O.F. Characterization of Decaaqua-mu-oxodi-iron(III) by Mossbauer and Vibrational Spec- ¨ troscopy. Acta. Chem. Scand. Sect. A, 1975, 29 (9), P. 833–839.

The authors declare that there are no conflicts of interest present.