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Synthesis and characterization of hierarchical titanium-containing silicas using different size templates

  • Aleksey Fedosov
  • Marina Fedosova
  • Irina Postnikova
  • Sergey Orekhov
  • Aleksey Gushchin
  • Denis Ryabinin
  • Ilya ChuzhaykinEmail author
Regular Article
  • 49 Downloads

Abstract

The development of hierarchical catalytic heterogeneous catalytic systems with a controlled micro/mesopore ratio is an important issue in catalysis. The main purpose of the paper is to the establish influence of the size of the template molecule on the main characteristics of hierarchical titanium-containing silicas (H-TS). The H-TS were successfully synthesized by a bi-template method using tetrapropylammonium hydroxide (TPAG) as permanent template of MFI topology and tetramethylammonium bromide (TMAB), tetraethylammonium bromide (TEAB), tetrabutylammonium hydroxide (TBAG), dodecyltrimethylammonium bromide (DTMAB), cetyltrimethylammonium bromide (CTAB), didecyldimethylammonium chloride (DDAC), tetradecylbenzyldimethylammonium bromide (TBDAB) as variable structure-directing agent (SDA) of a different size. The structure and morphology were characterized by X-ray diffraction, a Fourier transform infrared spectroscopy, a Raman spectroscopy, a scanning electron microscopy and low-temperature nitrogen adsorption-desorption. The catalytic properties of the prepared titanium-containing micro-mesoporous silicas for hydroxylation of phenol with \(\hbox {H}_{2}\hbox {O}_{2}\) have been evaluated, and their activities have been compared with those of TS-1 with only micropores. The findings of the research illustrate that with an increase in the molecule volume of the structure-directing agent, there is a decrease in the proportion of the crystalline phase and in the degree of the inclusion of \(\hbox {Ti}^{4+}\) atoms in the structure of the zeolite material. Increase in the volume of the structure-directing agent leads to the decrease of the crystallinity of the samples and decrease in the specific surface area of the material and in the specific volume of micropores. The result of this research will be used to create a theoretical model of controlled micro-/mesoporous ratio in silicas and it may open new perspectives for their potential application in selective oxidation reactions involving large molecules.

Graphic Abstract

SYNOPSIS Synthesis and characterization of hierarchical titanium-containing silicas produced by a bi-template method are reported. The findings of the research illustrate that the size of the template influences the main textural properties of titanium-containing silicas.

Keywords

Hierarchical silica titanium silicalite bi-template synthesis mixed templates 

Notes

Acknowledgements

The study was financially supported by The Ministry of Education and Science of the Russian Federation (State assignment No. 10.2326.2017/PP).

The SEM study was carried out on the equipment of the Collective Usage Center “New Materials and Resource-saving Technologies” (Lobachevsky State University of Nizhny Novgorod).

The Raman spectroscopy was carried out in the Laboratory of Functional Nanomaterials (Lobachevsky State University of Nizhny Novgorod).

Supplementary material

12039_2019_1652_MOESM1_ESM.pdf (1009 kb)
Supplementary material 1 (pdf 1008 KB)

References

  1. 1.
    Clark J H and Rhodes C N 2000 In Clean Synthesis Using Porous Inorganic Solid Catalysts and Supported Reagents C N Rhodes (Ed.) (Cambridge: The Royal Society of Chemistry) p. 115Google Scholar
  2. 2.
    Centi G, Cavani F and Trifirò F 2001 In Selective Oxidation by Heterogeneous Catalysis. Fundamental and Applied Catalysis M V Twigg and M S Spencer (Eds.) (Boston: Springer) p. 505Google Scholar
  3. 3.
    Cubillas P and Anderson M W 2010 Synthesis Mechanism: Crystal Growth and Nucleation. In: Zeolites and Catalysis Synthesis, Reactions and Applications Vol.1 J Cejka (Ed.) (Weinheim: WILEY-VCH Verlag GmbH & Co.) p. 56Google Scholar
  4. 4.
    J Cejka and H Bekkum (Eds.) 2005 Zeolites and Ordered Mesoporous Materials: Progress and Prospects G Centi (Series Ed.) (Prague: Gulf Professional Publishing)Google Scholar
  5. 5.
    Maspero F and Romano U 1994 Oxidation of Alcohols with \(\text{ H }_{2}\text{ O }_{2}\) Catalyzed by Titanium Silicalite-1 J. Catal. 146 476CrossRefGoogle Scholar
  6. 6.
    Shulpin G B, Sooknoi T, Romakh V B, Süss-Fink G and Shulpina L S 2006 Regioselective Alkane Oxygenation with \(\text{ H }_{2}\text{ O }_{2}\) Catalyzed by Titanosilicalite TS-1 Tetrahedron Lett. 47 3071CrossRefGoogle Scholar
  7. 7.
    Lin M, Xia C, Zhua B, Li H and Shu X 2016 Green and efficient epoxidation of propylene with hydrogen peroxide (HPPO process) catalyzed by hollow TS-1 zeolite: A 1.0 kt/a pilot-scale study Chem. Eng. J. 295 370CrossRefGoogle Scholar
  8. 8.
    Wilde N, Worch C, Suprun W and Gläser R 2012 Epoxidation of biodiesel with hydrogen peroxide over Ti-containing silicate catalysts Micropor. Mesopor. Mater. 164 182CrossRefGoogle Scholar
  9. 9.
    Kholdeeva O A and Trukhan N N 2006 Mesoporous titanium silicates as catalysts for the liquid-phase selective oxidation of organic compounds Russ. Chem. Rev. 75 460CrossRefGoogle Scholar
  10. 10.
    Corma A, Blasco T, Navarro M T and Pariente J P 1995 Synthesis, Characterization, and Catalytic Activity of Ti-MCM-41 Structures J. Catal. 156 65CrossRefGoogle Scholar
  11. 11.
    Zhang W and Pinnavaia T J 1996 Transition metal substituted derivatives of cubic MCM-48 mesoporous molecular sieves Catal. Lett. 38 261CrossRefGoogle Scholar
  12. 12.
    Serrano D P, Escola J M and Pizarro P 2013 Synthesis strategies in the search for hierarchical zeolites Chem. Soc. Rev. 42 4004CrossRefGoogle Scholar
  13. 13.
    Yu W, Deng L, Yuan P, Liu D, Yuan W and Chen F 2015 Preparation of hierarchically porous diatomite/MFI-type zeolite composites and their performance for benzene adsorption: The effects of desilication Chem. Eng. J. 270 450CrossRefGoogle Scholar
  14. 14.
    Werner A, Bludovsky P, Selzer C, Koch U, Giebeler L, Oswald S and Kaskel S 2017 Hierarchical Ti-Beta Obtained by Simultaneous Desilication and Titanation as an Efficient Catalyst for Cyclooctene Epoxidation ChemCatChem. 9 3860CrossRefGoogle Scholar
  15. 15.
    Verboekend D, Groen J C and Pérez-Ramírez J 2010 Interplay of Properties and Functions upon Introduction of Mesoporosity in ITQ-4 Zeolite Adv. Funct. Mater. 20 1441CrossRefGoogle Scholar
  16. 16.
    Abello S, Bonilla A and Perez-Ramırez J 2009 Mesoporous ZSM-5 zeolite catalysts prepared by desilication with organic hydroxides and comparison with NaOH leaching Appl. Catal. A 364 191CrossRefGoogle Scholar
  17. 17.
    Verboekend D, Vilé G and Pérez-Ramírez J 2012 Hierarchical Y and USY Zeolites Designed by Post-Synthetic Strategies Adv. Funct. Mater. 22 916CrossRefGoogle Scholar
  18. 18.
    Verboekend D, Mitchell S, Milina M, Groen J C and Pérez-Ramírez J 2011 Full Compositional Flexibility in the Preparation of Mesoporous MFI Zeolites by Desilication J. Phys. Chem. 115 14193Google Scholar
  19. 19.
    Du Q, Guo Y, Duan H, Li H, Chen Y and Liu H 2017 Synthesis of hierarchical TS-1 zeolite via a novel three-step crystallization method and its excellent catalytic performance in oxidative desulfurization Fuel 188 232CrossRefGoogle Scholar
  20. 20.
    Du S, Sun Q, Wang N, Chen X, Jia M and Yu J 2017 Synthesis of hierarchical TS-1 zeolites with abundant and uniform intracrystalline mesopores and their highly efficient catalytic performance for oxidation desulfurization J. Mater. Chem. A 5 7992CrossRefGoogle Scholar
  21. 21.
    Zuo Y, Zhang T, Liu M, Ji Y, Song C and Guo X 2018 Mesoporous/Microporous Titanium Silicalite with Controllable Pore Diameter for Cyclohexene Epoxidation Ind. Eng. Chem. Res. 57 512CrossRefGoogle Scholar
  22. 22.
    Rani P, Srivastava R and Satpati B 2016 One-Step Dual Template Mediated Synthesis of Nanocrystalline Zeolites of Different Framework Structures Cryst. Growth Des. 16 3323CrossRefGoogle Scholar
  23. 23.
    Xing J, Jiang S, Pang J, Yuan E, Ma X, Lam K, Xue Q and Zhan K 2015 One-pot pseudomorphic crystallization of mesoporous porous silica to hierarchical porous zeolites Mater. Charact. 107 161CrossRefGoogle Scholar
  24. 24.
    Molinspiration. Calculation of Molecular Properties and Bioactivity Score https://www.molinspiration.com/cgi-bin/properties (accessed on 20 February 2019)
  25. 25.
    Boccuti M R, Rao K M, Zecchina A, Leofanti G and Petrini G 1989 Spectroscopic Characterization of Silicalite and Titanium-Silicalite Stud. Surf. Sci. Catal. 48 133CrossRefGoogle Scholar
  26. 26.
    Fan F, Feng Z and Li C 2010 UV Raman Spectroscopic Studies on Active Sites and Synthesis Mechanisms of Transition Metal-Containing Microporous and Mesoporous Materials Acc. Chem. Res. 43 378CrossRefGoogle Scholar
  27. 27.
    Li C, Xiong G, Xin Q, Liu J, Ying P, Feng Z, Li J, Yang W, Wang Y and Wang G 1999 UV Resonance Raman Spectroscopic Identification of Titanium Atoms in the Framework of TS-1 Zeolite Angew. Chem. Int. Ed. 38 2220CrossRefGoogle Scholar
  28. 28.
    Deo G, Turek A M, Wachs I E, Huybrechts D R and Jacobs P A 1993 Characterization of titania silicalites Zeolites 13 365CrossRefGoogle Scholar
  29. 29.
    Marra G L, Artioli G, Fitch A N, Milanesio M and Lamberti C 2000 Orthorhombic to monoclinic phase transition in high-Ti-loaded TS-1: an attempt to locate Ti in the MFI framework by low temperature XRD Micropor. Mesopor. Mater. 40 85CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2019

Authors and Affiliations

  • Aleksey Fedosov
    • 1
  • Marina Fedosova
    • 1
  • Irina Postnikova
    • 1
  • Sergey Orekhov
    • 1
  • Aleksey Gushchin
    • 2
  • Denis Ryabinin
    • 3
  • Ilya Chuzhaykin
    • 1
    • 2
    Email author
  1. 1.Nizhny Novgorod State Technical University n.a. R.E. AlekseevDzerzhinskRussia
  2. 2.Lobachevsky State University of Nizhny Novgorod, National Research UniversityNizhny NovgorodRussia
  3. 3.University of AlbertaEdmontonCanada

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