Journal of Materials Science

, Volume 54, Issue 6, pp 4601–4618 | Cite as

Preparation of carboxyethyltin group-functionalized highly ordered mesoporous organosilica composite material with double acid sites

  • Si-Qing He
  • Jing Wang
  • Dan-Dan Wu
  • Xiao-Jing Sang
  • Fang SuEmail author
  • Zai-Ming ZhuEmail author
  • Lan-Cui ZhangEmail author
Chemical routes to materials


A series of highly ordered mesoporous ethane-bridged organosilica composite materials functionalized by carboxyethyltin group, SnR–Si(Et)Si–X (SnR and Si(Et)Si denote [Sn(CH2)2COOH]3+ and ethane-bridged organosilica groups, respectively), were successfully designed through one-step co-condensation–hydrothermal method. The pore morphology and textural properties, Sn(IV) coordination environment, the type of acid site, Brönsted and Lewis acid strength were systematically characterized by LXRD, TEM observation, N2 porosimetry measurements, MAS NMR (29Si, 13C, 119Sn), UV–Vis diffuse reflectance spectrum, as well as 1H and 31P MAS NMR, FT-IR analysis of adsorbed pyridine, acid–base titration. Composite materials SnR–Si(Et)Si–X possess Brönsted and Lewis acid sites, which originates from –COOH in [Sn(CH2)2COOH]3+ group and bridging OH in [Si(OH)SnR] group as well as tetrahedral coordination framework Sn(IV) in the open configuration [SnR(SiO)3(OH)], respectively. The above 2D hexagonal mesoporous structure with unique textural properties, double acid sites (Brönsted and Lewis acid sites) and hydrophobic surface make SnR–Si(Et)Si–X exhibit excellent acid catalytic activity, reusability and water tolerance toward ketalization of cyclohexanone with glycol in absence of azeotrope agent at low temperature.



This work was supported by the Natural Science Foundation of China (21503103, 21671091).

Compliance with ethical standards

Conflict of interest

There are no conflicts to declare.

Supplementary material

10853_2018_3207_MOESM1_ESM.docx (515 kb)
Supplementary material 1 (DOCX 516 kb)


  1. 1.
    Lari GM, Dapsens PY, Scholz D, Mitchell S, Mondelli C, Pérez-Ramírez J (2016) Deactivation mechanisms of tin-zeolites in biomass conversions. Green Chem 18:1249–1260Google Scholar
  2. 2.
    Delidovich I, Hoffmann A, Willms A, Rosel M (2017) Porous tin-organic frameworks as selective epimerization catalysts in aqueous solutions. ACS Catal 7:3792–3798Google Scholar
  3. 3.
    van der Graaff WNP, Tempelman CHL, Hendriks FC, Ruiz-Martinez J, Bals S, Weckhuysen BM, Pidko EA, Hensen EJM (2018) Deactivation of Sn-Beta during carbohydrate conversion. Appl Catal A Chem 564:113–122Google Scholar
  4. 4.
    Zhu ZG, Xu H, Jiang JG, Guan YJ, Wu P (2018) Sn-Beta zeolite derived from a precursor synthesized via an organotemplate-free route as efficient Lewis acid catalys. Appl Catal A Chem 556:52–63Google Scholar
  5. 5.
    Moliner M (2014) State of the art of Lewis acid-containing zeolites: lessons from fine chemistry to new biomass transformation processes. Dalton Trans 43:4197–4208Google Scholar
  6. 6.
    Gounder R, Davis ME (2013) Monosaccharide and disaccharide isomerization over Lewis acid sites in hydrophobic and hydrophilic molecular sieves. J Catal 308:176–188Google Scholar
  7. 7.
    Tang B, Dai WL, Wu GJ, Guan NJ, Li LD, Hunge M (2014) Improved postsynthesis strategy to Sn-Beta zeolites as Lewis acid catalysts for the ring-opening hydration of epoxides. ACS Catal 4:2801–2810Google Scholar
  8. 8.
    Wolf P, Hammond C, Conrad S, Hermans I (2014) Post-synthetic preparation of Sn-, Ti- and Zr-beta: a facile route to water tolerant, highly active Lewis acidic zeolites. Dalton Trans 43:4514–4519Google Scholar
  9. 9.
    Gaydhankar TR, Joshi PN, Kalita P, Kumar R (2007) Optimal synthesis parameters and application of Sn-MCM-41 as an efficient heterogeneous catalyst in solvent-free Mukaiyama-type aldol condensation. J Mol Catal A: Chem 265:306–315Google Scholar
  10. 10.
    Hayashi Y, Sasaki Y (2005) Tin-catalyzed conversion of trioses to alkyl lactates in alcohol solution. Chem Commun 36:2716–2718Google Scholar
  11. 11.
    Gunther WR, Michaelis VK, Caporini MA, Griffin RG, Román-Leshkov Y (2014) Dynamic nuclear polarization NMR enables the analysis of Sn-Beta zeolite prepared with natural abundance 119Sn precursors. J Am Chem Soc 136:6219–6222Google Scholar
  12. 12.
    Roy S, Bakhmutsky K, Mahmoud E, Lobo RF, Gorte RJ (2013) Probing Lewis acid sites in Sn-Beta zeolite. ACS Catal 3:573–580Google Scholar
  13. 13.
    Dapsens PY, Mondelli C, Jagielski J, Hauert R, Pérez-Ramírez J (2014) Hierarchical Sn-MFI zeolites prepared by facile top-down methods for sugar isomerisation. Catal Sci Technol 4:2302–2311Google Scholar
  14. 14.
    Li P, Liu GQ, Wu HH, Liu YY, Jiang JJ, Wu P (2011) Postsynthesis and selective oxidation properties of nanosized Sn-Beta zeolite. J Phys Chem C 115:3663–3670Google Scholar
  15. 15.
    Wang XX, Xu HB, Fu XZ, Liu P, Lefebvre F, Basset JM (2005) Characterization and catalytic properties of tin-containing mesoporous silicas prepared by different methods. J Mol Catal A Chem 238:185–191Google Scholar
  16. 16.
    Román-Leshkov Y, Davis ME (2011) Activation of carbonyl-containing molecules with solid Lewis acids in aqueous media. ACS Catal 1:1566–1580Google Scholar
  17. 17.
    Choudhary V, Mushrif SH, Ho C, Anderko A, Nikolakis V, Marinkovic NS, Frenkel AI, Sandler SI, Vlachos DG (2013) Insights into the interplay of Lewis and Brønsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl)furfural and levulinic acid in aqueous media. J Am Chem Soc 135:3997–4006Google Scholar
  18. 18.
    Roy S, Mpourmpakis G, Hong DY, Vlachos DG, Bhan A, Gorte RJ (2012) Mechanistic study of alcohol dehydration on γ-Al2O3. ACS Catal 2:1846–1853Google Scholar
  19. 19.
    Sun CH, Liu LM, Selloni A, Lu GQ, Smith SC (2010) Titania-water interactions: a review of theoretical studies. J Mater Chem 20:10319–10334Google Scholar
  20. 20.
    Giovambattista N, Debenedetti PG, Rossky PJ (2007) Hydration behavior under confinement by nanoscale surfaces with patterned hydrophobicity and hydrophilicity. J Phys Chem C 111:1323–1332Google Scholar
  21. 21.
    Blasco T, Camblor MA, Corma A, Esteve P, Guil JM, Martinez A, Perdigon-Melon JA, Valencia S (1998) Direct synthesis and characterization of hydrophobic aluminum-free Ti–Beta zeolite. J Phys Chem B 102:75–88Google Scholar
  22. 22.
    Chan CK, Tsai YL, Chang MY (2017) CuI mediated one-pot cycloacetalization/ketalization of o-carbonyl allylbenzenes: synthesis of benzobicyclo[3.2.1]octane core. Org Lett 19:1870–1873Google Scholar
  23. 23.
    Pérez WA, Echeverri DA, Rios LA (2017) Ketalization of epoxidized methyl oleate using acidic resins. J Chem Technol Biotechnol 92:536–547Google Scholar
  24. 24.
    Rossa V, Pessanha Y da SP, Díaz GC, Câmara LDT, Pergher SBC, Aranda DAG (2017) Reaction kinetic study of solketal production from glycerol ketalization with acetone. Ind Eng Chem Res 56:479–488Google Scholar
  25. 25.
    Xu CM, Zhang L, Luo SZ (2015) Catalytic asymmetric oxidative α-C–H N, O-ketalization of ketones by chiral primary amine. Org Lett 17:4392–4395Google Scholar
  26. 26.
    Nielsen CB, Ashraf RS, Rossbauer S, Anthopoulos T, McCulloch I (2013) Post-polymerization ketalization for improved organic photovoltaic materials. Macromolecules 46:7727–7732Google Scholar
  27. 27.
    Yang ZW, Lei C, Zhao X, Liu RX, Wei H, Ma YL, Meng SY, Cao Q, Wei JH, Wang XH (2017) Preparation and catalytic properties of carbon carrier-supported ruthenium catalysts for acetalization/ketalization reactions. ChemistrySelect 2:9377–9386Google Scholar
  28. 28.
    Poyraz AS, Kuo CH, Kim E, Meng YT, Seraji MS, Suib SL (2014) Tungsten-promoted mesoporous group 4 (Ti, Zr, and Hf) transition-metal oxides for room-temperature solvent-free acetalization and ketalization reactions. Chem Mater 26:2803–2813Google Scholar
  29. 29.
    Li ZM, Zhou Y, Tao DJ, Huang W, Chen XS, Yang Z (2014) MOR zeolite supported Brønsted acidic ionic liquid: an efficient and recyclable heterogeneous catalyst for ketalization. RSC Adv 4:12160–12167Google Scholar
  30. 30.
    Liu JH, Wei XF, Yu YL, Song JL, Wang X, Li A, Liu XW, Deng WQ (2010) Uniform core-shell titanium phosphate nanospheres with orderly open nanopores: a highly active Brønsted acid catalyst. Chem Commun 46:1670–1672Google Scholar
  31. 31.
    Wu SS, Dai WL, Yin SF, Li WS, Au CT (2008) Bismuth subnitrate as an efficient heterogeneous catalyst for acetalization and ketalization of carbonyl compounds with diols. Catal Lett 124:127–132Google Scholar
  32. 32.
    Shimizu K, Hayashi E, Hatamachi T, Kodama T, Higuchi T, Satsuma A, Kitayama Y (2005) Acidic properties of sulfonic acid-functionalized FSM-16 mesoporous silica and its catalytic efficiency for acetalization of carbonyl compounds. J Catal 231:131–138Google Scholar
  33. 33.
    Patel SM, Chudasama UV, Ganeshpure PA (2003) Ketalization of ketones with diols catalyzed by metal(IV) phosphates as solid acid catalysts. J Mole Catal A Chem 194:267–271Google Scholar
  34. 34.
    Jermy BR, Pandurangan A (2006) Al-MCM-41 as an efficient heterogeneous catalyst in the acetalization of cyclohexanone with methanol, ethylene glycol and pentaerythritol. J Mole Catal A Chem 265:184–192Google Scholar
  35. 35.
    Climent MJ, Velty A, Corma A (2002) Design of a solid catalyst for the synthesis of a molecule with blossom orange scent. Green Chem 4:565–569Google Scholar
  36. 36.
    Hutton RE, Burley JW, Oakes V (1978) β-substituted alkyltin halides: I. Monoalkyltin trihalides: synthetic, mechanistic and spectroscopic aspects. J Organomet Chem 156:369–382Google Scholar
  37. 37.
    Rakiewicz EF, Peters AW, Wormsbecher RF, Sutovich KJ, Mueller KT (1998) Characterization of acid sites in zeolitic and other inorganic systems using solid-State 31P NMR of the probe molecule trimethylphosphine oxide. J Phys Chem B 102:2890–2896Google Scholar
  38. 38.
    Li L, Collard X, Bertrand A, Sels BF, Pescarmona PP, Aprile C (2014) Extra-small porous Sn-silicate nanoparticles as catalysts for the synthesis of lactates. J Catal 314:56–65Google Scholar
  39. 39.
    Zhang XH, Su F, Song DY, An S, Lu B, Guo YH (2015) Preparation of efficient and recoverable organosulfonic acid functionalized alkyl-bridged organosilica nanotubes for esterification and transesterification. Appl Catal B Environ 163:50–62Google Scholar
  40. 40.
    Nesterenko NS, Thibault-Starzyk F, Montouilliout V, Yushchenko VV, Fernandez C, Gilson JP, Fajula F, Ivanova II (2006) The use of the consecutive adsorption of pyridine bases and carbon monoxide in the IR spectroscopic study of the accessibility of acid sites in microporous/mesoporous materials. Kinet Catal 47:40–48Google Scholar
  41. 41.
    Wang M, Zhang H, Li YX, Zhao B (2010) Synthesis of cyclohexanone ethylene ketal catalyzed by SO4 2−/ZrO2–TiO2 solid acid. Ind Catal 18:62–65Google Scholar
  42. 42.
    Zhou XF, Qiao SZ, Hao N, Wang XL, Yu CZ, Wang LZ, Zhao DY, Lu GQ (2007) Synthesis of ordered cubic periodic mesoporous organosilicas with ultra-large pores. Chem Mater 19:1870–1876Google Scholar
  43. 43.
    Wu ZY, Wang HJ, Sun LB, Wang YM, Zhu JH (2008) Multiple functionalization of mesoporous silica in one-pot: direct synthesis of aluminum-containing plugged SBA-15 from aqueous nitrate solutions. Adv Funct Mater 18:82–94Google Scholar
  44. 44.
    Hao N, Wang HT, Webley PA, Zhao DY (2010) Synthesis of uniform periodic mesoporous organosilica hollow spheres with large-pore size and efficient encapsulation capacity for toluene and the large biomolecule bovine serum albumin. Microporous Mesoporous Mater 132:543–551Google Scholar
  45. 45.
    Su F, Ma L, Guo YH, Li W (2012) Preparation of ethane-bridged organosilica group and keggin type heteropoly acid co-functionalized ZrO2 hybrid catalyst for biodiesel synthesis from eruca sativa gars oil. Catal Sci Technol 2:2367–2374Google Scholar
  46. 46.
    Boglio C, Micoine K, Derat É, Thouvenot R, Hasenknopf B, Thorimbert S, Lacôte E, Malacria M (2008) Regioselective activation of oxo ligands in functionalized Dawson polyoxotungstates. J Am Chem Soc 130:4553–4561Google Scholar
  47. 47.
    Tan MX, Gu LQ, Li NN, Ying JY, Zhang YG (2013) Mesoporous poly-melamine-formaldehyde (mPMF)—a highly efficient catalyst for chemoselective acetalization of aldehydes. Green Chem 15:1127–1132Google Scholar
  48. 48.
    Burleigh MC, Jayasundera S, Spector MS, Thomas CW, Markowitz MA, Gaber BP (2004) A new family of copolymers: multifunctional periodic mesoporous organosilicas. Chem Mater 16:3–5Google Scholar
  49. 49.
    Beletskiy EV, Hou XL, Shen ZL, Gallagher JR, Miller JT, Wu YY, Li TH, Kung MC, Kung HH (2016) Supported tetrahedral oxo-Sn catalyst: single site, two modes of catalysis. J Am Chem Soc 138:4294–4297Google Scholar
  50. 50.
    Corma A, Domaine ME, Valencia S (2003) Water-resistant solid Lewis acid catalysts: Meerwein–Ponndorf–Verley and Oppenauer reactions catalyzed by tin-beta zeolite. J Catal 215:294–304Google Scholar
  51. 51.
    Dapsens PY, Mondelli C, Kusema BT, Verel R, Pérez-Ramírez J (2014) A continuous process for glyoxal valorisation using tailored Lewis-acid zeolite catalysts. Green Chem 16:1176–1186Google Scholar
  52. 52.
    Perathoner S, Lanzafame P, Passalacqua R, Centi G, Schlögl R, Su DS (2006) Use of mesoporous SBA-15 for nanostructuring titania for photocatalytic applications. Microporous Mesoporous Mater 90:347–361Google Scholar
  53. 53.
    Wang X, Dai WL, Wu GJ, Li LD, Guan NJ, Hunger M (2014) Verifying the dominant catalytic cycle of the methanol-to-hydrocarbon conversion over SAPO-41. Catal Sci Technol 4:688–696Google Scholar
  54. 54.
    Hungera M, Andersonb MW, Ojo A, Pfelfer H (1993) Study of the geometry and location of the bridging OH groups in aluminosilicate and silicoaluminophosphate type zeolites using 1H MAS NMR sideband analysis and CP/MAS NMR. Microporous Mater 1:17–32Google Scholar
  55. 55.
    Zibrowius B, Löffler E, Hunger M (1992) Multinuclear MAS NMR and IR spectroscopic study of silicon incorporation into SAPO-5, SAPO-31, and SAPO-34 molecular sieves. Zeolites 12:167–174Google Scholar
  56. 56.
    Klinowski J, Hamdan H, Corma A, Forniès V, Hunger M, Freude D (1989) 1H MAS NMR and IR studies of the acidic properties of realuminated zeolite Y. Catal Lett 3:263–272Google Scholar
  57. 57.
    Zhang A, Huang SJ, Liu SB, Deng F (2011) Acid properties of solid acid catalysts characterized by solid-state 31P NMR of adsorbed phosphorous probe molecules. Phys Chem Chem Phys 13:14889–14901Google Scholar
  58. 58.
    Seo Y, Cho K, Jung Y, Ryoo R (2013) Characterization of the surface acidity of MFI zeolite nanosheets by 31P NMR of adsorbed phosphine oxides and catalytic cracking of decalin. ACS Catal 3:713–720Google Scholar
  59. 59.
    Lewis JD, Ha M, Luo H, Faucher A, Michaelis VK, Román-Leshkov Y (2018) Distinguishing active site identity in Sn-Beta zeolites using 31P MASNMR of adsorbed trimethylphosphine oxide. ACS Catal 8:3076–3086Google Scholar
  60. 60.
    Li L, Stroobants C, Lin KF, Jacobs PA, Sels BF, Pescarmona PP (2011) Selective conversion of trioses to lactates over Lewis acid heterogeneous catalysts. Green Chem 13:1175–1181Google Scholar
  61. 61.
    de Clippel F, Dusselier M, Van Rompaey R, Vanelderen P, Dijkmans J, Makshina E, Giebeler L, Oswald S, Baron GV, Denayer JFM, Pescarmona PP, Jacobs PA, Sels BF (2012) Fast and selective sugar conversion to alkyl lactate and lactic acid with bifunctional carbon-silica catalysts. J Am Chem Soc 134:10089–10101Google Scholar
  62. 62.
    Chen LF, Wang JA, Noreña LE, Aguilar J, Navarrete J, Salas P, Montoya JA, Del Ángel P (2007) Synthesis and physicochemical properties of Zr-MCM-41 mesoporous molecular sieves and Pt/H3PW12O40/Zr-MCM-41 catalysts. J Solid State Chem 180:2958–2972Google Scholar
  63. 63.
    Ni BQ, Liu H, Fan MM, Zhang PB (2017) Construction and properties of SO4 2−/ZrO2–SiO2 immobilized ionic liquid catalysts with double-acid active sites. Chin J Inorg Chem 33:97–105Google Scholar

Copyright information

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

Authors and Affiliations

  1. 1.School of Chemistry and Chemical EngineeringLiaoning Normal UniversityDalianPeople’s Republic of China

Personalised recommendations