najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2023-14-2-272-278najo-153Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХComparative study of transport properties of membranes based on graphene oxide prepared by Brodie and improved Hummers’ methodsСравнительное исследование транспортных свойств мембран на основе оксида графена, полученных методом Броди и усовершенствованным методом Хаммерсаhttps://orcid.org/0000-0002-5812-9515ЧерноваЕ. А.ChernovaE. A.

 Ekaterina A. Chernova - Faculty of Materials Science

119991, Moscow, GSP-1,1-73 Leninskiye Gory

300012, Tula, Lenina avenue 92

chernova.msu@gmail.comГурьяновК. Е.GurianovK. E.

Konstantin E. Gurianov - Faculty of Materials Science

119991, Moscow, GSP-1, 1-73 Leninskiye Gory

gurianovke@yandex.ruhttps://orcid.org/0000-0002-8374-9265БроцманВ. А.BrotsmanV. A.

Victor A. Brotsman – Faculty of Chemistry

119991, Moscow, GSP-1, 1-3 Leninskiye Gory,

brotsmanva@mail.ruhttps://orcid.org/0000-0001-8981-8527ВалеевР. Г.ValeevR. G.

Rishat G. Valeev

Izhevsk, st. them. Tatiana Baramzina 34, 426067

rishatvaleev@mail.ruhttps://orcid.org/0000-0002-7384-3426КапитановаО. О.KapitanovaO. O.

Olesya O. Kapitanova – Faculty of Chemistry

119991, Moscow, GSP-1, 1-3 Leninskiye Gory

olesya.kapitanova@gmail.comБерекчиянМ. В.BerekchiianM. V.

Mikhail V. Berekchiian – Faculty of Materials Science

119991, Moscow, GSP-1, 1-73 Leninskiye Gory

mikhail.berekchiyan@yandex.ruЛукашинА. В.LukashinA. V.

Alexei V. Lukashin – Faculty of Materials Science

119991, Moscow, GSP-1, 1-73 Leninskiye Gory

alexey.lukashin@gmail.comLomonosov Moscow State University; Tula State UniversityRussian FederationLomonosov Moscow State UniversityRussian FederationUdmurt Federal Research Center of the Ural Brunch of Russian Academy of Sciences (UdmFRC of UB RAS)Russian Federation202303062025142272278Copyright © Chernova E.A., Gurianov K.E., Brotsman V.A., Valeev R.G., Kapitanova O.O., Berekchiian M.V., Lukashin A.V., 20252025Чернова Е.А., Гурьянов К.Е., Броцман В.А., Валеев Р.Г., Капитанова О.О., Берекчиян М.В., Лукашин А.В.Chernova E.A., Gurianov K.E., Brotsman V.A., Valeev R.G., Kapitanova O.O., Berekchiian M.V., Lukashin A.V.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/153

A comparative study of transport characteristics of composite membranes based on graphene oxide prepared by Hummers’ (H-GO) and Brodie (B-GO) methods is presented. By using Raman and XPS spectroscopy combined with gas and vapor measurements at non-zero pressure drop, it is shown that the dif ference in preparation methods results not only in different composition and microstructure of the membranes, but also in different water vapor permeability and resistance towards pressure drops during membrane perfor mance. TheH-GOsamplesarefoundtobemoredefective and stronger oxidized with C/O ratio of 1.8, whereas B-GO revealed a total C/O ratio of 2.6 with more perfect microstructure. The higher oxidation degree of H-GO membranes allows one to achieve higher water vapor permeability (up to 170 Barrer at 100 % humidity) but dramatically lower stability towards pressure revealing the irreversible loss in permeability up to 46 % dur ing the application of pressure drop of 1 bar. In contrast, B-GO membranes show slightly lower permeability ( 140Barrer at 100 % humidity) but enhanced pressure stability revealing the irreversible permeability loss of only 4 % at pressure drop of 1 bar which is about 10-fold smaller compared to H-GO stability. This could be explained by the difference in microstructural features of the H-GO and B-GO. Graphene oxide prepared by Hummer’s method has more flexible and defective nanosheets, whereas Brodie’s method gives rise to more rigid nanosheets with more perfect microstructure. The obtained results suggest that it is possible to prepare graphene oxide membranes with high resistance towards pressure using only the composition-microstructure interplay without additional modification with pressure-stabilizing agents.

В работе представлено сравнительное исследование свойств композиционных мембран на основе оксида графена, синтезированного методами Хаммерса (оксид графена H-GO) и Броди (оксид графена B-GO). Методами КР- и РФЭС- спектроскопии в комплексе с измерениями проницаемости мембран по газам и водяным парам при ненулевом перепаде давления показано, что различия в методах синтеза влияют не только на состав и микроструктуру мембран оксида графена, но также на их проницаемость и устойчивость к перепадам давления. Показано, что мембраны на основе H-GO содержат больше кислородных групп (соотношение С/О 1.8) и являются более дефектными, по сравнению с мембранами на основе B-GO (С/О 2.6). Более высокая концентрация кислородных групп в мембранах H-GO позволяет достичь высоких проницаемостей по водяным парам (~170 Баррер при 100% влажности сырьевого потока), однако это сопровождается достаточно низкой устойчивостью при перепадах давления (необратимая потеря проницаемости вплоть до 46% при перепаде давления 1 бар). Напротив, мембраны на основе B-GO, при проницаемости ~140 Баррер, характеризуются необратимой потерей проницаемости всего 4% при том же перепаде давления, что в 10 раз меньше по сравнению с мембранами H-GO. Наблюдаемые различия могут быть следствием разной микроструктуры мембран H-GO и B-GO. Оксид графена, синтезированный методом Хаммерса, обладает более гибкими и дефектными нанолистами, в то время как метод Броди позволяет получить более жесткие нанолисты с меньшим содержанием дефектов. Полученные результаты свидетельствуют, что повысить устойчивость мембран оксида графена к перепадам давления можно за счет контроля состава и микроструктуры в процессе синтеза, без каких-либо модификаций реагентами, устойчивыми к давлению.

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