Skip to main content
SpringerLink
Log in

Mesoporous Silsesquioxanes with High Contents of Surface Amine Groups

  • Original Paper
  • Published:
Silicon Aims and scope Submit manuscript

Abstract

The objective of this work is the synthesis of highly functionalized hybrid organic/inorganic materials by the polycondensation of bis[3-(trimethoxysilyl) propyl]amine in the presence of surfactants. High contents of amine groups were achieved by carrying out the syntheses without an inorganic cross-linker. The silsesquioxanes obtained had a mesoporous structure. The stability of their porous system in the absence of an inorganic cross-linker was enhanced by the precursor’s bridged structure. The material structures were studied by FT-IR spectroscopy, Porosimetry, X-Ray Diffraction and Small Angle X-Ray Scattering methods. A material prepared in the presence of dodecylamine as a template had a higher surface area and narrower pore size distribution while the use of sodium dodecyl sulfate resulted in the formation of mesopores with a wide size distribution. Surface amine groups in silsesquioxanes were accessible for adsorption of small molecules of acidic nature.

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

  1. Yang Q, Liu J, Zhang L, Li C (2009) Functionalized periodic mesoporous organosilicas for catalysis. J Mater Chem 19:1945–1955

    Article  CAS  Google Scholar 

  2. Clark JH, Macquarrie DJ, Tavener SJ (2006) The application of modified mesoporous silicas in liquid phase catalysis. Dalton Trans. 4297–4309

  3. Walcarius A, Mercier L (2010) Mesoporous organosilica adsorbents: nanoengineered materials for removal of organic and inorganic pollutants. J Mater Chem 20:4478–4511

    Article  CAS  Google Scholar 

  4. Husing N (2007) Porous hybrid materials. In: Kickelbick G (ed) Hybrid materials: synthesis, characterization, and applications. Wiley, Weinheim, pp 175–224

    Google Scholar 

  5. Hoffmann F, Cornelius M, Morell J, Fröba M (2006) Silica-based mesoporous organic–inorganic hybrid materials. Angew Chem Int Ed 45:3216–3251

    Article  CAS  Google Scholar 

  6. Husing N (2004) Porous inorganic-organic hybrid materials. In: Gómez-Romero P, Sánchez C (eds) Functional hybrid materials. Wiley, Weinheim, pp 86–121

    Google Scholar 

  7. Kaneko Y, Iyi N, Kurashima K, Matsumoto T (2004) Hexagonal-structured polysiloxane material prepared by sol-gel reaction of aminoalkyltrialkoxysilane without using surfactants. Chem Mater 16:3417–3423

    Article  CAS  Google Scholar 

  8. Kaneko Y, Iyi N, Matsumoto T, Fujii K, Kurashima K, Fujita T (2003) Synthesis of ion-exchangeable layered polysiloxane by sol–gel reaction of aminoalkyltrialkoxysilane: a new preparation method for layered polysiloxane materials. J Mater Chem 13:2058–2060

    Article  CAS  Google Scholar 

  9. da Trindade CM, Stoll GC, Pereira AS, Costa TMH, Benvenutti EV (2009) An innovative series of layered nanostructured aminoalkylsilica hybrid material. J Braz Chem Soc 20:737–743

    Article  Google Scholar 

  10. Han L, Chen Q, Wang Y, Gao C, Che S (2011) Synthesis of amino group functionalized monodispersed mesoporous silica nanospheres using anionic surfactant. Micropor Mesoporous Mater 139:94–103

    Article  CAS  Google Scholar 

  11. Hunks WJ, Ozin GA (2005) Challenges and advances in the chemistry of periodic mesoporous organosilicas (PMOs). J Mater Chem 15:3716–3724

    Article  CAS  Google Scholar 

  12. Wahab MA, Kim I, Ha C-S (2004) Bridged amine-functionalized mesoporous organosilica materials from 1,2-bis(triethoxysilyl)ethane and bis[(3-trimethoxysilyl) propyl]amine. J Solid State Chem 177:3439–3447

    Article  CAS  Google Scholar 

  13. Shea J, Loy DA (2001) Bridged polysilsesquioxanes. Molecular-engineered hybrid organic-inorganic materials. Chem Mater 13:3306–3319

    Article  CAS  Google Scholar 

  14. Barczak M, Borowski P, Dąbrowski A (2009) Structure-adsorption properties of ethylene-bridged polysilsesquioxanes and polysiloxanes functionalized with different groups. Colloid Surface A 347:114–120

    Article  CAS  Google Scholar 

  15. Hu L-C, Shea KJ (2011) Organo–silica hybrid functional nanomaterials: how do organic bridging groups and silsesquioxane moieties work hand-in-hand? Chem Soc Rev 40:688–695

    Article  CAS  Google Scholar 

  16. Corriu R, Mehdi A, Reye C (2004) Nanoporous materials: a good opportunity for nanosciences. J Organomet Chem 689:4437–4450

    Article  CAS  Google Scholar 

  17. Alauzun J, Mehdi A, Reye C, Corriu RJP (2006) An original synthesis of highly ordered organosilica with a high content of thiol groups. Chem Commun 347–349

  18. Kim S-N, Son W-J, Choi J-S, Ahn W-S (2008) CO2 adsorption using amine-functionalized mesoporous silica prepared via anionic surfactant-mediated synthesis. Micropor Mesoporous Mater 115:497–503

    Article  CAS  Google Scholar 

  19. Vonk CG (1974) FFSAXS’s program for the processing of small-angle X-ray scattering data. DSM, Geleen

    Google Scholar 

  20. Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl Chem 57:603–619

    Article  CAS  Google Scholar 

  21. Tilgner IC, Fischer P, Bohnen FM, Rehage H, Maier WF (1995) Effect of acidic, basic and fluoride-catalyzed sol-gel transitions on the preparation of sub-nanostructured silica. Microporous Mater 5:77–90

    Article  CAS  Google Scholar 

  22. Larsen G, Lotero E, Marquez M (2000) Use of polypropyleneimine tetrahexacontaamine (DAB-Am-64) dendrimer as a single-molecule template to produce mesoporous silicas. Chem Mater 12:1513–1515

    Article  CAS  Google Scholar 

  23. Moreau JJE, Vellutini L, Dieudonné P, Man MWC, Bantignies J-L, Sauvajol J-L, Bied C (2005) Structural ordering of self-assembled alkylene-bridged silsesquioxanes probed by X-ray diffraction experiments. J Mater Chem 15:4943–4948

    Article  CAS  Google Scholar 

  24. Khatib IS, Parish RV (1989) Insoluble ligands and their applications: I. A comparison of silica-immobilized ligands and functionalized polysiloxanes. J Organomet Chem 369:9–16

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, East Tennessee State University, PO Box 70695, Johnson City, TN, 37614, USA

    Kolade O. Ojo & Aleksey N. Vasiliev

  2. Institute of Bioorganic Chemistry and Petrochemistry, NAS of Ukraine, 1 Murmanska St., Kiev, 02094, Ukraine

    Leonid V. Golovko

  3. Institute of Macromolecular Chemistry, NAS of Ukraine, 48 Kharkivske Shosse, Kiev, 02150, Ukraine

    Yury P. Gomza

Authors
  1. Kolade O. Ojo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Leonid V. Golovko
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yury P. Gomza
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Aleksey N. Vasiliev
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Aleksey N. Vasiliev.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ojo, K.O., Golovko, L.V., Gomza, Y.P. et al. Mesoporous Silsesquioxanes with High Contents of Surface Amine Groups. Silicon 4, 189–195 (2012). https://doi.org/10.1007/s12633-012-9122-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12633-012-9122-2

Keywords

Search

Navigation