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Synthesis and characterization of tungstophosphoric acid-modified mesoporous sponge-like TUD-1 materials

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

Mesoporous sponge-like siliceous materials (TUD-1) were synthesized using TEOS (tetraethylorthosilicate) as a precursor of silica and TEA (triethanolamine) as a mesostructure-directing agent. Different TEOS/TEA molar ratios and hydrotreatment times were used, and their influence on the textural and morphological properties of the solids was evaluated. They were characterized by transmission electron microscopy (TEM), X-ray diffraction, and N2 adsorption/desorption isotherm analysis. By changing the TEOS/TEA molar ratio, micro-mesoporous and mesoporous (with a narrow or wide pore size distribution) materials were obtained. The increment of hydrotreatment times increased the average pore size of TUD-1 and significantly reduced the specific surface area. TEM images showed that the solids were formed by agglomerates of rather spherical particles whose size increased with the increment of the TEA amount used. The structure and morphology of TUD-1 solids modified with tungstophosphoric acid (TPA) were similar to those of the mesoporous silica used as support. Their diffraction patterns did not display any of the characteristic peaks of TPA or its more common hydrates, suggesting that TPA was well dispersed on the support as a noncrystalline phase. In addition, the characterization of all the solids impregnated with TPA by FT-IR and 31P NMR indicated the presence of undegraded [PW12O40]3− and [H3−XPW12O40]X− species interacting electrostatically with the ≡Si–OH2+ groups, and by potentiometric titration it was estimated that the solids presented very strong acid sites. The TUD-1 solids modified with TPA gave excellent yield in the solvent-free synthesis of 2,4,5-triphenyl-1H-imidazole, without formation of by-products resulting from competitive reactions or decomposition products. In summary, they are good candidates to be used in multicomponent reactions catalyzed by acids.

Highlights

  • TUD-1 materials were synthetized using different TEOS/TEA molar ratios and hydrotreatment times.

  • Their influence on the textural and morphological properties was evaluated.

  • The TUD-1 materials were impregnated with tungstophosphoric acid.

  • They gave excellent yield in the in the solvent-free synthesis of 2,4,5-triphenyl-1H-imidazole.

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References

  1. Rivera TS, Sosa A, Romanelli GP, Blanco MN, Pizzio LR (2012) Tungstophosphoric acid/zirconia composites prepared by the sol–gel method: an efficient and recyclable green catalyst for the one-pot synthesis of 14-aryl-14H-dibenzo[a,j]xanthenes. Appl Catal A Gen 443–444:207–213

    Article  Google Scholar 

  2. Rengifo-Herrera JA, Frenzel RA, Blanco MN, Pizzio LR (2014) Visible-light-absorbing mesoporous TiO2 modified with tungstosilicic acid as photocatalyst in the photodegradation of 4-chlorophenol. J Photochem Photobiol A Chem 289:22–30

    Article  Google Scholar 

  3. Kozhevnikov IV, Sinnema A, RJJ Jansen, Pamin K, van Bekkum H (1995) New acid catalyst comprising heteropoly acid on a mesoporous molecular sieve MCM-4. Catal Lett 30:241–252

    Article  Google Scholar 

  4. Beck JS, Vartuli JC, Kresge CT, Roth WJ, Leonowicz ME, Kresge CT, Schmitt KD (1992) A new family of mesoporous molecular sieves prepared with liquid crystal templates. J Am Chem Soc 114:10834–10843

    Article  Google Scholar 

  5. Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS (1992) Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359:710–712

    Article  Google Scholar 

  6. Zhao D, Feng J, Huo Q, Melosh N, Fredrickson GH, Chmelka BF, Stucky GD (1998) Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 279:548–552

    Article  Google Scholar 

  7. Ryoo R, Joo SH, Jun S (1999) Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformation. J Phys Chem B 103:7743–7746

    Article  Google Scholar 

  8. Jansen JC,Shan Z,Marchese L,Zhou W,Van der Puil N,aschmeyer T (2001) A new templating method for three-dimensional mesopore networks Chem Commun 2010:713–714

    Article  Google Scholar 

  9. Anand R, Maheswari R, Hanefeld U (2006) Catalytic properties of the novel mesoporous aluminosilicate AlTUD-1. J Catal 242:82–91

    Article  Google Scholar 

  10. Hamdy MS, Mul G, Jansen JC, Ebaid A, Shan Z, Overweg AR, Maschmeyer T (2005) Synthesis, characterization, and unique catalytic performance of the mesoporous material Fe-TUD-1 in Friedel–Crafts benzylation of benzene. Catal Today 100:255–260

    Article  Google Scholar 

  11. Ramanathan A, Villalobos MCC, Kwakernaak C, Telalovic S, Hanefeld U (2008) Zr-TUD-1: a lewis acidic, three-dimensional, mesoporous, zirconium-containing catalyst. Chem Eur J 14:961–972

    Article  Google Scholar 

  12. Anand R, Hamdy MS, Hanefeld U, Maschmeyer T (2004) Liquid-phase oxidation of cyclohexane over Co-TUD-1. Catal Lett 95:113–117

    Article  Google Scholar 

  13. Hamdy MS, Ramanathan A, Maschmeyer T, Hanefeld U, Jansen JC (2006) Co-TUD-1: a ketone-selective catalyst for cyclohexane oxidation. Chem Eur J 12:1782–1789

    Article  Google Scholar 

  14. Gorsd MN, Sathicq G, Romanelli GP, Pizzio LR, Blanco MN (2016) Tungstophosphoric acid supported on core-shell polystyrene-silica microspheres or hollow silica spheres catalyzed trisubstituted imidazole synthesis by multicomponent reaction. J Mol Catal A Chem 420:294–302

    Article  Google Scholar 

  15. Heravi MM, Fard MV, Faghihi Z. (2013) Heteropoly acids-catalyzed organic reactions in water: doubly green reactions. Green Chem Lett Rev 6:282–300.

  16. Misono M, Mizuno N, Katamura K, Kasai A, Konishi Y, Sakata K, Okura T, Yoneda Y (1982) Catalysis by heteropoly compounds-3. The structure and properties of 12-heteropoly acids of molybdenum and tungsten (H3PMo12-XWx O40) and their salts pertinent to heterogenous catalysis. Bull Chem Soc Jpn 55:400–406

    Article  Google Scholar 

  17. Shikata S, Nakata S, Okuhara T, Misono M (1997) Catalysis by heteropoly compounds. 32. Synthesis of methyltert-butyl ether catalyzed by heteropoly acids supported on silica. J Catal 166:263–271

    Article  Google Scholar 

  18. Fuchs VM, Pizzio LR, Blanco MN (2008) Synthesis and characterization of aluminum or copper tungstophosphate and tungstosilicate immobilized in a polymeric blend. Eur Polym J 44:801–807

    Article  Google Scholar 

  19. Gorsd MN, Pizzio LR, Blanco MN (2011) Trifluoromethanesulfonic acid immobilized on zirconium oxide obtained by the sol-gel method as catalyst in paraben synthesis. Appl Catal A Gen 400:91–98

    Article  Google Scholar 

  20. Sosa AA, Rivera TS, Blanco MN, Pizzio LR, Romanelli GP (2013) Tungstophosphoric acid supported on zirconia: a recyclable catalyst for the green synthesis on quinoxaline derivatives under solvent-free conditions. Phosphorus Sulfur Silicon Relat Elem 188(8):10714–11079

    Article  Google Scholar 

  21. Orellana MA, Osiglio L, Arnal PM, Pizzio LR (2017) Titania hollow spheres modified with tungstophosphoric acid with enhanced visible light absorption for the photodegradation of 4-chlorophenol. Photochem Photobiol Sci 16(1):46–52

    Article  Google Scholar 

  22. Frenzel RA, Sathicq AG, Blanco MN, Romanelli GP, Pizzio LR (2015) Carbon-supported metal-modified lacunary tungstosilicic polyoxometallates used as catalysts in the selective oxidation of sulfides. J Mol Catal A Chem 403:27–36

    Article  Google Scholar 

  23. Kapustin GI, Brueva TR, Klyachko AL, Timofeeva MN, Kulikov SM, Kozhevnikov IV (1990) A study of the acidity of heteropoly acids. Kinet Katal 3:1017–1020

    Google Scholar 

  24. Moffat JB, Kasztelan S (1988) The oxidation of methane on heteropolyoxometalates II. Nature and stability of the supported species. J Catal 109:206–211

    Article  Google Scholar 

  25. Kasztelan S, Payen E, Moffat JB (1988) The formation of molybdosilicic acid on Mo/SiO2 catalysts and its relevance to methane oxidation. J Catal 112:320–324

    Article  Google Scholar 

  26. Pizzio LR, Cáceres CV, Blanco MN (1998) Acid catalysts prepared by impregnation of tungstophosphoric acid solutions on different supports. Appl Catal A Gen 167:283–294

    Article  Google Scholar 

  27. Gorsd MN, Blanco MN, Pizzio LR (2016) Polystyrene/silica microspheres with core/shell structure as support of tungstophosphoric acid. Mater Chem Phys 171:281–289

    Article  Google Scholar 

  28. Liu D, Quek XY, Hu S, Li L, Lim HM, Yang Y (2009) Mesostructured TUD-1 supported molybdophosphoric acid (HPMo/TUD-1) catalysts for n-heptane hydroisomerization. Catal Today 147S:51–57

    Article  Google Scholar 

  29. Leofanti G, Padovan M, Tozzola G, Venturelli B (1998) Surface area and pore texture of catalysts. Catal Today 41:207

    Article  Google Scholar 

  30. Brunauer S, Emmett PH, Teller E (1983) Adsorption of gases in multimolecular layers. J Chem Soc Chem 60:309–319

    Article  Google Scholar 

  31. Mikhail RSh, Brunauer S, Bodor EE (1968) Investigations of a complete pore structure analysis: I. Analysis of micropores. J Colloid Interface Sci 26:45–53

    Article  Google Scholar 

  32. Aquino C, Maschmeyer T (2009) A New family of mesoporous oxides—synthesis, characterisation and applications of TUD-1. In: Valentin V, Svetlana M, Michael T (eds) Ordered porous solids, recent advances and prospects, Elsevier, The Netherlands, UK, p 3–30.

  33. Ranoux A, Djanashivili K, Arends IWCE, Hanefeld U (2013) B-TUD-1: a versatile mesoporous catalyst. RSC Adv 3(44):21524–21534

    Article  Google Scholar 

  34. Pizzio LR, Vázquez PG, Cáceres CV, Blanco MN (2003) Supported Keggin type heteropolycompounds for ecofriendly reactions. Appl Catal A Gen 256:125–139

    Article  Google Scholar 

  35. Rocchiccioli-Deltcheff C, Thouvenot R, Franck R (1976) Spectres i.r. et Raman d’hétéropolyanions α-XM12O40 n− de structure de type Keggin (X = BIII, SiIV, GeIV, PV, AsV et M = WVI et MoVI). Spectrochim Acta A 32:587–597

    Article  Google Scholar 

  36. Pizzio LR, Blanco MN (2003) Isoamyl acetate production catalyzed by H3PW12O40 on their partially substituted Cs or K salts. Appl Catal A Gen 255:265–277

    Article  Google Scholar 

  37. Chimienti ME, Pizzio LR, Cáceres CV, Blanco MN (2001) Tungstophosphoric and tungstosilicic acids on carbon as acidic catalysts. Appl Catal A Gen 208:7–19

    Article  Google Scholar 

  38. Lefebvre F (1992) 31P MAS-NMR study of H3PW12O40 supported on silica: formation of (SiOH2 +)(H2PW12O40 –). J Chem Soc Chem Commun 10:756–757

    Article  Google Scholar 

  39. Essayem N, Tong YY, Jobic H, Vedrine JC (2000) Characterization of protonic sites in H3PW12O40 and Cs1.9H1.1PW12O40: a solid-state 1H, 2H, 31P MAS-NMR and inelastic neutron scattering study on samples prepared under standard reaction conditions. Appl Catal A Gen 194-195:109–122

    Article  Google Scholar 

  40. Okuhara T, Nishimura T, Watanabe H, Na K, Misono M (1994) “Acid-base catalysis II”, 4.8 novel catalysis of cesium salt of heteropoly acid and its characterization by solid-state NMR. Kodansha, Tokyo, Elsevier, Amsterdam, p 419

    Google Scholar 

  41. Massart R, Contant R, Fruchart J, Ciabrini J, Fournier M (1977) 31P NMR studies on molybdic and tungstic heteropoly anions. Correlation between structure and chemical shift. Inorg Chem 16:2916–2921

    Article  Google Scholar 

  42. Rengifo-Herrera JA, Blanco MN, Wist J, Florian P, Pizzio LR (2016) TiO2 modified with polyoxotungstates should induce visible-light absorption and high photocatalytic activity through the formation of surface complexes. Appl Catal B Environ 189:99–109

    Article  Google Scholar 

  43. Frenzel R, Morales D, Romanelli GP, Sathicq GA, Blanco MN, Pizzio LR (2016) Synthesis, characterization and catalytic evaluation of H3PW12O40 included in acrylic acid/acrylamide polymer for the selective oxidation of sulfides. J Mol Catal A Chem 420:124–130

    Article  Google Scholar 

  44. 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  Google Scholar 

  45. Dominguez JM, Hernandez JL, Sandoval G (2000) Surface and catalytic properties of Al2O3–ZrO2 solid solutions prepared by sol–gel methods. Appl Catal A Gen 197:119–130

    Article  Google Scholar 

  46. Kumar P, Pandey RK, Bodas MS, Dagade SP, Dongare MK, Ramaswamy AV (2002) Acylation of alcohols, thiols and amines with carboxylic acids catalyzed by yttria-zirconia-based Lewis acid. J Mol Catal A Chem 181:207–213

    Article  Google Scholar 

  47. El-Sharkawy ESA (2006) Non aqueous titration and catalytic conversion of cyclohexanol as a test of surface acidity. Mon Chem 137:1487–1498

    Article  Google Scholar 

  48. Reddy KM, Lingaiah N, Sai Prasad PS, Suryanarayana I (2006) Acidity constants of supported salts of heteropoly acids using a methodology related to the potentiometric mass titration technique. J Solut Chem 35:407–423

    Article  Google Scholar 

  49. Pizzio LR, Blanco MN (2003) Isoamyl acetate production catalyzed by H3PW12O40 on their partially substituted Cs or K salts. J Solut Chem 35:407–423

    Google Scholar 

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Acknowledgements

The authors thank the experimental contribution of E. Soto, P. Fetsis, G. Valle, M. Theiller, and L. Osiglio, and the financial support of CONICET (PIP 0449) and Universidad Nacional de La Plata (X-773).

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  1. Centro de Investigación y Desarrollo en Ciencias Aplicadas “Dr. Jorge J. Ronco” (CINDECA), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata-CCT La Plata, CONICET, Calle 47N° 257, 1900, La Plata, Argentina

    Marina N. Gorsd, Alexis A. Sosa, Romina A. Frenzel & Luis R. Pizzio

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  1. Marina N. Gorsd
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  2. Alexis A. Sosa
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Correspondence to Marina N. Gorsd or Luis R. Pizzio.

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Gorsd, M.N., Sosa, A.A., Frenzel, R.A. et al. Synthesis and characterization of tungstophosphoric acid-modified mesoporous sponge-like TUD-1 materials. J Sol-Gel Sci Technol 87, 204–215 (2018). https://doi.org/10.1007/s10971-018-4677-z

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  • DOI: https://doi.org/10.1007/s10971-018-4677-z

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