najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМО10.17586/2220-8054-2023-14-2-264-271najo-152Research ArticleCHEMISTRY AND MATERIALS SCIENCEХИМИЯ И НАУКА О МАТЕРИАЛАХFormation of a 10 ˚A phase with halloysite structure under hydrothermal conditions with varying initial chemical compositionОбразование 10 Å фазы со структурой галлуазита в гидротермальных условиях при варьировании химической предыстории исходной композицииhttps://orcid.org/0000-0001-8886-0731ЛеоновН. А.LeonovN. A.

Nikita A. Leonov

26 Politekhnicheskaya, 194021, St. Petersburg

nikita_leonov_1998@mail.ruhttps://orcid.org/0000-0003-0620-8016КозловД. А.KozlovD. A.

Daniil A. Kozlov

Leninsky gory, 1, 119991, Moscow

Leninsky pr., 31, 119991, Moscow

kozlov@inorg.chem.msu.ruhttps://orcid.org/0000-0002-1571-209XКириленкоД. А.KirilenkoD. A.

Demid A. Kirilenko

26 Politekhnicheskaya, 194021, St. Petersburg

zumsisai@gmail.comhttps://orcid.org/0000-0001-6136-4877БертН. А.BertN. A.

Nikolay A. Bert

26 Politekhnicheskaya, 194021, St. Petersburg

nikolay.bert@mail.ioffe.ruhttps://orcid.org/0009-0000-6320-2011ПелагейкинаА. О.PelageikinaA. O.

Anna O. Pelageikina

26 Politekhnicheskaya, 194021, St. Petersburg

Pelaanna@yandex.ruhttps://orcid.org/0000-0002-9895-6822НечитайловА. А.NechitailovA. A.

Andrey A. Nechitailov

26 Politekhnicheskaya, 194021, St. Petersburg

aan.shuv@mail.ioffe.ruhttps://orcid.org/0000-0002-0770-9675АликинМ. Б.AlikinM. B.

Mikhail B. Alikin

190013, St. Petersburg

alikinmix@gmail.comhttps://orcid.org/0000-0002-3938-3024КрасилинА. А.KrasilinA. A.

Andrei A. Krasilin

26 Politekhnicheskaya, 194021, St. Petersburg

ikrasilin@mail.ioffe.ruIoffe InstituteRussian FederationLomonosov Moscow State University; Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of SciencesRussian FederationSt. Petersburg State Technological University (Technical University)Russian Federation202303062025142264271Copyright © Leonov N.A., Kozlov D.A., Kirilenko D.A., Bert N.A., Pelageikina A.O., Nechitailov A.A., Alikin M.B., Krasilin A.A., 20252025Леонов Н.А., Козлов Д.А., Кириленко Д.А., Берт Н.А., Пелагейкина А.О., Нечитайлов А.А., Аликин М.Б., Красилин А.А.Leonov N.A., Kozlov D.A., Kirilenko D.A., Bert N.A., Pelageikina A.O., Nechitailov A.A., Alikin M.B., Krasilin A.A.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/152

We studied the process of obtaining nanostructured halloysite by varying the parameters for cre ating the initial composition. The initial composition was synthesized by co-hydrolysis of (C3H7O)3Al and (C2H5O)4Si in the C6H14–NH3H2O system. Aluminum hydrosilicate with the composition Al2Si2O5(OH)4 was synthesized under hydrothermal conditions (220 C, 2 MPa, 96 h). Particles of plate-like morphology with av erage length 100– 200 nm and 60 nm thickness were obtained. The PXRD patterns revealed the presence of two phases. Plate-like kaolinites are found. Also we observed the formation of a halloysite-like phase. Studies of synthesized samples by IR spectroscopy and thermal analysis revealed the presence of organic-modified hydrosilicate with phase transition around 412 C. The resulting phase is promising for studying the processes of adsorption and further exfoliation.

Мы изучили процесс получения наноструктурного галлуазита путем варьирования параметров для создания исходной композиции. Исходная композиция была синтезирована совместным гидролизом (C3H7O)3Al и (C2H5O)4Si в системе C6H14–NH3·H2O. Гидросиликат алюминия состава Al2Si2O5(OH)4  был синтезирован в гидротермальных условиях (220°C, 2 МПа, 96 ч). Были получены частицы пластинчатой морфологии со средней длиной 100-200 нм и толщиной 60 нм. Анализ образцов методом порошковой дифрактометрии выявил наличие двух фаз: пластинчатого каолинита, а другой - образование галлуазитоподобной фазы. Исследования синтезированных образцов методом ИК-спектроскопии и термического анализа выявили присутствие органически модифицированного гидросиликата с фазовым переходом около 412 °С. Полученная фаза перспективна для изучения процессов адсорбции и дальнейшей эксфолиации.

алюминийгидросиликатыгидротермальная обработкакаолинитгаллуазитaluminumhydrosilicateshydrothermal synthesiskaolinitehalloysiteThe research was supported by the President of the Russian Federation grant MK 1962.2021.1.3. STEM studies were carried out using the equipment of the JRC PMR IGIC RAS. TEM studies were partially performed in the Joint Research Center ‘Materials science and characterization in advanced technology’. The XRPD and IR studies were performed using the equipment of the Engineering Centre of St. Petersburg State Technological Institute (Technical University).ReferencesPimneva L.A. Study of the adsorption of manganese ions (II) in natural kaolinite. Modern high technologies, 2017, 7, P. 61–65.Pimneva L.A. Study of the adsorption of manganese ions (II) in natural kaolinite. Modern high technologies, 2017, 7, P. 61–65.Minyukova T.P., Shtertser N.V., Khassin A.A., Plyasova L.M., Kustova G.N., Zaikovskii V.I., Baronskaya N.A., Kuznetsova A.V., Davydova L.P., Yur’eva T.M., Shvedenkov Yu.G., Van Den Heuvel J.C. Evolution of Cu–Zn–Si oxide catalysts in the course of reduction and reoxidation as studied by in situ x-ray diffraction analysis, transmission electron microscopy, and magnetic susceptibility methods. Kinetics and Catalysis, 2008, 49 (6), P. 821–830.Minyukova T.P., Shtertser N.V., Khassin A.A., Plyasova L.M., Kustova G.N., Zaikovskii V.I., Baronskaya N.A., Kuznetsova A.V., Davydova L.P., Yur’eva T.M., Shvedenkov Yu.G., Van Den Heuvel J.C. Evolution of Cu–Zn–Si oxide catalysts in the course of reduction and reoxidation as studied by in situ x-ray diffraction analysis, transmission electron microscopy, and magnetic susceptibility methods. Kinetics and Catalysis, 2008, 49 (6), P. 821–830.Bikbau M.Ya. Nano cement morphological peculiarities, structure properties and concrete on their base. Concrete technology, 2014, 4, P. 38–44.Bikbau M.Ya. Nano cement morphological peculiarities, structure properties and concrete on their base. Concrete technology, 2014, 4, P. 38–44.Koji Wada, Naganori Yoshinaga. The structure of “imogolite”. American Mineralogist, 1969, 52 (1–2), P. 50–71.Koji Wada, Naganori Yoshinaga. The structure of “imogolite”. American Mineralogist, 1969, 52 (1–2), P. 50–71.Levin A., Khrapova E., Kozlov D., Krasilin A., Gusarov V. Structure refinement, microstrains and crystallite sizes of Mg–Ni-phyllosilicate nano scroll powders. J. Appl. Cryst., 2022, 55, P. 484–502.Levin A., Khrapova E., Kozlov D., Krasilin A., Gusarov V. Structure refinement, microstrains and crystallite sizes of Mg–Ni-phyllosilicate nano scroll powders. J. Appl. Cryst., 2022, 55, P. 484–502.Bates T.F., Sand L.B., Mink J.F. Tubular Crystals of Chrysotile Asbestos. Science, 1950, 111, P. 512–513.Bates T.F., Sand L.B., Mink J.F. Tubular Crystals of Chrysotile Asbestos. Science, 1950, 111, P. 512–513.Bates T.F., Hildebrand F.A., Swineford A. Morphology and structure of endellite and halloysite. American Mineralogist, 1950, 35 (7–8), P. 463 484.Bates T.F., Hildebrand F.A., Swineford A. Morphology and structure of endellite and halloysite. American Mineralogist, 1950, 35 (7–8), P. 463 484.Lukuttsova N.P., Golovin S.N. Aggregative stability of aqueous suspensions of halloysite nanotubes. Construction materials, 2018, 1 (2), P. 4–10.Lukuttsova N.P., Golovin S.N. Aggregative stability of aqueous suspensions of halloysite nanotubes. Construction materials, 2018, 1 (2), P. 4–10.Arsent’ev M.Y., Golubeva O.Y. Comparative Study of Internal Mechanical Stresses in the Structures of Montmorillonite and Halloysite. Glass Phys. Chem., 2020, 46, P. 598–604.Arsent’ev M.Y., Golubeva O.Y. Comparative Study of Internal Mechanical Stresses in the Structures of Montmorillonite and Halloysite. Glass Phys. Chem., 2020, 46, P. 598–604.Szczepanik B., Slomkiewicz P., Garnuszek M., Czech K., Banas D., Kubala-Kukus A., Stabrawa I. The effect of chemical modification on the physico-chemical characteristics of halloysite: FTIR, XRF, and XRD studies. J. of Molecular Structure, 2015, 1084, P. 16–22.Szczepanik B., Slomkiewicz P., Garnuszek M., Czech K., Banas D., Kubala-Kukus A., Stabrawa I. The effect of chemical modification on the physico-chemical characteristics of halloysite: FTIR, XRF, and XRD studies. J. of Molecular Structure, 2015, 1084, P. 16–22.Krasilin A.A., Khrapova E.K., Maslennikova T.P. Cation Doping Approach for Nanotubular Hydrosilicates Curvature Control and Related Appli cations. Crystals, 2020, 10, 654.Krasilin A.A., Khrapova E.K., Maslennikova T.P. Cation Doping Approach for Nanotubular Hydrosilicates Curvature Control and Related Appli cations. Crystals, 2020, 10, 654.Parfitt R.L., Furkert R. J., Henmi T. Identification and Structure of Two Types of Allophane from Volcanic Ash Soils and Tephra. Clays and Clay Minerals, 1980, 28, P. 328–334.Parfitt R.L., Furkert R. J., Henmi T. Identification and Structure of Two Types of Allophane from Volcanic Ash Soils and Tephra. Clays and Clay Minerals, 1980, 28, P. 328–334.Krasilin A.A., Khrapova E.K., Nomin´e A., Ghanbaja J., Belmonte T., Gusarov V.V. Cation Redistribution along the Spiral of Ni-Doped Phyllosil icate Nanoscrolls: Energy Modelling and STEM/EDS Study. Chem. Phys. Chem., 2019, 20, P. 1–9.Krasilin A.A., Khrapova E.K., Nomin´e A., Ghanbaja J., Belmonte T., Gusarov V.V. Cation Redistribution along the Spiral of Ni-Doped Phyllosil icate Nanoscrolls: Energy Modelling and STEM/EDS Study. Chem. Phys. Chem., 2019, 20, P. 1–9.Kirichenko O.A., Shuvalova E.V., Redina, E.A. Low-temperature copper hydrosilicates: catalysts for reduction of aromatic nitro compounds with molecular hydrogen. Russ. Chem. Bull., 2019, 68, P. 2048–2052.Kirichenko O.A., Shuvalova E.V., Redina, E.A. Low-temperature copper hydrosilicates: catalysts for reduction of aromatic nitro compounds with molecular hydrogen. Russ. Chem. Bull., 2019, 68, P. 2048–2052.Hara T., Mascotto S., Weidmann C., Smarsly B.M. The effect of hydrothermal treatment on column performance for monolithic silica capillary columns. J. of Chromatography A, 2011, 1218, P. 3624–3635.Hara T., Mascotto S., Weidmann C., Smarsly B.M. The effect of hydrothermal treatment on column performance for monolithic silica capillary columns. J. of Chromatography A, 2011, 1218, P. 3624–3635.Krasilin A.A., Bodalyov I.S., Malkov A.A., Khrapova E.K., Maslennikova T.P., Malygin A.A. On an adsorption/photocatalytic performance of nanotubular Mg3Si2O5(OH)4/TiO2 composite. Nanosystems: Phys. Chem. Math., 2018, 9 (3), P. 410–416.Krasilin A.A., Bodalyov I.S., Malkov A.A., Khrapova E.K., Maslennikova T.P., Malygin A.A. On an adsorption/photocatalytic performance of nanotubular Mg3Si2O5(OH)4/TiO2 composite. Nanosystems: Phys. Chem. Math., 2018, 9 (3), P. 410–416.Krasilin A.A., Straumal E.A., Yurkova L.L., Khrapova E.K., Tomkovich M.V., Shunina I.G., Vasil’eva L.P., Lermontov S.A., Ivanov V.K. Sulfated Halloysite Nanoscrolls as Superacid Catalysts for Oligomerization of Hexene-1. Russ. J. Appl. Chem., 2019, 92, P. 1251–1257.Krasilin A.A., Straumal E.A., Yurkova L.L., Khrapova E.K., Tomkovich M.V., Shunina I.G., Vasil’eva L.P., Lermontov S.A., Ivanov V.K. Sulfated Halloysite Nanoscrolls as Superacid Catalysts for Oligomerization of Hexene-1. Russ. J. Appl. Chem., 2019, 92, P. 1251–1257.Sidorenko A.Yu., Kravtsova A.V., Aho A., Heinmaa I., W¨arna J., Pazniak H., Volcho K.P., Salakhutdinov N.F., Murzin D.Yu., Agabekov V.E. Highly selective Prins reaction over acid-modified halloysite nanotubes for synthesis of isopulegol-derived 2H-chromene compounds. J. of Catal ysis, 2019, 374, P. 360–377.Sidorenko A.Yu., Kravtsova A.V., Aho A., Heinmaa I., W¨arna J., Pazniak H., Volcho K.P., Salakhutdinov N.F., Murzin D.Yu., Agabekov V.E. Highly selective Prins reaction over acid-modified halloysite nanotubes for synthesis of isopulegol-derived 2H-chromene compounds. J. of Catal ysis, 2019, 374, P. 360–377.Thill A., Picot P., Bellon L. A mechanism for the sphere/tube shape transition of nanoparticles with an imogolite local structure (imogolite and allophane). Applied Clay Science, 2017, 141, P. 308–315.Thill A., Picot P., Bellon L. A mechanism for the sphere/tube shape transition of nanoparticles with an imogolite local structure (imogolite and allophane). Applied Clay Science, 2017, 141, P. 308–315.Pigni`e M.-C., Shcherbakov V., Charpentier T., Moskura M., Carteret C., Denisov S., Mostafavi M., Thill A., Ca¨er S. Confined water radiolysis in aluminosilicate nanotubes: the importance of charge separation effects. Nanoscale, 2021, 13, P. 3092–3105.Pigni`e M.-C., Shcherbakov V., Charpentier T., Moskura M., Carteret C., Denisov S., Mostafavi M., Thill A., Ca¨er S. Confined water radiolysis in aluminosilicate nanotubes: the importance of charge separation effects. Nanoscale, 2021, 13, P. 3092–3105.Cavallaro G., Lazzara G., Milioto S., Parisi F., Sanzillo V. Modified Halloysite Nanotubes: Nanoarchitectures for Enhancing the Capture of Oils from Vapor and Liquid Phases. ACS Appl. Mater. Interfaces, 2014, 6, P. 606–612.Cavallaro G., Lazzara G., Milioto S., Parisi F., Sanzillo V. Modified Halloysite Nanotubes: Nanoarchitectures for Enhancing the Capture of Oils from Vapor and Liquid Phases. ACS Appl. Mater. Interfaces, 2014, 6, P. 606–612.Krasilin A.A. Energy modeling of competition between tubular and platy morphologies of chrysotile and halloysite layers. Clays and Clay Miner als, 2020, 1, P. 1–12.Krasilin A.A. Energy modeling of competition between tubular and platy morphologies of chrysotile and halloysite layers. Clays and Clay Miner als, 2020, 1, P. 1–12.Krasilin A.A., Khrapova E.K. Effect of hydrothermal treatment conditions on formation of nickel hydrogermanate with platy morphology. Russ. J. Appl. Chem., 2017, 90, P. 22–27.Krasilin A.A., Khrapova E.K. Effect of hydrothermal treatment conditions on formation of nickel hydrogermanate with platy morphology. Russ. J. Appl. Chem., 2017, 90, P. 22–27.White R.D., Bavykin D.V., Walsh F.C. Spontaneous Scrolling of Kaolinite Nanosheets into Halloysite Nanotubes in an Aqueous Suspension in the Presence of GeO2. J. of Physical Chemistry, 2012, 116, P. 8824–8833.White R.D., Bavykin D.V., Walsh F.C. Spontaneous Scrolling of Kaolinite Nanosheets into Halloysite Nanotubes in an Aqueous Suspension in the Presence of GeO2. J. of Physical Chemistry, 2012, 116, P. 8824–8833.Perbost R., Amouric M., Olives J. Influence of Cation Size on the Curvature of Serpentine Minerals: HRTEM-AEM Study and Elastic Theory. Clays Clay Miner., 2003, 51, P. 430–438.Perbost R., Amouric M., Olives J. Influence of Cation Size on the Curvature of Serpentine Minerals: HRTEM-AEM Study and Elastic Theory. Clays Clay Miner., 2003, 51, P. 430–438.Maslennikova T.P., Korytkova E.N., Pivovarova L.N. Hydrothermal synthesis of nanotube composition Al2Si2O5(OH)4 2H2O with halloysite structure. Physics and Chemistry of Glass, 2012, S6, P. 890–893.Maslennikova T.P., Korytkova E.N., Pivovarova L.N. Hydrothermal synthesis of nanotube composition Al2Si2O5(OH)4 2H2O with halloysite structure. Physics and Chemistry of Glass, 2012, S6, P. 890–893.Golubeva O.Yu, Alikina Y.A., Kalashnikova T.A. Influence of hydrothermal synthesis conditions on the morphology and sorption properties of porous aluminosilicates with kaolinite and halloysite structures. Applied Clay Science, 2020, 199, P. 1–12.Golubeva O.Yu, Alikina Y.A., Kalashnikova T.A. Influence of hydrothermal synthesis conditions on the morphology and sorption properties of porous aluminosilicates with kaolinite and halloysite structures. Applied Clay Science, 2020, 199, P. 1–12.Mak´ oa ´ E., Kov´ acs A., Antal V., Krist´of T. Thin-walled nanoscrolls by multi-step intercalation from tubular halloysite-10 ˚ A and its rearrangement upon peroxide treatment. Applied Clay Science, 2017, 146, P. 131–139.Mak´ oa ´ E., Kov´ acs A., Antal V., Krist´of T. Thin-walled nanoscrolls by multi-step intercalation from tubular halloysite-10 ˚ A and its rearrangement upon peroxide treatment. Applied Clay Science, 2017, 146, P. 131–139.Xiaoguang Li, Qinfu Liu, Hongfei Cheng, Sridhar Komarneni. High-yield production of mesoporous nanoscrolls from kaolinite by ultrasonic assisted exfoliation. Microporous and Mesoporous Materials, 2017, 241, P. 66–71.Xiaoguang Li, Qinfu Liu, Hongfei Cheng, Sridhar Komarneni. High-yield production of mesoporous nanoscrolls from kaolinite by ultrasonic assisted exfoliation. Microporous and Mesoporous Materials, 2017, 241, P. 66–71.Kloprogge J.T. Characterisation of Halloysite by Spectroscopy. Developm. Clay Sci., 2016, 7, P. 115–136.Kloprogge J.T. Characterisation of Halloysite by Spectroscopy. Developm. Clay Sci., 2016, 7, P. 115–136.Jiangyan Yuan, Jing Yang, Hongwen Ma, Shuangqing Su, Qianqian Chang, Sridhar Komarneni. Hydrothermal synthesis of nano-kaolinite from K-feldspar. Ceramics International, 2018, 44 (13), P. 15611–15617.Jiangyan Yuan, Jing Yang, Hongwen Ma, Shuangqing Su, Qianqian Chang, Sridhar Komarneni. Hydrothermal synthesis of nano-kaolinite from K-feldspar. Ceramics International, 2018, 44 (13), P. 15611–15617.Tan D., Yuan P., Liu D., Du P. Chapter 8- Surface Modifications of Halloysite. Developm. Clay Sci., 2016, 7, P. 167–201.Tan D., Yuan P., Liu D., Du P. Chapter 8- Surface Modifications of Halloysite. Developm. Clay Sci., 2016, 7, P. 167–201.Weng On Yah, Atsushi Takahara, Yuri M. Lvov. Selective Modification of Halloysite Lumen with Octadecylphosphonic Acid: New Inorganic Tubular Micelle. J. of the American Chemical Society, 2012, 134 (3), P. 1853–1859.Weng On Yah, Atsushi Takahara, Yuri M. Lvov. Selective Modification of Halloysite Lumen with Octadecylphosphonic Acid: New Inorganic Tubular Micelle. J. of the American Chemical Society, 2012, 134 (3), P. 1853–1859.Li Y., Zhang Y., Zhang Y., Liu M., Zhang F., Wang L. Thermal behavior analysis of halloysite selected from Inner Mongolia Autonomous Region in China. J. Therm. Anal. Calorim., 2017, 129, P. 1333–1339.Li Y., Zhang Y., Zhang Y., Liu M., Zhang F., Wang L. Thermal behavior analysis of halloysite selected from Inner Mongolia Autonomous Region in China. J. Therm. Anal. Calorim., 2017, 129, P. 1333–1339.Erzs´ebet Horv´ath, Ray L. Frost, ´ Eva Mak´ o, J´anos Krist´ of, Tam´ as Cseh. Thermal treatment of mechanochemically activated kaolinite. Thermochim ica Acta, 2003, 404 (1–2), P. 227–234.Erzs´ebet Horv´ath, Ray L. Frost, ´ Eva Mak´ o, J´anos Krist´ of, Tam´ as Cseh. Thermal treatment of mechanochemically activated kaolinite. Thermochim ica Acta, 2003, 404 (1–2), P. 227–234.G´abor M., T´oth M., Krist´ of J., Kom´aromi-Hiller G. Thermal Behavior and Decomposition of Intercalated Kaolinite. Clays Clay Miner., 1995, 43, P. 223–228.G´abor M., T´oth M., Krist´ of J., Kom´aromi-Hiller G. Thermal Behavior and Decomposition of Intercalated Kaolinite. Clays Clay Miner., 1995, 43, P. 223–228.Krasilin A.A., Danilovich D.P., Yudina E.B., Bruyere S., Ghanbaja J., Ivanov V.K. Crystal violet adsorption by oppositely twisted heat-treated halloysite and pecoraite nanoscrolls. Applied Clay Science, 2019, 173, P. 1–11.Krasilin A.A., Danilovich D.P., Yudina E.B., Bruyere S., Ghanbaja J., Ivanov V.K. Crystal violet adsorption by oppositely twisted heat-treated halloysite and pecoraite nanoscrolls. Applied Clay Science, 2019, 173, P. 1–11.Joussein E., Petit S., Churchman J., Theng B., Righi D., Delvaux B. Halloysite clay minerals– a review. Clay Minerals, 2005, 40, P. 383–426.Joussein E., Petit S., Churchman J., Theng B., Righi D., Delvaux B. Halloysite clay minerals– a review. Clay Minerals, 2005, 40, P. 383–426.

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