Preparation of ordered meso/macroporous HPW/titania–silica catalyst for efficient oxidative desulfurization of model fuel

  • Yue Du
  • Lina Zhou
  • Zhenran Guo
  • Xiaodi Du
  • Jiaheng LeiEmail author


In this study, ordered meso-macroporous titania–silica–polyoxometalate (HPW/SiO2–TiO2) material was prepared in one-pot by evaporation-induced self-assembly (EISA) method, with non-ionic surfactant (P123) and monodisperse polystyrene microspheres applied as co-structure-directing agents. And the oxidative desulfurization (ODS) application of as-synthesized hierarchical nanocomposite materials was tested in model fuel. The characterization results of catalyst suggested that Keggin-type polyoxometalate was successfully incorporated into the ordered meso-macroporous SiO2–TiO2 framework. Moreover, the effect of Lewis acid center of the HPW/SiO2–TiO2 catalyst on ODS process was investigated. The optimum proportion of titanium and silicon ratio on catalyst was found to be 1:1, which exhibited remarkable catalytic performance on aromatic sulfur compounds at mild conditions. It revealed that Lewis acid sites played an important role in selectively adsorb DBT and its derivatives. What’s More, the combination of Lewis acid sites and ordered meso/macroporous architecture of catalyst will further facilitated the mass transport in ODS process. No decrease in the activity was observed after six runs, indicating a good stability of as-prepared catalyst.


Meso/macroporous catalyst Oxidative desulfurization Keggin heteropolyacids Titania–silica nanocomposite 



This work was supported by the National Nature Science Foundation of China (Grant Nos. 21476177, 51502218). We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted.

Supplementary material

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Supplementary material 1 (DOC 5516 KB)


  1. 1.
    F.S. Mjalli, O.U. Ahmed, T. Al-Wahaibi, Y. Al-Wahaibi, I.M. AlNashef, Deep oxidative desulfurization of liquid fuels. Rev. Chem. Eng. 30, 337–378 (2014)CrossRefGoogle Scholar
  2. 2.
    S. Xun, W. Zhu, D. Zheng, L. Zhang, H. Liu, S. Yin et al., Synthesis of metal-based ionic liquid supported catalyst and its application in catalytic oxidative desulfurization of fuels. Fuel 136, 358–365 (2014)CrossRefGoogle Scholar
  3. 3.
    B. Li, Z. Liu, C. Han, W. Ma, S. Zhao, In situ synthesis, characterization, and catalytic performance of tungstophosphoric acid encapsulated into the framework of mesoporous silica pillared clay. J. Colloid Interf. Sci. 377, 334–341 (2012)CrossRefGoogle Scholar
  4. 4.
    X. Ma, S. Velu, J.H. Kim, C. Song, Deep desulfurization of gasoline by selective adsorption over solid adsorbents and impact of analytical methods on ppm-level sulfur quantification for fuel cell applications. Appl. Catal. B 56, 137–147 (2005)CrossRefGoogle Scholar
  5. 5.
    J.D. Holbrey, I. Lopez-Martin, G. Rothenberg, K.R. Seddon, G. Silvero, X. Zheng, Desulfurisation of oils using ionic liquids: selection of cationic and anionic components to enhance extraction efficiency. Green Chem. 10, 87–92 (2008)CrossRefGoogle Scholar
  6. 6.
    R. Abro, A.A. Abdeltawab, S.S. Al-Deyab, G.R. Yu, A.B. Qazi, S.R. Gao, X.C. Chen, A review of extractive desulfurization of fuel oils using ionic liquids. Rsc Adv. 4, 35302–35317 (2014)CrossRefGoogle Scholar
  7. 7.
    Z. Abdalla, B.S. Li, Preparation of MCM-41 supported (Bu4N)(4)H3(PW11O39) catalyst and its performance in oxidative desulfurization. Chem. Eng. J. 200, 113–121 (2012)CrossRefGoogle Scholar
  8. 8.
    P.Y.,S.Z. Du, Y. Lei, J. Synthesis of ordered meso/macroporous H3PW12O40/SiO2 and its catalytic performance in oxidative desulfurization. Rsc Adv. 6, 53860–53866 (2016)CrossRefGoogle Scholar
  9. 9.
    X.M. Yan, P. Mei, J.H. Lei, Y.Z. Mi, L. Xiong, L.P. Guo, Synthesis and characterization of mesoporous phosphotungstic acid/TiO2 nanocomposite as a novel oxidative desulfurization catalyst. J. Mol. Catal. A-Chem. 304, 52–57 (2009)CrossRefGoogle Scholar
  10. 10.
    X. Yan, J. Lei, D. Liu, Y. Wu, W. Liu, Synthesis and catalytic properties of mesoporous phosphotungstic acid/SiO2 in a self-generated acidic environment by evaporation-induced self-assembly. Mater. Res. Bull. 42, 1905–1913 (2007)CrossRefGoogle Scholar
  11. 11.
    J.H. Lei, L.N. Chen, P. Yang, X.D. Du, X.M. Yan, Oxidative desulfurization of diesel fuel by mesoporous phosphotungstic acid/SiO2 the effect of preparation methods on catalytic performance. J. Porous Mater. 20, 1379–1385 (2013)CrossRefGoogle Scholar
  12. 12.
    L. Tang, G. Luo, M. Zhu, L. Kang, B. Dai, Preparation, characterization and catalytic performance of HPW-TUD-1 catalyst on oxidative desulfurization. J. Ind. Eng. Chem. 19, 620–626 (2013)CrossRefGoogle Scholar
  13. 13.
    M. Zhang, W. Zhu, H. Li, S. Xun, W. Ding, J. Liu et al., One-pot synthesis, characterization and desulfurization of functional mesoporous W-MCM-41 from POM-based ionic liquids. Chem. Eng. J. 243, 386–393 (2014)CrossRefGoogle Scholar
  14. 14.
    M. Zhang, Y. Wei, R. Li, W. Zhu, H. Li, Q. Zhang et al., Magnetic POM-based mesoporous silica for fast oxidation of aromatic sulfur compounds. Fuel 209, 545–551 (2017)CrossRefGoogle Scholar
  15. 15.
    M. Zhang, W. Zhu, S. Xun, H. Li, Q. Gu, Z. Zhao, Q. Wang, Deep oxidative desulfurization of dibenzothiophene with POM-based hybrid materials in ionic liquids. Chem. Eng. J. 220, 328–336 (2013)CrossRefGoogle Scholar
  16. 16.
    L. Yang, Y. Qi, X. Yuan, J. Shen, J. Kim, Direct synthesis, characterization and catalytic application of SBA-15 containing heteropolyacid H3PW12O40. J. Mol. Catal. A: Chem. 229, 199–205 (2005)CrossRefGoogle Scholar
  17. 17.
    D. Yue, J. Lei, Y. Peng, J. Li, X. Du, Hierarchical ordered meso/macroporous H3PW12O40/SiO2 catalysts with superior oxidative desulfurization activity. J. Porous Mater. 25, 727–734 (2017)CrossRefGoogle Scholar
  18. 18.
    D. Yue, Y. Peng, S. Zhou, J. Li, X. Du, J. Lei, Direct synthesis of ordered meso/macrostructured phosphotungstic acid/SiO2 by EISA method and its catalytic performance of fuel oil. Mater. Res. Bull. 97, 42–48 (2018)CrossRefGoogle Scholar
  19. 19.
    P. Yang, S. Zhou, Y. Du, J. Li, J. Lei, Self-assembled meso/macroporous phosphotungstic acid/TiO2 as an efficient catalyst for oxidative desulfurization of fuels. J. Porous Mater. 24:531–539 (2017)CrossRefGoogle Scholar
  20. 20.
    X.M. Yan, P. Mei, L. Xiong, L. Gao, Q.F. Yang, L.J. Gong, Mesoporous titania-silica-polyoxometalate nanocomposite materials for catalytic oxidation desulfurization of fuel oil. Catal. Sci. Technol. 3:1985–1992 (2013)CrossRefGoogle Scholar
  21. 21.
    A.H.M.S. Hussain, B.J. Tatarchuk, Adsorptive desulfurization of jet and diesel fuels using Ag/TiOx-Al2O3 and Ag/TiOx-SiO2 adsorbents. Fuel 107, 465–473 (2013)CrossRefGoogle Scholar
  22. 22.
    L.F. Wang, B.D. Sun, F.H. Yang, R.T. Yang, Effects of aromatics on desulfurization of liquid fuel by pi-complexation and carbon adsorbents. Chem. Eng. Sci. 73, 208–217 (2012)CrossRefGoogle Scholar
  23. 23.
    B.T. Holland, C.F. Blanford, T. Do, A. Stein, Synthesis of highly ordered, three-dimensional, macroporous structures of amorphous or crystalline inorganic oxides, phosphates, and hybrid composites. Chem. Mater. 11, 795–805 (1999)CrossRefGoogle Scholar
  24. 24.
    Z. Abdalla, B.S. Li, A. Tufail, Direct synthesis of mesoporous (C19H42N)4H3(PW11O39)/SiO2 and its catalytic performance in oxidative desulfurization. Colloid Surf. A 341, 86–92 (2009)CrossRefGoogle Scholar
  25. 25.
    J. Xiong, W.S. Zhu, W.J. Ding, L. Yang, Y.H. Chao, H.P. Li et al., Phosphotungstic acid immobilized on ionic liquid-modified SBA-15: efficient hydrophobic heterogeneous catalyst for oxidative desulfurization in fuel. Ind. Eng. Chem. Res. 53, 19895–19904 (2014)CrossRefGoogle Scholar
  26. 26.
    J. Dhainaut, J. Dacquin, A.F. Lee, K. Wilson, Hierarchical macroporous–mesoporous SBA-15 sulfonic acid catalysts for biodiesel synthesis. Green Chem. 12, 296–303 (2010)CrossRefGoogle Scholar
  27. 27.
    D. Liu, L.J. Xia, D. Qu et al., Synthesis of hierarchical fiberlike ordered mesoporous carbons with excellent electrochemical capacitance performance by a strongly acidic aqueous cooperative assembly route. J. Mater. Chem. A 48, 15447–15458 (2013)CrossRefGoogle Scholar
  28. 28.
    W. Kim, S. Bae, Hee Choi, J.S. Lee, Quantitative analysis of Ti–O–Si and Ti–O–Ti bonds in Ti–Si binary oxides by the linear combination of XANES. J. Phys. Chem. 104, 8670–8678 (2001)CrossRefGoogle Scholar
  29. 29.
    R. Camposeco, S. Castillo, I. Mejia-Centeno, J. Navarrete, N. Nava, Boosted surface acidity in TiO2 and Al2O3-TiO2 nanotubes as catalytic supports. Appl. Surf. Sci. 356, 115–123 (2015)CrossRefGoogle Scholar
  30. 30.
    X. Yan, Z. Mei, P. Mei, Q. Yang, Self-assembled HPW/silica-alumina mesoporous nanocomposite as catalysts for oxidative desulfurization of fuel oil. J. Porous Mater. 21, 729–737 (2014)CrossRefGoogle Scholar
  31. 31.
    D.C. Duncan, R.C. Chambers, E. Hecht, C.L. Hill, Mechanism and dynamics in the H3[PW12O40]-catalyzed selective epoxidation of terminal olefins by H2O2. Formation, reactivity, and stability of {PO4[WO(O2)2]4}3–. J. Am. Chem. Soc. 2, 681–691 (1995)CrossRefGoogle Scholar
  32. 32.
    Y. Du, J. Lei, Y. Peng, J. Li, X. Du, Three-dimensional ordered phosphotungstic acid/TiO2 with superior catalytic activity for oxidative desulfurization. Fuel 226, 148–155 (2018)CrossRefGoogle Scholar
  33. 33.
    M. Te, C. Fairbridge, Z. Ring, Oxidation reactivities of dibenzothiophenes in polyoxometalate/H2O2 and formic acid/H2O2 systems. Appl. Catal. A 219, 267–280 (2001)CrossRefGoogle Scholar
  34. 34.
    J. Zhang, A.J. Wang, Y.J. Wang, H.Y. Wang, J.Z. Gui, Heterogeneous oxidative desulfurization of diesel oil by hydrogen peroxide: catalysis of an amphipathic hybrid material supported on SiO2. Chem. Eng. J. 245, 65–70 (2014)CrossRefGoogle Scholar
  35. 35.
    C. Shen, Y.J. Wang, J.H. Xu, G.S. Luo, Synthesis of TS-1 on porous glass beads for catalytic oxidative desulfurization. Chem. Eng. J. 259, 552–561 (2015)CrossRefGoogle Scholar
  36. 36.
    J. Zhang, A.J. Wang, X. Li, X.H. Ma, Oxidative desulfurization of dibenzothiophene and diesel over [Bmim](3)PMo12O40. J. Catal. 279, 269–275 (2011)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Yue Du
    • 1
  • Lina Zhou
    • 1
  • Zhenran Guo
    • 2
  • Xiaodi Du
    • 2
  • Jiaheng Lei
    • 2
    Email author
  1. 1.School of Materials Science and EngineeringWuhan University of TechnologyWuhanPeople’s Republic of China
  2. 2.Department of ChemistryWuhan University of TechnologyWuhanPeople’s Republic of China

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