Skip to main content
SpringerLink
Log in

Immobilization of tungsten chelate complexes on functionalized mesoporous silica SBA-15 as heterogeneous catalysts for oxidation of cyclopentene

  • Chemical routes to materials
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

An efficient hybrid mesoporous heterogeneous catalyst system was synthesized via covalently grafting tungsten chelate complex W-N,N (N,N = (3-triethoxysilylpropyl) [3-(2-pyridyl)-1-pyrazolyl] acetamide, N,N-chelating ligand) in organic moieties (diphenyldichlorosilane, DPHS)-functionalized mesoporous silica SBA-15 or pure SBA-15. Characterization of synthesized materials via N2 sorption, XRD, TEM, UV–Vis DRS, 29Si MAS NMR, element analysis, and FT-IR indicated that W-N,N was successfully anchored and highly dispersed in the mesochannels of SBA-15 and the mesostructure of SBA-15 was maintained during the grafting course. The synthesized hybrid catalysts were highly active and authentically heterogeneous in triphasic oxidation reaction of cyclopentene (CPE) with H2O2. W,N-N immobilized on functionalized SBA-15 with DPHS moieties (W-N,N-DPHS-SBA-15) showed better catalytic properties (activity and stability) than its unmodified counterpart W-N,N-SBA-15 catalyst. Besides, possible catalytic reaction route for CPE oxidation with H2O2 over W-N,N-DPHS-SBA-15 catalyst was proposed. The amphiphilic mesochannels of W-N,N-DPHS-SBA-15 provided suitable accommodation for both hydrophilic H2O2 and hydrophobic CPE molecules and acted as nanoreactors for CPE/H2O2/solid triphase reaction.

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

Scheme 1
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Scheme 2
Scheme 3
Figure 11
Figure 12

Similar content being viewed by others

References

  1. Ballantyne B, Jordan SL (2001) Toxicological, medical and industrial hygiene aspects of glutaraldehyde with particular reference to its biocidal use in cold sterilization procedures. J Appl Toxicol 21:131–151

    Article  CAS  Google Scholar 

  2. Dartiguenave MC, Bertrand MJ, Waldron KC (2004) Glutaraldehyde: behavior in aqueous solution, reaction with proteins, and application to enzyme crosslinking. Biotechniques 37:790–796

    Article  Google Scholar 

  3. Thomas S, Russell AD (1974) Studies on the mechanism of the sporicidal action of glutaraldehyde. J Appl Bacteriol 37:83–92

    Article  CAS  Google Scholar 

  4. Sato K, Aoki M, Noyori R (1998) A “Green” route to adipic acid: direct oxidation of cyclohexenes with 30 percent hydrogen peroxide. Science 281:1646–1647

    Article  CAS  Google Scholar 

  5. Grigoropoulou G, Clark JH, Elings JA (2003) Recent developments on the epoxidation of alkenes using hydrogen peroxide as an oxidant. Green Chem 5:1–7

    Article  CAS  Google Scholar 

  6. Noyori R, Aoki M, Sato K (1977) Green oxidation with aqueous hydrogen peroxide. Chem Commun 34:1977–1986

    Google Scholar 

  7. Filip M, Todorova S, Shopska M, Ciobanu M, Papa F, Somacescu S, Munteanu C, Parvulescu V (2018) Effects of Ti loading on activity and redox behavior of metals in PtCeTi/KIT-6 catalysts for CH4 and CO oxidation. Catal Today 306:138–144

    Article  CAS  Google Scholar 

  8. Xun S, Jiang W, Guo T, He MQ, Ma RL, Zhang M, Zhu WS, Li HM (2019) Magnetic mesoporous nanospheres supported phosphomolybdate-based ionic liquid for aerobic oxidative desulfurization of fuel. J Colloid Interface Sci 534:239–247

    Article  CAS  Google Scholar 

  9. Singh R, Belgamwar R, Dhiman M, Polshettiwar V (2018) Dendritic fibrous nano-silica supported gold nanoparticles as an artificial enzyme. J Mater Chem B 6:1600–1604

    Article  CAS  Google Scholar 

  10. Das P, Silva AR, Carvalho AP, Pires J, Freire C (2009) Organo-functionalized mesoporous supports for Jacobsen-type catalyst: laponite versus MCM-41. J Mater Sci 44:2865–2875. https://doi.org/10.1007/s10853-009-3379-x

    Article  CAS  Google Scholar 

  11. Zhong NJ, Li Y, Cai CS, Gao YQ, Liu N, Liu GQ, Tan WY, Zeng YY (2018) Enhancing the catalytic performance of candida antarctica lipase B by immobilization onto the ionic liquids modified SBA-15. Eur J Lipid Sci Technol 120:1700357–1700363

    Article  CAS  Google Scholar 

  12. Jin MM, Guo ZM, Ge XP, Lv ZG (2018) Tungsten-based organic mesoporous SBA-15 materials: characterization and catalytic properties in the oxidation of cyclopentene to glutaric acid with H2O2. React Kinet Mech Catal 125:1139–1157

    Article  CAS  Google Scholar 

  13. Peña ML, Dellarocca V, Rey F, Corma A, Coluccia S, Marchese L (2001) Elucidating the local environment of Ti(IV) active sites in Ti-MCM-48: a comparison between silylated and calcined catalysts. Microporous Mesoporous Mater 44–45:345–356

    Article  Google Scholar 

  14. Yuan ZL, Chen S, Liu B (2017) Nitrogen-doped reduced graphene oxide-supported Mn3O4: an efficient heterogeneous catalyst for the oxidation of vanillyl alcohol to vanillin. J Mater Sci 52:164–172. https://doi.org/10.1007/s10853-016-0318-5

    Article  CAS  Google Scholar 

  15. Lizama LY, Klimova TE (2009) SBA-15 modified with Al, Ti, or Zr as supports for highly active NiW catalysts for HDS. J Mater Sci 44:6617–6628. https://doi.org/10.1007/s10853-009-3613-6

    Article  CAS  Google Scholar 

  16. Xun SH, Hou CZ, Li HP, He MQ, Ma RL, Zhang M, Zhu WS, Li HM (2018) Synthesis of WO3/mesoporous ZrO2 catalyst as a high-efficiency catalyst for catalytic oxidation of dibenzothiophene in diesel. J Mater Sci 53:15927–15938. https://doi.org/10.1007/s10853-018-2720-7

    Article  CAS  Google Scholar 

  17. Lu G, Li XY, Qu ZP, Wang YX, Chen GH (2008) Selective oxidation of cyclopentene to glutaraldehyde over the WO3/SiO2 catalyst. Appl Surf Sci 255:3117–3120

    Article  CAS  Google Scholar 

  18. Yang XL, Gao RH, Dai WL, Fan KN (2008) Influence of tungsten precursors on the structure and catalytic properties of WO3/SBA-15 in the selective oxidation of cyclopentene to glutaraldehyde. J Phys Chem C 112:3819–3826

    Article  CAS  Google Scholar 

  19. Yang XL, Dai WL, Chen H, Xu JH, Cao Y, Li HX, Fan KN (2005) Novel tungsten-containing mesoporous HMS material: its synthesis, characterization and catalytic application in the selective oxidation of cyclopentene to glutaraldehyde by aqueous H2O2. Appl Catal A Gen 283:1–8

    Article  CAS  Google Scholar 

  20. Yang XL, Dai WL, Gao RH, Fan KN (2007) Characterization and catalytic behavior of highly active tungsten-doped SBA-15 catalyst in the synthesis of glutaraldehyde using an anhydrous approach. J Catal 249:278–288

    Article  CAS  Google Scholar 

  21. Jia MJ, Seifert A, Thiel WR (2003) Mesoporous MCM-41 materials modified with oxodiperoxo molybdenum complexes: efficient catalysts for the epoxidation of cyclooctene. Chem Mater 15:2174–2180

    Article  CAS  Google Scholar 

  22. Tang JY, Wang L, Liu G, Liu Y, Hou YZ, Zhang WX, Jia MJ, Thiel WR (2009) Mesoporous SBA-15 materials modified with oxodiperoxo tungsten complexes as efficient catalysts for the epoxidation of olefins with hydrogen peroxide. J Mol Catal A: Chem 313:31–37

    Article  CAS  Google Scholar 

  23. Mimoun H, Roch ISD, Sajus L (1970) Epoxydation des olefines par les complexes peroxydiques covalents du molybdene-VI. Tetrahedron 26:37–50

    Article  CAS  Google Scholar 

  24. Dickman MH, Pope MT (1994) Peroxo and superoxo complexes of chromium, molybdenum, and tungsten. Chem Rev 94:569–584

    Article  CAS  Google Scholar 

  25. Zhao DY, Huo QS, Feng JL, Chmelka BF, Stucky GD (1998) 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

    Article  CAS  Google Scholar 

  26. Cutrufello MG, Rombi E, Cannas C, Casu M, Virga A, Fiorilli S, Onida B, Ferino I (2009) Synthesis, characterization and catalytic activity of Au supported on functionalized SBA-15 for low temperature CO oxidation. J Mater Sci 44:6644–6653. https://doi.org/10.1007/s10853-009-3510-z

    Article  CAS  Google Scholar 

  27. Orlov A, Zhai QZ, Klinowski J (2006) Photocatalytic properties of the SBA-15 mesoporous silica molecular sieve modified with titanium. J Mater Sci 41:2187–2193. https://doi.org/10.1007/s10853-006-7184-5

    Article  CAS  Google Scholar 

  28. Huang ZD, Bensch W, Sigle W, Aken PAV, Kienle L, Vitoya T, Modrow H, Ressler T (2008) The modification of MoO3 nanoparticles supported on mesoporous SBA-15: characterization using X-ray scattering, N2 physisorption, transmission electron microscopy, high-angle annular darkfield technique, Raman and XAFS spectroscopy. J Mater Sci 43:244–253. https://doi.org/10.1007/s10853-007-2173-x

    Article  CAS  Google Scholar 

  29. Szegedi Á, Popova M, Minchev C (2009) Catalytic activity of Co/MCM-41 and Co/SBA-15 materials in toluene oxidation. J Mater Sci 44:6710–6716. https://doi.org/10.1007/s10853-009-3600-y

    Article  CAS  Google Scholar 

  30. Karimi B, Khorasani M (2013) Selectivity adjustment of SBA-15 based tungstate catalyst in oxidation of sulfides by incorporating a hydrophobic organic group inside the mesochannels. ACS Catal 3:1657–1664

    Article  CAS  Google Scholar 

  31. Li KG, Wang J, Zou YC, Song XJ, Gao HC, Zhu WC, Zhang WX, Yu JH, Jia MJ (2014) Surfactant-assisted sol–gel synthesis of zirconia supported phosphotungstates or Ti-substituted phosphotungstates for catalytic oxidation of cyclohexene. Appl Catal A Gen 482:84–91

    Article  CAS  Google Scholar 

  32. Pretsch E, Clerc T, Seibl J, Simon W (1983) Tables of spectral data for structure determination of organic compounds. Springer, Berlin

    Book  Google Scholar 

  33. Thu PTT, Thanh TT, Phi HN, Kim SJ, Vo V (2010) Adsorption of lead from water by thiol-functionalized SBA-15 silicas. J Mater Sci 45:2952–2957. https://doi.org/10.1007/s10853-010-4288-8

    Article  CAS  Google Scholar 

  34. Shi XY, Han XY, Ma WJ, Wei JF, Li J, Zhang Q, Chen ZG (2011) Peroxotungstates immobilized on multilayer ionic liquid brushes-modified silica as an efficient and reusable catalyst for selective oxidation of sulfides with H2O2. J Mol Catal A: Chem 341:57–62

    Article  CAS  Google Scholar 

  35. Takei T, Houshito O, Yonesaki Y, Kumada N, Kinomura N (2007) Porous properties of silylated mesoporous silica and its hydrogen adsorption. J Solid State Chem 180:1180–1187

    Article  CAS  Google Scholar 

  36. Zhu WS, Li HM, He XY, Zhang Q, Shu HM, Yan YS (2008) Synthesis of adipic acid catalyzed by surfactant-type peroxotungstates and peroxomolybdates. Catal Commun 9:551–555

    Article  CAS  Google Scholar 

  37. Li H, Xu Y, Yang HX, Zhang F, Li HX (2009) Ni-B amorphous alloy deposited on an aminopropyl and methyl co-functionalized SBA-15 as a highly active catalyst for chloronitrobenzene hydrogenation. J Mol Catal A: Chem 307:105–114

    Article  CAS  Google Scholar 

  38. Morales V, Villajos JA, García RA (2013) Simultaneous synthesis of modified Binol-periodic mesoporous organosilica SBA-15 type material. Application as catalysts in asymmetric sulfoxidation reactions. J Mater Sci 48:5990–6000. https://doi.org/10.1007/s10853-013-7395-5

    Article  CAS  Google Scholar 

  39. Pursch M, Sander LC, Albert K (1996) Chain order and mobility of high-density C18 phases by solid-state NMR spectroscopy and liquid chromatography. Anal Chem 68:4107–4113

    Article  CAS  Google Scholar 

  40. Zhao XS, Lu GQ (1998) Modification of MCM-41 by surface silylation with trimethylchlorosilane and adsorption study. J Phys Chem B 102(1998):1556–1561

    Article  CAS  Google Scholar 

  41. Farahani MM, Modarres M (2016) Wells-Dawson heteropoly acid immobilized inside the nanocages of SBA-16 with ship-in-a-bottle method: a new recoverable catalyst for the epoxidation of olefins. J Mol Catal A: Chem 417:81–88

    Article  CAS  Google Scholar 

  42. Zhao XS, Lu GQ, Whittaker AK, Millar GJ, Zhu HY (1997) Comprehensive study of surface chemistry of MCM-41 using 29Si CP/MAS NMR, FTIR, Pyridine-TPD, and TGA. J Phys Chem B 101:6525–6531

    Article  CAS  Google Scholar 

  43. Bordoloi A, Sahoo S, Lefebvre F, Halligudi SB (2008) Heteropoly acid-based supported ionic liquid-phase catalyst for the selective oxidation of alcohols. J Catal 259:232–239

    Article  CAS  Google Scholar 

  44. Wang L, Shylesh S, Dehe D, Philippi T, Dörr G, Seifert A, Zhou Z, Hartmann M, Taylor RNK, Jia MJ, Ernat S, Thiel WR (2012) Covalent immobilization of imidazolium cations inside a silica support: palladium-catalyzed olefin hydrogenation. Chemcatchem 4:395–400

    Article  CAS  Google Scholar 

  45. Tan R, Liu C, Feng ND, Xiao J, Zheng WG, Zheng AM, Yin DH (2012) Phosphotungstic acid loaded on hydrophilic ionic liquid modified SBA-15 for selective oxidation of alcohols with aqueous H2O2. Microporous Mesoporous Mater 158:77–87

    Article  CAS  Google Scholar 

  46. Zhang RY, Ding W, Tu B, Zhao DY (2007) Mesoporous silica: an efficient nanoreactor for liquid–liquid biphase reactions. Chem Mater 19:4379–4381

    Article  CAS  Google Scholar 

  47. Hulea V, Dumitriu E, Patcas F, Ropot R, Graffin P, Moreau P (1998) Cyclopentene oxidation with H2O2 over Ti-containing zeolites. Appl Catal A Gen 170:169–175

    Article  CAS  Google Scholar 

  48. Clerici MG, Ingallina P (1993) Epoxidation of lower olefins with hydrogen peroxide and titanium silicalite. J Catal 140:71–83

    Article  CAS  Google Scholar 

  49. Jin RH, Xia X, Dai WL, Deng JF, Li HX (1999) An effective heterogeneous WO3/TiO2–SiO2 catalyst for selective oxidation of cyclopentene to glutaraldehyde by H2O2. Catal Lett 62:201–207

    Article  CAS  Google Scholar 

  50. Chibani S, Michel C, Delbecq F, Pinel C, Besson M (2013) On the key role of hydroxyl groups in platinum-catalysed alcohol oxidation in aqueous medium. Catal Sci Technol 3:339–350

    Article  CAS  Google Scholar 

  51. Deng JF, Xu XH, Chen HY, Jiang AR (1992) A new process for preparing dialdehydes by catalytic oxidation of cyclic olefins with aqueous hydrogen peroxide. Tetrahedron 48:3503–3514

    Article  CAS  Google Scholar 

  52. Jin RH, Li HX, Deng JF (2001) Selective oxidation of cyclopentene to glutaraldehyde by H2O2 over the WO3/SiO2 Catalyst. J Catal 203:75–81

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by Major Program of Shandong Province Natural Science Foundation [ZR2017ZC0632] and National Natural Science Foundation of China [NSFC21376128].

Author information

Authors and Affiliations

  1. State Key Laboratory Base for Eco-chemical Engineering, College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China

    Manman Jin & Zhiguo Lv

  2. College of Marine Science and Biological Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China

    Zhenmei Guo

Authors
  1. Manman Jin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zhenmei Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhiguo Lv
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Zhiguo Lv.

Ethics declarations

Conflict of interest

The authors declare no conflict of interest.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Jin, M., Guo, Z. & Lv, Z. Immobilization of tungsten chelate complexes on functionalized mesoporous silica SBA-15 as heterogeneous catalysts for oxidation of cyclopentene. J Mater Sci 54, 6853–6866 (2019). https://doi.org/10.1007/s10853-019-03361-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-019-03361-7

Search

Navigation