Hostname: page-component-669899f699-chc8l Total loading time: 0 Render date: 2025-04-26T22:26:50.798Z Has data issue: false hasContentIssue false
  • English
  • Français

Modification of Halloysite Nanotubes for Enhancement of Gas-Adsorption Capacity

Published online by Cambridge University Press:  01 January 2024

Sungho Lim ,
Sooji Park  and
Daewon Sohn Open the ORCID record for Daewon Sohn [Opens in a new window]
Sungho Lim
Affiliation:
Department of Chemistry and Research Institute for Convergence of Basic Science, Hanyang University, Seoul 04763, Korea
Sooji Park
Affiliation:
Department of Chemistry and Research Institute for Convergence of Basic Science, Hanyang University, Seoul 04763, Korea
Daewon Sohn*
Affiliation:
Department of Chemistry and Research Institute for Convergence of Basic Science, Hanyang University, Seoul 04763, Korea
*
*E-mail address of corresponding author: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

Structure control and quantitative evaluation of porous materials are essential for many industrial and consumer applications of clay minerals, and nanotubular halloysite (HNT) has been used extensively for such purposes; performance enhancements are still needed, however. The objective of the present study was to improve the gas-adsorption capacity of HNT by controlling the particle size and porosity. This was accomplished through acid treatment and particle-size fractionation by centrifugation. Various particle sizes were obtained and porosities ranged from macropores to mesopores. Natural halloysite nanotubes were modified by sulfuric acid in various concentrations to selectively remove the alumina composition of the tubes. X-ray diffraction and energy dispersive X-ray spectroscopy were used to verify the mineralogical and compositional changes. Surface modification by the acid treatment increased the inner space volume of the tubes and decreased the mass of the nanotubes because of the elimination of alumina. The gas adsorption capacity of both natural and modified halloysite nanotubes was measured quantitatively using N2 adsorption and the Brunauer-Emmett-Teller (BET) method, and the morphology was determined from transmission electron microscopy (TEM) images. The results showed that the modified halloysite nanotube was 7.47 times more efficient at gas adsorption than pristine halloysite. Moreover, the dealumination of the surface increased the inner space. Greatly increased porosity characteristics, including gas adsorption and macroporosity, were obtained through modification by acid treatment.

Keywords

Gas adsorptionHalloysitePorous materialsSelective surface modification
Type
Article
Information
Clays and Clay Minerals , Volume 68 , Issue 3 , June 2020 , pp. 189 - 196
Copyright
Copyright © Clay Minerals Society 2020

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Article purchase

Temporarily unavailable

References

Abdullayev, E., Sakakibara, K., Okamoto, K., Wei, W., Ariga, K., & Lvov, Y. (2011). Natural tubule clay template synthesis of silver nanorods for antibacterial composite coating. ACS Applied Materials & Interfaces, 3, 4040–4046.CrossRefGoogle ScholarPubMed
Abdullayev, E., Joshi, A., Wei, W., Zhao, Y., & Lvov, Y. (2012). Enlargement of halloysite clay nanotube lumen by selective etching of aluminum oxide. ACS Nano, 6, 7216–7226.CrossRefGoogle ScholarPubMed
Baiju, K., Shukla, S., Biju, S., Reddy, M., & Warrier, K. (2009). Hydrothermal processing of dye-adsorbing one-dimensional hydrogen titanate. Materials Letters, 63, 923–926.CrossRefGoogle Scholar
Barrett, E. P., Joyner, L. G., & Halenda, P. P. (1951). The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. Journal of the American Chemical Society, 73, 373–380.CrossRefGoogle Scholar
Chao, C., Liu, J., Wang, J., Zhang, Y., Zhang, B., Zhang, Y., Xiang, X., & Chen, R. (2013). Surface modification of halloysite nanotubes with dopamine for enzyme immobilization. ACS Applied Materials & Interfaces, 5, 10559–10564.CrossRefGoogle ScholarPubMed
Costanzo, P., & Giese, R. (1985). Dehydration of synthetic hydrated kaolinites: a model for the dehydration of halloysite (10 Å). Clays and Clay Minerals, 33, 415–423.CrossRefGoogle Scholar
De Silva, R., Pasbakhsh, P., Goh, K., Chai, S.-P., & Ismail, H. (2013). Physico-chemical characterisation of chitosan/halloysite composite membranes. Polymer Testing, 32, 265–271.CrossRefGoogle Scholar
Gorrasi, G. (2015). Dispersion of halloysite loaded with natural antimicrobials into pectins: characterization and controlled release analysis. Carbohydrate Polymers, 127, 47–53.CrossRefGoogle ScholarPubMed
Guimaraes, L., Enyashin, A. N., Seifert, G., & Duarte, H. A. (2010). Structural, electronic, mechanical properties of single-walled halloysite nanotube models. Journal of Physical Chemistry C, 114, 11358–11363.CrossRefGoogle Scholar
Guo, M., Wang, A., Muhammad, F., Qi, W., Ren, H., Guo, Y., & Zhu, G. (2012). Halloysite nanotubes, a multifunctional nanovehicle for anticancer drug delivery. Chinese Journal of Chemistry, 30, 2115–2120.CrossRefGoogle Scholar
Hong, C. H., Liu, Y. D., & Choi, H. J. (2013). Carbonyl iron suspension with halloysite additive and its magnetorheology. Applied Clay Science, 80, 366–371.CrossRefGoogle Scholar
Joo, Y., Sim, J. H., Jeon, Y., Lee, S. U., & Sohn, D. (2013). Opening and blocking the inner-pores of halloysite. Chemical Communications, 49, 4519–4521.CrossRefGoogle ScholarPubMed
Kamble, R., Ghag, M., Gaikawad, S., & Panda, B. K. (2012). Halloysite nanotubes and applications: a review. Journal of Advanced Scientific Research, 3, 25–29.Google Scholar
Kaneko, K. (1994). Determination of pore size and pore size distribution: 1. Adsorbents and catalysts. Journal of Membrane Science, 96, 59–89.CrossRefGoogle Scholar
Ko, J., Lee, J., Yoo, B., Ryu, J., & Sohn, D. (2016). Capillarity-induced selective ex-situ synthesis of metal–organic framework inside mesoporous nanotubes. Microporous and Mesoporous Materials, 220, 16–20.CrossRefGoogle Scholar
Lazzara, G., Cavallaro, G., Panchal, A., Fakhrullin, R., Stavitskaya, A., Vinokurov, V., & Lvov, Y. (2018). An assembly of organic-inorganic composites using halloysite clay nanotubes. Current Opinion in Colloid & Interface Science, 35, 42–50.CrossRefGoogle Scholar
Lippens, B. C., & De Boer, J. (1965). Studies on pore systems in catalysts: V. The t method. Journal of Catalysis, 4, 319–323.CrossRefGoogle Scholar
Liu, M., Zhang, Y., Wu, C., Xiong, S., & Zhou, C. (2012). Chitosan/halloysite nanotubes bionanocomposites: structure, mechanical properties and biocompatibility. International Journal of Biological Macromolecules, 51, 566–575.CrossRefGoogle ScholarPubMed
Luan, Z., He, H., Zhou, W., Cheng, C.-F., & Klinowski, J. (1995). Effect of structural aluminium on the mesoporous structure of MCM-41. Journal of the Chemical Society, Faraday Transactions, 91, 2955–2959.CrossRefGoogle Scholar
Luo, Z., Song, H., Feng, X., Run, M., Cui, H., Wu, L., Gao, J., & Wang, Z. (2013). Liquid crystalline phase behavior and sol–gel transition in aqueous halloysite nanotube dispersions. Langmuir, 29, 12358–12366.CrossRefGoogle ScholarPubMed
Lvov, Y., Aerov, A., & Fakhrullin, R. (2014). Clay nanotube encapsulation for functional biocomposites. Advances in Colloid and Interface Science, 207, 189–198.CrossRefGoogle ScholarPubMed
Lvov, Y., Wang, W., Zhang, L., & Fakhrullin, R. (2016). Halloysite clay nanotubes for loading and sustained release of functional compounds. Advanced Materials, 28, 1227–1250.CrossRefGoogle ScholarPubMed
Massaro, M., Riela, S., Cavallaro, G., Gruttadauria, M., Milioto, S., Noto, R., & Lazzara, G. (2014). Eco-friendly functionalization of natural halloysite clay nanotube with ionic liquids by microwave irradiation for Suzuki coupling reaction. Journal of Organometallic Chemistry, 749, 410–415.CrossRefGoogle Scholar
Mroczek, K., Kalisz, S., Pronobis, M., & Sołtys, J. (2011). The effect of halloysite additive on operation of boilers firing agricultural biomass. Fuel Processing Technology, 92, 845–855.CrossRefGoogle Scholar
Owoseni, O., Nyankson, E., Zhang, Y., Adams, S. J., He, J., McPherson, G. L., Bose, A., Gupta, R. B., & John, V. T. (2014). Release of surfactant cargo from interfacially-active halloysite clay nanotubes for oil spill remediation. Langmuir, 30, 13533–13541.CrossRefGoogle ScholarPubMed
Schull, C. (1948). The determination of pore size distribution from gas adsorption data. Journal of the American Chemical Society, 70, 1405–1410.CrossRefGoogle Scholar
Shi, Y.-F., Tian, Z., Zhang, Y., Shen, H.-B., & Jia, N.-Q. (2011). Functionalized halloysite nanotube-based carrier for intracellular delivery of antisense oligonucleotides. Nanoscale Research Letters, 6, 608.CrossRefGoogle ScholarPubMed
Shu, Z., Chen, Y., Zhou, J., Li, T., Yu, D., & Wang, Y. (2015). Nanoporous-walled silica and alumina nanotubes derived from halloysite: controllable preparation and their dye adsorption applications. Applied Clay Science, 112, 17–24.CrossRefGoogle Scholar
Szczepanik, B., Słomkiewicz, P., Garnuszek, M., Rogala, P., Banaś, D., Kubala-Kukuś, A., & Stabrawa, I. (2017). Effect of temperature on halloysite acid treatment for efficient chloroaniline removal from aqueous solutions. Clays and Clay Minerals, 65, 155–167.CrossRefGoogle Scholar
Tan, D., Yuan, P., Annabi-Bergaya, F., Yu, H., Liu, D., Liu, H., & He, H. (2013). Natural halloysite nanotubes as mesoporous carriers for the loading of ibuprofen. Microporous and Mesoporous Materials, 179, 89–98.CrossRefGoogle Scholar
Tazaki, K. (2005). Microbial formation of a halloysite-like mineral. Clays and Clay Minerals, 53, 224–233.CrossRefGoogle Scholar
Vergaro, V., Abdullayev, E., Lvov, Y. M., Zeitoun, A., Cingolani, R., Rinaldi, R., & Leporatti, S. (2010). Cytocompatibility and uptake of halloysite clay nanotubes. Biomacromolecules, 11, 820–826.CrossRefGoogle ScholarPubMed
Wu, H., Watanabe, H., Ma, W., Fujimoto, A., Higuchi, T., Uesugi, K., Takeuchi, A., Suzuki, Y., Jinnai, H., & Takahara, A. (2013). Robust liquid marbles stabilized with surface-modified halloysite nanotubes. Langmuir, 29, 14971–14975.CrossRefGoogle ScholarPubMed
Wu, X., Liu, C., Qi, H., Zhang, X., Dai, J., Zhang, Q., Zhang, L., Wu, Y., & Peng, X. (2016). Synthesis and adsorption properties of halloysite/carbon nanocomposites and halloysite-derived carbon nanotubes. Applied Clay Science, 119, 284–293.CrossRefGoogle Scholar
Xi, L., Xiaojie, J., Rui, X., Jiang, M., Jie, W., & Liangyin, C. (2013). Halloysite nanotube composited thermo-responsive hydrogel system for controlled-release. Chinese Journal of Chemical Engineering, 21, 991–998.Google Scholar
Yah, W. O., Takahara, A., & Lvov, Y. M. (2012a). Selective modification of halloysite lumen with octadecylphosphonic acid: new inorganic tubular micelle. Journal of the American Chemical Society, 134, 1853–1859.CrossRefGoogle ScholarPubMed
Yah, W. O., Xu, H., Soejima, H., Ma, W., Lvov, Y., & Takahara, A. (2012b). Biomimetic dopamine derivative for selective polymer modification of halloysite nanotube lumen. Journal of the American Chemical Society, 134, 12134–12137.CrossRefGoogle ScholarPubMed
Zhang, A.-B., Pan, L., Zhang, H.-Y., Liu, S.-T., Ye, Y., Xia, M.-S., & Chen, X.-G. (2012). Effects of acid treatment on the physico-chemical and pore characteristics of halloysite. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 396, 182–188.CrossRefGoogle Scholar