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Titania-heteropolyacid composites (TiO2-HPA) as catalyst for the green oxidation of trimethylphenol to 2,3,5-trimethyl-p-benzoquinone

  • Original Paper: Sol–gel and hybrid materials for catalytic, photoelectrochemical and sensor applications
  • Published:
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Abstract

New catalysts containing phosphomolybdic acid (PMA) and vanadophosphomolybdic acid (VPMA) in a titania matrix were synthesized by the sol–gel process with different heteropolyacid loads (5%, 15%, and 30% (w/w): 5PMA-TiO2, 15PMA-TiO2, 30PMA-TiO2, 5VPMA-TiO2, 15VPMA-TiO2, and 30VPMA-TiO2). The techniques used to characterize the materials were XRD, DRS, SEM, FT-IR, 31P MAS-NMR, potentiometric titration with n-butylamine, and N2 physisorption at −196 °C. The materials were used as heterogeneous catalysts in the oxidation of 2,3,6-trimethylphenol (TMP) to 2,3,5-trimethyl-p-benzoquinone (TMBQ), a key intermediate in vitamin E synthesis. The catalysts allowed an ecofriendly TMBQ synthesis, using ethanol as solvent and aqueous hydrogen peroxide as a clean oxidizing agent, at room temperature. The conversion of TMP reached 90% and 99% for the samples with 15PMA-TiO2 and 15VPMA-TiO2, respectively, after 4 h. The amount of Mo and V in the reaction medium was determined by ICP-MS, which showed leaching of only 17–18% Mo, but 48% V. Reuse of the catalysts was performed. For 15PMA-TiO2, the conversion was maintained in the second cycle. A homolytic mechanism was proposed for TMBQ synthesis, which involved the formation of a peroxometallic species through an HPA-Ti center.

Highlights

  • Titania-heteropolyacid composites were obtained by the sol–gel method.

  • The composites were tested as catalysts in the liquid phase oxidation of 2,3,6-trimethylphenol with aqueous hydrogen peroxide.

  • For the catalyst with 15% phosphomolybdic acid, conversions of 90 and 85% were observed for the first and second cycles.

  • The formation of a peroxometallic species through an HPA-Ti center was proposed as part of the homolytic mechanism.

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References

  1. Heravi MM, Sadjadi S (2009) Recent developments in use of heteropolyacids, their salts and polyoxometalates in organic synthesis. J Iran Chem Soc 6:1–54

    Article  CAS  Google Scholar 

  2. Omwoma S, Gore CT, Ji Y, Hu C, Song Y-F (2015) Environmentally benign polyoxometalate materials. Coord Chem Rev 286:17–29

    Article  CAS  Google Scholar 

  3. Kholdeeva OA, Maksimchuk NV, Maksimov GM (2010) Polyoxometalate-based heterogeneous catalysts for liquid phase selective oxidations: comparison of different strategies. Catal Today 157:107–113

    Article  CAS  Google Scholar 

  4. Bagheri S, Muhd Julkapli N, Bee Abd Hamid S (2014) Titanium dioxide as a catalyst support in heterogeneous catalysis. Sci World J 2014:1–21

    Article  Google Scholar 

  5. Kang TH, Choi JH, Gim MY, Choi JS, Joe W, Song YK (2016) Dehydration of glycerin to acrolein over H3PW12O40 catalyst supported on mesoporous titania. J Nanosci Nanotechnol 16:10829–10834

    Article  CAS  Google Scholar 

  6. Ladera RM, Garcia Fierro JL, Ojeda M, Rojas S (2014) TiO2-supported heteropoly acids for low-temperature synthesis of dimethyl ether from methanol. J Catal 312:195–203

    Article  CAS  Google Scholar 

  7. Shamsi T, Amoozadeh A, Tabrizian E, Sajjadi SM (2017) A new zwitterionic nano-titania supported Keggin phosphotungstic heteropolyacid: an efficient and recyclable heterogeneous nanocatalyst for the synthesis of 2,4,5-triaryl substituted imidazoles. Reac Kinet Mech Cat 121:505–522

    Article  CAS  Google Scholar 

  8. Palacio M, Villabrille PI, Romanelli GP, Vazquez PG, Caceres CV (2012) Preparation, characterization and use of V2O5-TiO2 mixed xerogels as catalysts for sustainable oxidation with hydrogen peroxide of 2,3,6-trimethylphenol. Appl Catal A: Gen 417-418:273–280

    Article  CAS  Google Scholar 

  9. Bellardita M, García-López EI, Marcì G, Megna B, Pomilla FR, Palmisano L (2015) Photocatalytic conversion of glucose in aqueous suspensions of heteropolyacid-TiO2 composites. RSC Adv 5:59037–59047

    Article  CAS  Google Scholar 

  10. De Souza Lourenço RER, Passoni LC, Canela MC (2014) The synergistic effect of TiO2 and H5PW10V2O40 in photocatalysis as a function of the irradiation source. J Mol Catal A: Chem 392:284–289

    Article  Google Scholar 

  11. Fuchs VM, Soto EL, Blanco MN, Pizzio LR (2008) Direct modification with tungstophosphoric acid of mesoporous titania synthesized by urea-templated sol–gel reactions. J Colloid Interface Sci 327:403–411

    Article  CAS  Google Scholar 

  12. Mercier C, Chabardes P (1994) Organometallic chemistry in industrial vitamin A and vitamin E synthesis. Pure Appl Chem 66:1509–1518

    Article  CAS  Google Scholar 

  13. Gao X, An J, Gu J, Li L, Li Y (2017) A green template-assisted synthesis of hierarchical TS-1 with excellent catalytic activity and recyclability for the oxidation of 2,3,6-trimethylphenol. Micropor Mesopor Mat 239:381–389

    Article  CAS  Google Scholar 

  14. Netscher T, Malaisé G, Bonrath W, Breuninger M (2007) A new route to Vitamin E key-intermediates by olefin cross-metathesis. Catal Today 121:71–75

    Article  CAS  Google Scholar 

  15. Kholdeeva OA, Zalomaeva OV (2016) Recent advances in transition-metal-catalyzed selective oxidation of substituted phenols and methoxyarenes with environmentally benign oxidants. Coord Chem Rev 306:302–330

    Article  CAS  Google Scholar 

  16. Packer L, WebeR SU, Rimbach G (2001) Molecular aspects of α-tocotrienol antioxidant action and cell signaling. J Nutr 131:3695–3735

    Article  Google Scholar 

  17. Saux C, Pizzio LR, Pierella LB (2003) 2,3,5-Trimethylphenol oxidation over Co-based solid catalysts. Appl Catal A: Gen 452:17–23

    Article  Google Scholar 

  18. Yamamura S (2003) Oxidation of phenols. Rappoport Z (ed). Willey, New York

  19. Hu MSL, Yu J, Xin H, An Z, Sun W (2017) Aerobic water–based oxidation of 2,3,6-trimethylphenol to trimethyl-1,4-benzoquinone over Copper(II) Nitrate catalyst. Chem Sel 2:949–952

    CAS  Google Scholar 

  20. Kozhevnikov IV (1998) Catalysis by heteropoly acids and multicomponent polyoxometalates in liquid-phase reactions. Chem Rev 98:171–198

    Article  CAS  Google Scholar 

  21. Evtushok VY, Suboch AN, Podyacheva OY, Stonkus OA, Zaikovskii VI, Chesalov YA, Kibis LS, Kholdeeva OA (2018) Highly efficient catalysts based on divanadium-substituted polyoxometalate and N-doped carbon nanotubes for selective oxidation of alkylphenols. ACS Catal 8:1297–1307

    Article  CAS  Google Scholar 

  22. Arends IWCE, Sheldon RA (2002) Recent developments in selective catalytic epoxidations with H2O2. Top Catal 19:133–134

    Article  CAS  Google Scholar 

  23. Koreniuk A, Maresz K, Odrozek K, Mrowiec-Białon J (2016) Titania-silica monolithic multichannel microreactors. Proof of concept and fabrication/structure/catalytic properties in the oxidation of 2,3,6-trimethylphenol. Micropor Mesopor Mat 229:98–105

    Article  CAS  Google Scholar 

  24. Torbina VV, Vodyankin AA, Ivanchikov ID, Kholdeeva OA, Vodyankina OV (2015) Support pretreatment effect on the catalytic properties and reusability of silica-supported titania catalysts in 2,3,6-trimethylphenol oxidation with hydrogen peroxide. Kinet Catal 56:370–376

    Article  Google Scholar 

  25. Mikushina YU, Shishmakov AB, Petrov LA (2017) Oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethyl-1,4-benzoquinone over binary xerogels TiO2-SiO2 in the three-phase system. Russ Chem Bull 66:677–682

    Article  CAS  Google Scholar 

  26. Ivanchikova ID, Maksimchuk NV, Maksimovskaya RL, Maksimov GM, Kholdeeva OA (2014) Highly selective oxidation of alkylphenols to p-benzoquinones with aqueous hydrogen peroxide catalyzed by divanadium-substituted polyoxotungstates. ACS Catal 4:2706–2713

    Article  CAS  Google Scholar 

  27. Villabrille P, Romanelli G, Vázquez P, Cáceres C (2004) Vanadium-substituted Keggin heteropolycompounds as catalysts for ecofriendly liquid phase oxidation of 2,6-dimethylphenol to 2,6-dimethyl-1,4-benzoquinone. Appl Catal A: Gen 270:101–111

    Article  CAS  Google Scholar 

  28. Mayani SV, Mayani VJ, Wook Kim S (2013) Synthesis of molybdovanadophosphoric acid supported hybrid materials and their heterogeneous catalytic activity. Mater Lett 111:112–115

    Article  CAS  Google Scholar 

  29. Nur H, Hau NY, Misnon II, Hamdan H, Muhid MNM (2006) Hydrophobic fluorinated TiO2–ZrO2 as catalyst in epoxidation of 1-octene with aqueous hydrogen peroxide. Mater Lett 60:2274–2277

    Article  CAS  Google Scholar 

  30. Concellón A, Vázquez P, Blanco M, Cáceres C (1998) Molybdophosphoric acid adsorption on titania from ethanol–water solutions. J Colloid Interface Sci 204:256–267

    Article  Google Scholar 

  31. Khalameida SV, Sydorchuk VV, Skubiszewska-Zieba J, Leboda R, Zazhigalov VA (2014) Sol-gel synthesis and properties of compositions containing heteropoly compounds in porous silica matrix. Glass Phys Chem 40:8–16

    Article  CAS  Google Scholar 

  32. Cid R, Pecchi G (1985) Potentiometric method for determining the number and relative strength of acid sites in colored catalysts. Appl Catal 14:15–21

    Article  CAS  Google Scholar 

  33. Palermo V, Sathicq ÁG, Vázquez PG, Thomas HJ (2011) Doped Keggin heteropolyacids as catalysts in sulfide oxidation. Reac Kinet Mech Cat 104:181–195

    Article  CAS  Google Scholar 

  34. Villabrille P, Romanelli GP, Vázquez P, Cáceres C (2008) Supported heteropolycompounds as ecofriendly catalysts for 2,6-dimethylphenol oxidation to 2,6-dimethyl-1,4-benzoquinone. Appl Catal A: Gen 334:374–380

    Article  CAS  Google Scholar 

  35. Benadji S, Eloy P, Leonard A, Su B-L, Rabia C, Gaigneaux EM (2012) Characterization of H3+xPMo12-xVxO40 heteropolyacids supported on HMS mesoporous molecular sieve and their catalytic performance in propene oxidation. Micropor Mesopor Mat 154:153–163

    Article  CAS  Google Scholar 

  36. Predoeva A, Damyanova S, Gaigneaux EM, Petrov L (2007) The surface and catalytic properties of titania-supported mixed PMoV heteropoly compounds for total oxidation of chlorobenzene. Appl Catal A: Gen 319:14–24

    Article  CAS  Google Scholar 

  37. Klissurski O, Hadjiivanov K, Kantcheva M, Gyurova L (1990) Study of peroxide-modified titanium dioxide (Anatase). J Chem Soc Faraday Trans 86:385–388

    Article  Google Scholar 

  38. Arends IWCE, Sheldon RA (2001) Activities and stabilities of heterogeneous catalysts in selective liquid phase oxidations: recent developments. Appl Catal A: Gen 212:175–187

    Article  CAS  Google Scholar 

  39. Li K, Yang X, Guo Y, Ma F, Li H, Chen L, Guo Y (2010) Design of mesostructured H3PW12O40–titania materials with controllable structural orderings and pore geometries and their simulated sunlight photocatalytic activity towards diethyl phthalate degradation. Appl Catal B: Environ 99:364–375

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors thank CONICET and UNLP for their financial support; and Dr José J. Martínez Zambrano for his collaboration in the discussion of results.

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Authors and Affiliations

  1. CINDECA (CONICET-CIC-UNLP), Dpto. Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Calle 47 No 257, B1900AJK, La Plata, Argentina

    Magdalena Palacio, Paula I. Villabrille, Valeria Palermo & Gustavo P. Romanelli

  2. Dpto. Exactas, Facultad de Ciencias Agrarias y Forestales, Universidad Nacional de La Plata, Calles 60 y 119 s/n, B1904AAN, La Plata, Argentina

    Paula I. Villabrille & Gustavo P. Romanelli

Authors
  1. Magdalena Palacio
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  2. Paula I. Villabrille
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  3. Valeria Palermo
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  4. Gustavo P. Romanelli
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Correspondence to Valeria Palermo.

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Palacio, M., Villabrille, P.I., Palermo, V. et al. Titania-heteropolyacid composites (TiO2-HPA) as catalyst for the green oxidation of trimethylphenol to 2,3,5-trimethyl-p-benzoquinone. J Sol-Gel Sci Technol 95, 321–331 (2020). https://doi.org/10.1007/s10971-020-05239-6

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  • DOI: https://doi.org/10.1007/s10971-020-05239-6

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