journal article·2012-03

Immobilized polyoxometalates onto mesoporous organically-modified silica aerogels as selective heterogeneous catalysts of anthracene oxidation

Rami Al-Oweini, Shant Aghyarian, Houssam El-Rassy

Publisher page

Abstract

Immobilized molybdovanadophosphoric acids onto organically surface-modified silica aerogels were successfully prepared and investigated in heterogeneous catalysis of anthracene oxidation. The catalysts were obtained by supporting mono- and di-vanadium substituted molybdophosphoric acids on hybrid silica materials synthesized via the sol–gel process followed by surface amino-functionalization. The FTIR, DR UV–vis, and AA spectroscopy confirmed the loading and distribution of the polyoxometalate molecules on the surface of the aerogels. The nitrogen adsorption–desorption technique revealed a systematic decrease in the specific surface area and pore volume after the immobilization of the polyoxometalates. The application of the supported molecules as catalysts for anthracene oxidation showed 100% selectivity for 9,10-anthraquinone as opposed to the reactions conducted under homogeneous conditions. Moreover, at certain conditions, the catalytic activity of the supported polyoxometalates was greater than their corresponding free polyoxometalates with a clear effect of the surface chemical groups of the supporting silica aerogels. Additionally, the oxidant and solvent nature showed a crucial effect on the catalytic activity and selectivity of the immobilized polyoxometales. The heterogeneous catalysts were regenerated and reused over consecutive catalytic cycles reflecting a potential economic interest in these materials besides their high efficiency in heterogeneous catalysis.
Source: openaire · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Polyoxometalates: Synthesis and Applications · Mesoporous Materials and Catalysis · Catalysis and Oxidation Reactions

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (40)

Show source-provided references
1. Berzelius JJ (1826) Poggendorf’s Annalen der Physik und Chemie 6:369–38010.1002/andp.18260820402 ↗
2. Keggin JF (1933) Structure of the molecule of 12-phosphotungstic acid. Nature 131(3321):908–90910.1038/131908b0 ↗
3. Long D-L, Burkholder E, Cronin L (2007) Polyoxometalate clusters, nanostructures and materials: from self assembly to designer materials and devices. Chem Soc Rev 36(1):105–12110.1039/B502666K ↗
4. Bassil BS, Ibrahim M, Al-Oweini R, Asano M, Wang Z, van Tol J, Dalal NS, Choi K-Y, Ngo Biboum R, Keita B, Nadjo L, Kortz U (2011) A planar {Mn19(OH)12}26+ unit incorporated in a 60-Tungsto-6-silicate polyanion. Angew Chem Int Ed 50(26):5961–596410.1002/anie.201007617 ↗
5. Katsoulis DE (1998) A survey of applications of polyoxometalates. Chem Rev 98(1):359–38810.1021/cr960398a ↗
6. Al-Kadamany G, Mal SS, Milev B, Donoeva BG, Maksimovskaya RI, Kholdeeva OA, Kortz U (2010) Hexazirconium- and hexahafnium-containing tungstoarsenates(III) and their oxidation catalysis properties. Chem Eur J 16 (39):11797–1180010.1002/chem.201000786 ↗
7. Antonova NS, Carbó JJ, Kortz U, Kholdeeva OA, Poblet JM (2010) Mechanistic insights into alkene epoxidation with H2O2 by Ti- and other TM-containing polyoxometalates: role of the metal nature and coordination environment. J Am Chem Soc 132(21):7488–749710.1021/ja1023157 ↗
8. Jahier C, Felpin F-X, Méliet C, Agbossou-Niedercorn F, Hierso J-C, Nlate S (2009) 1,1′-Binaphthyl-2-methylpyridinium-based peroxophosphotungstate salts: synthesis, characterization, and their use as oxidation catalysts. Eur J Inorgan Chem (34):5148–515510.1002/ejic.200900682 ↗
9. Bi L-H, Al-Kadamany G, Chubarova EV, Dickman MH, Chen L, Gopala DS, Richards RM, Keita B, Nadjo L, Jaensch H, Mathys G, Kortz U (2009) Organo-ruthenium supported heteropolytungstates: synthesis, structure, electrochemistry, and oxidation catalysis. Inorg Chem 48(21):10068–1007710.1021/ic9009306 ↗
10. Donoeva BG, Trubitsina TA, Antonova NS, Carbó JJ, Poblet JM, Al-Kadamany G, Kortz U, Kholdeeva OA (2010) Epoxidation of alkenes with H2O2 catalyzed by dititanium-containing 19-tungstodiarsenate(III): experimental and theoretical studies. Eur J Inorgan Chem 33:5312–531710.1002/ejic.201000615 ↗
11. Mizuno N, Misono M (1998) Heterogeneous catalysis. Chem Rev 98(1):199–21810.1021/cr960401q ↗
12. Bordoloi A, Lefebvre F, Halligudi SB (2007) Selective oxidation of anthracene using inorganic-organic hybrid materials based on molybdovanadophosphoric acids. J Catal 247(2):166–17510.1016/j.jcat.2007.01.020 ↗
13. Santacesaria E, Di Serio M, Russo A, Leone U, Velotti R (1999) Kinetic and catalytic aspects in the hydrogen peroxide production via anthraquinone. Chem Eng Sci 54(13–14):2799–280610.1016/S0009-2509(98)00377-7 ↗
14. Manisankar P, Gomathi A (2005) Electrocatalysis of oxygen reduction at polypyrrole modified glassy carbon electrode in anthraquinone solutions. J Mol Catal A Chem 232(1–2):45–5210.1016/j.molcata.2005.01.001 ↗
15. Chen Q (2008) Development of an anthraquinone process for the production of hydrogen peroxide in a trickle bed reactor—from bench scale to industrial scale. Chem Eng Process Process Intensif 47(5):787–79210.1016/j.cep.2006.12.012 ↗
16. Ge P, Russell RA (1997) The synthesis of anthraquinone derivatives as potential anticancer agents. Tetrahedron 53(51):17469–1747610.1016/S0040-4020(97)10195-8 ↗
17. Cairns D, Michalitsi E, Jenkins TC, Mackay SP (2002) Molecular modelling and cytotoxicity of substituted anthraquinones as inhibitors of human telomerase. Bioorgan Med Chem 10(3):803–80710.1016/S0968-0896(01)00337-6 ↗
18. Huang H-S, Chiou J-F, Fong Y, Hou C–C, Lu Y-C, Wang J-Y, Shih J-W, Pan Y-R, Lin J–J (2003) Activation of human telomerase reverse transcriptase expression by some new symmetrical bis-substituted derivatives of the anthraquinone. J Med Chem 46(15):3300–330710.1021/jm020492l ↗
19. Izumi Y, Ono M, Kitagawa M, Yoshida M, Urabe K (1995) Silica-included heteropoly compounds as solid acid catalysts. Microporous Mater 5(4):255–26210.1016/0927-6513(95)00059-3 ↗
20. Guo Y, Wang Y, Hu C, Wang Y, Wang E, Zhou Y, Feng S (2000) Microporous polyoxometalates POMs/SiO2: synthesis and photocatalytic degradation of aqueous organocholorine pesticides. Chem Mater 12(11):3501–350810.1021/cm000074+ ↗
21. Hu C-w, He Q-l, Zhang Y-h, Liu Y-y, Zhang Y-f, Tang T-d, Zhang J-y, Wang E-b (1996) Synthesis of new types of polyoxometallate pillared anionic clays: 31P and 27Al MAS NMR study of the orientation of intercalated PW11VO404. Chem Commun 2:121–122
22. Kumar D, Landry CC (2007) Immobilization of a Mo, V-polyoxometalate on cationically modified mesoporous silica: synthesis and characterization studies. Microporous Mesoporous Mater 98(1–3):309–31610.1016/j.micromeso.2006.09.023 ↗
23. Maksimchuk NV, Melgunov MS, Chesalov YA, Mrowiec-Bialon J, Jarzebski AB, Kholdeeva OA (2007) Aerobic oxidations of [alpha]-pinene over cobalt-substituted polyoxometalate supported on amino-modified mesoporous silicates. J Catal 246(2):241–24810.1016/j.jcat.2006.11.026 ↗
24. Pozniczek J, Lubanska A, Micek-Ilnicka A, Mucha D, Lalik E, Bielanski A (2006) TiO2 and SiO2 supported Wells-Dawson heteropolyacid H6P2W18O62 as the catalyst for ETBE formation. Appl Catal A General 298:217–22410.1016/j.apcata.2005.10.013 ↗
25. Song H, Rioux RM, Hoefelmeyer JD, Komor R, Niesz K, Grass M, Yang P, Somorjai GA (2006) Hydrothermal growth of mesoporous SBA-15 silica in the presence of PVP-stabilized Pt nanoparticles: synthesis, characterization, and catalytic properties. J Am Chem Soc 128(9):3027–303710.1021/ja057383r ↗
26. Brinker CJ, Scherer GW (1990) Sol-gel science. The physics and chemistry of sol-gel processing. Academic Press, New York
27. Huesing N, Schwertfeger F, Tappert W, Schubert U (1995) Influence of supercritical drying fluid on structure and properties of organically modified silica aerogels. J Non-Cryst Solids 186:37–4310.1016/0022-3093(95)00031-3 ↗
28. Pierre AC, Pajonk GM (2002) Chemistry of aerogels and their applications. Chem Rev 102(11):4243–426510.1021/cr0101306 ↗
29. Al-Oweini R, El-Rassy H (2009) Synthesis and characterization by FTIR spectroscopy of silica aerogels prepared using several Si(OR)4 and R’’Si(OR’)3 precursors. J Mol Struct 919(1–3):140–14510.1016/j.molstruc.2008.08.025 ↗
30. Al-Oweini R, El-Rassy H (2010) Surface characterization by nitrogen adsorption of silica aerogels synthesized from various Si(OR)4 and R’’Si(OR’)3 precursors. Appl Surf Sci 257(1):276–28110.1016/j.apsusc.2010.06.086 ↗
31. Joseph T, Halligudi SB (2005) Oxyfunctionalization of limonene using vanadium complex anchored on functionalized SBA-15. J Mol Catal A Chem 229(1–2):241–24710.1016/j.molcata.2004.12.008 ↗
32. Tsigdinos GA, Hallada CJ (1968) Molybdovanadophosphoric acids and their salts. I. Investigation of methods of preparation and characterization. Inorgan Chem 7(3):437–441
33. 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(2):232–23910.1016/j.jcat.2008.08.010 ↗
34. Gunzler H, Gremlich H-U (2002) IR spectroscopy: an introduction. Wiley-VCH, London
35. Durand N, Mariot D, Améduri B, Boutevin B, Ganachaud F (2011) Tailored covalent grafting of hexafluoropropylene oxide oligomers onto silica nanoparticles: toward thermally stable, hydrophobic, and oleophobic nanocomposites. Langmuir 27(7):4057–406710.1021/la1048826 ↗
36. Barrett EP, Joyner LG, Halenda PP (1951) The determination of pore volume and area distributions in porous substances. I. Computations from Nitrogen isotherms. J Am Chem Soc 73(1):373–380
37. Brunauer S, Emmett PH, Teller E (1938) Adsorption of gases in multimolecular layers. J Am Chem Soc 60(2):309–31910.1021/ja01269a023 ↗
38. Strukul G (1992) Introduction and activation principles. In: Strukul G (ed) Catalytic oxidations with hydrogen peroxide as oxidant. Kluwer, Dordrecht, pp 1–1110.1007/978-94-017-0984-2_1 ↗
39. Ishii Y, Yamawaki K, Ura T, Yamada H, Yoshida T, Ogawa M (1988) Hydrogen peroxide oxidation catalyzed by heteropoly acids combined with cetylpyridinium chloride. Epoxidation of olefins and allylic alcohols, ketonization of alcohols and diols, and oxidative cleavage of 1,2-diols and olefins. J Organ Chem 53(15):3587–3593
40. Selvaraj M, Kawi S (2007) Direct synthesis of mesoporous CrSBA-15 catalyst and its high activity and selectivity for oxidation of anthracene. Microporous Mesoporous Mater 101(1–2):240–24910.1016/j.micromeso.2006.12.020 ↗