State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Shanghai Research Institute of Petrochemical Technology, Sinopec, Shanghai 201208, China
Hierarchical ZSM-5 zeolite with radial mesopores is controllably synthesized using piperidine in a NaOH solution. The piperidine molecules enter the zeolite micropores and protect the zeolite framework from extensive desilication. The areas containing fewer aluminum atoms contain fewer piperidine protectant molecules and so they dissolve first. Small amounts of mesopores are then gradually generated in areas with more aluminum atoms and more piperidine protectant. In this manner, radial mesopores are formed in the ZSM-5 zeolite with a maximal preservation of the micropores and active sites. The optimal hierarchical ZSM-5 zeolite, prepared with a molar ratio of piperidine to zeolite of 0.03, had a mesopore surface area of 136 m2·g−1 and a solid yield of 80%. The incorporation of the radial mesopores results in micropores that are interconnected which shortened the average diffusion path length. Compared to the parent zeolite, the hierarchical ZSM-5 zeolite possesses more accessible acid sites and has a higher catalytic activity and a longer lifetime for the alkylation of benzene.
A Corma. Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions. Chemical Reviews, 1995, 95(3): 559–614 https://doi.org/10.1021/cr00035a006
2
C S Cundy, P A Cox. The hydrothermal synthesis of zeolites: History and development from the earliest days to the present time. Chemical Reviews, 2003, 103(3): 663–702 https://doi.org/10.1021/cr020060i
3
A Corma. From microporous to mesoporous molecular sieve materials and their use in catalysis. Chemical Reviews, 1997, 97(6): 2373–2420 https://doi.org/10.1021/cr960406n
4
Y S Tao, H Kanoh, L Abrams, K Kaneko. Mesopore-modified zeolites: Preparation, characterization, and applications. Chemical Reviews, 2006, 106(3): 896–910 https://doi.org/10.1021/cr040204o
5
H Zheng, D Zhai, L Zhao, C Zhang, S Yu, J Gao, C Xu. Insight into the contribution of isolated mesopore on diffusion in hierarchical zeolites: The effect of temperature. Industrial & Engineering Chemistry Research, 2018, 57(15): 5453–5463 https://doi.org/10.1021/acs.iecr.8b00515
6
J Han, J Cho, J C Kim, R Ryoo. Confinement of supported metal catalysts at high loading in the mesopore network of hierarchical zeolites, with access via the microporous windows. ACS Catalysis, 2018, 8(2): 876–879 https://doi.org/10.1021/acscatal.7b04183
7
L Y Jia, M Raad, S Hamieh, J Toufaily, T Hamieh, M M Bettahar, G Mauviel, M Tarrighi, L Pinard, A Dufour. Catalytic fast pyrolysis of biomass: Superior selectivity of hierarchical zeolites to aromatics. Green Chemistry, 2017, 19(22): 5442–5459 https://doi.org/10.1039/C7GC02309J
8
J C Groen, T Bach, U Ziese, A M Paulaime-van Donk, K P de Jong, J A Moulijn, J Pérez-Ramírez. Creation of hollow zeolite architectures by controlled desilication of Al-zoned ZSM-5 crystals. Journal of the American Chemical Society, 2005, 127(31): 10792–10793 https://doi.org/10.1021/ja052592x
I Schmidt, A Boisen, E Gustavsson, K Stahl, S Pehrson, S Dahl, A Carlsson, C J H Jacobsen. Carbon nanotube templated growth of mesoporous zeolite single crystals. Chemistry of Materials, 2001, 13(12): 4416–4418 https://doi.org/10.1021/cm011206h
11
Y Tao, H Kanoh, K Kaneko. ZSM-5 monolith of uniform mesoporous channels. Journal of the American Chemical Society, 2003, 125(20): 6044–6045 https://doi.org/10.1021/ja0299405
12
K Zhu, K Egeblad, C H Christensen. Mesoporous carbon prepared from carbohydrate as hard template for hierarchical zeolites. European Journal of Inorganic Chemistry, 2007, 2007(25): 3955–3960 https://doi.org/10.1002/ejic.200700218
13
F Xiao, L Wang, C Yin, K Lin, Y Di, J Li, R Xu, D Su, R Schlögl, T Yokoi, T Tatsumi. Catalytic properties of hierarchical mesoporous zeolites templated with a mixture of small organic ammonium salts and mesoscale cationic polymers. Angewandte Chemie International Edition, 2006, 45(19): 3090–3093 https://doi.org/10.1002/anie.200600241
14
Z Zhao, Y Liu, H Wu, X Li, M He, P Wu. Hydrothermal synthesis of mesoporous titanosilicate with the aid of amphiphilic organosilane. Journal of Porous Materials, 2010, 17(4): 399–408 https://doi.org/10.1007/s10934-009-9316-1
15
H Liu, S Zhang, S Xie, W Zhang, W Xin, S Liu, L Xu. Synthesis, characterization, and catalytic performance of hierarchical ZSM-11 zeolite synthesized via dual-template route. Chinese Journal of Catalysis, 2018, 39(1): 167–180 https://doi.org/10.1016/S1872-2067(17)62984-X
16
X Wang, H Chen, F Meng, F Gao, C Sun, L Sun, S Wang, L Wang, Y Wang. CTAB resulted direct synthesis and properties of hierarchical ZSM-11/5 composite zeolite in the absence of template. Microporous and Mesoporous Materials, 2017, 243: 271–280 https://doi.org/10.1016/j.micromeso.2017.02.054
17
J C Groen, J C Jansen, J A Moulijn, J Pérez-Ramírez. Optimal aluminum-assisted mesoporosity development in MFI zeolites by desilication. Journal of Physical Chemistry B, 2004, 108(35): 13062–13065 https://doi.org/10.1021/jp047194f
18
J C Groen, L A A Peffer, J A Moulijn, J Pérez-Ramírez. Mechanism of hierarchical porosity development in MFI zeolites by desilication: The role of aluminium as a pore‐directing agent. Chemistry (Weinheim an der Bergstrasse, Germany), 2005, 11(17): 4983–4994 https://doi.org/10.1002/chem.200500045
19
M Rutkowska, I Pacia, S Basąg, A Kowalczyk, Z Piwowarska, M Duda, K A Tarach, K Góra-Marek, M Michalik, U Díaz, L Chmielarz. Catalytic performance of commercial Cu-ZSM-5 zeolite modified by desilication in NH3-SCR and NH3-SCO processes. Microporous and Mesoporous Materials, 2017, 246: 193–206 https://doi.org/10.1016/j.micromeso.2017.03.017
20
S Oruji, R Khoshbin, R Karimzadeh. Preparation of hierarchical structure of Y zeolite with ultrasonic-assisted alkaline treatment method used in catalytic cracking of middle distillate cut: the effect of irradiation time. Fuel Processing Technology, 2018, 176: 283–295 https://doi.org/10.1016/j.fuproc.2018.03.035
21
J C Groen, T Sano, J A Moulijn, J Pérez-Ramírez. Alkaline-mediated mesoporous mordenite zeolites for acid-catalyzed conversions. Journal of Catalysis, 2007, 251(1): 21–27 https://doi.org/10.1016/j.jcat.2007.07.020
22
J Pérez-Ramírez, S Abello, L A Villaescusa, A Bonilla. Toward functional clathrasils: Size- and composition-controlled octadecasil nanocrystals by desilication. Angewandte Chemie International Edition, 2008, 47(41): 7913–7917 https://doi.org/10.1002/anie.200802393
23
D Verboekend, J Pérez-Ramírez. Desilication mechanism revisited: Highly mesoporous all-silica zeolites enabled through pore-directing agents. Chemistry (Weinheim an der Bergstrasse, Germany), 2011, 17(4): 1137–1147 https://doi.org/10.1002/chem.201002589
24
K Sadowska, A Wach, Z Olejniczak, P Kustrowski, J Datka. Hierarchic zeolites: Zeolite ZSM-5 desilicated with NaOH and NaOH/tetrabutylamine hydroxide. Microporous and Mesoporous Materials, 2013, 167(3): 82–88 https://doi.org/10.1016/j.micromeso.2012.03.045
25
J C Groen, L A A Peffer, J A Moulijn, J Pérez-Ramírez. Mesoporosity development in ZSM-5 zeolite upon optimized desilication conditions in alkaline medium. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2004, 241(1-3): 53–58 https://doi.org/10.1016/j.colsurfa.2004.04.012
26
J Pérez-Ramírez, D Verboekend, A Bonilla, S Abello. Zeolite catalysts with tunable hierarchy factor by pore-growth moderators. Advanced Functional Materials, 2009, 19(24): 3972–3979 https://doi.org/10.1002/adfm.200901394
27
M Milina, S Mitchell, P Crivelli, D Cooke, J Pérez-Ramírez. Mesopore quality determines the lifetime of hierarchically structured zeolite catalysts. Nature Communications, 2014, 5(1): 3922–3931 https://doi.org/10.1038/ncomms4922
28
D Wang, L Zhang, L Chen, H Wu, P Wu. Postsynthesis of mesoporous ZSM-5 zeolite by piperidine-assisted desilication and its superior catalytic properties in hydrocarbon cracking. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2015, 3(7): 3511–3521 https://doi.org/10.1039/C4TA06438K
29
D Wang, L Xu, P Wu. Hierarchical, core-shell meso-ZSM-5@mesoporous aluminosilicate-supported Pt nanoparticles for bifunctional hydrocracking. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2014, 2(37): 15535–15545 https://doi.org/10.1039/C4TA02740J
K S W Sing, D H Everett, R A W Haul, L Moscou, R A Pierotti, J Rouquerol, V T Siemieniewska. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure and Applied Chemistry, 1985, 57(4): 603–619 https://doi.org/10.1351/pac198557040603
32
J C Groen, J A Moulijn, J Pérez-Ramírez. Desilication: On the controlled generation of mesoporosity in MFI zeolites. Journal of Materials Chemistry, 2006, 16(22): 2121–2131 https://doi.org/10.1039/B517510K
33
W C Yoo, X Zhang, M Tsapatsis, A Stein. Synthesis of mesoporous ZSM-5 zeolites through desilication and re-assembly processes. Microporous and Mesoporous Materials, 2012, 149(1): 147–157 https://doi.org/10.1016/j.micromeso.2011.08.014
34
J Pérez-Ramírez, S Abelló, A Bonilla, J C Groen. Tailored mesoporosity development in zeolite crystals by partial detemplation and desilication. Advanced Functional Materials, 2009, 19(1): 164–172 https://doi.org/10.1002/adfm.200800871
35
E Gornicka, J E Rode. Raczynska, E D, Dasiewicz B, Dobrowolski J C. Vibrational Spectroscopy, 2004, 36: 105–115
36
G T Kokotailo, S L Lawton, D H Olson, W M Meier. Structure of synthetic zeolite ZSM-5. Nature, 1978, 272(5652): 437–438 https://doi.org/10.1038/272437a0
37
K Zhu, J Sun, J Liu, L Wang, H Wan, J Hu, Y Wang, C H F Peden, Z Nie. Solvent evaporation assisted preparation of oriented nanocrystalline mesoporous MFI zeolites. ACS Catalysis, 2011, 1(7): 682–690 https://doi.org/10.1021/cs200085e
38
Y Liu, W Zhang, Z Liu, S Xu, Y Wang, Z Xie, X Han, X Bao. Direct observation of the mesopores in ZSM-5 zeolites with hierarchical porous structures by laser-hyperpolarized 129Xe NMR. Journal of Physical Chemistry C, 2008, 112(39): 15375–15381 https://doi.org/10.1021/jp802813x
39
R Schumacher, H G Karge. Sorption kinetics study of the diethylbenzene isomers in MFI-type zeolites. Microporous and Mesoporous Materials, 1999, 30(2-3): 307–314 https://doi.org/10.1016/S1387-1811(99)00041-4
40
J Zhou, Z Liu, Y Wang, H Gao, L Li, W Yang, Z Xie, Y Tang. Enhanced accessibility and utilization efficiency of acid sites in hierarchical MFI zeolite catalyst for effective diffusivity improvement. RSC Advances, 2014, 4(82): 43752–43755 https://doi.org/10.1039/C4RA03986F
41
W Yang, Z Wang, H Sun, B Zhang. Advances in development and industrial applications of ethylbenzene processes. Chinese Journal of Catalysis, 2016, 37(1): 16–26 https://doi.org/10.1016/S1872-2067(15)60965-2
42
S K Saxena, N Viswanadham. Hierarchically nano porous nano crystalline ZSM-5 for improved alkylation of benzene with bio-ethanol. Applied Materials Today, 2016, 5: 25–32 https://doi.org/10.1016/j.apmt.2016.09.006
43
Z Lei, L Liu, C Dai. Insight into the reaction mechanism and charge transfer analysis for the alkylation of benzene with propylene over H-β zeolite. Molecular Catalysis, 2018, 454: 1–11 https://doi.org/10.1016/j.mcat.2018.05.010
44
C H Christensen, K Johannsen, I Schmidt, C H Christensen. Catalytic benzene alkylation over mesoporous zeolite single crystals: Improving activity and selectivity with a new family of porous materials. Journal of the American Chemical Society, 2003, 125(44): 13370–13371 https://doi.org/10.1021/ja037063c
