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2007 | 5 | 2 | 420-454

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Behaviour of pure water and water mixture with benzene or chloroform adsorbed onto ordered mesoporous silicas


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Structural characteristics of synthesized ordered mesoporous silicas MCM-41, MCM-48 and SBA-15 were studied using XRD, nitrogen adsorption and FTIR methods. Pure water and mixtures with water/benzene and water/chloroform-d adsorbed onto silicas were studied by 1H NMR spectroscopy with layer-by-layer freezing-out of bulk and interfacial liquids. Concentrated aqueous suspensions of MCM-48 and SBA-15 were studied by thermally stimulated depolarization current (TSDC) method. Benzene and chloroform-d can displace a portion of water to broad pores from the pore walls and from narrower pores, especially in the case of a large excess of an organic solvent. This process is accompanied by diminution of both interaction energy of water with an adsorbent surface and freezing temperature depression of adsorbed water. The effect of nonpolar benzene on pore water is much stronger than that of weakly polar chloroform-d. Modifications of the Gibbs-Thomson relation to describe the freezing point depression of mixtures of immiscible liquids confined in pores allow us to determine distribution functions of sizes of structures with unfrozen pore water and benzene. [...]










Physical description


1 - 6 - 2007
26 - 1 - 2007


  • Institute of Surface Chemistry, 03164, Kiev, Ukraine
  • Institute of Surface Chemistry, 03164, Kiev, Ukraine
  • Taras Shevchenko University, Kiev, 01030, Ukraine
  • Institute of Surface Chemistry, 03164, Kiev, Ukraine
  • Taras Shevchenko University, Kiev, 01030, Ukraine
  • Institute of Surface Chemistry, 03164, Kiev, Ukraine
  • Institute of Surface Chemistry, 03164, Kiev, Ukraine
  • Institute of Surface Chemistry, 03164, Kiev, Ukraine


  • [1] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt, C.T.W. Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B. Higgins and J.L. Schlenker: “A new family of mesoporous molecular sieves prepared with liquid crystal templates”, J. Am. Chem. Soc., Vol. 114, (1992), pp. 10834–10843. http://dx.doi.org/10.1021/ja00053a020[Crossref]
  • [2] L. Bonneviot, F. Belard, C. Danumah, S. Giasson and S. Kaliaguine (Eds.: Mesoporous Molecular Sieves, Studies in Surface Science and Catalysis, Vol. 117, Elsevier, Amsterdam, 1998.
  • [3] A. Davidson: “Modifying the walls of mesoporous silicas prepared by supramolecular-templating”, Curr. Opin. Colloid In. Sci., Vol. 7, (2002), pp. 92–106. http://dx.doi.org/10.1016/S1359-0294(02)00011-0[Crossref]
  • [4] U. Ciesla and F. Schüth: “Ordered mesoporous materials”, Micropor. Mesopor. Mater., Vol. 27, (1999), pp. 131–149. http://dx.doi.org/10.1016/S1387-1811(98)00249-2[Crossref]
  • [5] C.J. Brinker and G.W. Scherer: Sol-Gel Science, The Physics and Chemistry of Sol-Gel Processing, Academic Press, New York, 1990.
  • [6] L.P. Legrand (Ed.): The Surface Properties of Silicas, Wiley, New York, 1998.
  • [7] M.M.L. Ribeiro Carrott, A.J.E. Candeias, P.J.M. Carrott, P.I. Ravikovitch, A.V. Neimark and A.D. Sequeira: “Adsorption of nitrogen, neopentane, n-hexane, benzene and methanol for evaluation of pore size in silica grades of MCM-41”, Micropor. Mesopor. Mater. Vol. 47, (2001), pp. 323–337. http://dx.doi.org/10.1016/S1387-1811(01)00394-8[Crossref]
  • [8] W. Zhou and J. Klinowski: “The mechanism of channel formation in the mesoporous molecular sieve MCM-41”, Chem. Phys. Lett., Vol. 292, (1998), pp. 207–212. http://dx.doi.org/10.1016/S0009-2614(98)00606-X[Crossref]
  • [9] V.V. Guliants, M.A. Carreon and Y.S. Lin: “Ordered mesoporous and macroporous inorganic films and membranes”, J. Membrane Sci., Vol. 235, (2004), 53–72. http://dx.doi.org/10.1016/j.memsci.2004.01.019[Crossref]
  • [10] M. Jaroniec, M. Kruk, H.J. Shin, R. Ryoo, Y. Sakamoto and O. Terasaki: “Comprehensive characterization of highly ordered MCM-41 silicas using nitrogen adsorption, thermogravimetry, X-ray difraction and transmission electron microscopy”, Micropor. Mesopor. Mater., Vol. 48, (2001), pp. 127–134. http://dx.doi.org/10.1016/S1387-1811(01)00335-3[Crossref]
  • [11] D. Kumar, K. Shumacher, C. du Fresne von Hohenesche, M. Grün and K.K. Unger: “MCM-41, MCM-48 and related mesoporous adsorbents: their synthesis and characterisation”, Colloid Surf. A, Vol. 187-188, (2001), pp. 109–116. http://dx.doi.org/10.1016/S0927-7757(01)00638-0[Crossref]
  • [12] M. Chaplin: “Water Structure and Behaviour”, http://www.lsbu.ac.uk/water/.
  • [13] V.M. Gun’ko, V.V. Turov, V.M. Bogatyrev, V.I. Zarko, R. Leboda, E.V. Goncharuk, A.A. Novza, A.V. Turov and A.A. Chuiko: “Unusual properties of water at hydrophilic/hydrophobic interfaces”, Adv. Colloid Interfac. Sci., Vol. 118, (2005), pp. 125–172.
  • [14] S. Sklari, H. Rahiala, V. Stathopoulos, J. Rosenhjlm and P. Pomonis: “The influence of surface acid density on the freezing behavior of water confined in mesoporous MCM-41 solids”, Micropor. Mesopor. Mater., Vol. 49, (2001), pp. 1–13. http://dx.doi.org/10.1016/S1387-1811(01)00371-7[Crossref]
  • [15] M. Sliwinska-Bartkowiak, G. Dudzoak, R. Gras, R. Sikorski, R. Radhakrishnan and K.E. Gubbins: “Freezing behavior in porous glasses and MCM-41”, Colloid Surf. A, Vol. 187-188, (2001), pp. 523–529. http://dx.doi.org/10.1016/S0927-7757(01)00637-9[Crossref]
  • [16] K. Morishige and H. Iwasaki: “X-ray study of freezing and melting of water confined within SBA-15”, Langmuir, Vol. 19, (2003), pp. 2808–2811. http://dx.doi.org/10.1021/la0208474[Crossref]
  • [17] J.H. Strange, J. Mitchell and J.B.W. Webber: “Pore surface exploration by NMR”, Magn. Res. Imaging, Vol. 21, (2003), pp. 221–226. http://dx.doi.org/10.1016/S0730-725X(03)00128-0[Crossref]
  • [18] D.P. Gallegos, K. Munn, D.M. Smith and D.L. Stermer: “A NMR technique for the analysis of pore structure: application to materials with well-defined pore structure”, J. Coll. In. Sci., Vol. 119, (1986), pp. 127–140. http://dx.doi.org/10.1016/0021-9797(87)90251-7[Crossref]
  • [19] D.W. Aksnes and L. Kimtys: “1H and 2H NMR studies of benzene confined in porous solids: melting point depression and pore size distribution”, Solid State Nucl. Mag., Vol. 25, (2004), pp. 146–152. http://dx.doi.org/10.1016/j.ssnmr.2003.03.001[Crossref]
  • [20] M.R. Landry: “Thermoporometry by differential scanning calorimetry: experimental considerations and applications”, Thermochim. Acta, Vol. 433, (2005), pp. 27–50. http://dx.doi.org/10.1016/j.tca.2005.02.015[Crossref]
  • [21] V.M. Gun’ko, V.V. Turov, J. Skubiszewska-Zięba, R. Leboda, M.D. Tsapko and D. Palijczuk: “Structural characteristics of a carbon adsorbent and influence of organic solvents on interfacial water”, Appl. Surf. Sci., Vol. 214, (2003), pp. 178–189. http://dx.doi.org/10.1016/S0169-4332(03)00345-3[Crossref]
  • [22] V.M. Gun’ko, V.V. Turov, R. Leboda, J. Skubiszewska-Zięba, M.D. Tsapko and D. Palijczuk: “Influence of organics on structure of water adsorbed on activated carbons”, Adsorption, Vol. 11, (2005), pp.163–168. http://dx.doi.org/10.1007/s10450-005-5916-5[Crossref]
  • [23] V.V. Turov, G.P. Prikhodko, S.Y. Brychka and M.D. Tsapko: “Joint Adsorption of Benzene and Water on Carbon Nanotubes“, Russ. J. Phys. Chem., Vol. 80, (2006), pp. 591–596. http://dx.doi.org/10.1134/S0036024406040194[Crossref]
  • [24] V.V. Turov, V.M. Gun’ko, M.D. Tsapko, V.M. Bogatyrev, J. Skubiszewska-Zięba, R. Leboda and J. Riczkowski: “Influence of organic solvents on interfacial water at surfaces of silica gel and partially silylated fumed silica”, Appl. Surf. Sci., Vol. 229, (2004), pp. 197–213. http://dx.doi.org/10.1016/j.apsusc.2004.01.070[Crossref]
  • [25] I.S. Berezovska, V.V. Yanishpolsky and V.A. Tertykh: “Nanoporous silicas with uniform spherical morphology of particles”, Nanostruct. Mater. Sci., Vol. 2-6, (2005), pp. 24–28.
  • [26] A. Wang and T. Kabe: “Fine-tuning of pore size of MCM-41 by adjusting the initial pH of the synthesis mixture”, Chem. Commun., Vol. 20, (1999), pp. 2067–2068. http://dx.doi.org/10.1039/a906275k[Crossref]
  • [27] K. Schumacher, P.I. Ravikovitch, A. Du Chesne, A.V. Neimark and K.K. Unger: “Characterization of MCM-48 Materials”, Langmuir, Vol. 16, (2000), pp. 4648–4654. http://dx.doi.org/10.1021/la991595i[Crossref]
  • [28] A. Lind, C. du Fresne von Hohenesche, J.-H. Smått, M. Lindén and K.K. Unger: “Spherical silica agglomerates possessing hierarchical porosity prepared by spray drying of MCM-41 and MCM-48 nanospheres”, Micropor. Mesopor. Mater., Vol. 66, (2003), pp. 219–227. http://dx.doi.org/10.1016/j.micromeso.2003.09.011[Crossref]
  • [29] R. Ryoo, S.H. Joo and S. Jun: “Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformation”, J. Phys. Chem. B, Vol. 103, (1999), pp. 7743–7746. http://dx.doi.org/10.1021/jp991673a[Crossref]
  • [30] D. Zhao, Q. Huo, J. Feng, B.F. Chmelka and D.G. Stucky: “Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures”, J. Am. Chem. Soc., Vol. 120, (1998), pp. 6024–6036. http://dx.doi.org/10.1021/ja974025i[WoS][Crossref]
  • [31] V.M. Gun’ko, V.I. Zarko, V.V. Turov, E.F. Voronin, I.F. Mironyuk and A.A. Chuiko: “Structural and adsorptive characteristics of fumed silicas in different media”, In: H.E. Bergna (Ed.): Coll. Silica: Fundamentals and Applications, Taylor & Francis LLC, Salisbury, 2005, pp. 499–530.
  • [32] V.M. Gun’ko and V.V. Turov: “Structure of hydrogen bonds and 1H NMR spectra of water at the interface of oxides”, Langmuir, Vol. 15, (1999), pp. 6405–6415. http://dx.doi.org/10.1021/la9809372[Crossref]
  • [33] S.W. Provencher: “A constrained regularization method for inverting data represented by linear algebraic or integral equations”, Comp. Phys. Comm., Vol. 27, (1982), pp. 213–227. http://dx.doi.org/10.1016/0010-4655(82)90173-4[Crossref]
  • [34] H.-R. Tang, J. Godward and B. Hills: “The distribution of water in native starch granules - a multinuclear NMR study” Carbohydrate Polym., Vol. 43, (2000), pp. 375–387. http://dx.doi.org/10.1016/S0144-8617(00)00183-1[Crossref]
  • [35] S.-G. Choi and W.L. Kerr: “Effects of chemical modification of wheat strach on molecular mobility as studied by pulsed 1H NMR”, Lebensm.-Wiss. U.-Technol., Vol. 36, (2003), pp. 105–112. http://dx.doi.org/10.1016/S0023-6438(02)00200-1[Crossref]
  • [36] V.P. Glushko (Ed.): Handbook of Thermodynamic Properties of Individual Substances, Nauka, Moskow, 1978.
  • [37] V.M. Gun’ko, V.I. Zarko, E.V. Goncharuk, L.S. Andriyko, V.V. Turov, Y.M. Nychiporuk, R. Leboda, J. Skubiszewska-Zięba, A.L. Gabchak, V.D. Osovskii, Y.G. Ptushinskii, G.R. Yurchenko, O.A. Mishchuk, P.P. Gorbik, P. Pissis, and J.P. Blitz: “TSDC spectroscopy of relaxational and interfacial phenomena”, Adv. Colloid Interface Sci., in press. [WoS]
  • [38] S.J. Gregg and K.S.W. Sing: Adsorption, Surface Area and Porosity, 2nd ed., Academic Press, London, 1982.
  • [39] M. Thommes, R. Köhn and M. Fröba: “Sorption and pore condensation behavior of pure fluids in mesoporous MCM-48 silica, MCM-41 silica, SBA-15 silica and controlled-pore glass at temperatures above and below the bulk triple point”, Appl. Surf. Sci., Vol. 196, (2002), pp. 239–249. http://dx.doi.org/10.1016/S0169-4332(02)00062-4[Crossref]
  • [40] C. Nguyen and D.D. Do: “A new method for the characterization of porous materials”, Langmuir, Vol. 15, (1999), pp. 3608–3615. http://dx.doi.org/10.1021/la981140d[Crossref]
  • [41] V.M. Gun’ko and S.V. Mikhalovsky: “Evaluation of slitlike porosity of carbon adsorbents”, Carbon, Vol. 42, (2004), pp. 843–849. http://dx.doi.org/10.1016/j.carbon.2004.01.059[Crossref]
  • [42] V.M. Gun’ko, O. Seledets, J. Skubiszewska-Zięba, V.I. Zarko, R. Leboda, W. Janusz and S. Chibowski: “Phosphorus-containing pyrocarbon deposits on silica gel Si-100”, Micropor. Mesopor. Mater., Vol. 87, (2005), pp. 133–145. http://dx.doi.org/10.1016/j.micromeso.2005.06.044[Crossref]
  • [43] W.B. Muniz, F.M. Ramos and H.F. de Campos Velho: “Entropy-and Tikhonov-based regularization techniques applied to the backwards heat equation”, Comput. Mathem. Applic., Vol. 40, (2000), pp. 1071–1084. http://dx.doi.org/10.1016/S0898-1221(00)85017-8[Crossref]
  • [44] M. Jaroniec, M. Kruk and J.P. Olivier: “Standard nitrogen adsorption data for characterization of nanoporous silicas”, Langmuir, Vol. 15, (1999), pp. 5410–5413. http://dx.doi.org/10.1021/la990136e[Crossref]
  • [45] G.M. Sesler (Ed.): Electrets, Topics in Applied Physics, Vol. 33, Springer, Berlin, 1980.
  • [46] P.T. Tanev and T.J. Pinnavaia: “Mesoporous silica molecular sieves prepared by ionic and neutral surfactant templating: a comparison of physical properties”, Chem. Mater., Vol. 8, (1996), pp. 2068–2079. http://dx.doi.org/10.1021/cm950549a[Crossref]
  • [47] J. Wawryszczuk, J. Goworek, R. Zaleski and T. Goworek:”Positron lifetime in mesoporous silica of MCM-41 type”, Langmuir, Vol. 19, (2003), pp. 2599–2605. http://dx.doi.org/10.1021/la020280r[Crossref]
  • [48] M.J. Meziani, J. Zajac, J.-M. Douillard, D.J. Jones, S. Partyka and J. Rozière: “Evaluation of surface enthalpy of porous aluminosilicates of the MCM-41 type using immersional calorimetry: effect of the pore size and framework Si:Al ratio”, J. Colloid Interf. Sci., Vol. 233, (2001), pp. 219–226. http://dx.doi.org/10.1006/jcis.2000.7254[Crossref]

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