Abstract
Mesoporous materials constructed with microporous zeolitic frameworks (i.e., mesoporous zeolites) are of great interest owing to the very short diffusion path lengths across thin zeolite layers and the presence of large external surfaces containing strong Brønsted acid sites. These characteristics of mesoporous zeolites are highly advantageous for a wide range of applications, particularly in heterogeneous catalysis. The mesoporous materials show unprecedentedly high catalytic performances (e.g., high catalytic conversion and catalytic longevity) as zeolites in various petrochemical reactions and fine-chemical organic reactions and especially in reactions involving bulky molecules. In this chapter, we describe the various methods currently available for the synthesis of mesoporous zeolites.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Breck DW (1974) Zeolite molecular sieves: structure, chemistry, and use. Wiley, New York
Corma A (1997) From microporous to mesoporous molecular sieve materials and their use in catalysis. Chem Rev 97(6):2373–2419
Corma A (2003) State of the art and future challenges of zeolites as catalysts. J Catal 216(1–2):298–312
Perez-Ramirez J, Christensen CH, Egeblad K, Christensen CH, Groen JC (2008) Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design. Chem Soc Rev 37(11):2530–2542
Rinaldi R, Schuth F (2009) Design of solid catalysts for the conversion of biomass. Energy Environ Sci 2(6):610–626
Davis ME, Saldarriaga C, Montes C, Garces J, Crowder C (1988) A molecular-sieve with 18-membered rings. Nature 331(6158):698–699
Davis ME (2002) Ordered porous materials for emerging applications. Nature 417(6891):813–821
Corma A, Diaz-Cabanas MJ, Jorda JL, Martinez C, Moliner M (2006) High-throughput synthesis and catalytic properties of a molecular sieve with 18-and 10-member rings. Nature 443(7113):842–845
Freyhardt CC, Tsapatsis M, Lobo RF, Balkus KJ, Davis ME (1996) A high-silica zeolite with a 14-tetrahedral-atom pore opening. Nature 381(6580):295–298
Strohmaier KG, Vaughan DEW (2003) Structure of the first silicate molecular sieve with 18-ring pore openings, ECR-34. J Am Chem Soc 125(51):16035–16039
Corma A, Diaz-Cabanas MJ, Rey F, Nicolooulas S, Boulahya K (2004) ITQ-15: the first ultralarge pore zeolite with a bi-directional pore system formed by intersecting 14- and 12-ring channels, and its catalytic implications. Chem Commun 12:1356–1357
Corma A, Diaz-Cabanas M, Martinez-Triguero J, Rey F, Rius J (2002) A large-cavity zeolite with wide pore windows and potential as an oil refining catalyst. Nature 418(6897):514–517
Jiang JX, Yu JH, Corma A (2010) Extra-large-pore zeolites: bridging the gap between micro and mesoporous structures. Angew Chem Int Ed 49(18):3120–3145
Blasco T, Corma A, Diaz-Cabanas MJ, Rey F, Vidal-Moya JA, Zicovich-Wilson CM (2002) Preferential location of Ge in the double four-membered ring units of ITQ-7 zeolite. J Phys Chem B 106(10):2634–2642
Corma A, Navarro MT, Rey F, Valencia S (2001) Synthesis of pure polymorph C of beta zeolite in a fluoride-free system. Chem Commun 16:1486–1487
Sastre G, Pulido A, Castaneda R, Corma A (2004) Effect of the germanium incorporation in the synthesis of EU-1, ITQ-13, ITQ-22, and ITQ-24 zeolites. J Phys Chem B 108(26):8830–8835
Sun JL, Bonneau C, Cantin A, Corma A, Diaz-Cabanas MJ, Moliner M, Zhang DL, Li MR, Zou XD (2009) The ITQ-37 mesoporous chiral zeolite. Nature 458(7242):1154–1157
Mintova S, Olson NH, Bein T (1999) Electron microscopy reveals the nucleation mechanism of zeolite Y from precursor colloids. Angew Chem Int Ed 38(21):3201–3204
Tosheva L, Valtchev VP (2005) Nanozeolites: synthesis, crystallization mechanism, and applications. Chem Mater 17(10):2494–2513
Larlus O, Mintova S, Bein T (2006) Environmental syntheses of nanosized zeolites with high yield and monomodal particle size distribution. Microporous Mesoporous Mater 96(1–3):405–412
Larsen SC (2007) Nanocrystalline zeolites and zeolite structures: synthesis, characterization, and applications. J Phys Chem C 111(50):18464–18474
Tao YS, Kanoh H, Abrams L, Kaneko K (2006) Mesopore-modified zeolites: preparation, characterization, and applications. Chem Rev 106(3):896–910
Egeblad K, Christensen CH, Kustova M, Christensen CH (2008) Templating mesoporous zeolites. Chem Mater 20(3):946–960
Schuth F (2003) Endo- and exotemplating to create high-surface-area inorganic materials. Angew Chem Int Ed 42(31):3604–3622
Scherzer J (1978) De-aluminated faujasite-type structures with SiO2-Al2O3 ratios over 100. J Catal 54(2):285–288
Lynch J, Raatz F, Dufresne P (1987) Characterization of the textural properties of dealuminated HY forms. Zeolites 7(4):333–340
Cartlidge S, Nissen HU, Wessicken R (1989) Ternary mesoporous structure of ultrastable zeolite CSZ-1. Zeolites 9(4):346–349
Choifeng C, Hall JB, Huggins BJ, Beyerlein RA (1993) Electron-microscope investigation of mesopore formation and aluminum migration in USY catalysts. J Catal 140(2):395–405
Sasaki Y, Suzuki T, Takamura Y, Saji A, Saka H (1998) Structure analysis of the mesopore in dealuminated zeolite Y by high resolution TEM observation with slow scan CCD camera. J Catal 178(1):94–100
Janssen AH, Koster AJ, de Jong KP (2001) Three-dimensional transmission electron microscopic observations of mesopores in dealuminated zeolite Y. Angew Chem Int Ed 40(6):1102–1104
Janssen AH, Koster AJ, de Jong KP (2002) On the shape of the mesopores in zeolite Y: a three-dimensional transmission electron microscopy study combined with texture analysis. J Phys Chem B 106(46):11905–11909
Dutartre R, deMenorval LC, DiRenzo F, McQueen D, Fajula F, Schulz P (1996) Mesopore formation during steam dealumination of zeolites: influence of initial aluminum content and crystal size. Microporous Mater 6(5–6):311–320
McQueen D, Chiche BH, Fajula F, Auroux A, Guimon C, Fitoussi F, Schulz P (1996) A multitechnique characterization of the acidity of dealuminated mazzite. J Catal 161(2):587–596
Nesterenko NS, Thibault-Starzyk F, Montouillout V, Yuschenko VV, Fernandez C, Gilson JP, Fajula F, Ivanova II (2004) Accessibility of the acid sites in dealuminated small-port mordenites studied by FTIR of co-adsorbed alkylpyridines and CO. Microporous Mesoporous Mater 71(1–3):157–166
Lee KH, Ha BH (1998) Characterization of mordenites treated by HCl/steam or HF. Microporous Mesoporous Mater 23(3–4):211–219
Perez-Ramirez J, Kapteijn F, Groen JC, Domenech A, Mul G, Moulijn JA (2003) Steam-activated FeMFI zeolites: evolution of iron species and activity in direct N2O decomposition. J Catal 214(1):33–45
Lago RM, Haag WO, Mikovsky RJ, Olson DH, Hellring SD, Schmitt KD, Kerr GT (1986) The nature of the catalytic sites in HZSM-5- activity enhancement. In: Murakami AI Y, Ward JW (eds) Studies in surface science and catalysis, vol 28. Elsevier, Amsterdam, pp 677–684
Rozwadowski M, Kornatowski J, Wloch J, Erdmann K, Golembiewski R (2002) Attempt to apply the fractal geometry for characterisation of dealuminated ZSM-5 zeolite. Appl Surf Sci 191(1–4):352–361
Levanmao R, Vo NTC, Sjiariel B, Lee L, Denes G (1992) Mesoporous aluminosilicates – preparation from Ca-a zeolite by treatment with ammonium fluorosilicate. J Mater Chem 2(6):595–599
Triantafyllidis KS, Vlessidis AG, Evmiridis NP (2000) Dealuminated H-Y zeolites: influence of the degree and the type of dealumination method on the structural and acidic characteristics of H-Y zeolites. Ind Eng Chem Res 39(2):307–319
Beyer HK, Belenykaja I (1980) A new method for the dealumination of faujasite-type zeolites. In: Imelik B, Naccache C, Ben Taarit Y, Vádrine JC, Condurier G, Praliaud H (eds) Studies in surface science and catalysis, vol 5. Elsevier, Amsterdam, pp 203–210
Scherzer J (1984) The preparation and characterization of aluminum-deficient zeolites. ACS Symp Ser 248:157–200
Goyvaerts D, Martens JA, Grobet PJ, Jacobs PA (1991) Factors affecting the formation of extra-framework species and mesopores during dealumination of zeolite Y. In: Poncelet G, Jacobs PA, Grange P, Delmon B (eds) Studies in surface science and catalysis, vol 63. Elsevier, Amsterdam, pp 381–395
Dessau RM, Valyocsik EW, Goeke NH (1992) Aluminum zoning in Zsm-5 as revealed by selective silica removal. Zeolites 12(7):776–779
Ogura M, Shinomiya SY, Tateno J, Nara Y, Nomura M, Kikuchi E, Matsukata M (2001) Alkali-treatment technique – new method for modification of structural and acid-catalytic properties of ZSM-5 zeolites. Appl Catal A Gen 219(1–2):33–43
Groen JC, Perez-Ramirez J, Peffer LAA (2002) Formation of uniform mesopores in ZSM-5 zeolite upon alkaline post-treatment? Chem Lett 1:94–95
Groen JC, Peffer LAA, Perez-Ramirez J (2003) Pore size determination in modified micro- and mesoporous materials: pitfalls and limitations in gas adsorption data analysis. Microporous Mesoporous Mater 60(1–3):1–17
Groen JC, Jansen JC, Moulijn JA, Perez-Ramirez J (2004) Optimal aluminum-assisted mesoporosity development in MFI zeolites by desilication. J Phys Chem B 108(35):13062–13065
Groen JC, Bach T, Ziese U, Donk AMPV, de Jong KP, Moulijn JA, Perez-Ramirez J (2005) Creation of hollow zeolite architectures by controlled desilication of Al-zoned ZSM-5 crystals. J Am Chem Soc 127(31):10792–10793
Groen JC, Moulijn JA, Perez-Ramirez J (2005) Decoupling mesoporosity formation and acidity modification in ZSM-5 zeolites by sequential desilication-dealumination. Microporous Mesoporous Mater 87(2):153–161; Groen JC, Moulijn JA, Perez-Ramirez J (2006) Desilication: on the controlled generation of mesoporosity in MFI zeolites. J Mater Chem 16(22):2121–2131; Verboekend D, Perez-Ramirez J (2011) Design of hierarchical zeolite catalysts by desilication. Catal Sci Technol 1(6):879–890; Milina M, Mitchell S, Crivelli P, Cooke D, Perez-Ramirez J (2014) Mesopore quality determines the lifetime of hierarchically structured zeolite catalysts. Nat Commun 5
Su LL, Liu L, Zhuang JQ, Wang HX, Li YG, Shen WJ, Xu YD, Bao XH (2003) Creating mesopores in ZSM-5 zeolite by alkali treatment: a new way to enhance the catalytic performance of methane dehydroaromatization on Mo/HZSM-5 catalysts. Catal Lett 91(3–4):155–167
Chal R, Cacciaguerra T, van Donk S, Gerardin C (2010) Pseudomorphic synthesis of mesoporous zeolite Y crystals. Chem Commun 46(41):7840–7842
de Jong KP, Zecevic J, Friedrich H, de Jongh PE, Bulut M, van Donk S, Kenmogne R, Finiels A, Hulea V, Fajula F (2010) Zeolite Y crystals with trimodal porosity as ideal hydrocracking catalysts. Angew Chem Int Ed 49(52):10074–10078; Verboekend D, Vile G, Perez-Ramirez J (2012) Hierarchical Y and USY zeolites designed by post-synthetic strategies. Adv Funct Mater 22(5):916–928
Jacobsen CJH, Madsen C, Houzvicka J, Schmidt I, Carlsson A (2000) Mesoporous zeolite single crystals. J Am Chem Soc 122(29):7116–7117
Christensen CH, Johannsen K, Schmidt I, Christensen CH (2003) Catalytic benzene alkylation over mesoporous zeolite single crystals: improving activity and selectivity with a new family of porous materials. J Am Chem Soc 125(44):13370–13371
Schmidt I, Boisen A, Gustavsson E, Stahl K, Pehrson S, Dahl S, Carlsson A, Jacobsen CJH (2001) Carbon nanotube templated growth of mesoporous zeolite single crystals. Chem Mater 13(12):4416–4418
Boisen A, Schmidt I, Carlsson A, Dahl S, Brorson M, Jacobsen CJH (2003) TEM stereo-imaging of mesoporous zeolite single crystals. Chem Commun 8:958–959
Janssen AH, Schmidt I, Jacobsen CJH, Koster AJ, de Jong KP (2003) Exploratory study of mesopore templating with carbon during zeolite synthesis. Microporous Mesoporous Mater 65(1):59–75
Zhu K, Egeblad K, Christensen CH (2007) Mesoporous carbon prepared from carbohydrate as hard template for hierarchical zeolites. Eur J Inorg Chem 25:3955–3960
Kustova M, Egeblad K, Zhu K, Christensen CH (2007) Versatile route to zeolite single crystals with controlled mesoporosity: in situ sugar decomposition for templating of hierarchical zeolites. Chem Mater 19(12):2915–2917
Tao YS, Kanoh H, Kaneko K (2003) ZSM-5 monolith of uniform mesoporous channels. J Am Chem Soc 125(20):6044–6045
Pekala RW, Alviso CT, Kong FM, Hulsey SS (1992) Aerogels derived from multifunctional organic monomers. J Non-Cryst Solids 145(1–3):90–98
Bekyarova E, Kaneko K (2000) Structure and physical properties of tailor-made Ce, Zr-doped carbon aerogels. Adv Mater 12(21):1625–1628
Hanzawa Y, Kaneko K, Yoshizawa N, Pekala RW, Dresselhaus MS (1998) The pore structure determination of carbon aerogels. Adsorption 4(3–4):187–195
Hanzawa Y, Hatori H, Yoshizawa N, Yamada Y (2002) Structural changes in carbon aerogels with high temperature treatment. Carbon 40(4):575–581
Tao YS, Kanoh H, Hanzawa Y, Kaneko K (2004) Template synthesis and characterization of mesoporous zeolites. Colloid Surf A 241(1–3):75–80
Kustova MY, Hasselriis P, Christensen CH (2004) Mesoporous MEL-type zeolite single crystal catalysts. Catal Lett 96(3–4):205–211
Wei XT, Smirniotis PG (2006) Synthesis and characterization of mesoporous ZSM-12 by using carbon particles. Microporous Mesoporous Mater 89(1–3):170–178
Pavlačková Z, Košová G, Žilková N, Zukal A, Čejka J (2006) Formation of mesopores in ZSM-5 by carbon templating. Stud Surf Sci Catal 162:905–912
Egeblad K, Kustova M, Klitgaard SK, Zhu KK, Christensen CH (2007) Mesoporous zeolite and zeotype single crystals synthesized in fluoride media. Microporous Mesoporous Mater 101(1–2):214–223
Sakthivel A, Huang SJ, Chen WH, Lan ZH, Chen KH, Kim TW, Ryoo R, Chiang AST, Liu SB (2004) Replication of mesoporous aluminosilicate molecular sieves (RMMs) with zeolite framework from mesoporous carbons (CMKs). Chem Mater 16(16):3168–3175
Yang ZX, Xia YD, Mokaya R (2004) Zeolite ZSM-5 with unique supermicropores synthesized using mesoporous carbon as a template. Adv Mater 16(8):727–732
Ryoo R, Joo SH, Jun S (1999) Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformation. J Phys Chem B 103(37):7743–7746
Ryoo R, Joo SH, Kruk M, Jaroniec M (2001) Ordered mesoporous carbons. Adv Mater 13(9):677–681
Fang YM, Hu HQ (2006) An ordered mesoporous aluminosilicate with completely crystalline zeolite wall structure. J Am Chem Soc 128(33):10636–10637
Fan W, Snyder MA, Kumar S, Lee PS, Yoo WC, McCormick AV, Penn RL, Stein A, Tsapatsis M (2008) Hierarchical nanofabrication of microporous crystals with ordered mesoporosity. Nat Mater 7(12):984–991
Tao YS, Kanoh H, Kaneko K (2005) Synthesis of mesoporous zeolite a by resorcinol-formaldehyde aerogel templating. Langmuir 21(2):504–507
Holland BT, Abrams L, Stein A (1999) Dual templating of macroporous silicates with zeolitic microporous frameworks. J Am Chem Soc 121(17):4308–4309
Cho HS, Ryoo R (2012) Synthesis of ordered mesoporous MFI zeolite using CMK carbon templates. Microporous Mesoporous Mater 151:107–112
Na K, Choi M, Ryoo R (2013) Recent advances in the synthesis of hierarchically nanoporous zeolites. Microporous Mesoporous Mater 166:3–19
Barton TJ, Bull LM, Klemperer WG, Loy DA, McEnaney B, Misono M, Monson PA, Pez G, Scherer GW, Vartuli JC, Yaghi OM (1999) Tailored porous materials. Chem Mater 11(10):2633–2656
Ciesla U, Schuth F (1999) Ordered mesoporous materials. Microporous Mesoporous Mater 27(2–3):131–149
Mehlhorn D, Valiullin R, Karger J, Cho K, Ryoo R (2012) Exploring mass transfer in mesoporous zeolites by NMR diffusometry. Materials 5(4):699–720; Mehlhorn D, Valiullin R, Karger J, Cho K, Ryoo R (2012) Intracrystalline diffusion in mesoporous zeolites. Chemphyschem 13(6):1495–1499; Karger J, Valiullin R (2013) Mass transfer in mesoporous materials: the benefit of microscopic diffusion measurement. Chem Soc Rev 42(9):4172–4197
Milina M, Mitchell S, Cooke D, Crivelli P, Pérez-Ramírez J (2015) Impact of pore connectivity on the design of long-lived zeolite catalysts. Angew Chem Int Ed 54(5):1591–1594
Ying JY, Mehnert CP, Wong MS (1999) Synthesis and applications of supramolecular-templated mesoporous materials. Angew Chem Int Ed 38(1–2):56–77
Raman NK, Anderson MT, Brinker CJ (1996) Template-based approaches to the preparation of amorphous, nanoporous silicas. Chem Mater 8(8):1682–1701
Beck JS, Vartuli JC, Roth WJ, Leonowicz ME, Kresge CT, Schmitt KD, Chu CTW, Olson DH, Sheppard EW, Mccullen SB, Higgins JB, Schlenker JL (1992) A new family of mesoporous molecular-sieves prepared with liquid-crystal templates. J Am Chem Soc 114(27):10834–10843
Zhao DY, Huo QS, Feng JL, Chmelka BF, Stucky GD (1998) Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures. J Am Chem Soc 120(24):6024–6036
Sayari A, Yang Y, Kruk M, Jaroniec M (1999) Expanding the pore size of MCM-41 silicas: use of amines as expanders in direct synthesis and postsynthesis procedures. J Phys Chem B 103(18):3651–3658
Schmidt-Winkel P, Lukens WW, Zhao DY, Yang PD, Chmelka BF, Stucky GD (1999) Mesocellular siliceous foams with uniformly sized cells and windows. J Am Chem Soc 121(1):254–255
Yanagisawa T, Shimizu T, Kuroda K, Kato C (1990) Trimethylsilyl derivatives of alkyltrimethylammonium-Kanemite complexes and their conversion to microporous SiO2 materials. Bull Chem Soc Jpn 63(5):1535–1537
Inagaki S, Fukushima Y, Kuroda K (1994) Synthesis and characterization of highly ordered mesoporous material – FSM-16, from a layered polysilicate. Zeolites Relat Microporous Mater State Art 84:125–132
Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS (1992) Ordered mesoporous molecular-sieves synthesized by a liquid-crystal template mechanism. Nature 359(6397):710–712
Zhao DY, Feng JL, Huo QS, Melosh N, Fredrickson GH, Chmelka BF, Stucky GD (1998) Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 279(5350):548–552
Monnier A, Schuth F, Huo Q, Kumar D, Margolese D, Maxwell RS, Stucky GD, Krishnamurty M, Petroff P, Firouzi A, Janicke M, Chmelka BF (1993) Cooperative formation of inorganic-organic interfaces in the synthesis of silicate mesostructures. Science 261(5126):1299–1303
Firouzi A, Kumar D, Bull LM, Besier T, Sieger P, Huo Q, Walker SA, Zasadzinski JA, Glinka C, Nicol J, Margolese D, Stucky GD, Chmelka BF (1995) Cooperative organization of inorganic-surfactant and biomimetic assemblies. Science 267(5201):1138–1143
Huo QS, Margolese DI, Ciesla U, Feng PY, Gier TE, Sieger P, Leon R, Petroff PM, Schuth F, Stucky GD (1994) Generalized synthesis of periodic surfactant inorganic composite-materials. Nature 368(6469):317–321
Moller K, Bein T (1998) Inclusion chemistry in periodic mesoporous hosts. Chem Mater 10(10):2950–2963
Hartmann M (2005) Ordered mesoporous materials for bioadsorption and biocatalysis. Chem Mater 17(18):4577–4593
Gusev VY, Feng XB, Bu Z, Haller GL, OBrien JA (1996) Mechanical stability of pure silica mesoporous MCM-41 by nitrogen adsorption and small-angle X-ray diffraction measurements. J Phys Chem 100(6):1985–1988
Jun S, Kim JM, Ryoo R, Ahn YS, Han MK (2000) Hydrothermal stability of MCM-48 improved by post-synthesis restructuring in salt solution. Microporous Mesoporous Mater 41(1–3):119–127
Cassiers K, Linssen T, Mathieu M, Benjelloun M, Schrijnemakers K, Van Der Voort P, Cool P, Vansant EF (2002) A detailed study of thermal, hydrothermal, and mechanical stabilities of a wide range of surfactant assembled mesoporous silicas. Chem Mater 14(5):2317–2324
Karlsson A, Stocker M, Schmidt R (1999) Composites of micro- and mesoporous materials: simultaneous syntheses of MFI/MCM-41 like phases by a mixed template approach. Microporous Mesoporous Mater 27(2–3):181–192
Liu Y, Zhang WZ, Pinnavaia TJ (2000) Steam-stable aluminosilicate mesostructures assembled from zeolite type Y seeds. J Am Chem Soc 122(36):8791–8792
Liu Y, Zhang WZ, Pinnavaia TJ (2001) Steam-stable MSU-S aluminosilicate mesostructures assembled from zeolite ZSM-5 and zeolite beta seeds. Angew Chem Int Ed 40(7):1255–1258
Zhang Z, Han Y, Xiao FS, Qiu S, Zhu L, Wang R, Yu Y, Zhang Z, Zou B, Wang Y, Sun H, Zhao D, Wei Y (2001) Mesoporous aluminosilicates with ordered hexagonal structure, strong acidity, and extraordinary hydrothermal stability at high temperatures. J Am Chem Soc 123(21):5014–5021
Liu Y, Pinnavaia TJ (2002) Assembly of hydrothermally stable aluminosilicate foams and large-pore hexagonal mesostructures from zeolite seeds under strongly acidic conditions. Chem Mater 14(1):3–5
Serrano DP, García RA, Vicente G, Linares M, Procházková D, Cejka J (2011) Acidic and catalytic properties of hierarchical zeolites and hybrid ordered mesoporous materials assembled from MFI protozeolitic units. J Catal 279(2):366–380
Xia YD, Mokaya R (2004) Are mesoporous silicas and aluminosilicas assembled from zeolite seeds inherently hydrothermally stable? Comparative evaluation of MCM-48 materials assembled from zeolite seeds. J Mater Chem 14(23):3427–3435
Naik SP, Chiang AST, Thompson RW (2003) Synthesis of zeolitic mesoporous materials by dry gel conversion under controlled humidity. J Phys Chem B 107(29):7006–7014
Huang L, Guo W, Deng P, Xue Z, Li Q (2000) Investigation of synthesizing MCM-41/ZSM-5 composites. J Phys Chem B 104(13):2817–2823
Xia Y, Mokaya R (2004) On the synthesis and characterization of ZSM-5/MCM-48 aluminosilicate composite materials. J Mater Chem 14(5):863–870
Guo W, Xiong C, Huang L, Li Q (2001) Synthesis and characterization of composite molecular sieves comprising zeolite Beta with MCM-41 structures. J Mater Chem 11(7):1886–1890
Guo W, Huang L, Deng P, Xue Z, Li Q (2001) Characterization of Beta/MCM-41 composite molecular sieve compared with the mechanical mixture. Microporous Mesoporous Mater 44–45(6):427–434
Prokešova P, Mintova S, Cejka J, Bein T (2003) Preparation of nanosized micro/mesoporous composites via simultaneous synthesis of Beta/MCM-48 phases. Microporous Mesoporous Mater 64(1–3):165–174
Naik SP, Chen JC, Chiang AST (2002) Synthesis of silicalite nanocrystals via the steaming of surfactant protected precursors. Microporous Mesoporous Mater 54(3):293–303
Hasan F, Singh R, Li G, Zhao D, Webley PA (2012) Direct synthesis of hierarchical LTA zeolite via a low crystallization and growth rate technique in presence of cetyltrimethylammonium bromide. J Colloid Interface Sci 382(1):1–12
Jo C, Jung J, Shin HS, Kim J, Ryoo R (2013) Capping with multivalent surfactants for zeolite nanocrystal synthesis. Angew Chem Int Ed 52(38):10014–10017
Choi M, Cho HS, Srivastava R, Venkatesan C, Choi DH, Ryoo R (2006) Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity. Nat Mater 5(9):718–723
Chmelka BF (2006) Zeolites – large molecules welcome. Nat Mater 5(9):681–682
Huttinger KJ, Jung MF (1989) Kinetics of the synthesis of trialkyl [−3-(trimethoxysilyl)propyl]-ammonium chloride and their antimicrobial action as fixed biocides. Chem Ing Tech 61(3):258–259
Ryoo R, Kim JM, Ko CH, Shin CH (1996) Disordered molecular sieve with branched mesoporous channel network. J Phys Chem 100(45):17718–17721
Galarneau A, Cambon H, Di Renzo F, Ryoo R, Choi M, Fajula F (2003) Microporosity and connections between pores in SBA-15 mesostructured silicas as a function of the temperature of synthesis. New J Chem 27(1):73–79
Cho K, Cho HS, de Menorval LC, Ryoo R (2009) Generation of mesoporosity in LTA zeolites by organosilane surfactant for rapid molecular transport in catalytic application. Chem Mater 21(23):5664–5673
Cho K, Ryoo R, Asahina S, Xiao C, Klingstedt M, Umemura A, Anderson MW, Terasaki O (2011) Mesopore generation by organosilane surfactant during LTA zeolite crystallization, investigated by high-resolution SEM and Monte Carlo simulation. Solid State Sci 13(4):750–756
Choi M, Lee DH, Na K, Yu BW, Ryoo R (2009) High catalytic activity of palladium(II)-exchanged mesoporous sodalite and NaA zeolite for bulky aryl coupling reactions: reusability under aerobic conditions. Angew Chem Int Ed 48(20):3673–3676
Valiullin R, Kärger J, Cho K, Choi M, Ryoo R (2011) Dynamics of water diffusion in mesoporous zeolites. Microporous Mesoporous Mater 142(1):236–244
Choi M, Srivastava R, Ryoo R (2006) Organosilane surfactant-directed synthesis of mesoporous aluminophosphates constructed with crystalline microporous frameworks. Chem Commun 42:4380–4382
Inayat A, Knoke I, Spiecker E, Schwieger W (2012) Assemblies of mesoporous FAU-type zeolite nanosheets. Angew Chem Int Ed 51(8):1962–1965
Kim J, Jo C, Lee S, Ryoo R (2014) Bulk crystal seeding in the generation of mesopores by organosilane surfactants in zeolite synthesis. J Mater Chem A 2(30):11905–11912
Srivastava R, Choi M, Ryoo R (2006) Mesoporous materials with zeolite framework: remarkable effect of the hierarchical structure for retardation of catalyst deactivation. Chem Commun 43:4489–4491
Shetti VN, Kim J, Srivastava R, Choi M, Ryoo R (2008) Assessment of the mesopore wall catalytic activities of MFI zeolite with mesoporous/microporous hierarchical structures. J Catal 254(2):296–303
Lee DH, Choi M, Yu BW, Ryoo R (2009) Organic functionalization of mesopore walls in hierarchically porous zeolites. Chem Commun 1:74–76
Vuong GT, Do TO (2007) A new route for the synthesis of uniform nanozeolites with hydrophobic external surface in organic solvent medium. J Am Chem Soc 129(13):3810–3811
Wang H, Pinnavaia TJ (2006) MFI zeolite with small and uniform intracrystal mesopores. Angew Chem Int Ed 45(45):7603–7606
Xiao FS, Wang L, Yin C, Lin K, Di Y, Li J, Xu R, Su DS, Schlögl R, Yokoi T, Tatsumi T (2006) Catalytic properties of hierarchical mesoporous zeolites templated with a mixture of small organic ammonium salts and mesoscale cationic polymers. Angew Chem Int Ed 45(19):3090–3093
Choi M, Na K, Kim J, Sakamoto Y, Terasaki O, Ryoo R (2009) Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts. Nature 461(7261):246–249
Corma A (2009) Materials chemistry catalysts made thinner. Nature 461(7261):182–183
Park W, Yu D, Na K, Jelfs KE, Slater B, Sakamoto Y, Ryoo R (2011) Hierarchically structure-directing effect of multi-ammonium surfactants for the generation of MFI zeolite nanosheets. Chem Mater 23(23):5131–5137
Jung J, Jo C, Cho K, Ryoo R (2012) Zeolite nanosheet of a single-pore thickness generated by a zeolite-structure-directing surfactant. J Mater Chem 22(11):4637–4640
Na K, Choi M, Park W, Sakamoto Y, Terasaki O, Ryoo R (2010) Pillared MFI zeolite nanosheets of a single-unit-cell thickness. J Am Chem Soc 132(12):4169–4177
Maheshwari S, Jordan E, Kumar S, Bates FS, Penn RL, Shantz DF, Tsapatsis M (2008) Layer structure preservation during swelling, pillaring, and exfoliation of a zeolite precursor. J Am Chem Soc 130(4):1507–1516
Tsapatsis M, Maheshwari S (2008) Pores by pillaring: not always a maze. Angew Chem Int Ed 47(23):4262–4263
Roth WJ, Cejka J (2011) Two-dimensional zeolites: dream or reality? Catal Sci Technol 1(1):43–53
Schnell SK, Wu L, Koekkoek AJJ, Kjelstrup S, Hensen EJM, Vlugt TJH (2013) Adsorption of argon on MFI nanosheets: experiments and simulations. J Phys Chem C 117(46):24503–24510
Na K, Park W, Seo Y, Ryoo R (2011) Disordered assembly of MFI zeolite nanosheets with a large volume of intersheet mesopores. Chem Mater 23(5):1273–1279
Corma A (1995) Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions. Chem Rev 95(3):559–614
Cejka J, Centi G, Perez-Pariente J, Roth WJ (2012) Zeolite-based materials for novel catalytic applications: opportunities, perspectives and open problems. Catal Today 179(1):2–15
Seo Y, Cho K, Jung Y, Ryoo R (2013) Characterization of the surface acidity of MFI zeolite nanosheets by P-31 NMR of adsorbed phosphine oxides and catalytic cracking of decalin. ACS Catal 3(4):713–720
Lunsford JH, Rothwell WP, Shen W (1985) Acid sites in zeolite Y – a solid-state NMR and infrared study using trimethylphosphine as a probe molecule. J Am Chem Soc 107(6):1540–1547
Baltusis L, Frye JS, Maciel GE (1986) Phosphine oxide as NMR probes for adsorption sites on surfaces. J Am Chem Soc 108(22):7119–7120
Rakiewicz EF, Peters AW, Wormsbecher RF, Sutovich KJ, Müller KT (1998) Characterization of acid sites in zeolitic and other inorganic systems using solid-state P-31 NMR of the probe molecule trimethylphosphine oxide. J Phys Chem B 102(16):2890–2896
Zhao Q, Chen WH, Huang SJ, Wu YC, Lee HK, Liu SB (2002) Discernment and quantification of internal and external acid sites on zeolites. J Phys Chem B 106(17):4462–4469
Jo C, Cho K, Kim J, Ryoo R (2014) MFI zeolite nanosponges possessing uniform mesopores generated by bulk crystal seeding in the hierarchical surfactant-directed synthesis. Chem Commun 50(32):4175–4177
Na K, Jo C, Kim J, Cho K, Jung J, Seo Y, Messinger RJ, Chmelka BF, Ryoo R (2011) Directing zeolite structures into hierarchically nanoporous architectures. Science 333(6040):328–332
Möller K, Bein T (2011) Pores within pores-How to craft ordered hierarchical zeolites. Science 333(6040):297–298
Kore R, Srivastava R, Satpati B (2014) ZSM-5 zeolite nanosheets with improved catalytic activity synthesized using a new class of structure-directing agents. Chem Eur J 20(36):11511–11521
Jo C, Jung J, Ryoo R (2014) Mesopore expansion of surfactant-directed nanomorphic zeolites with trimethylbenzene. Microporous Mesoporous Mater 194:83–89
Kim W, Kim JC, Kim J, Seo Y, Ryoo R (2013) External surface catalytic sites of surfactant-tailored nanomorphic zeolites for benzene isopropylation to cumene. ACS Catal 3(2):192–195
Seo Y, Lee S, Jo C, Ryoo R (2013) Microporous aluminophosphate nanosheets and their nanomorphic zeolite analogues tailored by hierarchical structure-directing amines. J Am Chem Soc 135(24):8806–8809
Kim J, Choi M, Ryoo R (2010) Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process. J Catal 269(1):219–228
Kim J, Park W, Ryoo R (2011) Surfactant-directed zeolite nanosheets: a high-performance catalyst for gas-phase Beckmann rearrangement. ACS Catal 1(4):337–341
Kim JC, Cho K, Ryoo R (2014) High catalytic performance of surfactant-directed nanocrystalline zeolites for liquid-phase Friedel-Crafts alkylation of benzene due to external surfaces. Appl Catal A Gen 470:420–426
Koekkoek AJJ, Kim W, Degirmenci V, Xin H, Ryoo R, Hensen EJM (2013) Catalytic performance of sheet-like Fe/ZSM-5 zeolites for the selective oxidation of benzene with nitrous oxide. J Catal 299:81–89
Zou W, Xie P, Hua W, Wang Y, Kong D, Yue Y, Ma Z, Yang W, Gao Z (2014) Catalytic decomposition of N2O over Cu-ZSM-5 nanosheets. J Mol Catal A Chem 394:83–88
Hu S, Shan J, Zhang Q, Wang Y, Liu Y, Gong Y, Wu Z, Dou T (2012) Selective formation of propylene from methanol over high-silica nanosheets of MFI zeolite. Appl Catal A Gen 445:215–220
Kim J, Kim W, Seo Y, Kim JC, Ryoo R (2013) n-Heptane hydroisomerization over Pt/MFI zeolite nanosheets: effects of zeolite crystal thickness and platinum location. J Catal 301:187–197
Verheyen E, Jo C, Kurttepeli M, Vanbutsele G, Gobechiya E, Korányi TI, Bals S, Tendeloo GV, Ryoo R (2013) Molecular shape-selectivity of MFI zeolite nanosheets in n-decane isomerization and hydrocracking. J Catal 300:70–80
Reddy JK, Motokura K, Koyama TR, Miyaji A, Baba T (2012) Effect of morphology and particle size of ZSM-5 on catalytic performance for ethylene conversion and heptane cracking. J Catal 289:53–61
Martens JA, Jacobs PA (1986) The potential and limitations of the normal-decane hydroconversion as a test reaction for characterization of the void space of molecular-sieve zeolites. Zeolites 6(5):334–348
Martens JA, Tielen M, Jacobs PA (1984) Estimation of the void structure and pore dimensions of molecular-sieve zeolites using the hydroconversion of normal-decane. Zeolites 4(2):98–107
Holm MS, Taarning E, Egeblad K, Christensen CH (2011) Catalysis with hierarchical zeolites. Catal Today 168(1):3–16
Lee HW, Park SH, Jeon JK, Ryoo R, Kim W, Suh DJ, Park YK (2014) Upgrading of bio-oil derived from biomass constituents over hierarchical unilamellar mesoporous MFI nanosheets. Catal Today 232:119–126
Liu F, Willhammar T, Wang L, Zhu L, Sun Q, Meng X, Carrillo-Cabrera W, Zou X, Xiao FS (2012) ZSM-5 zeolite single crystals with b-axis-aligned mesoporous channels as an efficient catalyst for conversion of bulky organic molecules. J Am Chem Soc 134(10):4557–4560
Boltz M, Losch P, Louis B, Rioland G, Tzanis L, Daou TJ (2014) MFI-type zeolite nanosheets for gas-phase aromatics chlorination: a strategy to overcome mass transfer limitations. RSC Adv 4(52):27242–27249
Heitmann GP, Dahlhoff G, Hölderich WF (1999) Catalytically active sites for the Beckmann rearrangement of cyclohexanone oxime to epsilon-caprolactam. J Catal 186(1):12–19
Degnan TF (2003) The implications of the fundamentals of shape selectivity for the development of catalysts for the petroleum and petrochemical industries. J Catal 216(1–2):32–46
Sastre G, Corma A (2009) The confinement effect in zeolites. J Mol Catal A Chem 305(1–2):3–7
Kim JC, Lee S, Cho K, Na K, Lee C, Ryoo R (2014) Mesoporous MFI zeolite nanosponge supporting cobalt nanoparticles as a Fischer-Tropsch catalyst with high yield of branched hydrocarbons in the gasoline range. ACS Catal 4(11):3919–3927
Na K, Jo C, Kim J, Ahn WS, Ryoo R (2011) MFI titanosilicate nanosheets with single-unit-cell thickness as an oxidation catalyst using peroxides. ACS Catal 1(8):901–907
Wang J, Xu L, Zhang K, Peng H, Wu H, Jiang JG, Liu Y, Wu P (2012) Multilayer structured MFI-type titanosilicate: synthesis and catalytic properties in selective epoxidation of bulky molecules. J Catal 288:16–23
Luo HY, Bui L, Gunther WR, Min E, Román-Leshkov Y (2012) Synthesis and catalytic activity of Sn-MFI nanosheets for the Baeyer-Villiger oxidation of cyclic ketones. ACS Catal 2(12):2695–2699
Schick J, Daou TJ, Caullet P, Paillaud J, Patarin J, Mangold-Callarec C (2011) Surfactant-modified MFI nanosheets: a high capacity anion-exchanger. Chem Commun 47(3):902–904
Kabalan I, Rioland G, Nouali H, Lebeau B, Rigolet S, Fadlallah MB, Toufaily J, Hamiyeh T, Daou TJ (2014) Synthesis of purely silica MFI-type nanosheets for molecular decontamination. RSC Adv 4(70):37353–37358
Varoon K, Zhang X, Elyassi B, Brewer DD, Gettel M, Kumar S, Lee JA, Maheshwari S, Mittal A, Sung CY, Cococcioni M, Francis LF, McCormick AV, Mkhoyan KA, Tsapatsis M (2011) Dispersible exfoliated zeolite nanosheets and their application as a selective membrane. Science 334(6052):72–75
Jo C, Seo Y, Cho K, Kim J, Shin HS, Lee M, Kim JC, Kim SO, Lee JY, Ihee H, Ryoo R (2014) Random-graft polymer-directed synthesis of inorganic mesostructures with ultrathin frameworks. Angew Chem Int Ed 53(20):5117–5121
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2016 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Ryoo, R., Cho, K., Mota, F.M. (2016). Mesostructured Zeolites. In: Xiao, FS., Meng, X. (eds) Zeolites in Sustainable Chemistry. Green Chemistry and Sustainable Technology. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-47395-5_4
Download citation
DOI: https://doi.org/10.1007/978-3-662-47395-5_4
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-662-47394-8
Online ISBN: 978-3-662-47395-5
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)