Skip to main content
SpringerLink
Log in

Adsorption hysteresis in ordered mesoporous silicas

  • Published:
Adsorption Aims and scope Submit manuscript

Abstract

We review some recent progress in experimental studies of the adsorption hysteresis of simple molecules in ordered mesoporous silicas. We show that the nature of the adsorption hysteresis due to capillary condensation can be examined with less ambiguity by measuring the hysteresis loop for the ordered mesoporous silicas with three types of pore geometries (cylindrical, interconnected cylindrical, and interconnected spherical) over a wide temperature range. The adsorption hysteresis arises from the metastability of a confined phase and the temperature at which the hysteresis disappears is lower than the critical temperature of vapor-liquid equilibrium in pores. The hysteresis occurs mainly on the desorption rather than adsorption branch, irrespective of the pore geometries.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Beck, J.S., Vartuli, J.C., Roth, W.J., Leonowicz, M.E., Kresge, C.T., Schmitt, K.D., Chu, C.T.-W., Olson, D.H., Sheppard, E.W., McCullen, S.B., Higgins, J.B., Schlenker, J.L.: A new family of mesoporous molecular sieves prepared with liquid crystal templates. J. Am. Chem. Soc. 114, 10834–10843 (1992)

    Article  CAS  Google Scholar 

  • Burgess, C.G.V., Everett, D.H., Nuttall, S.: Adsorption hysteresis in porous materials. Pure Appl. Chem. 61, 1845–1852 (1989)

    Article  CAS  Google Scholar 

  • Carlsson, A., Kaneda, M., Sakamoto, Y., Terasaki, O., Ryoo, R., Joo, S.H.: The structure of MCM-48 determined by electron crystallography. J. Electron Microsc. 48, 795–798 (1999)

    CAS  Google Scholar 

  • Coasne, B., Hung, F.R., Pellenq, R.J.-M., Siperstein, F.R., Gubbins, K.E.: Adsorption of simple gases in MCM-41 materials: the role of surface roughness. Langmuir 22, 194–202 (2006)

    Article  CAS  Google Scholar 

  • Cohan, L.H.: Sorption hysteresis and the vapor pressure of concave surfaces. J. Am. Chem. Soc. 60, 433–435 (1938)

    Article  CAS  Google Scholar 

  • Evans, R., Marconi, U.M.B., Tarazona, P.: Capillary condensation and adsorption in cylindrical and slit-like pores. J. Chem. Soc. Faraday Trans. 2 82, 1763–1787 (1986)

    Article  Google Scholar 

  • Gelb, L.D.: The ins and outs of capillary condensation in cylindrical pores. Mol. Phys. 100, 2049–2057 (2002)

    Article  CAS  Google Scholar 

  • Kleitz, F., Liu, D., Anilkumar, G.M., Park, I.-S., Solovyov, L.A., Shmakov, A.N., Ryoo, R.: Large cage face-centered-cubic Fm3m mesoporous silica: synthesis and structure. J. Phys. Chem. B 107, 14296–14300 (2003)

    Article  CAS  Google Scholar 

  • Morishige, K., Ishino, M.: Lower closure point of adsorption hysteresis in ordered mesoporous silicas. Langmuir 23, 11021–11026 (2007)

    Article  CAS  Google Scholar 

  • Morishige, K., Ito, M.: Capillary condensation of nitrogen in MCM-41 and SBA-15. J. Chem. Phys. 117, 8036–8041 (2002)

    Article  CAS  Google Scholar 

  • Morishige, K., Nakamura, Y.: Nature of adsorption and desorption branches in cylindrical pores. Langmuir 20, 4503–4506 (2004)

    Article  CAS  Google Scholar 

  • Morishige, K., Tarui, N.: Capillary condensation of nitrogen in ordered mesoporous silica with bicontinuous gyroid structure. J. Phys. Chem. C 111, 280–285 (2007)

    Article  CAS  Google Scholar 

  • Morishige, K., Tateishi, N.: Adsorption hysteresis in ink-bottle pore. J. Chem. Phys. 119, 2301–2306 (2003)

    Article  CAS  Google Scholar 

  • Morishige, K., Tateishi, N., Fukuma, S.: Capillary condensation of nitrogen in MCM-48 and SBA-16. J. Phys. Chem. B 107, 5177–5181 (2003)

    Article  CAS  Google Scholar 

  • Morishige, K., Tateishi, M., Hirose, F., Aramaki, K.: Change in desorption mechanism from pore blocking to cavitation with temperature for nitrogen in ordered silica with cagelike pores. Langmuir 22, 9220–9224 (2006)

    Article  CAS  Google Scholar 

  • Neimark, A.V., Vishnyakov, A.: Phase transitions and criticality in small systems: vapor-liquid transition in nanoscale spherical cavities. J. Phys. Chem. B 110, 9403–9412 (2006)

    Article  CAS  Google Scholar 

  • Peterson, B.K., Gubbins, K.E.: Phase transitions in a cylindrical pore: Grand Canonical Monte Carlo, mean field theory and the Kelvin equation. Mol. Phys. 62, 215–226 (1987)

    Article  CAS  Google Scholar 

  • Puibasset, J.: Generalized isobaric-isothermal ensemble: application to capillary condensation and cavitation in heterogeneous nanopores. Mol. Phys. 104, 3021–3032 (2006)

    Article  CAS  Google Scholar 

  • Ravikovitch, P.I., Neimark, A.V.: Experimental confirmation of different mechanisms of evaporation from ink-bottle type pores: equilibrium, pore blocking, and cavitation. Langmuir 18, 9830–9837 (2002)

    Article  CAS  Google Scholar 

  • Ravikovitch, P.I., Neimark, A.V.: Density functional theory model of adsorption on amorphous and microporous silica materials. Langmuir 22, 11171–11179 (2006)

    Article  CAS  Google Scholar 

  • Ravikovitch, P.I., Domhnaill, S.C.Ó., Neimark, A.V., Schüth, F., Unger, K.K.: Capillary hysteresis in nanopores: theoretical and experimental studies of nitrogen adsorption on MCM-41. Langmuir 11, 4765–4772 (1995)

    Article  CAS  Google Scholar 

  • Sakamoto, Y., Kaneda, M., Terasaki, O., Zhao, D.Y., Kim, J.M., Stucky, G., Shin, H.J., Ryoo, R.: Direct imaging of the pores and cages of three-dimensional mesoporous materials. Nature 408, 449–453 (2000)

    Article  CAS  Google Scholar 

  • Sakamoto, Y., Kim, T.-W., Ryoo, R., Terasaki, O.: Three-dimensional structure of large-pore mesoporous cubic Ia3d silica with complementary pores and its carbon replica by electron crystallography. Angew. Chem. Int. Ed. 43, 5231–5234 (2004)

    Article  CAS  Google Scholar 

  • Sarkisov, L., Monson, P.A.: Modeling of adsorption and desorption in pores of simple geometry using molecular dynamics. Langmuir 17, 7600–7604 (2001)

    Article  CAS  Google Scholar 

  • Schreiber, A., Reinhardt, S., Findenegg, G.H.: The lower closure point of the adsorption hysteresis loop of fluids in mesoporous silica materials. In: Rodriguez-Reinoso, F., McEnancy, B., Rouquerol, J., Unger, K. (eds.) Studies in Surface Science and Catalysis, vol. 144, pp. 177–184. Elsevier, Amsterdam (2002)

    Google Scholar 

  • Sing, K.S.W., Everett, D.H., Haul, R.A.W., Moscou, L., Pierotti, R.A., Rouquérol, J., Siemieniewska, T.: Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl. Chem. 57, 603–619 (1985)

    Article  CAS  Google Scholar 

  • Solovyov, L.A., Belousov, O.V., Dinnebier, R.E., Shmakov, A.N., Kirik, S.D.: X-ray diffraction structure analysis of MCM-48 mesoporous silica. J. Phys. Chem. B 109, 3233–3237 (2005)

    Article  CAS  Google Scholar 

  • Sonwane, C.G., Bhatia, S.K.: Adsorption in mesopores: a molecular-continuum model with application to MCM-41. Chem. Eng. Sci. 53, 3143–3156 (1998)

    Article  CAS  Google Scholar 

  • Ustinov, E.A., Do, D.D.: Modeling of adsorption and nucleation in infinite cylindrical pores by two-dimensional density functional theory. J. Phys. Chem. B 109, 11653–11660 (2005)

    Article  CAS  Google Scholar 

  • Vishnyakov, A., Neimark, A.V.: Studies of liquid-vapor equilibria, criticality, and spinodal transitions in nanpores by the gauge cell Monte Carlo simulation method. J. Phys. Chem. B 105, 7009–7020 (2001)

    Article  CAS  Google Scholar 

  • Wall, G.C., Brown, R.J.C.: The determination of pore-size distributions from sorption isotherms and mercury penetration in interconnected pores: the application of percolation theory. J. Colloid Interface Sci. 82, 141–149 (1981)

    Article  CAS  Google Scholar 

  • Zhao, D., Huo, Q., Feng, J., Chmelka, B.F., Stucky, G.D.: Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures. J. Am. Chem. Soc. 120, 6024–6036 (1998)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Okayama University of Science, 1-1 Ridai-cho, Okayama, 700-0005, Japan

    Kunimitsu Morishige

Authors
  1. Kunimitsu Morishige
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kunimitsu Morishige.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Morishige, K. Adsorption hysteresis in ordered mesoporous silicas. Adsorption 14, 157–163 (2008). https://doi.org/10.1007/s10450-007-9086-5

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10450-007-9086-5

Keywords

Search

Navigation