Journal of Sol-Gel Science and Technology

, Volume 60, Issue 3, pp 260–265 | Cite as

Bi-functionalization of silica spheres with sulfonic and carboxylic groups via a co-condensation route

  • Sonia Fiorilli
  • Dario Caldarola
  • Hao Ma
  • Barbara Onida
Original Paper


Silica spheres with uniform size of 230–250 nm were functionalized with sulfonic groups and bi-functionalized with carboxylic and sulfonic groups via a co-condensation route, by adding the organosilanes (3-(triethoxysilyl)mercaptopropyl and 4-(triethoxysilyl)butyronitrile) to a pre-hydrolized TEOS solution. The conversion of mercapto and cyano groups to, respectively, sulfonic and carboxylic groups was carried out by treating both the samples with nitric acid solution. The presence of alkyl-SO3H and alkyl-COOH species at the silica surface in an approximate molar ratio of 1:1 was assessed by TG and NMR. FT-IR spectroscopy showed that both Brønsted acidic groups are accessible and give proton-transfer reaction to ammonia with the formation of ammonium ion. Sulfonic groups react irreversibly with ammonia at room temperature at variance with carboxylic groups which give a reversible proton-transfer, in agreement with the stronger Brønsted acidity of the former.


Silica spheres Functionalization Co-condensation Brønsted acidic groups 

Supplementary material

10971_2011_2484_MOESM1_ESM.doc (262 kb)
Supplementary material 1 (DOC 262 kb)


  1. 1.
    Fendler J (1996) Special issue on nanostructured materials. Chem. Mater 8:1616Google Scholar
  2. 2.
    Fendler JH (ed) (1998) Nanoparticles and nanostructured films. Wiley, WeinheimGoogle Scholar
  3. 3.
    Häfeli U, Schütt W, Teller J, Zborowski M (eds) (1997) Scientific and clinical applications of magnetic carriers. Plenum, New YorkGoogle Scholar
  4. 4.
    Reetz MT, Waldvogel SR (1997) Angew Chem 109:870CrossRefGoogle Scholar
  5. 5.
    Reetz MT, Waldvogel SR (1997) Angew Chem Int Ed Engl 36:865CrossRefGoogle Scholar
  6. 6.
    Matting A, Brockmann W (1968) Angew Chem 80:641CrossRefGoogle Scholar
  7. 7.
    Matting A, Brockmann W (1968) Angew Chem Int Ed Engl 7:598CrossRefGoogle Scholar
  8. 8.
    Jain S, Goossens H, Picchioni F, Magusin P, Mezari B, Duin MV (2005) Polymer 46:6666CrossRefGoogle Scholar
  9. 9.
    Chen Y, Zhou S, Chen G, Wu L (2005) Prog Org Coat 54:120CrossRefGoogle Scholar
  10. 10.
    Hasan MM, Zhou Y, Mahfuz H, Jeelani S (2006) Mater Sci Eng A 429:181CrossRefGoogle Scholar
  11. 11.
    Salata OVJ (2004) Nanobiotechnol 2:1CrossRefGoogle Scholar
  12. 12.
    Bagwe RP, Hilliard LR, Tan W (2006) Langmuir 22:4357CrossRefGoogle Scholar
  13. 13.
    Lim HM, Stein A (1999) Chem Mater 11:3285CrossRefGoogle Scholar
  14. 14.
    Brunel D, Cauvel A, Di Renzo F, Fajula F, Fubini B, Onida B, Garrone E (2000) New J Chem 24:807CrossRefGoogle Scholar
  15. 15.
    Stöber W, Fink A, Bohn E (1968) J Colloid Interface Sci 26:62CrossRefGoogle Scholar
  16. 16.
    Marini M, Pourabbas B, Pilati F, Fabbri P (2008) Colloid Surf A Physicochem Eng Aspects 317:473CrossRefGoogle Scholar
  17. 17.
    Gill CS, Price BA, Jones CW (2007) J Catal 251:14CrossRefGoogle Scholar
  18. 18.
    He X, Nie H, Wang K, Tan W, Wu X, Zhang P (2008) Anal Chem 80(24):9597CrossRefGoogle Scholar
  19. 19.
    Suryani LiuYL (2009) J Membr Sci 332(1–2):121CrossRefGoogle Scholar
  20. 20.
    Chang JH, Kang KH, Choi J, Jeong YK (2008) Superlattices microstruct 44:442CrossRefGoogle Scholar
  21. 21.
    Kumar R, Roy I, Ohulchanskyy TY, Goswami LN, Bonoiu AC, Bergey EJ, Tramposch KM, Maitra A, Prasad PN (2008) ACS Nano 2(3):449CrossRefGoogle Scholar
  22. 22.
    Yang QH, Kapoor MP, Inagaki SJ (2002) Am Chem Soc 124:9694CrossRefGoogle Scholar
  23. 23.
    Margolese D, Melero JA, Christiansen SC, Chmelka BF, Stucky GD (2000) Chem Mater 12:2448CrossRefGoogle Scholar
  24. 24.
    Marschall R, Bannat I, Feldhoff A, Wang L, Lu GQ, Wark M (2009) Small 5:854CrossRefGoogle Scholar
  25. 25.
    Mauder D, Akcakayiran D, Lesnichin SB, Findenegg GH, Shenderovich IG (2009) J Phys Chem C 113:19185CrossRefGoogle Scholar
  26. 26.
    Zecchina A, Marchese L, Bordiga S, Pazè C, Gianotti E (1997) J Phys Chem B 101:10128CrossRefGoogle Scholar
  27. 27.
    Men LJ, Wang YS (2006) Rapid Commun Mass Spectrom 20:777CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2011

Authors and Affiliations

  • Sonia Fiorilli
    • 1
  • Dario Caldarola
    • 1
  • Hao Ma
    • 1
  • Barbara Onida
    • 1
  1. 1.Dipartimento di Scienza dei Materiali e Ingegneria ChimicaPolitecnico di TorinoTorinoItaly

Personalised recommendations