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Dehydration studies of natrolites: Role of monovalent extra-framework cations and degree of hydration

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Veröffentlicht/Copyright: 17. Juli 2017
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 102 Heft 7

Abstract

Rietveld refinements of natrolite analogs [M16Al16Si24O80·nH2O, M-NAT, M = Li, Na, Ag, K, NH4, Rb, and Cs, 14.0(1) < n <17.6(9)] at temperatures between 75 and 675 K using synchrotron X-ray powder diffraction reveal the impact H2O content and monovalent extra-framework cations (EFC) contained in the channels have on dehydration and thermal expansion. Dehydration temperatures are found to be inverse proportional to the size of the EFC. Isostructural K-, Rb-, and Cs-NAT with disordered EFC-H2O distribution exhibit negative thermal expansions before dehydration. The thermal expansion coefficients increase linearly from K-, Rb-, to Cs-NAT, the latter exhibits has the smallest thermal expansion coefficient of all NAT analogs [3.0(1) × 10−6 K−1]. After dehydration, the EFC distribution of K-, Rb-, and Cs-NAT becomes ordered and their thermal expansion coefficients become positive. In the isostructural Li-, Na-, and Ag-NAT with ordered EFC-H2O distribution, the thermal expansion coefficients are positive for the Li- and Ag-NAT and negative for Na-NAT. After dehydration, this behavior is reversed, and Li- and Ag-NAT show negative thermal expansion coefficients, whereas Na-NAT exhibits a positive thermal expansion. Upon dehydration, the channels in Li- and Ag-NAT reorient: the rotation angles of the fibrous chain units, ψ, change from 26.4(2)° to –29.6(2)° in Li-NAT and from 22.3(2)° to –23.4(2)° in Ag-NAT. The structure models of the dehydrated Li- and Ag-NAT reveal that the change in the channel orientation is due to the migration of the Li+ and Ag+ cations from the middle of the channel to the walls where they are then coordinated by four framework oxygen atoms. Further heating of these dehydrated phases results in structural collapse and amorphization. X-ray O1s K-edge absorption spectroscopy reveals that the binding energy between the EFC and the oxygen of the framework (Of) is larger in Li- and Ag-NAT than in Cs-NAT due to an increase of the basicity of the framework oxygen. The interaction between the H2O molecules and EFCs allow a clear separation in structures with disordered H2O molecules in the center of the channels (K-, NH4-, Rb-, and Cs-NAT) and those in close proximity to the aluminosilicate framework (Li-, Na-, and Ag-NAT), which leads to systematic dehydration and thermal expansion behaviors. Our structure work indicates that the effects of EFCs are more important to stabilize the NAT structure than the degree of hydration.

Keywords: Thermal expansion; natrolite; dehydration; rietveld refinement; oxygen K-edge X-ray absorption spectroscopy

Acknowledgments

This work was supported by the Global Research Laboratory (NRF-2009-00408) and National Research Laboratory (NRF-2015R1A2A1A01007227) Programs of the Korean Ministry of Science ICT and Planning (MSIP). We also thank the support of the NRF grants 2016K1A4A3914691 and 2016K1A3A7A09005244. In situ XRD experiment was performed at PAL, supported in part by the MEST and POSTECH, and at NSLS. XAS experiment was carried out at the SSRL, a Directorate of SLAC and an Office of Science User Facility operated by Stanford University for the U.S. Department of Energy Office of Science.

References cited

Baur, W.H., and Joswig, W. (1996) The phases of natrolite occuring during dehydration and rehydration studied by single-crystal X-ray diffraction methods between room temperature and 923K. Neues Jahrbuch für Mineralogie, 171–187.Suche in Google Scholar

Dollase, W.A. (1986) Correction of intensities for preferred orientation in powder diffractometry: Application of the March Model. Journal of Applied Crystallography, 19, 267–272.10.1107/S0021889886089458Suche in Google Scholar

Fang, J.H. (1963) Cell dimensions of dehydrated natrolite. American Mineralogist, 48, 414–417.Suche in Google Scholar

Hwang, G.C., Shin, T.J., Blom, D.A., Vogt, T., and Lee, Y. (2015) Pressure-induced amorphization of small pore zeolites—the role of cation-H2O topology and anti-glass formation. Scientific Reports, 5, 15056.10.1038/srep15056Suche in Google Scholar PubMed PubMed Central

Klaproth, M.H. (1803) Gesellschaft Naturforschende Freunde zu Berlin, Neue Schriften, 4, 243–248.Suche in Google Scholar

Kremleva, A., Vogt, T., and Rösch, N. (2013) Monovalent cation-exchanged natrolites and their behavior under pressure. A computational study. Journal of Physical Chemistry C,117, 19,020–19,030.10.1021/jp406037cSuche in Google Scholar

Larson, A., and von Dreele, R.B. (1986) General Structure Analysis System (GSAS). Los Alamos National Laboratory, New Mexico, Report LAUR, 86-748.Suche in Google Scholar

Lee, Y., Lee, Y., and Seoung, D. (2010) Natrolite may not be a “soda-stone” anymore: Structural study of fully K-, Rb-, and Cs-exchanged natrolite. American Mineralogist, 95, 1636–1641.10.2138/am.2010.3607Suche in Google Scholar

Lee, Y., Seoung, D., Jang, Y.N., Bai, J., and Lee, Y. (2011a) Structural studies of NH4-exchanged natrolites at ambient conditions and high temperature. American Mineralogist, 96, 1308–1315.10.2138/am.2011.3833Suche in Google Scholar

Lee, Y., Seoung, D., and Lee, Y. (2011b) Natrolite is not a “soda-stone” anymore: Structural study of alkali (Li+), alkaline-earth (Ca2+, Sr2+, Ba2+) and heavy metal (Cd2+, Pb2+, Ag+) cation-exchanged natrolites. American Mineralogist, 96, 1718–1724.10.2138/am.2011.3853Suche in Google Scholar

Lee, Y., Seoung, D., Liu, D., Park, M.B., Hong, S.B., Chen, H., Bai, J., Kao, C.-C., Vogt, T., and Lee, Y. (2011c) In-situ dehydration studies of fully K-, Rb-, and Cs-exchanged natrolites. American Mineralogist, 96, 393–401.10.2138/am.2011.3678Suche in Google Scholar

Lee, Y., Lee, J.-S., Kao, C.-C., Yoon, J.-H., Vogt, T., and Lee, Y. (2013) Role of cation–water disorder during cation exchange in small-pore zeolite sodium natrolite. The Journal of Physical Chemistry C,117, 16119–16126.10.1021/jp405360sSuche in Google Scholar

Pauling, L. (1930) The structure of some sodium and calcium aluminosilicates. Proceedings of the National Academy of Sciences,16, 453–459.10.1073/pnas.16.7.453Suche in Google Scholar PubMed PubMed Central

Reeuwijk, V. (1972) High-temperature phases of zeolites of the natrolite group. American Mineralogist, 57, 499–510.Suche in Google Scholar

Rietveld, H.M. (1969) A profile refinement method for nuclear and magnetic structures. Journal of Applied Crystallography, 2, 65–71.10.1107/S0021889869006558Suche in Google Scholar

Rinne, F. (1890) Über die umänderungen welche die zeolithe durch erwärmen bei und nach dem trübwerden erfahren. Sitzungsberichte der Preussischen Akademie der Wissenschaften, Physikalisch-Mathematische Klasse, 46, 1163–1207.Suche in Google Scholar

Seoung, D., Lee, Y., Kao, C.C., Vogt, T., and Lee, Y. (2013) Super-hydrated zeolites: Pressure-induced hydration in natrolites. Chemistry—A European Journal, 19, 10,876–10,883.10.1002/chem.201300591Suche in Google Scholar

Seoung, D., Lee, Y., Kao, C.C., Vogt, T., and Lee, Y. (2015) Two-step pressure-induced superhydration in small pore natrolite with divalent extra-framework cations. Chemistry of Materials, 27, 3874–3880.10.1021/acs.chemmater.5b00506Suche in Google Scholar

Stahl,K., and Hanson, J. (1994) Real-time X-ray synchrotron powder diffraction studies of the dehydration processes in scolecite and mesolite. Journal of Applied Crystallography, 27, 543–550.10.1107/S002188989301235XSuche in Google Scholar

Thompson, P., Cox, D.E., and Hastings, J.B. (1987) Rietveld refinement of Debye-Scherrer synchrotron X-ray data from Al2O3. Journal of Applied Crystallography, 20, 79–83.10.1107/S0021889887087090Suche in Google Scholar

Toby, B.H. (2001) EXPGUI, a graphical user interface for GSAS. Journal of Applied Crystallography, 34, 210–213.10.1107/S0021889801002242Suche in Google Scholar

Vayssilov, G.N., and Rösch, N. (1999) Density functional studies of alkali-exchanged zeolites: Basicity and core-level shifts of framework oxygen atoms. Journal of Catalysis, 186, 423–432.10.1006/jcat.1999.2571Suche in Google Scholar

Wang, H.-W., and Bish, D.L. (2008) A PH2O-dependent structural phase transition in the zeolite natrolite. American Mineralogist, 93, 1191–1194.10.2138/am.2008.2949Suche in Google Scholar

Wernet, P., Nordlund, D., Bergmann, U., Cavalleri, M., Odelius, N., Ogasawara, H., Näslund, L.Å., Hirsch, T.K., Ojamäe, L., Glatzel, P., Pettersson, L.G.M., and Nilsson, A. (2004) The structure of the first coordination shell in liquid water. Science, 304, 995–999.10.1126/science.1096205Suche in Google Scholar

Wu, L., Navrotsky, A., Lee, Y., and Lee, Y. (2013) Thermodynamic study of alkali and alkaline-earth cation-exchanged natrolites. Microporous and Mesoporous Materials, 167, 221–227.10.1016/j.micromeso.2012.09.003Suche in Google Scholar

Yamazaki, A., Otsuka, R., and Nishido, H. (1986) The thermal behavior of K-exchanged forms of natrolite. Thermochimica Acta, 109, 237–242.10.1016/0040-6031(86)85024-9Suche in Google Scholar

Received: 2016-6-27
Accepted: 2017-2-26
Published Online: 2017-7-17
Published in Print: 2017-7-26

© 2017 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2017-5902
Schlagwörter für diesen Artikel
Thermal expansion; natrolite; dehydration; rietveld refinement; oxygen K-edge X-ray absorption spectroscopy

Artikel in diesem Heft

  1. Editorial
  2. A new high JIF for American Mineralogist (by all early indications), why you shouldn’t care, and a note on values
  3. Highlights and Breakthroughs
  4. Sapphire, a not so simple gemstone
  6. Radon emanation coefficients of several minerals: How they vary with physical and mineralogical properties
  7. Actinides in geology, energy, and the environment
  8. Cabvinite, Th2F7(OH)⋅3H2O, the first natural actinide halide
  9. Special collection: apatite: a common mineral, uncommonly versatile
  10. Cathodoluminescence images and trace element compositions of fluorapatite from the Hongge layered intrusion in SW China: A record of prolonged crystallization and overprinted fluid metasomatism
  11. Special Collection: Nanominerals and Mineral Nanoparticles
  12. Structural characterization of marine nano-quartz in chalk and flint from North Sea Tertiary chalk reservoirs for oil and gas
  13. Special collection: Geology and geobiology of lassen volcanic national park
  14. Secondary minerals associated with Lassen fumaroles and hot springs: Implications for martian hydrothermal deposits
  16. Phillipsite and Al-tobermorite mineral cements produced through low-temperature water-rock reactions in Roman marine concrete
  18. The origin of needle-like rutile inclusions in natural gem corundum: A combined EPMA, LA-ICP-MS, and nanoSIMS investigation
  20. Dehydration studies of natrolites: Role of monovalent extra-framework cations and degree of hydration
  22. Mineralogical and compositional features of rock fulgurites: A record of lightning effects on granite
  24. Formation of basic lead phases during fire-setting and other natural and man-made processes
  26. Revisiting the nontronite Mössbauer spectra
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  30. Hydrothermal alteration of monazite-(Ce) and chevkinite-(Ce) from the Sin Quyen Fe-Cu-LREE-Au deposit, northwestern Vietnam
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  35. Letter
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  38. New Mineral Names
  40. Erratum
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