Synthesis of Single-Crystalline Mesoporous ZSM-5 with Three

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Synthesis of Single-Crystalline Mesoporous ZSM-5 with Three-Dimensional Pores via the Self-Assembly of a Designed Triply Branched Cationic Surfactant Bhupendra Kumar Singh, Dongdong Xu, Lu Han, Jian Ding, Yimeng Wang, and Shunai Che Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/cm503919h • Publication Date (Web): 03 Dec 2014 Downloaded from http://pubs.acs.org on December 9, 2014

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Chemistry of Materials

Synthesis of Single-Crystalline Mesoporous ZSM-5 with Three-Dimensional Pores via the Self-Assembly of a Designed Triply Branched Cationic Surfactant Bhupendra K. Singh1†, Dongdong Xu1†, Lu Han1, Jian Ding2, Yimeng Wang2* and Shunai Che1* 1 School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China. 2Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, 3663 North Zhongshan Road, Shanghai, 200062, China.

Supporting Information Abstract: A single-crystalline mesoporous ZSM-5 (SCMZ) with sheet-like pores, a uniform thickness of ~2 nm and a wide range of lengths (5-50 nm) along the a- and c-axes was synthesised using an amphiphilic template with three diquaternary ammoniumterminated alkyl chain branches that were bound to a benzene ring in the 1,3,5-positions. The triply branched diquaternary ammonium head groups of template broke the extending of lamellar assembly along the a- and c-axes, which led to the formation of SCMZ with three-dimensional (3D) mesopores having abundant crystal faces along the a-, b- and c-axes. By increasing the length of the hydrophobic chain, we obtained the mesoporous ZSM-5 with intercrossed nanosheets (MZIN) with only a-c planes, whose mesopores were maintained after calcination because of the structural connectivity around the crossed joints. The SCMZ exhibited significantly higher catalytic efficiencies and unique selectivity compared with the conventional MFI and MZIN.

INTRODUCTION The synthesis of mesoporous zeolites has remained an enormous challenge in chemistry and materials science because of their potential applications in catalysis, the petrochemical industry, adsorption, nanoreactors, sensors, and electrical and optical devices.1-5 In the past few years, soft and hard templating routes have been extensively used to synthesise mesoporous zeolites, which possess different mesoscale structures and zeolitic frameworks.6-9 Among the various synthesis routes, templating by using amphiphilic molecules to synthesise mesostructured zeolites is considered the most promising route on the basis of the templates’ self-assembling micellar structures.10-13 Ryoo et al. found that the head groups of multiquaternary ammonium connected to hydrophobic alkyl chains are important for forming lamellar-structured MFI nanosheets that are stacked along the b-axis.13-16 Recently, we found that aromatic groups introduced into the hydrophobic tails of amphiphilic molecules not only stabilise the mesoscale micellar structure due to π-π stacking but also geometrically match the MFI zeolitic framework to form crystallographically ordered, lamellar-structured MFI nanosheets.17 Furthermore, the dual stabilisation effects of multiple-ammonium heads and the strong π-π interactions in the template energetically favoured the formation of MFI framework with 90° rotational structure. However, after the template was removed, either the lamellar structures collapsed and formed nonporous bulk zeolites, or only the (010) facet exposed in randomly stacked sheets or in the 90° rotational boundary. Both of these formations limit the range of interactions that can occur between the molecules and zeolites in the practical applications such as catalyses and separations. Herein, we designed a template for synthesising a singlecrystalline mesoporous zeolite by introducing triply branched diquaternary ammonium head groups onto a benzene ring to form a cationic template of Ph-(O-C10H20-N+(Me)2-C6H12N+(Me)2-C6H13·2Br-)3 (denoted as TCPh-10-6-6, Figure S1). The dual stabilisation effects of the diquaternary ammonium head groups and the strong π-π interactions in the hydrophobic core may energetically favour the formation of micellar-structured zeolites,18,19 that can further facilitate the self-assembly of templates with aromatic moieties to geometrically match the

zeolitic frameworks.20,21 Furthermore, the three branches that were bound to a benzene ring in the 1,3,5-positions directed the MFI framework in three directions (i.e., the a-, b- and c-axes) to form SCMZ with 3D mesopores. EXPERIMENTAL SECTION Synthesis of SCMZ. 0.10 g NaOH was added in 14.4 g of Millipore water having resistivity of 18.2 MΩ cm and stirred until the solution become clear. 0.015 g NaAlO2 was added in the solution and stirred for 10 minutes. 1.80 g of template TCPh-10-6-6 was mixed in the former solution and it was stirred for 1h followed by addition of 3.0 g TBOS. The resultant mixture of molar composition 1.0 TCPh-10-6-6: 9.3 SiO2: 2.5 NaOH: 0.18 NaAlO2: 800 H2O with Si/Al ratio of 52 was stirred for 2h at ambient temperature. The obtained gel was transferred into a Teflon-lined stainless-steel autoclave and crystallization was carried out by heating autoclave at 150 °C for 4 days in an oven at tumbling rate of 40 rpm. After predetermined time, the autoclaves were cooled in water; products were filtered, washed with distilled water and dried at 110 °C for overnight. In order to remove the organic contents, synthesized ZSM-5 powder was air calcined at 550 °C for 6 h. Synthesis of 90° rotational MZIN. In a typical synthesis of MFI nanosheets, the template TCPh-12-6-6, NaOH, NaAlO2 and distilled water were mixed together about 0.5 h under constant stirring. Tetraethyl orthosilicate (TEOS, TCI, 98%) was added to give an original molar composition of 1.0 TCPh-12-6-6: 13.52 SiO2: 2.5 NaOH: 0.25 NaAlO2: 800 H2O with Si/Al ratio of 75. The resultant mixture was stirred for two hours. Rest processes were same as it was applied for the synthesis of SCMZ. Characterization. Synthesized template was analysed by 1H NMR and UV-Visible spectra. Whereas, X-ray diffraction, scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and N2 adsorption/desorption analysis were applied for characterization of synthesized ZSM-5. Powder XRD patterns were recorded on a Rigaku X-ray diffractometer D/MAX-2200/PC equipped with Cu KR radiation (35 kV, 200 mA) at the rate 10°/min over the range of 2θ value 5-40°. The scanning electron microscope (SEM) observation was performed with a JEOL JSM-7401F microscope. The transmission electron microscope (TEM) observation was

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performed with a JEOL JEM-2100 microscope operated at 200 kV (Cs 1.0 mm, point resolution 2.3 Å). Images were recorded with a Keen View CCD camera (resolution 1376 x 1032 pixels, pixel size 6.45 x 6.45 µm) at 50,000-1,20,000 times magnification under low-dose conditions. The specific surface area, pore volume and pore size distribution were analysed with N2 adsorption/desorption isotherms, which were measured at 77 K with a Quantachrome NOVA 4200 E Porosimeter analyser. Prior to the adsorption measurements, all the samples were degassed under a vacuum for 3 h at 423 K. The surface area was calculated from the adsorption branch in the P/P0 range between 0.05 and 0.30 using the Brunauer-Emmett-Teller (BET) equation. The pore size distributions were converted from the entire adsorption branch according to the Barrett-Joyner-Halenda (BJH) algorithm for approximation. The UV/Visible diffuse reflectance spectra was recorded (DRUV) on a Perkin-Elmer Lambda 20 UV/Vis spectrometer, whereas the UV/Vis absorption spectrum of the filter was measured with a Shimadzu UV-2450 spectrophotometer. The absorbance spectra were obtained from the reflectance spectra through Kubelka-Munk transformation. The 1H NMR spectra were recorded on a Varian MERCURY plus-400 (400 MHz) spectrometer with chemical shifts reported in ppm relative to the residual deuterated solvent and the internal standard tetramethylsilane (TMS).

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These primary particles are composed of secondary particles with a diameter of ~5 µm that are compacted with small nanoparticles (plate-like) with a diameter of ~100 nm (the crystal size was also estimated using Scherrer equation, Figure S3). A cross-sectional view of the self-assembled ZSM-5 is given in Figure 1d, which indicates that the ZSM-5 nanorods grew from the centre outwards.

RESULTS AND DISCUSSION Synthesis of SCMZ by TCPh-10-6-6. Figure 1a shows highangle X-ray diffraction (XRD) patterns of the as-prepared and calcined samples. These patterns indicate that high-quality ZSM5 were produced, with no evidence of the formation of other zeolites or amorphous silica. In addition, these results reflect the presence of major reflections (hkl) with high intensity that most likely correspond to single-crystalline ZSM-5 instead of MFI nanosheets (only h0l reflections, Figure S2).13,17 No reflections were observed in the low-angle XRD patterns, indicating that no periodic mesostructures were present in this sample. The scanning electron microscopy (SEM) images (Figures 1b and c) show that the sample exhibited a uniform self-assembled cauliflower-like morphology with an average size of ~50 µm.

Figure 1. (a) High-angle XRD patterns of the SCMZ before and after calcination. (b, c) SEM images taken at different magnifications (the scale bar of the inset image in c is 500 nm). (d) SEM image of a crosssection of the self-assembled SCMZ.

Figure 2. (a-c) TEM images and their SAED patterns (insets) taken along the a-, b- and c-axes of the SCMZ. (d) The N2 adsorption-desorption isotherm and pore size distribution obtained from the adsorption branch.

Figures 2a, b and c show high-resolution transmission electron microscopy (HRTEM) images of a sliced thin section of the calcined sample, where the images were taken along the a-axis, c-axis and b-axis, respectively. As evident in the TEM images, abundant and thin, sheet-like mesopores with a thickness of ~2 nm were observed from the a- and c-axes, confirming the pore size distribution results (vide post). The lengths of these sheets were in the range of ~5-50 nm and ~5-20 nm along c- and adirections, respectively. No open mesopores were observed along the b-axis. The selected-area electron diffraction (SAED) patterns (inset) corresponding to these images reveal the formation of single-crystalline ZSM-5 nanoparticles (see Figure S4 for the meaning of 'single-crystalline').22 The sheet-like mesopores were embedded in the ZSM-5 framework and prevented the destruction of the mesostructure after calcination. Consequently, SCMZ was formed (also see Figure S5). Figure 2d shows the N2 adsorption-desorption isotherm of the calcined SCMZ, which exhibits type-IV curve and H4-type hysteresis loop.23-25 The high uptake steps below P/P0=0.02 are similar to those observed in the curves of all conventional single-crystalline ZSM-5 and attributed to the presence of micropores. The capillary condensation loop and hysteresis loop at relative pressures in the range of P/P0=0.2-0.4 and 0.4-1.0 indicate the presence of lamellar slit-like mesopores. The Brunauer-EmmettTeller (BET) surface area and micropore and mesopore volumes of the sample were 496 m2/g, 0.10 cm3/g and 0.22 cm3/g, respectively. The surface area and mesopore volume are much higher than the values observed for the conventional ZSM-5, while the micropore volume is similar to ZSM-5 (Table S1). The sharp peaks at ~2.1 nm observed in the pore size distribution (Figure 2d) were approximately equal to the sheet thickness observed in the TEM images.

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To ensure a possible π-π stacking arrangement of template in this synthesis system, we performed diffuse-reflectance UVVisible (DRUV) absorption spectroscopy on the template in aqueous and solid form and on the as-synthesised SCMZ. Figure 3a shows a plot containing the DRUV-Visible spectra from all three systems. The energy transition from the π-HOMO to the π*LUMO decreases because two π-π molecular orbitals from the aromatic groups onerlap, which usually leads to a redshift of the absorption bands. Compared with the dilute aqueous state, the template molecules in solid form and the as-prepared zeolite possess more regular and dense packing, which results in obvious π-π interactions between the benzene groups. COnsequently, the corresponding absorption bands shifted towards longer wavelengths (redshift). The obvious shift from 198 to 211 nm provides evidence of the π-π interactions in the asprepared ZSM-5. In addition, the presence of a new band at 228 nm was attributed to the π-π interactions.26 The formation of SCMZ was speculated based on the corresponding arrangements of the triply branched templates in the MFI framework along the a- and c-axes (Figure 3b, which represents the c-axis only). The strong self-assembling ability and ordered arrangement of the benzene groups through π-π stacking resulted in sheet-like micelles. Simultaneously, the terminal quaternary ammonium groups directed the formation of MFI zeolite frameworks around the sheets, resulting in the construction of embedded sheet-like mesopores with abundant crystal faces along the a-, b- and c-axes. Two branches of the ammonium head groups was aligned with the b-axis micropore channels, and a third group directed the micropores along the zigzag channel. Some of the quaternary ammonium groups connected to the benzene ring in the centre of micelles did not direct the micropores but rather played a role in stabilising the zeolitic structure.

Figure 3. (a) DRUV spectra of the as-synthesised template (liquid and solid forms) and the as-prepared SCMZ. (b) Diquaternary ammonium groups of the template direct the formation of the ZSM-5 framework along the c-axis. Hexagonal shapes represent benzene groups, which are connected to the three branches of the hydrophobic part (black lines) and with the diquaternary ammonium head group (red dots).

Synthesis of MZIN by TCPh-12-6-6. To compare the catalytic activity between the ZSM-5 zeolites having mesopores with

abundant crystal faces along the a-, b- and c-axes, and with only a-c crystal planes, we synthesized MZIN by increasing the hydrophobic chain length of the above template by 2 carbon atoms: from TCPh-10-6-6 to TCPh-12-6-6. Wide-angle powder XRD patterns confirmed that the product possesses a pure MFI zeolite structure (Figure S6). The SEM images (Figures 4a and b) clearly revealed that the MZIN possesses the 90° intercrossed boundary structure. The internal structure of the sliced thin sections of calcined MZIN was observed by HRTEM. Figures 4c and d represent the TEM images along the common c-axis, where the (100) faces are overgrown on the (010) faces (inset SAED pattern) and expose only (010) faces.27-31 Hierarchical, 90° intercrossed, 30-50-nm-long MFI nanosheets with the distance of ~2-4 nm between layered nanosheets were obtained. The thickness of the nanosheets was observed to be in the range of 2~4 nm, which indicated that they are composed of one or two MFI unit cells (b-axis, thickness of one MFI unit cell=2 nm).29 The abundant mesopore structure of MZIN was maintained after calcination because of the interconnection of the short nanosheets (30-50 nm) at the crossed joints (Figure S7).

Figure 4. (a, b) SEM images showing the 90° intercrossed nanosheet-like morphology. (c, d) HRTEM images and SAED pattern (inset) of a calcined sample along the common c-axis. (e) N2 adsorption-desorption isotherm and BJH pore size distribution plot (inset). (f) Proposed model for MZIN formation along the common c-axis.

The nitrogen adsorption/desorption isotherms of the calcined MZIN revealed type-IV curves in the relative pressure range P/P0=0.4-0.8, which indicated the presence of abundant mesopores (Figure 4e). The MZIN exhibited a significantly greater surface area (551 m2/g) and mesopore volume (0.37 cm3/g) and a similar micropore volume (0.09 cm3/g ) relative to those of the SCMZ (Table S1). The pore size distribution curve

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of the sample indicates that the mesopores with pore diameter of ~2.9 nm (Figure 4e), which would be the average pore size observed from TEM images. The possible mechanism of the MZIN is illustrated in Figure 4f, which indicates that the (100) faces are overgrown on the (010) faces via the common c-axis in which the zigzag channels of one layer are interconnected with the straight channels of the other layer. The connectivity at the crossed joints could result from the formation of new Si-O-Si bonds. It can be considered that a proper chain length of the template is favourable for the formation of SCMZ, probably because of the proper micellar size of 2.1 nm (nearly one unit cell) that thermodynamically and kinetically facilitates the crystal growth along the b-axis and connects the domains by partial branches of the triply branched template. Too large micellar size formed by the template with longer chain length would be unfavourable for the formation of SCMZ, while the 90° intercrossed growth would be possible without strict distance (see Figure S8 for detailed description). The synthesis mechanism need more theoretical study in the future works. Catalytic properties of SCMZ and MZIN. The catalytic activities of SCMZ, MZIN and conventional bulk ZSM-5 (Figure S9, see Table S1 for textural parameters of these three zeolites) were first tested regarding the acetalisation of cyclohexanone with pentaerythritol (Figure S10). In this case, the diffusion of large molecules, such as the products of diacetal, constrains the reaction. As shown in Figure 5a, first, MZIN and SCMZ exhibited distinctly enhanced catalytic activities compared with those of conventional ZSM-5. This result was attributed to the presence of additional mesopores and to the larger external surface areas of these two mesoporous ZSM-5 zeolites. As for

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the acetalisation of cyclohexanone with pentaerythritol that mainly occurs on the external surface area, MZIN with the largest surface area among others showed the best activity. Second (Figure 5b), the cracking of 1-octene over a time-onstream reaction period of ~20 h was chosen to investigate the catalytic performance of SCMZ and MZIN using small molecules that can easily diffuse to and from the micropores of the ZSM-5 zeolite. The cracking of 1-octene can produce ethylene and propylene, including other small hydrocarbons such as methane, ethane, propane and butane, where isomerisation and hydrogen transfer occur simultaneously. In general, the selectivity toward light olefins increases with increasing reaction temperature.32 Therefore, a high reaction temperature (650 °C) was used to achieve a high selectivity for ethylene and propylene. Furthermore, to observe the changes in the catalytic performances of these zeolite samples over a short period, we used a substantially greater weight hourly space velocity for 1octene (121 h-1). Under the severe conditions used here, the activity of the conventional ZSM-5 toward 1-octene cracking quickly decreased within 6 h. However, the SCMZ and MZIN maintained a high conversion of 1-octene for up to ~13 h and ~8 h, respectively. Third (Figure 5c and Table S2), the isomeric conversion of oxylene to m-xylene and p-xylene, which could occur on the external surface and in the micropores of ZSM-5, were investigated for SCMZ and MZIN.33,34 The product distribution analysis indicated that the main products were xylene isomers and that almost no other reactions, including disproportionation, occurred. These results suggest that isomerisation dominated under the experimental conditions. Remarkably, the conversion rates of oxylene and yields of m-xylene were significantly decreased in the order of SCMZ, MZIN and the conventional ZSM-5.

Figure 5. Catalytic efficiency of synthesised SCMZ, MZIN and conventional ZSM-5. (a) The formation of diacetal from the acetalisation of cyclohexanone with pentaerythritol, (b) the cracking of 1-octene, and (c) the isomerisation of o-xylene into m-xylene and p-xylene and the yield of m-xylene.

The SCMZ, with a smaller surface area and a similar micropore volume relative to MZIN (Table S1), exhibits excellent catalytic properties and unique selectivity in 1-octene cracking and the isomeric conversion of o-xylene. The differences in the catalytic properties of SCMZ and MZIN would be attributed to their different exposed crystallographic faces. Because of the embedded sheet-like mesopores, numerous crystallographic faces along the a-b and b-c planes exist in SCMZ. For MZIN, the only predominant face lies along the a-c plane. The acid sites and the channels along the a-b and b-c planes of the MFI crystals may favour the conversion of 1-octene and o-xylene and result in greater selectivity because of the specific pore sizes (see the supplementary text below Table S2 for the detailed discussion). However, numerous distinct catalytic reactions must be explored to confirm this point. Related studies are underway in our laboratory and may be reported in our future publications.

We demonstrated the synthesis of highly stable SCMZ and MZIN via the self-assembly of designed triply branched cationic templates. This process is particularly interesting because it reflects the formation of sheet-like mesopores on both the a- and c-axes and the formation of mesoporous ZSM-5 with intercrossed nanosheets along the common c-axis. Interestingly, the structure remains unchanged even after calcination. The synthesised SCMZ and MZIN exhibited remarkable catalytic activities toward reactions involving smaller and larger molecules. We hope that our findings provide a new strategy for the development of inorganic-organic mesophases that could be used to fabricate highly ordered three-dimensional mesoporous zeolites. ASSOCIATED CONTENT Supporting Information

CONCLUSION

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Detailed synthesis procedures of surfactants, catalytic reactions, XRD, SEM, TEM and so on. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] & [email protected] Author Contributions †

These authors contributed equally to this work.

Notes The authors declare no competing financial interests. ACKNOWLEDGEMENTS This work was supported by the National Basic Research Program (2013CB934101) of China and Evonik Industries. REFERENCES (1) Hathaway, P. E.; Davis, M. E. J. Catal. 1989, 116, 263. (2) Corma, A.; Díaz-Cabañas, M. J.; Martínez-Triguero, J.; Rey, F.; Rius, J. Nature 2002, 418, 514. (3) Sato, S.; Yu-u, Y.; Yahiro, H.; Mizuno, N.; Iwamoto, M. Appl. catal. 1991, 70, L1. (4) Vermeiren, W.; Gilson, J.-P. Top. Catal. 2009, 52, 1131. (5) Xu, X.; Wang, J.; Long, Y. Sensors 2006, 6, 1751. (6) Schmidt, I.; Boisen, A.; Gustavsson, E.; Ståhl, K.; Pehrson, S.; Dahl, S.; Carlsson, A.; Jacobsen, C. J. Chem. Mater. 2001, 13, 4416. (7) Zhu, K.; Egeblad, K.; Christensen, C. H. Eur. J. Inorg. Chem. 2007, 2007, 3955. (8) Burton, A.; Elomari, S.; Chen, C. Y.; Medrud, R. C.; Chan, I. Y.; Bull, L. M.; Kibby, C.; Harris, T. V.; Zones, S. I.; Vittoratos, E. S. Chem. Eur. J. 2003, 9, 5737. (9) Inayat, A.; Knoke, I.; Spiecker, E.; Schwieger, W. Angew. Chem. Int. Ed. 2012, 51, 1962. (10) Choi, M.; Cho, H. S.; Srivastava, R.; Venkatesan, C.; Choi, D.-H.; Ryoo, R. Nat. Mater. 2006, 5, 718. (11) Xiao, F.-S.; Wang, L.; Yin, C.; Lin, K.; Di, Y.; Li, J.; Xu, R.; Su, D. S.; Schlögl, R.; Yokoi, T.; Tatsumi, T. Angew. Chem. Int. Ed. 2006, 45, 3090. (12) Liu, F.; Willhammar, T.; Wang, L.; Zhu, L.; Sun, Q.; Meng, X.; Carrillo-Cabrera, W.; Zou, X.; Xiao, F.-S. J. Am. Chem. Soc. 2012, 134, 4557.

(13) Na, K.; Jo, C.; Kim, J.; Cho, K.; Jung, J.; Seo, Y.; Messinger, R. J.; Chmelka, B. F.; Ryoo, R. Science 2011, 333, 328. (14) Choi, M.; Na, K.; Kim, J.; Sakamoto, Y.; Terasaki, O.; Ryoo, R. Nature 2009, 461, 246. (15) Na, K.; Park, W.; Seo, Y.; Ryoo, R. Chem. Mater. 2011, 23, 1273. (16) Na, K.; Choi, M.; Park, W.; Sakamoto, Y.; Terasaki, O.; Ryoo, R. J. Am. Chem. Soc. 2010, 132, 4169. (17) Xu, D.; Ma, Y.; Jing, Z.; Han, L.; Singh, B.; Feng, J.; Shen, X.; Cao, F.; Oleynikov, P.; Sun, H.; Terasaki, O.; Che, S. Nat. Commun. 2014, 5, DOI: 10.1038/ncomms5262. (18) Kresge, C.; Leonowicz, M.; Roth, W.; Vartuli, J.; Beck, J. nature 1992, 359, 710. (19) Beck, J.; Vartuli, J.; Kennedy, G.; Kresge, C.; Roth, W.; Schramm, S. Chem. Mater. 1994, 6, 1816. (20) Amabilino, D. B.; Stoddart, J. F. Chem. Rev. 1995, 95, 2725. (21) Claessens, C. G.; Stoddart, J. F. J. Phys. Org. Chem. 1997, 10, 254. (22) Zhu, J.; Zhu, Y.; Zhu, L.; Rigutto, M.; van der Made, A.; Yang, C.; Pan, S.; Wang, L.; Zhu, L.; Jin, Y.; Sun, Q.; Wu, Q.; Meng, X.; Zhang, D.; Han, Y.; Li, J.; Chu, Y.; Zheng, A.; Qiu, S.; Zheng, X.; Xiao, F. S. J. Am. Chem. Soc. 2014, 136, 2503. (23) Pierotti, R.; Rouquerol, J. Pure Appl. Chem. 1985, 57, 603. (24) Shen, J.-M.; Xu, L.; Liu, Y.-G.; Lu, C.-L.; Hou, W.-H.; Zhu, J.-J. Chem. Mater. 2008, 20, 3034. (25) Katcho, N. A.; Urones-Garrote, E.; Ávila-Brande, D.; GómezHerrero, A.; Urbonaite, S.; Csillag, S.; Lomba, E.; Agulló-Rueda, F.; Landa-Cánovas, A. R.; Otero-Díaz, L. C. Chem. Mater. 2007, 19, 2304. (26) Fukasawa, Y.; Sugawara, A.; Hirahara, H.; Shimojima, A.; Okubo, T. Chem. Lett. 2010, 39, 236. (27) Zhang, X.; Liu, D.; Xu, D.; Asahina, S.; Cychosz, K. A.; Agrawal, K. V.; Al Wahedi, Y.; Bhan, A.; Al Hashimi, S.; Terasaki, O. Science 2012, 336, 1684. (28) Karwacki, L.; Stavitski, E.; Kox, M. H.; Kornatowski, J.; Weckhuysen, B. M. Angew. Chem. Int. Ed. 2007, 119, 7366. (29) Ramsahye, N. A.; Slater, B. Chem. Commun. 2006, 442. (30) Bonilla, G.; Díaz, I.; Tsapatsis, M.; Jeong, H.-K.; Lee, Y.; Vlachos, D. G. Chem. Mater. 2004, 16, 5697. (31) Chaikittisilp, W.; Suzuki, Y.; Mukti, R. R.; Suzuki, T.; Sugita, K.; Itabashi, K.; Shimojima, A.; Okubo, T. Angew. Chem. Int. Ed. 2013, 125, 3439. (32) Rahimi, N.; Karimzadeh, R. Appl. Catal. A: General. 2011, 398, 1. (33) Zhang, H.; Song, K.; Wang, L.; Zhang, H.; Zhang, Y.; Tang, Y. ChemCatChem 2013, 5, 2874. (34) Liu, Y.; Zhou, X.; Pang, X.; Jin, Y.; Meng, X.; Zheng, X.; Gao, X.; Xiao, F. S. ChemCatChem 2013, 5, 1517.

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