Abstract
Metal-zeolite composite catalysts have found numerous applications in adsorption, gas separation, petroleum refining and chemical industry. The key issue in the design of these catalysts is localization of the metal within the zeolite structure. This paper focuses on a new approach to the synthesis of nickel–zeolite composite catalysts selectively containing metal nanoparticles inside the zeolite pores. In the catalysts prepared by conventional impregnation, metal particles from the external surface of the zeolites were selectively removed by extraction with bulky polymer molecules of poly-4-styrenesulfonic acid. The method is particularly suitable for the ZSM-5 zeolite with relatively narrow micropores. The nickel zeolite catalysts were tested in hydrogenation of toluene and 1,3,5-tri-isopropyl benzene (TIPB). The removal of nickel particles from the zeolite external surface leads to a considerable decrease in the hydrogenation rate of the bulky TIPB molecules, while toluene hydrogenation rate was affected to a much lesser extent and was almost proportional to the nickel content. The proposed methodology can be extended to other types of microporous catalysts.
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References
Guisnet M, Gilson J-P (2005) Zeolites for cleaner technologies. Catalytic science series—vol. 3 (Series Editor: G. J. Hutchings). Imperial College Press, London, p 368
Marcilly C (2001) Evolution of refining and petrochemicals. What is the place of zeolites? Stud Surf Sci Catal 135:37–60
Corma A, Martinez A (2005) Zeolites in refining and petrochemistry. Stud Surf Sci Catal 157:337–366
Marcilly C (2005) Acido-basic catalysis: application to refining and petrochemistry. Technip, Paris, p 821
Vermeiren W, Gilson J-P (2009) Impact of zeolites on the petroleum and petrochemical industry. Top Catal 52:1131–1161
Huber GW, Cortright RD, Dumesic JA (2004) Renewable alkanes by aqueous-phase reforming of biomass-derived oxygenates. Angew Chem 43:1549–1551
Guan G, Kaewpanha M, Hao X, Abudula A (2016) Catalytic steam reforming of biomass tar: prospects and challenges. Renew Sust Energy Rev 58:450–461
Héroguel F, Rozmysłowicz B, Luterbacher JS (2015) Improving heterogeneous catalyst stability for liquid-phase biomass conversion and reforming. Chimia 69:582–591
Zhang Q, Cheng K, Kang J, Deng W, Wang Y (2014) Fischer–Tropsch catalysts for the production of hydrocarbon fuels with high selectivity. ChemSusChem 7:1251–1264
Subramanian V, Zholobenko VL, Cheng K, Lancelot C, Heyte S, Thuriot J, Paul S, Ordomsky VV, Khodakov AY (2016) The role of steric effects and acidity in the direct synthesis of iso-paraffins from syngas on cobalt zeolite catalysts. ChemCatChem 8:380–389
Yang G, Tsubaki N, Shamoto J, Yoneyama Y, Zhang Y (2010) Confinement effect and synergistic function of H-ZSM-5/Cu–ZnO–Al2O3 capsule catalyst for one-step controlled synthesis. J Am Chem Soc 132:8129–8136
Masalska A (2005) Ni-loaded catalyst containing ZSM-5 zeolite for toluene hydrogenation. Appl Catal A 294:260–272
Lee D, Cho S, Kim G-J, Kim H, Lee I-K (2007) Efficient and selective hydrogenation of carboxylic acid catalyzed by Ni or Pd on ZSM-5. J Ind Eng Chem 13:1067–1075
Mihaylov M, Hadjiivanov K (2004) Redox couples in the selective catalytic reduction of NOx with hydrocarbons over Co–ZSM-5 and Ni–ZSM-5 catalysts: an FT-IR study. Chem Commun 19:2200–2201
Badrinarayanan S, Hegde RI, Balakrishnan I, Kulkarni SB, Ratnasamy P (1981) XPS study of nickel in NiHZSM5 catalysts. J Catal 71:439–442
Ziebro J, Łukasiewicz I, Borowiak-Palen E, Michalkiewicz B (2010) Low temperature growth of carbon nanotubes from methane catalytic decomposition over nickel supported on a zeolite. Nanotechnology 21:145308. https://doi.org/10.1088/0957-4484/21/14/145308
Finiels A, Fajula F, Hulea V (2014) Nickel-based solid catalysts for ethylene oligomerization: a review. Catal Sci Technol 4:2412–2426
Yuan H-X, Xia Q-H, Zhan H-J, Lu X-H, Su K-X (2006) Catalytic oxidation of cyclohexane to cyclohexanone and cyclohexanol by oxygen in a solvent-free system over metal-containing ZSM-5 catalysts. Appl Catal A 304:178–184
Vitale G, Molero H, Hernandez E, Aquino S, Birss V, Pereira-Almao P (2013) One-pot preparation and characterization of bifunctional Ni-containing ZSM-5 catalysts. Appl Catal A 452:75–87
Ertl G, Knözinger H, Weitkamp J (eds) (1999) Preparation of solid acids. Wiley, Weinheim, p 622
Weisz PB (1962) Polyfunctional heterogeneous catalysis. Adv Catal 13:137–190
Zečević J, Vanbutsele G, de Jong KP, Martens JA (2015) Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons. Nature 528:245–248
Samad JE, Blanchard J, Sayag C, Louis C, Regalbuto JR (2016) The controlled synthesis of metal-acid bifunctional catalysts: the effect of metal:acid ratio and metal-acid proximity in Pt silica–alumina catalysts for n-heptane isomerization. J Catal 342:203–212
Prins R (2012) Hydrogen spillover. Facts and fiction. Chem Rev 112:2714–2738
Im J, Shin H, Jang H, Kim H, Choi M (2014) Maximizing the catalytic function of hydrogen spillover in platinum-encapsulated aluminosilicates with controlled nanostructures. Nat Commun 5:3370. https://doi.org/10.1038/ncomms4370
Carvalho A, Marinova M, Batalha N, Marcilio NR, Khodakov AY, Ordomsky VV (2017) Design of nanocomposites with cobalt encapsulated in the zeolite micropores for selective synthesis of isoparaffins in Fischer–Tropsch reaction. Catal Sci Technol 7:5019–5027
Stakheev AY, Khodakov AY, Kustov LM, Kazansky VB, Minachev KM (1992) Localization of polyvalent cations in pentasil catalysts modified by metal oxides. Zeolites 12:866–869
He J, Liu Z, Yoneyama Y, Nishiyama N, Tsubaki N (2006) Multiple-functional capsule catalysts: a tailor-made confined reaction environment for the direct synthesis of middle isoparaffins from syngas. Chem Eur J 12:8296–8304
Li S, Tuel A, Laprune D, Meunier F, Farrusseng D (2015) Transition-metal nanoparticles in hollow zeolite single crystals as bifunctional and size-selective hydrogenation catalysts. Chem Mater 27:276–282
Goel S, Zones SI, Iglesia E (2014) Encapsulation of metal clusters within MFI via interzeolite transformations and direct hydrothermal syntheses and catalytic consequences of their confinement. J Am Chem Soc 136:15280–15290
Knapp C, Obuchi A, Uchisawa JO, Kushiyama S, Avila P (1999) Method for selective removal of supported platinum particles from external zeolite surfaces: characterisation of and application to a catalyst for the selective reduction of nitrogen oxide by hydrocarbons. Microporous Mesoporous Mater 31:23–31
Laprune D, Tuel A, Farrusseng D, Meunier FC (2017) Selective removal of external Ni nanoparticles on Ni@silicalite-1 single crystal nanoboxes: application to size-selective arene hydrogenation. Appl Catal A 535:69–76
Munnik P, De Jongh PE, De Jong KP (2015) Recent developments in the synthesis of supported catalysts. Chem Rev 115:6687–6718
Thommes M, Kaneko K, Neimark AV, Olivier JP, Rodriguez-Reinoso F, Rouquerol J, Sing KSW (2015) Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC technical report). Pure Appl Chem 87:1051–1069
Treacy MM, Higgins JB (2007) Collection of simulated XRD powder patterns for zeolites, 5th revised edn. Elsevier, Amsterdam, p 398
Tomiyama S, Takahashi R, Sato S, Sodesawa T, Yoshida S (2003) Preparation of Ni/SiO2 catalyst with high thermal stability for CO2-reforming of CH4. Appl Catal A 241:349–361
Soghrati E, Kay T, Ong C, Poh CK, Kawi S, Borgna A (2018) Zeolite–supported nickel phyllosilicate catalyst for CO hydrogenolysis of cyclic ethers and polyols. Appl Catal B 235:130–142
Maia AJ, Louis B, Lam YL, Pereira MM (2010) Ni-ZSM-5 catalysts: detailed characterization of metal sites for proper catalyst design. J Catal 269:103–109
Chen B-H, Chao Z-S, He H, Huang C, Liu Y-J, Yi W-J, Wei X-L, An J-F (2016) Towards a full understanding of the nature of Ni(II) species and hydroxyl groups over highly siliceous HZSM-5 zeolite supported nickel catalysts prepared by a deposition-precipitation method. Dalton Trans 45:2720–2739
Chen B-H, Liu W, Li A, Liu Y-J, Chao Z-S (2015) A simple and convenient approach for preparing core–shell-like silica@nickel species nanoparticles: highly efficient and stable catalyst for the dehydrogenation of 1,2-cyclohexanediol to catechol. Dalton Trans 44:1023–1038
Romero MD, de Lucas A, Calles JA, Rodriguez A (1996) Bifunctional catalyst NiHZSM-5: effects of the nickel incorporation method. Appl Catal A 146:425–441
Biju V, Abdul Khadar M (2002) Electronic structure of nanostructured nickel oxide using Ni 2p XPS analysis. J Nanoparticle Res 4:247–253
Uhlenbrock S, Scharfschwerdt C, Neumann M, Illing G, Freund H-J (1992) The influence of defects on the Ni 2p and O 1s XPS of NiO. J Phys Condens Matter 4:7973–7978
Alders D, Voogt FC, Hibma T, Sawatzky GA (1996) Nonlocal screening effects in 2p x-ray photoemission spectroscopy of NiO (100). Phys Rev B 54:7716–7719
Lenglet M, D’Huysser A, Jorgensen CK (1987) Optical spectra, x-ray photoelectron spectra and XANES of divalent nickel in mixed spinels NiFe2–xCrxO4. Inorg Chim Acta 133:61–65
Wrobel G, Sohier MP, D’Huysser A, Bonnelle JP (1993) Hydrogenation catalysts based on nickel and rare earth oxides: part II: XRD, electron microscopy and XPS studies of the cerium–nickel–oxygen–hydrogen system. Appl Catal A 101:73–93
Morales-Pacheco P, Domínguez JM, Bucio L, Alvarez F, Sedran U, Falco M (2011) Synthesis of FAU(Y)- and MFI(ZSM5)-nanosized crystallites for catalytic cracking of 1,3,5-triisopropylbenzene. Catal Today 166:25–38
Tarach KA, Góra-Marek K, Martinez-Triguero J, Melián-Cabrera I (2017) Acidity and accessibility studies of desilicated ZSM-5 zeolites in terms of their effectiveness as catalysts in acid-catalyzed cracking processes. Catal Sci Technol 7:858–873
Hoan VuX, Tam Truong T, Armbruster U (2018) Enhanced cracking of bulky hydrocarbons over hierarchical ZSM-5 materials: a comparative study. J Porous Mater. https://doi.org/10.1007/s10934-018-0633-0
Aghakhani MS, Khodadadi AA, Najafi Sh, Mortazavi Y (2014) Enhanced triisopropylbenzene cracking and suppressed coking on tailored composite of Y-zeolite/amorphous silica–alumina catalyst. J Ind Eng Chem 20:3037–3045
Vu XH, Bentrup U, Hunger M, Kraehnert R, Armbruster U, Martin A (2014) Direct synthesis of nanosized-ZSM-5/SBA-15 analog composites from preformed ZSM-5 precursors for improved catalytic performance as cracking catalyst. J Mater Sci 49:5676–5689. https://doi.org/10.1007/s10853-014-8287-z
Acknowledgements
The authors are grateful to Olivier Gardoll, Laurence Burylo, Pardis Simon, Martine Frère and Debora Strossi for help with TPR, XRD, XPS and TEM measurements. The authors thank International Cooperation Program CAPES/COFECUB Foundation funded by CAPES—Brazilian Federal Agency for Support and Evaluation of Graduate Education within the Ministry of Education of Brazil for providing Ph.D. stipends and financial support for this work. The authors acknowledge financial support of the French National Research Agency (Direct Syn BioFuel Project, Ref. ANR-15-CE06-0004 and NANO4-FUT, Ref. ANR-16-CE06-0013). The authors acknowledge financial support from the European Union (Interreg V Project PSYCHE).
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Peron, D.V., Zholobenko, V.L., de la Rocha, M.R. et al. Nickel–zeolite composite catalysts with metal nanoparticles selectively encapsulated in the zeolite micropores. J Mater Sci 54, 5399–5411 (2019). https://doi.org/10.1007/s10853-018-03250-5
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DOI: https://doi.org/10.1007/s10853-018-03250-5