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Microstructure of HDTMA+-Modified Montmorillonite and its Influence on Sorption Characteristics

Published online by Cambridge University Press:  01 January 2024

Hongping He ,
Qin Zhou ,
Wayde N. Martens ,
Theo J. Kloprogge ,
Peng Yuan ,
Yunfei Xi ,
Jianxi Zhu  and
Ray L. Frost
Hongping He*
Affiliation:
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, QLD 4001, Australia
Qin Zhou
Affiliation:
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China Graduate University of Chinese Academy of Sciences, Beijing 100039, China
Wayde N. Martens
Affiliation:
Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, QLD 4001, Australia
Theo J. Kloprogge
Affiliation:
Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, QLD 4001, Australia
Peng Yuan
Affiliation:
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
Yunfei Xi
Affiliation:
Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, QLD 4001, Australia
Jianxi Zhu
Affiliation:
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
Ray L. Frost
Affiliation:
Inorganic Materials Research Program, School of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, QLD 4001, Australia
*
*E-mail address of corresponding author: hehp@gig.ac.cn
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Abstract

A series of organoclays with monolayers, bilayers, pseudotrilayers, paraffin monolayers and paraffin bilayers were prepared from montmorillonite by ion exchange with hexadecyltrimethylammonium bromide (HDTMAB). The HDTMAB concentrations used for preparing the organoclays were 0.5, 0.7, 1.0, 1.5, 2.0 and 2.5 times the montmorillonite cation exchange capacity (CEC). The microstructural parameters, including the BET-N2 surface area, pore volume, pore size, and surfactant loading and distribution, were determined by X-ray diffraction, N2 adsorption-desorption and high-resolution thermogravimetric analysis (HRTG). The BET-N2 surface area decreased from 55 to 1 m2/g and the pore volume decreased from 0.11 to 0.01 cm3/g as surfactant loading was increased from Na-Mt to 2.5CEC-Mt. The average pore diameter increased from 6.8 to 16.3 nm as surfactant loading was increased. After modifying montmorillonite with HDTMAB, two basic organoclay models were proposed on the basis of HRTG results: (1) the surfactant mainly occupied the clay interlayer space (0.5CEC-Mt, 0.7CEC-Mt, 1.0CEC-Mt); and (2) both the clay interlayer space and external surface (1.5CEC-Mt, 2.0CEC-Mt, 2.5CEC-Mt) were modified by surfactant. In model 1, the sorption mechanism of p-nitrophenol to the organoclay at a relatively low concentration involved both surface adsorption and partitioning, whereas, in model 2 it mainly involved only partitioning. This study demonstrates that the distribution of adsorbed surfactant and the arrangement of adsorbed HDTMA+ within the clay interlayer space control the efficiency and mechanism of sorption by the organoclay rather than BET-N2 surface area, pore volume, and pore diameter.

Keywords

BET-N2 Surface AreaHDTMA+OrganoclayPore SizePore VolumeSorption EfficiencySurfactant LoadingSorption Mechanism
Type
Research Article
Information
Clays and Clay Minerals , Volume 54 , Issue 6 , December 2006 , pp. 689 - 696
Copyright
Copyright © 2006, The Clay Minerals Society

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References

Al-Asheh, S. Banat, F. and Abu-Aitah, L., (2003) Adsorption of phenol using different types of activated bentonites Separation and Purification Technology 33 1–10 10.1016/S1383-5866(02)00180-6.CrossRefGoogle Scholar
Banat, F.A. Al-Bashir, B. Al-Asheh, S. and Hayajneh, O., (2000) Adsorption of phenol by bentonite Environmental Pollution 107 391–398 10.1016/S0269-7491(99)00173-6.CrossRefGoogle ScholarPubMed
Barrett, E.P. Joyner, L.G. and 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 10.1021/ja01145a126.CrossRefGoogle Scholar
Bergaya, F. and Lagaly, G., (2001) Surface modification of clay minerals Applied Clay Science 19 1–6 10.1016/S0169-1317(01)00063-1.CrossRefGoogle Scholar
Boyd, S.A. Lee, J.F. and Mortland, M.M., (1988) Attenuating organic contaminant mobility by soil modification Nature 333 345–349 10.1038/333345a0.CrossRefGoogle Scholar
Boyd, S.A. Mortland, M.M. and Chiou, C.T., (1988) Sorption characteristics of organic compounds on hexadecyltrimethylammonium smectite Soil Science Society of America Journal 52 652–657 10.2136/sssaj1988.03615995005200030010x.CrossRefGoogle Scholar
Brunauer, S. Demming, L.S. Demming, W.S. and Teller, E., (1940) On a theory of the van der Waals adsorption of gases Journal of the American Chemical Society 62 1723–1732 10.1021/ja01864a025.CrossRefGoogle Scholar
Celis, R. Hermonsín, M.C. and Cornejo, J., (2000) Heavy metal adsorption by functionalized clays Environmental Science and Technology 34 4593–4599 10.1021/es000013c.CrossRefGoogle Scholar
Chun, Y. Sheng, G.Y. and Boyd, S.A., (2003) Sorptive characteristics of tetra-alkylammonium-exchanged smectite clays Clays and Clay Minerals 51 415–420 10.1346/CCMN.2003.0510407.CrossRefGoogle Scholar
Cruz-Guzmán, M. Celis, R. Hermosin, M.C. and Cornejo, J., (2004) Adsorption of the herbicide simazine by montmor-illonite modified with natural organic cations Environmental Science and Technology 38 180–186 10.1021/es030057w.CrossRefGoogle ScholarPubMed
Gregg, S.J. and Sing, K.S.W., (1982) Adsorption, Surface Area and Porosity 2nd New York Academic Press chapters 2 and 3.Google Scholar
He, H.P. Guo, J.G. Xie, X.D. and Pen, J.L., (2001) Location and migration of cations in Cu2+-adsorbed montmorillonite Environment International 26 347–352 10.1016/S0160-4120(01)00011-3.CrossRefGoogle ScholarPubMed
He, H.P. Frost, R.L. and Zhu, J.X., (2004) Infrared study of HDTMA+ intercalated montmorillonite Spectrochimica Acta Part A 60 2853–2859 10.1016/S1386-1425(03)00337-8.Google Scholar
He, H.P. Frost, R.L. Xi, Y.F. and Zhu, J.X., (2004) Raman spectroscopic study of organo-montmorillonites Journal of Raman Spectroscopy 35 316–323 10.1002/jrs.1165.CrossRefGoogle Scholar
He, H.P. Frost, R.L. Deng, F. Zhu, J.X. Weng, X.Y. and Yuan, P., (2004) Conformation of surfactant molecules in the interlayer of montmorillonite studied by 13C MAS NMR Clays and Clay Minerals 52 350–356 10.1346/CCMN.2004.0520310.CrossRefGoogle Scholar
He, H.P. Ding, Z. Zhu, J.X. Yuan, P. Xi, Y.F. Yang, D. and Frost, R.L., (2005) Thermal characterization of surfactant-modified montmorillonites Clays and Clay Minerals 53 286–292 10.1346/CCMN.2005.0530308.CrossRefGoogle Scholar
He, H.P. Frost, R.L. Bostrom, T. Yuan, P. Duong, L. Yang, D. Xi, Y.F. and Kloprogge, T.J., (2006) Changes in the morphology with HDTMA+ surfactant loading Applied Clay Science 31 262–271 10.1016/j.clay.2005.10.011.CrossRefGoogle Scholar
Ishii, R. Nakatsuji, M. and Ooi, K., (2005) Preparation of highly porous silica nanocomposites from clay mineral: a new approach using pillaring method combined with selective Microporous and Mesoporous Materials 79 111–119 10.1016/j.micromeso.2004.10.033.CrossRefGoogle Scholar
Jaynes, W.F. and Boyd, S.A., (1991) Clay mineral type and organic compound sorption by hexadecyltrimethylammonium-exchanged clays Soil Science Society of American Journal 55 43–48 10.2136/sssaj1991.03615995005500010007x.CrossRefGoogle Scholar
Juang, R.S. Lin, S.H. and Tsao, K.H., (2002) Mechanism of sorption of phenols from aqueous solutions onto surfactant-modified montmorillonite Journal of Colloid and Interface Science 254 234–241 10.1006/jcis.2002.8629.CrossRefGoogle ScholarPubMed
Lagaly, G., (1981) Characterization of clays by organic compounds Clay Minerals 16 1–21 10.1180/claymin.1981.016.1.01.CrossRefGoogle Scholar
Lagaly, G. and Ziesmer, S., (2003) Colloid chemistry of clay minerals: the coagulation of montmorillonite dispersions Advances in Colloid and Interface Science 100 105–128 10.1016/S0001-8686(02)00064-7.CrossRefGoogle Scholar
Lee, J.F. Mortland, M.M. Chiou, C.T. Kile, D.E. and Boyd, S.A., (1990) Adsorption of benzene, toluene, and xylene by tetramethylammonium-smectites having different charge densities Clays and Clay Minerals 38 113–120 10.1346/CCMN.1990.0380201.CrossRefGoogle Scholar
Lee, S.Y. and Kim, S.J., (2002) Expansion characteristics of organoclay as a precursor to nanocomposites Colloid Surface A 211 19–26 10.1016/S0927-7757(02)00215-7.CrossRefGoogle Scholar
Mandalia, T. and Bergaya, F., (2006) Organo clay mineral-melted polyolefin nanocomposites effect of surfactant/CEC ratio Journal of Physics and Chemistry of Solids 67 836–845 10.1016/j.jpcs.2005.12.007.CrossRefGoogle Scholar
Ray, S.S. and Okamoto, M., (2003) Polymer/layered silicate nanocomposites: a review from preparation to processing Progress in Polymer Science 28 1539–1641 10.1016/j.progpolymsci.2003.08.002.Google Scholar
Regev, O. and Khan, A., (1996) Alkyl chain symmetry effects in mixed cationic-anionic surfactant systems Journal of Colloid and Interface Science 182 95–109 10.1006/jcis.1996.0440.CrossRefGoogle Scholar
Shen, Y.-H., (2001) Preparations of organobentonite using non-ionic surfactants Chemosphere 44 989–995 10.1016/S0045-6535(00)00564-6.CrossRefGoogle Scholar
Smith, J.A. and Galan, A., (1995) Soption of nonionic organic contaminants to single and dual organic cation bentonites from water Environmental Science and Technology 29 685–692 10.1021/es00003a016.CrossRefGoogle Scholar
Stackmeyer, M.R., (1991) Adsorption of organic compounds on organophilic bentonites Applied Clay Science 6 39–57 10.1016/0169-1317(91)90009-X.CrossRefGoogle Scholar
Vaia, R.A. Teukolsky, R.K. and Giannelis, E.P., (1994) Interlayer structure and molecular environment of alkylammonium layered silicates Chemistry of Materials 6 1017–1022 10.1021/cm00043a025.CrossRefGoogle Scholar
Wang, C.C. Juang, L.C. Lee, C.K. Hsu, T.C. Lee, J.F. and Chao, H.P., (2004) Effects of exchanged surfactant cations on the pore structure and adsorption characteristics of montmorillonite Journal of Colloid and Interface Science 280 27–35 10.1016/j.jcis.2004.07.009.CrossRefGoogle ScholarPubMed
Xi, Y.F. Frost, R.L. He, H.P. Kloprogge, J.T. and Bostrom, T., (2005) Modification of Wyoming montmorillonite surfaces using a cationic surfactant Langmuir 21 8675–8680 10.1021/la051454i.CrossRefGoogle ScholarPubMed
Xie, W. Xie, R.C. Pan, W.P. Hunter, D. Koene, B. Tan, L.S. and Vaia, R., (2002) Thermal stability of quaternary phosphonium modified montmorillonites Chemistry of Materials 14 4837–4845 10.1021/cm020705v.CrossRefGoogle Scholar
Yariv, S., (2004) The role of charcoal on DTA curves of organo-clay complexes: an overview Applied Clay Science 24 225–236 10.1016/j.clay.2003.04.002.CrossRefGoogle Scholar
Yaron-Marcovich, D. Chen, Y. Nir, S. and Prost, R., (2005) High resolution electron microscopy structural studies of organo-clay nanocomposites Environmental Science and Technology 29 1231–1238 10.1021/es049020h.CrossRefGoogle Scholar
Yilmaz, N. and Yapar, S., (2004) Adsorption properties of tetradecyl- and hexadecyltrimethylammonium bentonites Applied Clay Science 27 223–228 10.1016/j.clay.2004.08.001.CrossRefGoogle Scholar
Yui, T. Yoshida, H. Tachibana, H. Tryk, D.A. and Inoue, H., (2002) Intercalation of polyfluorinated surfactants into clay minerals and the characterization of the hybrid compounds Langmuir 18 891–896 10.1021/la011297x.CrossRefGoogle Scholar
Zeng, Q.H. Yu, A.B. Lu, G.Q. and Standish, R.K., (2004) Molecular dynamics simulation of the structural and dynamic properties of dioctadecyldimethyl ammoniums in organoclays Journal of Physics and Chemistry B 108 10025–10033 10.1021/jp037245t.CrossRefGoogle Scholar
Zhu, J.X. He, H.P. Guo, J.G. Yang, D. and Xie, X.D., (2003) Arrangement models of alkylammonium cations in the interlayer of HDTMA+ pillared montmorillonites Chinese Science Bulletin 48 368–372.Google Scholar
Zhu, L.Z. and Chen, B.L., (2000) Sorption behavior of p-nitrophenol on the interface between anion-cation organo-bentonite and water Environmental Science and Technology 34 2997–3002 10.1021/es991460z.CrossRefGoogle Scholar
Zhu, L.Z. Ren, X.G. and Yu, S.B., (1998) Use of cetyltrimethylammonium bromide bentonite to remove organic contaminants of varying polar character from water Environmental Science and Technology 32 3374–3378 10.1021/es980353m.CrossRefGoogle Scholar
Zhu, L.Z. Chen, B.L. and Shen, X.Y., (2000) Sorption of phenol, p-nitrophenol and aniline to dual-cation organobentonites from water Environmental Science and Technology 34 468–475 10.1021/es990177x.CrossRefGoogle Scholar