Hostname: page-component-745bb68f8f-5r2nc Total loading time: 0 Render date: 2025-01-14T23:18:49.307Z Has data issue: false hasContentIssue false
  • English
  • Français

Near-infrared spectroscopic analysis of acid-treated organo-clays

Published online by Cambridge University Press:  01 January 2024

Jana Madejová ,
Helena Pálková ,
Martin Pentrák  and
Peter Komadel
Jana Madejová*
Affiliation:
Institute of Inorganic Chemistry, SAS, Dúbravská cesta 9, SK-845 36 Bratislava, Slovakia
Helena Pálková
Affiliation:
Institute of Inorganic Chemistry, SAS, Dúbravská cesta 9, SK-845 36 Bratislava, Slovakia
Martin Pentrák
Affiliation:
Institute of Inorganic Chemistry, SAS, Dúbravská cesta 9, SK-845 36 Bratislava, Slovakia
Peter Komadel
Affiliation:
Institute of Inorganic Chemistry, SAS, Dúbravská cesta 9, SK-845 36 Bratislava, Slovakia
*
* E-mail address of corresponding author: [email protected]
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

The potential use of near-infrared (NIR) spectroscopy as a characterization tool for organo-clays would be a great asset but little work has been done in this regard because the application of NIR to clay mineral studies is a relatively new phenomenon. The purpose of this study was to use NIR spectroscopy to investigate the effect of alkylammonium cations on the acid dissolution of a high-charge montmorillonite (SAz-1). Detailed analysis of the spectra of Li+-, TMA+- (tetramethylammonium), and HDTMA+- (hexadecyltrimethylammonium) saturated SAz-1 montmorillonite in the NIR region was achieved by comparing the first overtone (2ν) and combination (ν+δ) bands of XH groups (X = O, C) with the fundamental stretching (ν) and bending (δ) vibrations observed in the mid-infrared (MIR) region. Comprehensive analysis of the vibrational modes of CH3-N, CH3-C, and -CH2-C groups of TMA+ and HDTMA+ cations detected in the MIR and NIR regions was also performed. Both MIR and NIR spectra demonstrated that exchange of Li+ by TMA+ only slightly improved the resistance of SAz-1 layers to dissolution in 6 M HCl at 80°C, while exchange by the larger HDTMA+ cations almost completely protected the montmorillonite layers from acid attack. Use of NIR spectra in reaching these conclusions was crucial. Only in the NIR region could the creation of SiOH groups be monitored, which is an important indicator of the acidification of the montmorillonite surface. The OH-overtone region in the spectra of Li-SAz-1 and TMA-SAz-1 revealed that the SiOH band near 7315 cm−1 increases in intensity with enhanced acid treatment. In contrast, no SiOH groups were identified in the NIR spectra of HDTMA-SAz-1 treated in HCl, indicating that HDTMA+ completely covers the inner and outer surfaces of the montmorillonite and hinders access ofprotons to the Si-O− bonds created upon acid treatment.

Keywords

Acid TreatmentAlkylammonium CationsNIR SpectroscopyOrgano-claysStructural Modifications
Type
Article
Information
Clays and Clay Minerals , Volume 57 , Issue 3 , June 2009 , pp. 392 - 403
Copyright
Copyright © The Clay Minerals Society 2009

References

Balan, E. Lazzeri, M. Delattre, S. Méheut, M. Refson, K. and Winkler, B., 2007 Anharmonicity ofinner-OH stretching modes in hydrous phyllosilicates: assessment from first-principles frozen-phonon calculations Physics and Chemistry of Minerals 34 621–625 10.1007/s00269-007-0176-4.CrossRefGoogle Scholar
Bishop, J.L. Pieters, C.M. and Edwards, J.O., 1994 Infrared spectroscopic analyses on the nature ofwater in montmorillonite Clays and Clay Minerals 42 702–716 10.1346/CCMN.1994.0420606.CrossRefGoogle Scholar
Bishop, J.L. Murad, E. Lane, M.D. and Mancinelli, R.L., 2004 Multiple techniques for mineral identification on Mars: a study of hydrothermal rocks as potential analogues for astrobiology sites on Mars Icarus 169 311–323 10.1016/j.icarus.2003.12.025.CrossRefGoogle Scholar
Bishop, J.L. Noe Dobrea, E.Z. McKeown, N.K. Parente, M. Ehlmann, B.L. Michalski, J.R. Milliken, R.E. Poulet, F. Swayze, G.A. Mustard, J.F. Murchie, S.L. and Bibring, J.-P., 2008 Phyllosilicate diversity and past aqueous activity revealed at Mawrth Vallis, Mars Science 321 830–833 10.1126/science.1159699.CrossRefGoogle ScholarPubMed
Bishop, J.L. Lane, M.D. Dyar, M.D. and Brown, A.J., 2008 Reflectance and emission spectroscopy study of four groups of phyllosilicates: smectites, kaolinite-serpentines, chlorites and micas Clay Minerals 43 35–54 10.1180/claymin.2008.043.1.03.CrossRefGoogle Scholar
Bokobza, L., 1998 Near infrared spectroscopy Journal of Near Infrared Spectroscopy 6 3–17 10.1255/jnirs.116.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 2 652–657 10.2136/sssaj1988.03615995005200030010x.CrossRefGoogle Scholar
Breen, C. Watson, R. Madejová, J. Komadel, P. and Klapyta, Z., 1997 Acid-activated organo-clays: Preparation, characterization and catalytic activity of acid-treated tetraalkylammonium-exchanged smectites Langmuir 13 6473–6479 10.1021/la970507w.CrossRefGoogle Scholar
Breen, C. and Watson, R., 1998 Acid-activated organo-clays: preparation, characterisation and catalytic activity of polycation-treated bentonites Applied Clay Science 12 479 10.1016/S0169-1317(98)00006-4.CrossRefGoogle Scholar
Dill, H.G. Kaufhold, S. Khishigsuren, S. and Bulgamaa, J., 2005 Discovery and origin of a Palaeogene smectite-bearing clay deposit in the SE Gobi (Mongolia) Clay Minerals 40 351–367 10.1180/0009855054030178.CrossRefGoogle Scholar
Farmer, V.C. and Farmer, V.C., 1974 The layer silicates Infrared Spectra of Minerals London Mineralogical Society 331–363 10.1180/mono-4.15.CrossRefGoogle Scholar
Frost, R.L. Kloprogge, J.T. and Ding, Z., 2002 Near-infrared spectroscopic study of nontronites and ferruginous smectite Spectrochimica Acta A 58 1657–1668 10.1016/S1386-1425(01)00637-0.CrossRefGoogle ScholarPubMed
Frost, R.L. Zhou, Q. He, H.P. and Xi, Y.F., 2008 An infrared study of adsorption of para-nitrophenol on mono-, di- and tri-alkyl surfactant intercalated organo-clays Spectrochimica Acta A 69 239–244 10.1016/j.saa.2007.02.023.CrossRefGoogle Scholar
Gates, W.P. and Kloprogge, J.T., 2005 Infrared spectroscopy and the chemistry of dioctahedral smectites The Application of Vibrational Spectroscopy to Clay minerals and Layered Duble Hydroxides Aurora, Colorado, USA The Clay Minerals Society 126–168.Google Scholar
Gates, W.P. Slade, P. Manceau, A. and Lanson, B., 2002 Site occupancies by iron in nontronites Clays and Clay Minerals 50 223–239 10.1346/000986002760832829.CrossRefGoogle Scholar
Gionis, V. Kacandes, G.H. Kastritis, I.D. and Chryssikos, G.D., 2007 Combined near-infrared and X-ray diffraction investigation of the octahedral sheet composition of palygorskite Clays and Clay Minerals 55 543–553 10.1346/CCMN.2007.0550601.CrossRefGoogle Scholar
Hunt, G.R. and Salisbury, J.W., 1970 Visible and near infrared spectra of minerals and rocks: VI. Silicate minerals Modern Geology 1 283–300.Google Scholar
Klapyta, Z. Fujita, T. and Iyi, N., 2001 Adsorption of dodecyl- and octadecyltrimethylammonium ions on smectite and synthetic micas Applied Clay Science 19 5–10 10.1016/S0169-1317(01)00059-X.CrossRefGoogle Scholar
Komadel, P. Madejová, J., Bergaya, F. Theng, B.K.G. and Lagaly, G., 2006 Acid activation of clay minerals Handbook of Clay Science Amsterdam Elsevier Ltd. 263–287 10.1016/S1572-4352(05)01008-1.CrossRefGoogle Scholar
Komadel, P. Madejová, J. Janek, M. Gates, W.P. Kirkpatrick, R.J. and Stucki, J.W., 1996 Dissolution of hectorite in inorganic acids Clays and Clay Minerals 44 228–236 10.1346/CCMN.1996.0440208.CrossRefGoogle Scholar
Kooli, F. and Magusin, C.M.M., 2005 Adsorption of cethyltrimethylammonium ions on an acid-activated smectite and their thermal stability Clay Minerals 40 233–243 10.1180/0009855054020169.CrossRefGoogle Scholar
Lagaly, G. Ogawa, M. Dékány, I., Bergaya, F. Theng, B.K.G. and Lagaly, G., 2006 Clay mineral organic interactions Handbook of Clay Science 309–377 10.1016/S1572-4352(05)01010-X.CrossRefGoogle Scholar
Madejová, J. and Kloprogge, J.T., 2005 Studies of reduced-charge smectites by near infrared spectroscopy The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides Aurora, Colorado, USA The Clay Minerals Society 169–202.Google Scholar
Madejová, J. and Komadel, P., 2001 Baseline studies of the Clay Minerals Society Source Clays: Infrared methods Clays and Clay Minerals 49 410–432 10.1346/CCMN.2001.0490508.CrossRefGoogle Scholar
Madejová, J. Bujdák, J. Petit, S. and Komadel, P., 2000 Effects of chemical composition and temperature of heating on the infrared spectra of Li-saturated dioctahedral smectites: (II) Near-infrared region Clay Minerals 35 753–761 10.1180/000985500547205.CrossRefGoogle Scholar
Madejová, J. Andrejkoviěová, S. Bujdák, J. Čeklovský, A. Hrachová, J. Valúchová, J. and Komadel, P., 2007 Characterization of products obtained by acid leaching of Fe-bentonite Clay Minerals 42 527–540 10.1180/claymin.2007.042.4.09.CrossRefGoogle Scholar
Madejová, J. Pentrák, M. Pálková, H. and Komadel, P., 2009 Near-infrared spectroscopy: a powerful tool in studies of acid-treated clay minerals Vibrational Spectroscopy 49 211–218 10.1016/j.vibspec.2008.08.001.CrossRefGoogle Scholar
Malley, D.F. Yesmin, L. and Eilers, R.G., 2002 Rapid analysis of hog manure and manure-amended soils using near-infrared spectroscopy Soil Science Society of America Journal 66 1677–1686 10.2136/sssaj2002.1677.CrossRefGoogle Scholar
Moronta, A. Ferrer, V. Quero, J. Arteaga, G. and Choren, E., 2002 Influence of preparation method on the catalytic properties ofacid-activated tetramethylammonium-exchanged clays Applied Catalysis A: General 230 127–135 10.1016/S0926-860X(01)01001-8.CrossRefGoogle Scholar
Önal, M. and Sankaya, Y., 2008 Some physicochemical properties of methylammonium and ethylenediammonium smectites Colloids Surfaces A: Physicochemical Engineering Aspects 312 56–61 10.1016/j.colsurfa.2007.06.023.CrossRefGoogle Scholar
Pálková, H. Madejová, J. and Righi, D., 2003 Acid dissolution of reduced-charge Li- and Ni-montmorillonites Clays and Clay Minerals 51 133–142 10.1346/CCMN.2003.0510202.CrossRefGoogle Scholar
Petit, S. and Kloprogge, J.T., 2005 Crystal-chemistry of talcs: a NIR and MIR spectroscopic approach The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides Aurora, Colorado, USA The Clay Minerals Society 41–64.Google Scholar
Petit, S. Madejová, J. Decarreau, A. and Martin, F., 1999 Characterization of octahedral substitutions in kaolinites using near infrared spectroscopy Clays and Clay Minerals 47 103–108 10.1346/CCMN.1999.0470111.CrossRefGoogle Scholar
Petit, S. Caillaud, J. Righi, D. Madejová, J. Elsass, F. and Köster, H.M., 2002 Characterization and crystal chemistry ofa Fe-rich montmorillonite Clay Minerals 37 283–297 10.1180/0009855023720034.CrossRefGoogle Scholar
Petit, S. Decarreau, A. Martin, F. and Buchet, R., 2004 Refined relationship between the position of the fundamental OH stretching and the first overtones for clays Physics and Chemistry of Minerals 31 585–592 10.1007/s00269-004-0423-x.CrossRefGoogle Scholar
Prüfer, H. and Mamma, D., 1995 Near-infrared online analysis of motor octane number in gasoline with an acoustooptic tunable transmission spectrophotometer Analysis 23 M14–M18.Google Scholar
Slade, P.G. and Gates, W.P., 2004 The swelling of HDTMA smectites as influenced by their preparation and layer charge Applied Clay Science 25 93–101 10.1016/j.clay.2003.07.007.CrossRefGoogle Scholar
Slade, P.G. and Gates, W.P., 2007 HDTMA in the interlayers of high-charged Llano vermiculite Clays and Clay Minerals 55 131–139 10.1346/CCMN.2007.0550202.CrossRefGoogle Scholar
Stevens, J.J. and Anderson, S.J., 1996 An FTIR study of water sorption on TMA- and TMPA-montmorillonites Clays and Clay Minerals 44 142–150 10.1346/CCMN.1996.0440113.CrossRefGoogle Scholar
Theng, B.K.G., 1974 The Chemistry of Clay-Organic Reactions London Adam Hilger.Google Scholar
Tkáč, I. Komadel, P. and Müller, D., 1994 Acid-treated montmorillonites — a study by 29Si and 27Al MAS-NMR Clay Minerals 29 11–19 10.1180/claymin.1994.029.1.02.CrossRefGoogle Scholar
Williams, P. and Norris, K., 1987 Near-infrared Technology in the Agricultural and Food Industries St. Paul, Minnesota, USA American Association of Cereal Chemists.Google Scholar
Workman, J. and Weyer, L., 2008 Practical Guide to Interpretive Near-infrared Spectroscopy Boca Raton, Florida, USA Taylor & Francis Group.Google Scholar
Yariv, S., Yariv, S. and Cross, H., 2001 IR spectroscopy and Thermo-IR spectroscopy in the study of the fine structure of organo-clay complexes Organo-clay Complexes and Interactions New York Marcel Dekker, Inc 345–462 10.1201/9781482270945.CrossRefGoogle Scholar
Yariv, S. and Cross, H. (2001) Organo-clay Complexes and Interactions. (Yariv, S. and Cross, H., editors). Marcel Dekker, Inc. New York.CrossRefGoogle Scholar
Zeegers-Huyskens, T. and Bator, G., 1996 Fourier transform infrared and Fourier transform Raman investigation of alkylammonium hexachloroantimonates Vibrational Spectroscopy 13 41–49 10.1016/0924-2031(96)00033-1.CrossRefGoogle Scholar
Zhou, Q. Xi, Y. He, H. and Frost, R.L., 2008 Application of near infrared spectroscopy for the determination of adsorbed p-nitrophenol on HDTMA organo-clay — implications for the removal of organic pollutants from water Spectrochimica Acta A 69 835–841 10.1016/j.saa.2007.05.037.CrossRefGoogle Scholar
Zhu, J. He, H. Zhu, L. Wen, X. and Deng, F., 2005 Characterization of organic phases in the interlayer of montmorillonite using FTIR and C-13 NMR Journal of Colloid and Interface Science 286 239–244 10.1016/j.jcis.2004.12.048.CrossRefGoogle Scholar