Hostname: page-component-848d4c4894-jbqgn Total loading time: 0 Render date: 2024-07-01T00:59:28.993Z Has data issue: false hasContentIssue false
  • English
  • Français

Dehydration and rehydration of palygorskite and the influence of water on the nanopores

Published online by Cambridge University Press:  01 January 2024

Wenxing Kuang ,
Glenn A. Facey  and
Christian Detellier
Wenxing Kuang
Affiliation:
Center for Catalysis Research and Innovation and Department of Chemistry, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5
Glenn A. Facey
Affiliation:
Center for Catalysis Research and Innovation and Department of Chemistry, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5
Christian Detellier*
Affiliation:
Center for Catalysis Research and Innovation and Department of Chemistry, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5
*
*E-mail address of corresponding author: dete@science.uottawa.ca
Get access Rights & Permissions [Opens in a new window]

Abstract

The dehydration and rehydration processes of the clay mineral palygorskite (PFl-1) were studied by textural analysis, thermogravimetric analysis connected with mass spectrometry (TGA-MS), and 29Si and 1H solid-state NMR techniques. The TGA-MS results clearly reveal weight losses at maxima of 70°C, 190°C, 430°C and 860°C. PFl-1 is characterized by a micropore area of 93 m2/g, corresponding to a micropore volume of 47 mm3/g. These values are also obtained for the sample heated up to 200°C for 20 h. Further heating at 300°C produces a collapse of the structure, as shown by the almost complete loss of microporosity.

The 29Si NMR spectra of palygorskite show two main resonances at −92.0 and −97.5 ppm, attributed to one of the two pairs of equivalent Si nuclei in the basal plane. A minor resonance at −84.3 ppm is attributed to Q2(Si-OH) Si nuclei. The resonance at −92.0 ppm is assigned to the central Si position, while the resonance at −97.5 ppm is assigned to the edge Si sites. It is confirmed bysolid-state 29Si and 1H NMR that nearly complete rehydration is achieved by exposing palygorskite samples that have been partially dehydrated at 150°C and 300°C, to D2O or water vapor at room temperature. When the rehydration is accomplished with D2O, the atoms are disordered across all the protons sites.

Keywords

Clay MineralsMicroporosityPalygorskiteSepioliteTextural AnalysisTGA-MS29Si NMR
Type
Research Article
Information
Clays and Clay Minerals , Volume 52 , Issue 5 , October 2004 , pp. 635 - 642
Copyright
Copyright © 2004, The Clay Minerals Society

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.)

References

Artioli, G. and Galli, E., (1994) The crystal structures of orthorhombic and monoclinic palygorskite Materials Science Forum 166–169 647–652 10.4028/www.scientific.net/MSF.166-169.647.Google Scholar
Artioli, G., Galli, E., Burattini, E., Cappuccio, G. and Simeoni, S. (1994) Palygorskite from Bolca, Italy: a characterization byhigh-resolution synchrotron radiation powder diffraction and computer modeling. Neues Jahrbuch für Mineralogie, Monatshefte, 217–229.Google Scholar
Augsburger, M.S. Strasser, E. Perino, E. Mercader, R.C. and Pedregosa, J.C., (1998) FTIR and Mössbauer investigation of a substituted palygorskite: silicate with a channel structure Journal of Physics and Chemistry of Solids 59 175–180 10.1016/S0022-3697(97)00166-2.Google Scholar
Barrer, R.M. and Mackenzie, N., (1954) Sorption by attapulgite. I. Availabilityof intracrystalline channels Journal of Physical Chemistry 58 560–568 10.1021/j150517a013.Google Scholar
Barron, P.F. and Frost, R.L., (1985) Solid-state 29Si NMR examination of the 2:1 ribbon maganesium silicates, sepiolite and palygorskite American Mineralogist 70 758–766.Google Scholar
Birsoy, R., (2002) Formation of sepiolite-palygorskite and related minerals from solution Clays and Clay Minerals 50 736–745 10.1346/000986002762090263.Google Scholar
Borden, D. and Giese, R.F., (2001) Baseline studies of the Clay Minerals Societysource clays: cation exchange capacity measurements by the ammonia-electrode method Clays and Clay Minerals 49 444–445 10.1346/CCMN.2001.0490510.Google Scholar
Bradley, W.F., (1940) The structural scheme of attapulgite American Mineralogist 25 405–410.Google Scholar
Cases, J.M. Grillet, Y. Francois, M. Michot, L. Villieras, F. and Yvon, J., (1991) Evolution of the porous structure and surface area of palygorskite under vacuum thermal treatment Clays and Clay Minerals 39 191–201 10.1346/CCMN.1991.0390211.Google Scholar
Chahi, A. Petit, S. and Decarreau, A., (2002) Infrared evidence of dioctahedral-trioctahedral site occupancyin palygorskite Clays and Clay Minerals 50 306–313 10.1346/00098600260358067.Google Scholar
Chiari, G. Giustetto, R. and Ricchiardi, G., (2003) Crystal structure refinements of palygorskite and Maya Blue from molecular modelling and powder synchrotron diffraction European Journal of Mineralogy 15 21–33 10.1127/0935-1221/2003/0015-0021.Google Scholar
Chipera, S.J. and Bish, D.L., (2001) Baseline studies of the Clay Minerals Societysource clays: powder X-raydiffraction analyses Clays and Clay Minerals 49 398–409 10.1346/CCMN.2001.0490507.Google Scholar
Chisholm, J.E., (1990) An X-raypowder-diffraction study of palygorskite The Canadian Mineralogist 28 329–339.Google Scholar
Chisholm, J.E., (1992) Powder-diffraction patterns and structural models for palygorskite The Canadian Mineralogist 30 61–73.Google Scholar
Costanzo, P.M. and Guggenheim, S., (2001) editors () Baseline studies of the Clay Minerals Society source clays. Clays and Clay Minerals, 49, 371–452.Google Scholar
de la d’Espinose Caillerie, J.-B. and Fripiat, J.J., (1994) A reassessment of the 29Si MAS-NMR spectra of sepiolite and aluminated sepiolite Clay Minerals 29 313–318 10.1180/claymin.1994.029.3.02.Google Scholar
Fernandez, M.E. Ascencio, J.A. Mendoza-Anaya, D. Rodriguez Lugo, V. and Jose-Yacaman, M., (1999) Experimental and theoretical studies of palygorskite clays Journal of Materials Science 34 5243–5255 10.1023/A:1004724316051.Google Scholar
Fois, E. Gamba, A. and Tilocca, A., (2003) On the unusual stability of Maya blue paint: molecular dynamics simulations Microporous and Mesoporous Materials 57 263–272 10.1016/S1387-1811(02)00596-6.Google Scholar
Frost, R.L. and Ding, Z., (2003) Controlled rate thermal analysis and differential scanning calorimetry of sepiolites and palygorskites Thermochimica Acta 397 119–128 10.1016/S0040-6031(02)00228-9.Google Scholar
Frost, R.L. Cash, G.A. and Kloprogge, J.T., (1998) ‘Rocky Mountain leather’, sepiolite and attapulgite — an infrared emission spectroscopic study Vibrational Spectroscopy 16 173–184 10.1016/S0924-2031(98)00014-9.Google Scholar
Frost, R.L. Locos, O.B. Ruan, H. and Kloprogge, J.T., (2001) Near-infrared and mid-infrared spectroscopic study of sepiolites and palygorskites Vibrational Spectroscopy 27 1–13 10.1016/S0924-2031(01)00110-2.Google Scholar
Galán, E., (1996) Properties and applications of palygorskitesepiolite clays Clay Minerals 31 443–453 10.1180/claymin.1996.031.4.01.Google Scholar
Galán, E. and Carretero, M.I., (1999) A new approach to compositional limits for sepiolite and palygorskite Clays and Clay Minerals 47 399–409 10.1346/CCMN.1999.0470402.Google Scholar
Gonzalez, F. Pesquera, C. Blanco, C. Benito, I. Mendioroz, S. and Pajares, J.A., (1989) Structural and textural evolution of Al- and Mg-rich palygorskites, I. Under acid treatment Applied Clay Science 4 373–388 10.1016/0169-1317(89)90043-4.Google Scholar
Guggenheim, S. and van Koster Groos, A.F., (2001) Baseline studies of the ClayMinerals Societysource clays: thermal analysis Clays and Clay Minerals 49 433–443 10.1346/CCMN.2001.0490509.Google Scholar
Güven, N. de la d’Espinose Caillerie, J.-B. and Fripiat, J.J., (1992) The coordination of aluminum ions in the palygorskite structure Clays and Clay Minerals 40 457–461 10.1346/CCMN.1992.0400410.Google Scholar
Horvath, G. and Kawazoe, K., (1983) Method for the calculation of effective pore size distribution in molecular sieve carbon Journal of Chemical Engineering of Japan 16 470–475 10.1252/jcej.16.470.Google Scholar
Hubbard, B. Kuang, W. Moser, A. Facey, G.A. and Detellier, C., (2003) Structural study of Maya blue: textural, thermal and solid state multinuclear magnetic resonance characterization of the palygorskite-indigo and sepiolite-indigo adducts Clays and Clay Minerals 51 318–326 10.1346/CCMN.2003.0510308.Google Scholar
Jones, B.F. Galán, E. and Bailey, S.W., (1988) Sepiolite and palygorskite Hydrous Phyllosilicates Washington, D.C Mineralogical Society of America 631–674 10.1515/9781501508998-021.Google Scholar
Kleber, R. Masschelein-Kleiner, L. and Thissen, J., (1967) Study and identification of Maya blue Studies in Conservation 12 41–56 10.1179/sic.1967.s005.Google Scholar
Komarneni, S. Fyfe, C.A. and Kennedy, G.J., (1986) Detection of nonequivalent Si sites in sepiolite and palygorskite by solid-state 29Si Magic Angle Spinning-Nuclear Magnetic Resonance Clays and Clay Minerals 34 99–102 10.1346/CCMN.1986.0340113.Google Scholar
Kuang, W. Facey, G.A. Detellier, C. Casal, B. Serratosa, J.M. and Ruiz-Hitzky, E., (2003) Nanostructured hybrid materials formed bysequestration of pyridine molecules in the tunnels of sepiolite Chemistry of Materials 15 4956–4967 10.1021/cm034867i.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.Google Scholar
McKeown, D.A. Post, J.E. and Etz, E.S., (2002) Vibrational analysis of palygorskite and sepiolite Clays and Clay Minerals 50 667–680 10.1346/000986002320679549.Google Scholar
Mermut, A.R. and Cano, A.F., (2001) Baseline studies of the Clay Minerals Society source clays: chemical analysis of major elements Clays and Clay Minerals 49 381–386 10.1346/CCMN.2001.0490504.Google Scholar
Murray, H.H., (1991) Overview — clay mineral applications Applied Clay Science 5 379–395 10.1016/0169-1317(91)90014-Z.Google Scholar
Murray, H.H., (1999) Applied clay mineralogy today and tomorrow Clay Minerals 34 39–49 10.1180/000985599546055.Google Scholar
Murray, H.H., (2000) Traditional and new applications for kaolin, smectite, and palygorskite: a general overview Applied Clay Science 17 207–221 10.1016/S0169-1317(00)00016-8.Google Scholar
Polette, L.A. Meitzner, G. Yacamán, M.J. and Chianelli, R.R., (2002) Maya blue: application of XAS and HRTEM to materials science in art and archaeology Microchemical Journal 71 167–174 10.1016/S0026-265X(02)00008-5.Google Scholar
Preisinger, A., (1963) Sepiolite and related compounds: its stabilityand application Clays and Clay Minerals 10 365–371 10.1346/CCMN.1961.0100132.Google Scholar
Sanz, J., Moltana, A. and Burragato, F., (1990) Distribution of ions in phyllosilicates by NMR spectroscopy Absorption Spectroscopy in Mineralogy Amsterdam Elsevier 103–144.Google Scholar
Serna, C.J. and VanScoyoc, G.E., (1979) Infrared study of sepiolite and palygorskite surfaces Proceedings of the International Clay Conference, Oxford Amsterdam Elsevier 197–206 1978.Google Scholar
Serna, C. VanScoyoc, G.E. and Ahlrichs, J.L., (1977) Hydroxyl groups and water in palygorskite American Mineralogist 62 784–792.Google Scholar
Serratosa, J.M., (1979) Surface properties of fibrous clay minerals (palygorskite and sepiolite) Proceedings of the International Clay Conference, Oxford, 1978 Amsterdam Elsevier 99–109.Google Scholar
Shariatmadari, H. Mermut, A.R. and Benke, M.B., (1999) Sorption of selected cationic and neutral organic molecules on palygorskite and sepiolite Clays and Clay Minerals 47 44–53 10.1346/CCMN.1999.0470105.Google Scholar
Shore, J.S., DePaul, S., Ernst, M. and Phillips, B.L. (1998) Double-resonance and two-dimensional Silicon-29 NMR spectroscopy of minerals. Pp. 305–325 in: Solid-State Nuclear Magnetic Resonance of Inorganic Materials (Fitzgerald, J.J., editor). ACS Symposium Series, 717, American Chemical Society.Google Scholar
Shuali, U. Yariv, S. Steinberg, M. Muller-Vonmoos, M. Kahr, G. and Rub, A., (1988) Thermal analysis study of the adsorption of heavy water by sepiolite and palygorskite Thermochimica Acta 135 291–297 10.1016/0040-6031(88)87400-8.Google Scholar
Shuali, U. Steinberg, M. Yariv, S. Muller-Vonmoos, M. Kahr, G. and Rub, A., (1990) Thermal analysis of sepiolite and palygorskite treated with butylamine Clay Minerals 25 107–119 10.1180/claymin.1990.025.1.12.Google Scholar
Sidheswaran, P., (2002) Heat-induced structural modifications in palygorskite Clay Research 21 27–39.Google Scholar
Suárez Barrios, M. Flores González, L.V. Vicente Rodríguez, M.A. and Martín Pozas, J.M., (1995) Acid activition of a palygorskite with HCl: development of physico-chemical, textural and surface properties Applied Clay Science 10 247–258 10.1016/0169-1317(95)00007-Q.Google Scholar
van Olphen, H., (1966) Maya Blue: a clay mineral-organic pigment? Science 154 645–646 10.1126/science.154.3749.645.Google Scholar
van Olphen, H. and Fripiat, J.J., (1979) Data Handbook for Clay Materials and Other Non-Metallic Minerals Oxford, England Pergamon Press 346 pp.Google Scholar
VanScoyoc, G.E. Serna, C.J. and Ahlrichs, J.L., (1979) Structural changes in palygorskite during dehydration and dehydroxylation American Mineralogist 64 215–223.Google Scholar
Webb, P.A. and Orr, C., (1997) Analytical Methods in Fine Particle Technology Norcross, Georgia Micromeritics Instrument Corporation 301 pp.Google Scholar
Weir, M.R. Facey, G.A. and Detellier, C., (2000) 1H, 2H, and 29Si solid state NMR studyof guest acetone molecules occupying the zeolitic channels of partially dehydrated sepiolite clay Studies in Surface Science and Catalysis 129 551–558 10.1016/S0167-2991(00)80257-8.Google Scholar
Weir, M.R. Kuang, W. Facey, G.A. and Detellier, C., (2002) Solid state nuclear magnetic resonance study of sepiolite and partially dehydrated sepiolite Clays and Clay Minerals 50 240–247 10.1346/000986002760832838.Google Scholar
Wu, W., (2001) Baseline studies of the Clay Minerals Society source clays: Colloid and surface phenomena Clays and Clay Minerals 49 446–452 10.1346/CCMN.2001.0490511.Google Scholar
Yacamán, M.J. Rendon, L. Arenas, J. and Puche, M.C.S., (1996) Maya blue paint: an ancient nanostructured material Science 273 223–225 10.1126/science.273.5272.223.Google Scholar