Abstract
A core–shell HZSM-5@silicalite-1 zeolite coated with a relatively continuous b-oriented thin silicalite-1 shell has been synthesized by a self-assembly method of reversing the negative surface charge of ZSM-5 crystals before the secondary hydrothermal crystallization. The growth orientation of shell crystals is confirmed by electron microscopy technology. N2 adsorption–desorption, X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscope with energy-dispersive X-ray spectrometry (STEM-EDS) measurements reveal that the core ZSM-5 crystals are coated with a relatively continuous monocrystal-thick silicalite-1 shell. The surface acidity analysis (Pyridine-FTIR and 2,4,6-collidine-FTIR) combined with the two probe chemical reactions using molecules that are either too large or adequately sized to access MFI pores has confirmed the passivation of external surface acid sites without hindering the intrinsic activity of the parent HZSM-5, which is consistent with the results from the electron microscopy and textural analysis.
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References
R. Carvajal, P. Chu, J.H. Lunsford, The role of polyvalent cations in developing strong acidity: a study of lanthanum-exchanged zeolites. J. Catal. 125(1), 123–131 (1990)
A.A. Sokol, C.R. Catlow, J.M. Garces, A. Kuperman, Computational investigation into the origins of Lewis acidity in zeolites. Adv. Mater. 12(23), 1801–1805 (2000)
J.A. van Bokhoven, A.M.J. van der Eerden, D.C. Koningsberger, Three-Coordinate aluminum in zeolites observed with in situ x-ray absorption near-edge spectroscopy at the Al K-Edge: flexibility of aluminum coordinations in zeolites. J. Am. Chem. Soc. 125(24), 7435–7442 (2003)
R. Gounder, E. Iglesia, Catalytic consequences of spatial constraints and acid site location for monomolecular alkane activation on zeolites. J. Am. Chem. Soc. 131(5), 1958–1971 (2009)
D.V. Vu, M. Miyamoto, N. Nishiyama, S. Ichikawa, Y. Egashira, K. Ueyama, Catalytic activities and structures of silicalite-1/H-ZSM-5 zeolite composites. Microporous Mesoporous Mater. 115(1–2), 106–112 (2008)
Y. Seo, K. Cho, Y. Jung, R. Ryoo, Characterization of the surface acidity of MFI zeolite nanosheets by 31P NMR of adsorbed phosphine oxides and catalytic cracking of decalin. ACS Catal. 3(4), 713–720 (2013)
D. Mitsuyoshi, K. Kuroiwa, Y. Kataoka, T. Nakagawa, M. Kosaka, K. Nakamura, S. Suganuma, Y. Araki, N. Katad, Shape selectivity in toluene disproportionation into para-xylene generated by chemical vapor deposition of tetramethoxysilane on MFI zeolite catalyst. Microporous Mesoporous Mater. 242, 118–126 (2017)
T. Hibino, M. Niwa, Y. Murakami, Shape-selectivity over HZSM-5 modified by chemical vapor deposition of silicon alkoxide. J. Catal. 128(2), 551–558 (1991)
M. Niwa, M. Kato, T. Hattori, Y. Murakami, Fine control of the pore-opening size of zeolite ZSM-5 by chemical vapor deposition of silicon alkoxide. J. Phys. Chem. 90(23), 6233–6237 (1986)
J. Li, H. Xiang, M. Liu, Q. Wang, Z. Zhu, Z. Hu, The deactivation mechanism of two typical shape-selective HZSM-5 catalysts for alkylation of toluene with methanol. Catal. Sci. Technol. 4(8), 2639–2649 (2014)
S. Zheng, H. Tanaka, A. Jentys, J.A. Lercher, Novel model explaining toluene diffusion in HZSM-5 after surface modification. J. Phys. Chem. B 108(4), 1337–1343 (2004)
J.H. Ahn, R. Kolvenbach, S.S. Al-khattaf, A. Jentysa, J.A. Lercher, Enhancing shape selectivity without loss of activity–novel mesostructured ZSM5 catalysts for methylation of toluene to p-xylene. Chem. Commun. 49(90), 10584–10586 (2013)
F. Lónyi, J. Engelhardt, D. Kalló, Para-selectivity of toluene ethylation over ZSM-5 catalysts. Zeolites 11(2), 169–177 (2015)
J. Engelhardt, D.I. Zsinka, Ethylation of toluene and transformation of p-ethyltoluene on H-ZSM-5 and ZSM-5 modified with MgO. J. Catal. 135(1), 321–324 (1992)
W. Tan, M. Liu, Y. Zhao, K. Hou, H. Wu, A. Zhang, H. Liu, Y. Wang, C. Song, X. Guo, Para-selective methylation of toluene with methanol over nano-sized ZSM-5 catalysts: synergistic effects of surface modifications with SiO2, P2O5 and MgO. Microporous Mesoporous Mater. 196, 18–30 (2014)
J. Zhang, W. Qian, C. Kong, F. Wei, Increasing para-xylene selectivity in making aromatics from methanol with a surface-modified Zn/P/ZSM-5 catalyst. ACS Catal. 5(5), 2982–2988 (2015)
S. Zheng, H.R. Heydenrych, H.P. Röger, A. Jentys, J.A. Lercher, On the enhanced selectivity of HZSM-5 modified by chemical liquid deposition. Top. Catal. 22(1–2), 101–106 (2003)
P. Hou, H. Zhang, Z. Zi, L. Zhang, X. Xu, Core-shell and concentration-gradient cathodes prepared via co-precipitation reaction for advanced lithium-ion batteries. J. Mater. Chem. A 5(9), 4254–4279 (2017)
A. Leidner, S. Weigel, J. Bauer, J. Reiber, A. Angelin, M. Grösche, T. Scharnweber, C.M. Niemeyer, Biopebbles: DNA-functionalized core-shell silica nanospheres for cellular uptake and cell guidance studies. Adv. Funct. Mater. 28(18), 1707572 (2018)
B. Banerjee, R. Singuru, S.K. Kundu, K. Dhanalaxmi, L. Bai, Y. Zhao, B.M. Reddy, A. Bhaumik, J. Mondal, Towards rational design of core-shell catalytic nanoreactor with high performance catalytic hydrogenation of levulinic acid. Catal. Sci. Technol. 6, 5102–5115 (2016)
E. Edri, S. Aloni, H. Frei, Fabrication of core-shell nanotube array for artificial photosynthesis featuring an ultrathin composite separation membrane. ACS Nano 12(1), 533–541 (2018)
L.D. Rollmann, ZSM-5 containing aluminum-free shells on its surface. US Patent, 4088605, 1978
M. Miyamoto, T. Kamei, N. Nishiyama, Y. Egashira, K. Ueyama, Single crystals of ZSM-5/silicalite composites. Adv. Mater. 17(44), 1985–1988 (2005)
D.V. Vu, M. Miyamoto, N. Nishiyama, Y. Egashira, K. Ueyama, Selective formation of para-xylene over H-ZSM-5 coated with polycrystalline silicalite crystals. J. Catal. 243(2), 389–394 (2006)
M. Miyamoto, K. Mabuchi, J. Kamada, Y. Hirota, Y. Oumi, N. Nishiyama, S. Uemiya, para-Selectivity of silicalite-1 coated MFI type galloaluminosilicate in aromatization of light alkanes. J. Porous Mater. 22(3), 769–778 (2015)
A.I. Lupulescu, J.D. Rimer, In situ imaging of silicalite-1 surface growth reveals the mechanism of crystallization. Science 344(6185), 729–732 (2014)
A. Aerts, L.R.A. Follens, E. Biermans, S. Bals, G.V. Tendeloo, B. Loppinet, C.E.A. Kirschhock, J.A. Martens, Modelling of synchrotron SAXS patterns of silicalite-1 zeolite during crystallization. Phys. Chem. Chem. Phys. 13(10), 4318–4325 (2011)
Q. Lia, Z. Wang, J. Hedlund, D. Creaser, H. Zhang, X. Zou, A.J. Bons, Synthesis and characterization of colloidal zoned MFI crystals. Microporous Mesoporous Mater. 78(1), 1–10 (2005)
Y. Bouizi, L. Rouleau, V.P. Valtchev, Factors controlling the formation of core-shell zeolite-zeolite composites. Chem. Mater. 18(20), 4959–4966 (2006)
Y. Bouizi, I. Diaz, L. Rouleau, V.P. Valtchev, Core-shell zeolite microcomposites. Adv. Funct. Mater. 15(12), 1955–1960 (2005)
L. Gora, B. Sulikowski, E.M. Serwicka, Formation of structured silicalite-I/ZSM-5 composites by a self-assembly process. Appl. Catal. A 325(2), 316–321 (2007)
Y. Bouizi, G. Majano, S. Mintova, V.P. Valtchev, Beads comprising a hierarchical porous core and a microporous shell. J. Phys. Chem. C 111(12), 4535–4542 (2007)
M. Okamoto, Y. Osafune, MFI-type zeolite with a core-shell structure with minimal defects synthesized by crystal overgrowth of aluminum-free MFI-type zeolite on aluminum-containing zeolite and its catalytic performance. Microporous Mesoporous Mater. 143(2), 413–418 (2011)
J. Caro, M. Noack, P. Kölsch, R. Schäfer, Zeolite membranes–state of their development and perspective. Microporous Mesoporous Mater. 38(1), 3–24 (2000)
S. Li, X. Wang, D. Beving, Z. Chen, Y. Yan, Molecular sieving in a nanoporous b-oriented pure-silica-zeolite MFI monocrystal film. J. Am. Chem. Soc. 126(13), 4122–4123 (2004)
D. Mores, E. Stavitski, S.P. Verkleij, A. Lombard, A. Cabiac, L. Rouleau, J. Patarin, A. Simon-Masseron, B.M. Weckhuysen, Core-shell H-ZSM-5/silicalite-1 composites: Brønsted acidity and catalyst deactivation at the individual particle level. Phys. Chem. Chem. Phys. 13(35), 15985–15994 (2011)
H. Wu, M. Liu, W. Tan, K. Hou, A. Zhang, Y. Wang, X. Guo, Effect of ZSM-5 zeolite morphology on the catalytic performance of the alkylation of toluene with methanol. J. Energy Chem. 23(4), 491–497 (2014)
L. Xu, Y. Ren, H. Wu, Y. Liu, Z. Wang, Y. Zhang, J. Xu, H. Peng, P. Wu, Core/shell-structured TS-1@mesoporous silica-supported Au nanoparticles for selective epoxidation of propylene with H2 and O2. J. Mater. Chem. 21(29), 10852–10858 (2011)
V. Quaschning, J. Deutsch, P. Druska, H.J. Niclas, E. Kemnitz, Properties of modified zirconia used as friedel-crafts-acylation catalysts. J. Catal. 177(2), 164–174 (1998)
D. Liu, P. Yuan, H. Liu, J. Cai, D. Tan, H. He, J. Zhu, T. Chen, Quantitative characterization of the solid acidity of montmorillonite using combined FTIR and TPD based on the NH3 adsorption system. Appl. Clay Sci. 80–81(8), 407–412 (2013)
N.S. Nesterenko, F. Thibault-Starzyk, V. Montouilliout, V.V. Yushchenko, C. Fernandez, J.P. Gilson, F. Fajula, I.I. Ivanova, 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(1), 40–48 (2006)
N. Brodu, M.H. Manero, C. Andriantsiferana, J.S. Pic, H. Valdés, Role of Lewis acid sites of ZSM-5 zeolite on gaseous ozone abatement. Chem. Eng. J. 231, 281–286 (2013)
J.C. Groen, L.A.A. Peffer, J. Pérez-Ramı́rez, Pore size determination in modified micro- and mesoporous materials. Pitfalls and limitations in gas adsorption data analysis. Microporous Mesoporous Mater 60(1), 1–17 (2003)
Y. Liu, X. Zhou, X. Pang, Y. Jin, X. Meng, X. Zheng, X. Gao, F.S. Xiao, Improved para-xylene selectivity in meta-xylene isomerization over ZSM-5 crystals with relatively long b-axis length. Chemcatchem 5(6), 1517–1523 (2013)
G.T. Kokotailo, S.L. Lawton, D.H. Olson, Structure of synthetic zeolite ZSM-5. Nature 272(5652), 437–438 (1978)
A.E. Hughes, K.G. Wilshier, B.A. Sexton, P. Smart, Aluminum distribution in ZSM-5 as determined by X-ray photoelectron spectroscopy. J. Catal. 80(1), 221–227 (1983)
G. Mattogno, G. Righini, G. Montesperelli, E. Traversa, XPS analysis of the interface of ceramic thin films for humidity sensors. Appl. Surf. Sci. 70(93), 363–366 (1993)
G. Delahay, M. Mauvezin, B. Coq, S. Kieger, Selective catalytic reduction of nitrous oxide by ammonia on iron zeolite beta catalysts in an oxygen rich atmosphere: effect of iron contents. J. Catal. 202(1), 156–162 (2001)
F. Thibault-Starzyk, I. Stan, S. Abelló, A. Bonilla, K. Thomas, C. Fernandez, J.P. Gilson, J. Pérez-Ramírez, Quantification of enhanced acid site accessibility in hierarchical zeolites-The accessibility index. J. Catal. 264(1), 11–14 (2009)
O.A. Anunziata, G.A. Eimer, L.B. Pierella, Catalytic conversion of natural gas with added ethane and LPG over Zn-ZSM-11. Appl. Catal. A-Gen. 190(1), 169–176 (2000)
E.L. First, C.E. Gounaris, J. Wei, C.A. Floudas, Computational characterization of zeolite porous networks: an automated approach. Phys. Chem. Chem. Phys. 13(38), 17339–17358 (2011)
J.P. Marques, I. Gener, P. Ayrault, J.C. Bordado, J.M. Lopes, F.R. Ribeiro, M. Guisnet, Dealumination of HBEA zeolite by steaming and acid leaching: distribution of the various aluminic species and identification of the hydroxyl group. C. R. Chim. 8, 399–410 (2005)
P. Kalita, N.M. Gupta, R. Kumar, Synergistic role of acid sites in the Ce-enhanced activity of mesoporous Ce-Al-MCM-41 catalysts in alkylation reactions: FTIR and TPD-ammonia studies. J. Catal. 245(2), 338–347 (2007)
T. Odedairo, R.J. Balasamy, S. Al-Khattaf, Influence of mesoporous materials containing ZSM-5 on alkylation and cracking reactions. J. Mol. Catal. A 345(1), 21–36 (2011)
K.A. Tarach, J. Martinez-Triguero, F. Rey, K. Góra-Marek, Hydrothermal stability and catalytic performance of desilicated highly siliceous zeolites ZSM-5. J. Catal. 339, 256–269 (2016)
W. Kaeding, C. Chu, L. Young, B. Weinstein, S. Butter, Selective alkylation of toluene with methanol to produce para-xylene. J. Catal. 67(1), 159–174 (1981)
J. Wei, A mathematical theory of enhanced para-xylene selectivity in molecular sieve catalysts. J. Catal. 76(2), 433–439 (1982)
J. Zhang, X. Zhu, G. Wang, P. Wang, Z. Meng, C. Li, The origin of the activity and selectivity of silicalite-1 zeolite for toluene methylation to para-xylene. Chem. Eng. J. 327, 278–285 (2017)
P. Liu, Z. Fei, L. Li, X. Feng, W. Ji, W. Ding, Y. Chen, W. Yang, Z. Xie, Effects of controlled SiO2 deposition and phosphorus and nickel doping on surface acidity and diffusivity of medium and small sized HZSM-5 for para-selective alkylation of toluene by methanol. Appl. Catal. A 453, 302–309 (2013)
Acknowledgements
This project was financially supported by the National Science Foundation for Young Scientists of China (No. 21706065), the Open Project of State Key Laboratory of Chemical Engineering (SKL-ChE-18C02), the China Postdoctoral Science Foundation (No. 2017M621389) and the Shanghai Sailing Program (No. 18YF1406300).
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Yi, D., Xu, X., Meng, X. et al. Synthesis of core–shell ZSM-5 zeolite with passivated external surface acidity by b-oriented thin silicalite-1 shell using a self-assembly process. J Porous Mater 26, 1767–1779 (2019). https://doi.org/10.1007/s10934-019-00776-0
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DOI: https://doi.org/10.1007/s10934-019-00776-0