Journal of Thermal Analysis and Calorimetry

, Volume 116, Issue 1, pp 15–25 | Cite as

Thermogravimetric study of the surfactant–diethanolamine–titanium isopropoxide system behavior

  • A. Athanasiou
  • A. Mitsionis
  • G. Skouras
  • N. Todorova
  • C. Trapalis
  • T. Vaimakis


Mesoporous anatase TiO2 materials with specific surface areas between 70 and 110 m2 g−1 were prepared via sol–gel technique using surfactants oleic acid and Triton-X (TX), in the presence or absence of diethanolamine, in methanol. Surfactants like TX or oleic acid (OA), as well as a gelating and chelate agent like diethanolamine (DEA) are commonly used in TiO2 formation from a titanium isopropoxide solution. Thermogravimetric methods were applied in order to evaluate the effect of the addition of such molecules in a precursor suspension before TiO2 materials preparation. The in situ investigation of such systems showed that numerous interactions occur between large molecules such as TX and OA that attributed on both steric effects and hydrogen bond formation. Materials prepared through modified sol–gel technique seem to be stabilized through DEA addition in the precursor suspension.


Mesoporous TiO2 TG/DSC Oleic acid Triton-X Diethanolamine 



This research project has been co-financed by the European Union (European Regional Development Fund—ERDF) and Greek national funds through the Operational Program “THESSALY-MAINLAND GREECE AND EPIRUS-2007–2013” of the National Strategic Reference Framework (NSRF 2007–2013).


  1. 1.
    Serpone N, Pelizzetti E, Hidaka H, Ollis DF, Al-Ekabi H. Photocatalytic purification and treatment of water and air. Amsterdam: Elsevier; 1993. p. 225–50.Google Scholar
  2. 2.
    Bahnemann D, Cunningham J, Fox MA, Pelizzetti E, Pichat P, Serpone N, Helz G, Zepp R, Crosby D. Aquatic and surface photochemistry. Boca Raton: Lewis Publishers; 1994. p. 261–316.Google Scholar
  3. 3.
    Nosaka Y, Yamashita Y, Fukuyama H. Application of chemiluminescent probe to monitoring superoxide radicals and hydrogen peroxide in TiO2 photocatalysis. J Phys Chem B. 1997;101:5822–7.CrossRefGoogle Scholar
  4. 4.
    Kominami H, Kumamoto H, Kera Y, Ohtani B. Immobilization of highly active titanium (IV) oxide particles. A novel strategy of preparation of transparent photocatalytic coatings. Appl Catal B Environ. 2001;30:329–35.CrossRefGoogle Scholar
  5. 5.
    Yu JC, Yu J, Zhao J. Enhanced photocatalytic activity of mesoporous and ordinary TiO2 thin films by sulfuric acid treatment. Appl Catal B Environ. 2002;36:31–43.CrossRefGoogle Scholar
  6. 6.
    Ding Z, Lu GQ, Greenfield PF. Role of the crystallite phase of TiO2 in heterogeneous photocatalysis for phenol oxidation in water. J Phys Chem B. 2000;104:4815–20.CrossRefGoogle Scholar
  7. 7.
    Wang YQ, Tang XH, Huang W, Yin Y, Hacohen R, Gedanken A. Sonochemical synthesis of mesoporous titanium oxide with wormhole-like framework structures. Adv Mater. 2000;12:1183–6.CrossRefGoogle Scholar
  8. 8.
    Pucher P, Benmami M, Azouani R, Krammer G, Chhor K, Bocquet JF, Kanaev AV. Nano-TiO2 sols immobilized on porous silica as new efficient photocatalyst. Appl Catal A Gen. 2007;332:297–303.CrossRefGoogle Scholar
  9. 9.
    Hongo T, Yamazaki A. Synthesis and photocatalytic activity of mesoporous titania with wormhole-like framework structure consisted of TiO2 (B). J Mater Sci. 2010;45:275–83.CrossRefGoogle Scholar
  10. 10.
    Rathousky J, Kalousek V, Yarovyi V, Wark M, Jirkovsky J. A low-cost procedure for the preparation of mesoporous layers of TiO2 efficient in the environmental clean-up. J Photochem Photobiol A Chem. 2010;216:126–32.CrossRefGoogle Scholar
  11. 11.
    Ahn SH, Park JT, Koh JK, Roh DK, Kim JH. Graft copolymer directed synthesis of micron-thick organized mesoporous TiO2 films for solid-state dye-sensitized solar cells. Chem Commun. 2011;47:5882–4.CrossRefGoogle Scholar
  12. 12.
    Ahn SH, Son KJ, Ahn H, Koh WG, Ryu DY, Kim JH. Efficiency improvement of dye-sensitized solar cells using graft copolymer-templated mesoporous TiO2 films as an interfacial layer. J Mater Chem. 2011;21:1772–9.CrossRefGoogle Scholar
  13. 13.
    Meynen V, Cool P, Vansant EF. Verified syntheses of mesoporous materials. Microporous Mesoporous Mater. 2009;125:170–223.CrossRefGoogle Scholar
  14. 14.
    Sanchez C, Boissiere C, Grosso D, Lanerty C, Nicole L. Design, synthesis and properties of inorganic and hybrid thin films having periodically organized nanoporosity. Chem Mater. 2008;20:682–737.CrossRefGoogle Scholar
  15. 15.
    Kim EY, Choi H, Whang CM. Controlled growth of TiO2 nanorods capped with carboxylate groups by the solvothermal process. J Mater Sci. 2010;45:3895–900.CrossRefGoogle Scholar
  16. 16.
    Singh A, Mehrotra RC. Novel heterometallic alkoxide coordination systems of polyols (glycols, di- and tri-ethanolamines) derived from the corresponding homometallic moieties. Coord Chem Rev. 2004;248:101–18.CrossRefGoogle Scholar
  17. 17.
    Verma M, Kar DP, Singh J. Aging effect of diethanolamine derived precursor sol on TiO2 films deposited at different annealing temperatures. Sol Gel Sci Technol. 2010;54:129–38.CrossRefGoogle Scholar
  18. 18.
    Sharma M, Singh A, Mehrotra RC. Synthesis and characterization of homo- and heterobimetallic diethanolaminates of alkaline earth metals. Polyhedron. 2000;19:77–83.CrossRefGoogle Scholar
  19. 19.
    Kemmitt T, Ai-Salim NI, Gainsford GJ. Isolation and structural characterization of triethanolaminotitanatranes: X-ray structures of partial hydrolysis condensates. Inorg Chem. 2000;39:6067–71.CrossRefGoogle Scholar
  20. 20.
    Sharma MK, Singh A, Mehrotra RC. Synthesis and characterisation of triethanolaminates of titanium and zirconium. Indian J Chem A. 2001;40:568–72.Google Scholar
  21. 21.
    Varshney KG, Rafiquee MZA, Somya A. Synthesis, characterization and adsorption behaviour of TX-100 based Sn(IV) phosphate, a new hybrid ion exchanger. J Therm Anal Calorim. 2007;90:663–7.CrossRefGoogle Scholar
  22. 22.
    Soares VLP, Nascimento RSV, Albinante SR. Ester-additives as inhibitors of the gelification of soybean oil methyl esters in biodiesel. J Therm Anal Calorim. 2009;97:621–6.CrossRefGoogle Scholar
  23. 23.
    Delmon B. Preparation of heterogeneous catalysts. J Therm Anal Calorim. 2007;90:49–65.CrossRefGoogle Scholar
  24. 24.
    Mitsionis A, Vaimakis T. The effect of thermal treatment in TiO2 photocatalytic activity. J Therm Anal Calorim. 2013;112:621–8.CrossRefGoogle Scholar
  25. 25.
    Večeřa J, Dohnalová Z, Mikulášek P, Šulcová P. Anatase–rutile transformation at the synthesis of rutile pigments (Ti, Cr, Nb)O2 and their color properties. J Therm Anal Calorim. 2013;113:61–7.CrossRefGoogle Scholar
  26. 26.
    Mitsionis A, Vaimakis T, Trapalis C, Todorova N, Bahnemann D, Dillert R. Hydroxyapatite/titanium dioxide nanocomposites for controlled photocatalytic NO oxidation. Appl Catal B Environ. 2011;106:398–404.CrossRefGoogle Scholar
  27. 27.
    Varshney KG, Rafiquee MZA, Somya A. Triton X-100 based cerium(IV) phosphate as a new Hg(II) selective, surfactant based fibrous ion exchanger: synthesis, characterization and adsorption behavior. Coll Surf A Physicochem Eng Aspects. 2008;317:400–5.CrossRefGoogle Scholar
  28. 28.
    Mitsuda K, Kimura H, Murahashi T. Evaporation and decomposition of triton X-l00 under various gases and temperatures. J Mater Sci. 1989;24:413–9.CrossRefGoogle Scholar
  29. 29.
    del Hoyo C, Dorado C, Rodríguez-Cruz MS, Sánchez-Martín MJ. Physico-chemical study of selected surfactant-clay mineral systems. J Therm Anal Calorim. 2008;94:227–34.CrossRefGoogle Scholar
  30. 30.
    Ivanda M, Music S, Popovic S, Gotic M. XRD, Raman and FT-IR spectroscopic observations of nanosized TiO2 synthesized by the sol–gel method based on an esterification reaction. J. Mol Struct. 1999;481:645–9.CrossRefGoogle Scholar
  31. 31.
    Saoula N, Henda K, Kesri R. Influence of nitrogen content on the structural and mechanical properties of TiN thin films. J Plasma Fusion Res. 2009;8:1403–7.Google Scholar
  32. 32.
    Ghadwal RS, Singh A. Synthesis and spectroscopic properties of homo- and heterobimetallic complexes of oxovanadium(V). J Chem Sci. 2006;118:165–70.CrossRefGoogle Scholar
  33. 33.
    Yu JG, Yu JC, Cheng B, Hark SK, Iu K. The effect of F doping and temperature on the structural and textural evolution of mesoporous TiO2 powders. J Sol State Chem. 2003;174:372–80.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2013

Authors and Affiliations

  • A. Athanasiou
    • 1
  • A. Mitsionis
    • 1
  • G. Skouras
    • 1
  • N. Todorova
    • 2
  • C. Trapalis
    • 2
  • T. Vaimakis
    • 1
  1. 1.Department of ChemistryUniversity of IoanninaIoanninaGreece
  2. 2.Department of Material ScienceNational Research Center “Demokritos”AthensGreece

Personalised recommendations