Ultrasonic-assisted rapid liquid-phase exfoliation of MFI-type zeolite nanoparticle aggregates

doi:10.1016/j.cjche.2025.02.029

中国化学工程学报 ›› 2025, Vol. 83 ›› Issue (7): 38-50.DOI: 10.1016/j.cjche.2025.02.029

Ultrasonic-assisted rapid liquid-phase exfoliation of MFI-type zeolite nanoparticle aggregates

Xinyi Gao, Qiancheng Zheng, Zhengbao Wang

Key Laboratory of Biomass Chemical Engineering of Ministry of Education, ERC of Membrane and Water Treatment (MOE), College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China

收稿日期:2024-12-09 修回日期:2025-01-07 接受日期:2025-02-18 出版日期:2025-07-28 发布日期:2025-07-28
通讯作者: Zhengbao Wang,E-mail:zbwang@zju.edu.cn
基金资助:
This work is supported by the Natural Science Foundation of Zhejiang Province, China (LD24B060002), National Key Research and Development Program of China (2021YFB3801102) and the Fundamental Research Funds for the Central Universities (226- 2024-00060).

Ultrasonic-assisted rapid liquid-phase exfoliation of MFI-type zeolite nanoparticle aggregates

Xinyi Gao, Qiancheng Zheng, Zhengbao Wang

Key Laboratory of Biomass Chemical Engineering of Ministry of Education, ERC of Membrane and Water Treatment (MOE), College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China

Received:2024-12-09 Revised:2025-01-07 Accepted:2025-02-18 Online:2025-07-28 Published:2025-07-28
Contact: Zhengbao Wang,E-mail:zbwang@zju.edu.cn
Supported by:
This work is supported by the Natural Science Foundation of Zhejiang Province, China (LD24B060002), National Key Research and Development Program of China (2021YFB3801102) and the Fundamental Research Funds for the Central Universities (226- 2024-00060).

摘要/Abstract

摘要： The preparation of dispersible MFI-type zeolite nanoparticles with open micropores is challenging. Herein, a rapid and effective ultrasound-assisted liquid-phase exfoliation method along with a freezedrying process for redispersion of calcined silicalite-1 (S-1) zeolite nanoparticle aggregates using 3- aminopropanol as an exfoliating agent is demonstrated. The exfoliation of S-1 zeolite nanoparticles is characterized by X-ray diffraction, scanning electron microscopy and DLS particle size analysis. The effects of drying methods of as-synthesized zeolite nanoparticle suspension, zeolite contents in frozen nanoparticle suspension, exfoliating agent concentrations, and zeolite doses in ultrasonic suspension on exfoliation efficiency are systematically investigated. It is found that the S-1 zeolite nanoparticle (~70 nm) achieves a yield up to 95% through a 30 min ultrasonic exfoliation in a 3-aminopropanol solution along with a freeze-drying process. The proposed exfoliation mechanism involves two primary stages: guest molecule insertion followed by water expansion, both substantially enhanced by tip sonication. This work offers a comprehensive understanding of the exfoliation process, provides valuable insights into the dispersion of sintered zeolite nanoparticles.

关键词: Nanoparticles, Zeolite, Liquid phase exfoliation, Ultrasonic-assisted, Vacuum freeze drying, Sintering

Abstract: The preparation of dispersible MFI-type zeolite nanoparticles with open micropores is challenging. Herein, a rapid and effective ultrasound-assisted liquid-phase exfoliation method along with a freezedrying process for redispersion of calcined silicalite-1 (S-1) zeolite nanoparticle aggregates using 3- aminopropanol as an exfoliating agent is demonstrated. The exfoliation of S-1 zeolite nanoparticles is characterized by X-ray diffraction, scanning electron microscopy and DLS particle size analysis. The effects of drying methods of as-synthesized zeolite nanoparticle suspension, zeolite contents in frozen nanoparticle suspension, exfoliating agent concentrations, and zeolite doses in ultrasonic suspension on exfoliation efficiency are systematically investigated. It is found that the S-1 zeolite nanoparticle (~70 nm) achieves a yield up to 95% through a 30 min ultrasonic exfoliation in a 3-aminopropanol solution along with a freeze-drying process. The proposed exfoliation mechanism involves two primary stages: guest molecule insertion followed by water expansion, both substantially enhanced by tip sonication. This work offers a comprehensive understanding of the exfoliation process, provides valuable insights into the dispersion of sintered zeolite nanoparticles.

Key words: Nanoparticles, Zeolite, Liquid phase exfoliation, Ultrasonic-assisted, Vacuum freeze drying, Sintering

Xinyi Gao, Qiancheng Zheng, Zhengbao Wang. Ultrasonic-assisted rapid liquid-phase exfoliation of MFI-type zeolite nanoparticle aggregates[J]. 中国化学工程学报, 2025, 83(7): 38-50.

Xinyi Gao, Qiancheng Zheng, Zhengbao Wang. Ultrasonic-assisted rapid liquid-phase exfoliation of MFI-type zeolite nanoparticle aggregates[J]. Chinese Journal of Chemical Engineering, 2025, 83(7): 38-50.

参考文献

[1] J. Kobler, H. Abrevaya, S. Mintova, T. Bein, High-silica zeolite-b: from stable colloidal suspensions to thin films, J. Phys. Chem. C 112(37) (2008) 14274-14280.
[2] N.V. Kolesnichenko, N.N. Ezhova, O.V. Yashina, Formation of MFI-type zeolite nanoparticles and zeolite-based suspensions, Petrol. Chem. 56(9) (2016) 827-831.
[3] J. Zhou, W. Fan, Y.D. Wang, Z.K. Xie, The essential mass transfer step in hierarchical/nano zeolite: surface diffusion, Natl. Sci. Rev. 7(11) (2019) 1630-1632.
[4] M. Rutkowska, L. Chmielarz, D. Macina, Z. Piwowarska, B. Dudek, A. Adamski, S. Witkowski, Z. Sojka, L. Obalova, C.J. van Oers, P. Cool, Catalytic decompo- sition and reduction of N₂O over micro-mesoporous materials containing beta zeolite nanoparticles, Appl. Catal. B Environ. 146(2014) 112-122.
[5] L. Tosheva, B. Mihailova, L.H. Wee, B. Gasharova, K. Garbev, A.M. Doyle, Indirect observation of structured incipient zeolite nanoparticles in clear precursor solutions, Angew. Chem. Int. Ed. 47(45) (2008) 8650-8653.
[6] T.M. Davis, T.O. Drews, H. Ramanan, C. He, J.S. Dong, H. Schnablegger, M.A. Katsoulakis, E. Kokkoli, A.V. McCormick, R.L. Penn, M. Tsapatsis, Mechanistic principles of nanoparticle evolution to zeolite crystals, Nat. Mater. 5(2006) 400-408.
[7] P. Guo, J. Shin, A.G. Greenaway, J.G. Min, J. Su, H.J. Choi, L. Liu, P.A. Cox, S.B. Hong, P.A. Wright, X. Zou, A zeolite family with expanding structural complexity and embedded isoreticular structures, Nature 524(7563) (2015) 74-78.
[8] P.Y. Yu, G. Yang, Y.M. Chai, L. Tosheva, C.Z. Wang, H.Q. Jiang, C.G. Liu, H.L. Guo, Self-limiting growth of thin dense LTA membranes boosts H₂ gas separation performance, Chem. Eng. J. 479(2024) 147629.
[9] X.Q. Wang, P.C. Xu, L. Tang, Y. Chen, X.X. Li, Nano beta zeolites catalyticcracking effect on hydrochlorofluorocarbon molecule for specific detection of Freon, J. Mater. Chem. A 9(27) (2021) 15321-15328.
[10] Y.E. Yan, X. Guo, Y.H. Zhang, Y. Tang, Future of nano-/hierarchical zeolites in catalysis: gaseous phase or liquid phase system, Catal. Sci. Technol. 5(2) (2015) 772-785.
[11] H. Yan, N.K. Ma, Z.Y. Zhan, Z.B. Wang, Fabrication of zeolite NaA membranes on hollow fibers using nano-sized seeds exfoliated from mesoporous zeolite crystals, Microporous Mesoporous Mater. 215(2015) 244-248.
[12] K. Lazarova, H. Awala, S. Thomas, M. Vasileva, S. Mintova, T. Babeva, Vapor responsive one-dimensional photonic crystals from zeolite nanoparticles and metal oxide films for optical sensing, Sensors 14(7) (2014) 12207-12218.
[13] M. Tsotsalas, M. Busby, E. Gianolio, S. Aime, L. De Cola, Functionalized nanocontainers as dual magnetic and optical probes for molecular imaging applications, Chem. Mater. 20(18) (2008) 5888-5893.
[14] J.H. Ye, J.C. Tan, High-performance triboelectric nanogenerators incorporating chlorinated zeolitic imidazolate frameworks with topologically tunable dielectric and surface adhesion properties, Nano Energy 114(2023) 108687.
[15] G. Calzaferri, S. Huber, H. Maas, C. Minkowski, Host-guest antenna materials, Angew. Chem. Int. Ed. 42(32) (2003) 3732-3758.
[16] H.S. Kim, N.C. Jeong, K.B. Yoon, Photovoltaic effects of CdS and PbS quantum dots encapsulated in zeolite Y, Langmuir 27(23) (2011) 14678-14688.
[17] P. Lakhera, V. Chaudhary, S. Singh, N. Vishwakarma, C. Sanchez Huertas, P. Kumar, S. Kumar, Detection of glycosylated hemoglobin on boronic acidmodified zeolitic imidazolate framework-8 nanoparticles, ACS Appl. Nano Mater. 6(24) (2023) 22857-22864.
[18] S. Gutierrez-Rubio, M. Shamzhy, C. J, D.P. Serrano, I. Moreno, J.M. Coronado, Vapor phase acylation of guaiacol with acetic acid over micro, nano and hierarchical MFI and BEA zeolites, Appl. Catal. B Environ. 285(2021) 119826.
[19] C.Y. Chuah, J. Lee, Y.P. Bao, J.H. Song, T.H. Bae, High-performance porous carbon-zeolite mixed-matrix membranes for CO₂/N₂ separation, J. Membr. Sci. 622(2021) 119031.
[20] K. Zarshenas, A. Raisi, A. Aroujalian, Mixed matrix membrane of nano-zeolite NaX/poly (ether-block-amide) for gas separation applications, J. Membr. Sci. 510(2016) 270-283.
[21] Q.C. Zheng, H.Y. Zhang, H.F. Tan, Z.B. Wang, Rapid and facile synthesis of nanosized silicalite-1 zeolites from solid silica in a semisolid-like system via a two-step crystallization method, Ind. Eng. Chem. Res. 63(14) (2024) 6121-6131.
[22] Q.C. Zheng, H.Y. Zhang, J. Li, X.T. Yu, X.Y. Gao, Z.B. Wang, Amino acid assistedconstruction of 2D-hierarchical MFI zeolites for adsorption of Rhodamine B, Sep. Purif. Technol. 358(2025) 130414.
[23] H. Konno, T. Tago, Y. Nakasaka, R. Ohnaka, J.I. Nishimura, T. Masuda, Effectiveness of nano-scale ZSM-5 zeolite and its deactivation mechanism on catalytic cracking of representative hydrocarbons of naphtha, Microporous Mesoporous Mater. 175(2013) 25-33.
[24] C.S. Zhang, S.Q. Chu, J. Jiang, J.C. Zhao, S. Wen, B. Sun, W. Xu, Minute-scale synthesis of nano silicalite-1 zeolites, Front. Chem. 10(2022) 860795.
[25] J. Grand, S.N. Talapaneni, A. Vicente, C. Fernandez, E. Dib, H.A. Aleksandrov, G. N. Vayssilov, R. Retoux, P. Boullay, J.P. Gilson, V. Valtchev, S. Mintova, One-pot synthesis of silanol-free nanosized MFI zeolite, Nat. Mater. 16(10) (2017) 1010-1015.
[26] C.S. Zhang, Q.M. Wu, C. Lei, S.C. Han, Q.Y. Zhu, S. Maurer, D. Dai, A.N. Parvulescu, U. Müller, X.J. Meng, F.S. Xiao, An efficient, rapid, and noncentrifugation synthesis of nanosized zeolites by accelerating the nucleation rate, J. Mater. Chem. A 6(42) (2018) 21156-21161.
[27] Q. Zhang, G.R. Chen, Y.Y. Wang, M.Y. Chen, G.Q. Guo, J. Shi, J. Luo, J.H. Yu, High-quality single-crystalline MFI-type nanozeolites: a facile synthetic strategy and MTP catalytic studies, Chem. Mater. 30(8) (2018) 2750-2758.
[28] Y. Guo, T.J. Sun, X.W. Liu, Q.L. Ke, X.L. Wei, Y.M. Gu, S.D. Wang, Cost-effective synthesis of CHA zeolites with controllable morphology and size, Chem. Eng. J. 358(2019) 331-339.
[29] S. Mintova, J.P. Gilson, V. Valtchev, Advances in nanosized zeolites, Nanoscale 5(15) (2013) 6693-6703.
[30] H.T. Wang, Z.B. Wang, Y.S. Yan, Colloidal suspensions of template-removed zeolite nanocrystals, Chem. Commun. 23(2000) 2333-2334.
[31] Y. Li, W.B. Krantz, T.S. Chung, A novel primer to prevent nanoparticle agglomeration in mixed matrix membranes, AIChE. J. 53(9) (2007) 2470-2475.
[32] H. Chen, Y. Zhou, Z. To sner, C. Ji rí, M. Opanasenko, Synthesis of aggregationresistant MFI nanoparticles, Catal. Today 354(2020) 151-157.
[33] W.J. Roth, T. Sasaki, K. Wolski, Y.J. Song, D.M. Tang, Y. Ebina, R.Z. Ma, J. Grzybek, K. Kałahurska, B. Gil, M. Mazur, S. Zapotoczny, J. Cejka, Liquid dispersions of zeolite monolayers with high catalytic activity prepared by softchemical exfoliation, Sci. Adv. 6(12) (2020) eaay8163.
[34] A. Corma, V. Fornes, S.B. Pergher, T.L.M. Maesen, J.G. Buglass, Delaminated zeolite precursors as selective acidic catalysts, Nature 396(6709) (1998) 353-356.
[35] W.J. Roth, T. Sasaki, K. Wolski, B. Gil, S. Zapotoczny, J. Cejka, M. Kub u, M. Mazur, Y. Ebina, N. Sakai, D.M. Tang, R.Z. Ma, Exfoliating layered zeolite MFI into unilamellar nanosheets in solution as precursors for the synthesis of hierarchical nanocomposites and oriented films, Inorg. Chem. Front. 10(5) (2023) 1511-1521.
[36] P. Loch, D. Schuchardt, G. Algara-Siller, P. Markus, K. Ottermann, S. Rosenfeldt, T. Lunkenbein, W. Schwieger, G. Papastavrou, J. Breu, Nematic suspension of a microporous layered silicate obtained by forceless spontaneous delamination via repulsive osmotic swelling for casting high-barrier all-inorganic films, Sci. Adv. 8(20) (2022) eabn9084.
[37] W.J. Roth, T. Sasaki, K. Wolski, Y. Ebina, D.M. Tang, Y. Michiue, N. Sakai, R.Z. Ma, O. Cretu, J. Kikkawa, K. Kimoto, K. Kalahurska, B. Gil, M. Mazur, S. Zapotoczny, J. Cejka, J. Grzybek, A. Kowalczyk, Exfoliated ferrierite-related unilamellar nanosheets in solution and their use for preparation of mixed zeolite hierarchical structures, J. Am. Chem. Soc. 143(29) (2021) 11052-11062.
[38] B. Wang, N.N. Wang, X.W. Li, R.F. Zhou, W.H. Xing, Exfoliation of lamellar SAPO-34 zeolite to nanosheets and synthesis of thin SAPO-34 membranes by a nanosheet-seeded secondary growth approach, J. Membr. Sci. 645(2022) 120177.
[39] K. Varoon Agrawal, X. Zhang, B. Elyassi, D.D. Brewer, M. Gettel, S. Kumar, J.A. Lee, S. Maheshwari, A. Mittal, C.Y. Sung, M. Cococcioni, L.F. Francis, A.V. McCormick, K.A. Mkhoyan, M. Tsapatsis, Dispersible exfoliated zeolite nanosheets and their application as a selective membrane, Science 334(6052) (2011) 72-75.
[40] L. Liu, P.J. Fang, C.H. Yan, J.J. Ma, J.Z. Zhang, J.D. Zhou, H. Sun, X. Ji, C.Z. Xu, Z. W. Tong, Ultrasonic-assisted rapid and highly efficient liquid-phase exfoliation of a-zirconium phosphate, J. Mater. Sci. 57(12) (2022) 6619-6628.
[41] K. Li, Ceramic membranes and membrane processes, in: Ceramic Membranes for Separation and Reaction, Wiley, 2007.
[42] A.I. Orlova, M.I. Ojovan, Ceramic mineral waste-forms for nuclear waste immobilization, Materials 12(16) (2019) 2638.
[43] H. Jin, M.B. Ansari, S.E. Park, Mesoporous MFI zeolites by microwave induced assembly between sulfonic acid functionalized MFI zeolite nanoparticles and alkyltrimethylammonium cationic surfactants, Chem. Commun. 47(26) (2011) 7482-7484.
[44] T. Suzuki, T. Okuhara, Change in pore structure of MFI zeolite by treatment with NaOH aqueous solution, Microporous Mesoporous Mater. 43(1) (2001) 83-89.
[45] C.D. Lago, H.P. Decolatti, L.G. Tonutti, B.O. Dalla Costa, C.A. Querini, Gas phase glycerol dehydration over H-ZSM-5 zeolite modified by alkaline treatment with Na2CO₃, J. Catal. 366(2018) 16-27.
[46] J.C. Groen, J.A. Moulijn, J. Perez-Ramírez, Desilication: on the controlled generation of mesoporosity in MFI zeolites, J. Mater. Chem. 16(22) (2006) 2121-2131.

Ultrasonic-assisted rapid liquid-phase exfoliation of MFI-type zeolite nanoparticle aggregates

Ultrasonic-assisted rapid liquid-phase exfoliation of MFI-type zeolite nanoparticle aggregates

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