Advances in Mesoporous Molecular Sieve MCM-41 - Industrial

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REVIEWS Advances in Mesoporous Molecular Sieve MCM-41 Xiu S. Zhao,† G. Q. (Max) Lu,*,† and Graeme J. Millar‡ Department of Chemical Engineering and Department of Chemistry, The University of Queensland, Brisbane, Queensland 4072, Australia

The discovery of mesoporous molecular sieves, MCM-41, which possesses a regular hexagonal array of uniform pore openings, aroused a worldwide resurgence in this field. This is not only because it has brought about a series of novel mesoporous materials with various compositions which may find applications in catalysis, adsorption, and guest-host chemistry, but also it has opened a new avenue for creating zeotype materials. This paper presents a comprehensive overview of recent advances in the field of MCM-41. Beginning with the chemistry of surfactant/ silicate solutions, progresses made in design and synthesis, characterization, and physicochemical property evaluation of MCM-41 are enumerated. Proposed formation mechanisms are presented, discussed, and identified. Potential applications are reviewed and projected. More than 100 references are cited. Contents 1. Introduction 2. General Background 3. Chemistry of Surfactant/Silicate Aqueous Solution 3.1. Behavior of Surfactant Molecules in an Aqueous Solution 3.2. Chemistry of Silicates/ Aluminosilicates in an Alkaline Aqueous Solution 4. Synthesis of MCM-41 4.1. Expanding Synthesis Conditions 4.2. Synthesis of Aluminum-Rich MCM-41 4.3. Synthesis of Hybrid Atom MCM-41 5. Formation Mechanism 5.1. Liquid Crystal Templating (LCT) Mechanism 5.2. Transformation Mechanism from Lamellar to Hexagonal Phase 5.3. “Folded Sheets” Mechanism 5.4. Identifying the Formation Mechanism 6. Characterization, Physicochemical Properties, and Structure Model 6.1. Characterization and Structure Model 6.2. Acidity 6.3. Stability 6.4. Interaction with Water 7. Application 7.1. Catalysis 7.2. Ship in a Bottle 7.3. Model Adsorbent

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8. Perspective 8.1. Host -Guest Encapsulation 8.2. Modification 8.3. Adsorbent 8.4. Environment 9. Acknowledgment 10. Literature Cited

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Over the past 15 years, there has been a dramatic increase in the literature of design, synthesis, characterization and property evaluation of zeolites and molecular sieves for catalysis, adsorption and separation, environmental pollution control, and intrazeolite fabricating technology. Progress has been made in a variety of disciplines, including inorganic and materials chemistry (Davis and Lobo, 1992; Ozin, 1992), mineralogy and crystallography (Smith, 1988), petrochemistry (Chen et al., 1989; Corma, 1995a), environmental science (Armor, 1992; Iwamoto, 1994; Tabata, 1994), and even biochemistry (Mann, 1993). As excellent examples, bicontinuous phases have been used to orient organic species which are then photopolymerized (Davis, 1993). After the extraction of the unpolymerized components, porous organic monoliths resulted. This process has led to a new concept of self-assembled microstructure serving as structure-directing agents. Again, material scientists have used large organic molecules to intercalate into layered clays to generate novel materials with controllable pore size (Yanagisawa et al., 1990). Biochemists have established a model that makes use of the cooperative organization of inorganic and organic * Author to whom all correspondence should be addressed at the Department of Chemical Engineering, The University of Queensland, Brisbane, Queensland 4072, Australia. Phone: 61 7 33653708. Fax: 61 7 33654199. E-mail: maxlu@ cheque.uq.edu.au. † Department of Chemical Engineering. ‡ Department of Chemistry.

© 1996 American Chemical Society

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Table 1. Pore Size Definition of Zeolites and Molecular Sieves pore size (Å)

definition

>500 20-500 95 -

a Conditions: 0.1 g of catalyst, 80 °C, 2 h, 5 mmol of 2,6-DTBP or 10 mmol of benzene, 0.13 mol of acetone as solvent, 29 mmol of 30% aqueous H2O2.

Thus, the conclusion could be drawn that siliceous MCM-41 is hydrophobic, while aluminosilicate MCM41 is slightly hydrophilic. 7. Application Figure 15. TGA curves of MCM-41 with different Si/Al ratios (Zhao et al., 1994).

samples (Chen et al., 1993a; Corma et al., 1994b). We have also studied the various stabilities of MCM-41 (see Table 4). When MCM-41 was hydrothermally treated at 450 °C for 2 h, considerable losses of both the BET surface area and the benzene sorption capacity occurred. Calcination of MCM-41 in dry air resulted in slight loss of BET surface area, indicating that the thermal stability was satisfactory. When MCM-41 was impregnated in 20% nitric acid overnight, both the BET surface area and the benzene sorption amount were slightly increased. This observation may be associated with the removal of some blockages in the channels of MCM-41. In sharp contrast with the acid treatment, the basic treatment in 5% potassium hydroxide bought about almost complete destruction of the MCM-41 structure demonstrated by both the nitrogen and benzene adsorption and XRD spectra (only a broad intensity at extremely low angle regions was detected). These data indicate that MCM-41 material is thermally stable with high acid resistance, but hydrothermally unstable and with low base tolerance. 6.4. Interaction with Water. The adsorption of water steam over MCM-41 characterized by a type V isotherm reveals an initially repulsive character followed by a capillary condensation step of water, indicating that MCM-41 possesses both hydrophobic and hydrophilic properties (Llewellyn et al., 1995). Three distinct stages were obtained in the TGA curves (Figure 15) (Zhao et al., 1994). The first stage at 25-150 °C is associated with the desorption of physically adsorbed water and other gases; the second stage at 150-380 °C is attributed to the decomposition and combustion of organic species, and the third stage at 380-800 °C may be related to the water losses due to condensation of silanol groups to form siloxane bonds (Chen et al., 1993a). In addition, with the increase of the aluminum content in MCM-41 framework the amount of water desorbed increases and the organic species decrease.

7.1. Catalysis. A US patent (Pelrine et al., 1992) claimed good catalytic activity of MCM-41 impregnated with Cr for olefin oligomerization to produce lube oil additives. Both the pour points and the viscosity indexes were improved on Cr-MCM-41 catalyst compared with the commercial catalyst (Cr-SiO2). The support (MCM-41, alumina-silica, and USY) effect on the catalytic activity of hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and mild hydrocracking (MHC) was also investigated by Corma et al. (1995b). A very high activity was observed on Ni,Mo-MCM-41 catalyst which was attributed to a combination of high surface area and large pore size that favors a high dispersion of the active species coupled with easy accessibility of the large feedstock molecules. Use of MCM-41 as an acid catalyst for Friedel-Crafts alkylation of 2,4-di-tert-butylphenol (bulky aromatic) with cinnamyl alcohol (Kloetstra et al., 1995a) and for the tetrahydropyranylation of alcohol and phenol (Armengol et al., 1995) was reported where the advantages of MCM-41 were manifested. Besides being an acid catalyst, Na-MCM-41 and Cs-MCM-41 catalysts exhibit satisfactory performance in base catalysis (Kloetstra et al., 1995b). For example, in the Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate, 81% conversion of benzaldehyde and 75% selectivity to the desired product were obtained at 150 °C within 7 h, and 90% conversion of benzaldehyde and ca. 100% selectivity were observed at 100 °C within 3 h in water solvent. Ti(V,Cr)-MCM-41 materials exhibit excellent catalytic oxidation performance in the presence of hydrogen peroxide or even the bulky oxidant THP (terbutyl hydroperoxide), as reported by Tanev et al. (1994) and Corma et al. (1994a). A typical example from Tanev et al. (1994) is shown in Table 5. Both Ti-MCM-41 and TS-1 are effective catalysts for the hydroxylation of benzene, but for substrate 2,6-DTBP, this is not the case because the medium-sized pore structure of TS-1 (MFI) cannot permit such a large molecule to diffuse into the

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Table 6. Catalytic Activity of MCM-41 in SCR of NOx NOx conversion (%) catalyst

350 °C

450 °C

6.1%Ti, 2.5%V/MCM-41 3.0%Ti, 2.6%V/SiO2 2.0%V2O5, 8.0WO3/TiO2

81 70 95

41 2 63

structures of MCM-41, thus, offer an opportunity to investigate this fundamental problem. Reports regarding this issue are readily available (Branton et al., 1993, 1994, 1995; Rathousky et al., 1994, 1995). 8. Perspective

a

Conditions: 2.0 g of catalyst, WHSV ) 400 mL/min, 125 ppm NO, 125 ppm NH3, 0.12% O2, helium balance.

internal surface where the active sites (isolated Ti species) are located. Molecular sieves have drawn much interest in environmental catalysis in the past few years (Dartt and Davis, 1994; Iwamoto, 1994), in particular in decomposition of nitrogen oxides (Iwamoto, 1994; Tabata, 1994). The activity of selective catalytic reduction of NO on Ti,V/MCM-41, Ti,V/SiO2, and a commercial catalyst V,W/TiO2 has been compared (Beck et al., 1992b) as shown in Table 6. Ti,V/MCM-41 catalyst exhibits a higher NOx conversion than the silica-based catalyst but is less active than the commercial one. This was explained in terms of the fact that although MCM-41 is capable of supporting more active components than silica due to its high BET surface area it has a low redox performance. In a recent study, we have demonstrated that MCM-41 can be a potential NO decomposition catalyst support with considerably higher activity than ZSM-5 (Zhao and Lu, 1995). 7.2. Ship in a Bottle. The large cavities and uniformed pore structures provide zeolites and molecular sieves with many interesting characteristics. For example, they can act just as molecular “factories” (bottles) where quantum-sized particles (ships) can be manufactured inside (Ozin, 1992; Dag and Ozin, 1995; Mitchell, 1991). The huge “workshop” and broad channels (without “traffic block”) for MCM-41 are expected to manifest itself with specified characteristics in the area of “ship in a bottle” as Fisher (1995) pointed out. Nanosized catalysts, such as low-valent transition metal moieties, e.g., Me3SnMo(CO)3(η-C5H5), have been introduced into the channels of MCM-41 by combining calcined MCM-41 with Me3SnMo(CO)3(η-C5H5) in hexane solvent for 18 h under stirring, and importantly these larger ligands seem to be very stable (Huber et al., 1994). When the attached complexes were heated, they were converted into nanometer bimetallic clusters in MCM-41 channels, which displayed high catalytic activity. The fabrication of stable carbon wires in the channels of MCM-41 was reported by Wu et al. (1994). The MCM-41 host was contacted with acrylonitrile vapor at room temperature for 4 h and then briefly evacuated, resulting in a large amount of adsorbed acrylonitrile. Polymerization of acrylonitrile in the channels of MCM-41 was carried out through a freeradical reaction process initiated by adding K2S2O8 and NaHSO3 at 40 °C. Finally, the sample was thermally treated in a nitrogen flow between 350 and 1000 °C for 24 h. The final nanosized carbon wires exhibited a high thermal stability (more than 800 °C) and low-field conductivity. 7.3. Model Adsorbent. As shown in Figure 11, MCM-41 materials exhibit an interesting nitrogen adsorption-desorption isotherms without hysteresis loop. However, it was found that this is not the case for other adsorptives (Branton et al., 1995) and at different temperatures (Rathousky et al., 1995). This reflects the importance of the pore shape and the network of adsorbent. The well-controlled uniform pore

As indicated above, the marked characteristics of MCM-41 are as follows: (1) well-defined pore structure with apertures in the range of 15-100 Å which can be controlled by careful choice of surfactants, auxiliary chemicals, and reaction parameters, (2) high thermal stability, (3) mild acidity, (4) large BET surface area and pore volume, and (5) hydrophobic/hydrophilic property which can be modified by changing Si/Al ratios. Therefore, MCM-41 materials have a promising potential in catalysis, adsorption, and advanced molecular sievebased materials. 8.1. Host-Guest Encapsulation. Semiconductor clusters anchored in molecular sieves have received much attentions as advanced composite materials (Stucky and Mac Dougall, 1990; Ozin, 1992) and photocatalysts (Liu et al., 1993; Tanguay et al., 1989). In this case, the uniform pore structures of molecular sieves can act as solid solvents to control both the size and topology of the particles encapsulated inside. Nevertheless, it was found that introduction of such species, in particular large transition metal species (e.g., MoO3) could result in partial collapse of the host structures (Fierro et al., 1987) and ultimately lead to the decrease in surface area as well as the catalytic activity. From this consideration, MCM-41 should exhibit superior properties compared to other common molecular sieves because of its mesopore structure. As an example, we have successfully encapsulated nanosized TiO2 or MoO3 particles in the MCM-41 channels through either ion exchange or impregnation approaches (Zhao et al., 1995b). X-ray powder diffraction patterns show that no structure collapse occurred. Furthermore, no diffraction peaks attributed to these metal oxides at the external surface of MCM-41 could be observed for carefully purified samples. This result was also confirmed by X-ray photoelectron spectroscopy. A remarkable increase in the band gaps of these composite materials was observed in the UV-vis absorption spectra due to quantum size effect (Brus, 1986), indicating that nanometer TiO2 clusters were indeed formed in the MCM41 channels. Metals with two different, stable oxidation states, such as Co(II)/Co(III), Fe(II)/Fe(III), Cr(II)/Cr(V), and Cu(I)/Cu(II), were found to be effective oxygen carriers for catalysis (Imamura and Lunsford, 1985; Mortier and Schoonheydt, 1985; Thomas, 1994). It was found, however, that the oxygen-carrying ability of these ligands was due to the formation of M-O-M (M ) Cu, Cr, Fe, etc.) bridges in the cubooctahedra. This would lead to diffusion limitations of reactants and products into and out of the cubooctahedra. On the other hand, metal-organic supermolecule complexes encapsulated in zeolite cavities were also found to be effective gas carriers and reaction centers for catalysis (Ozin and Gil, 1989; Mallouk and Lee, 1990; Mitchell, 1991). It was pointed out that the degree of [CoII(bpy)(terpy)]2+ complex formation inside a NaY zeolite was very low, hence the efficiency for the utilization was low. In addition, some complexes are impossible to be encapsulated inside the cages of the traditional zeolites because of their too large dynamic diameters (e.g., the ligand of [Co(phthalo-

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Figure 16. Schematic representation of [Co(phthalocyanine)]2+ metal complex entrapped in MCM-41 channels.

Figure 17. Comparison of p-nitroaniline molecule alignment in the channel of (A) AlPO4-5 and (B) MCM-41.

cyanine)]2+ with a diameter of 15 Å cannot be encapsulated by NaY zeolite). All of these drawbacks can now be overcome by taking advantage of MCM-41 materials, as shown in Figure 16, because the advantages of MCM41 (high surface area and mesoporous structure) can offer the possibility to support a large amount of chemical ligands with a large dynamic diameter. Attempts have also been made to make zeolite-based solids capable of generating nonlinear optical properties which are dramatically different from those of either host or guest in recent years. For example, p-nitroaniline (pNA), a centrosymmetric crystal, does not exhibit second harmonic generation (SHG), nor does AlPO4-5 molecular sieve. However, when pNA molecules were introduced into the one-dimensional channels of AlPO4-5, a high SHG signal will be detected because the polar host crystal forces alignment of the guest molecules so as to enhance the SHG (Marlow et al., 1994). If one imagines the p-nitroaniline molecules being aligned in the MCM-41 channels with a 40 Å pore diameter as indicated in Figure 17, the SHG signal generated might be expected to be 5-7 factors more than that for AlPO4-5. 8.2. Modification. From the consideration of the uniform mesoporous structure, mild acid properties, and acid proof stability, introduction of superacid (e.g., SO42-, F-) or heteropoly acid into the MCM-41 channels to modify the acidity seems to be both practical and promising. Kozhernikov et al. (1995) recently reported results for the introduction of tungstophosphoric acid (H3PW12O40) into the MCM-41 pores. By shaking MCM41 with H3PW12O40 solution overnight, finely dispersed H3PW12O40 species on the surface of MCM-41 were obtained, which exhibited strong Brønsted acid sites similar to those of H3PW12O40 supported on amorphous silica. The catalytic activity of this composite material was tested for the alkylation of TBP with isobutene as a model reaction. H3PW12O40/MCM-41 shows a high catalytic activity which is 3-4 times higher than that

for the bulk H3PW12O40 catalyst. Supported SO4- and SO4--ZrO2 over MCM-41 may be a promising approach to get highly dispersed superacids. The pore sizes of MCM-41 materials were claimed to be distributed in the range of 15-100 Å. It generally ranged from 20 to 40 Å. The gap between 13 and 20 Å makes it inconvenient to use this material. Although mesoporous materials with pore sizes in the range of 14-22 Å have been reported through the gallerytemplated route (Galarneau et al., 1995), this is not satisfactory to zeolite and molecular sieve workers. Therefore, precise control of the pore structures by either hydrothermal synthesis or postmodified approach (Beck et al., 1993) in order to make this novel material a true molecular recognizer is an urgent need. 8.3. Adsorbent. MCM-41 may be expected to find application as an adsorbent since it exhibits both hydrophobic and hydrophilic character depending upon the exact composition and/or postmodification. Removal of hydrocarbons from water, storage of gases (e.g., H2, O2, CH4), adsorptive xylene separation, and separation of biological and pharmaceutical compounds now seems to be potential areas for developing MCM-41 applications. 8.4. Environment. MCM-41 may find wide applications in environmentally safe processes, i.e., replacement of environmentally hazardous catalysts in existing processes. Titanium-containing MCM-41, Ru(II), Co(II), and Ni(II) complexes and Mo(CO)6 ligands encapsulated within the intrasurface of MCM-41, etc. are very promising heterogeneous catalysts to replace traditional homogeneous catalysts because of their ready regenerability, shape selectivity, and easy separation and recovery. 9. Acknowledgment The authors are grateful to Dr. D. Y. Zhao, the Weizmann Institute of Science, Israel, for some valuable discussions. We also thank Mr. David Page, Center for Microscopy and Microanalysis at the University of Queensland, for his help in XRD characterization. X.S.Z. wishes to thank Dalian Institute of Chemical Physics, Chinese Academy of Sciences, where part of the work on MCM-41 was conducted, for permitting a sabbatical leave. 10. Literature Cited Abe, T.; Tachibana, Y.; Uematsu, T.; Iwamoto, M. Preparation and Characterisation of Fe2O3 Nanoparticles in Mesoporous Silicate. J. Chem. Soc., Chem. Commun. 1995, 1617-1618. Alfredsson, V.; Keung, M.; Monnier, A.; Stucky, G. D.; Unger, K. K.; Schu¨th, F. High-Resolution Transmission Electron Microscopy of Mesoporous MCM-41 Type Materials. J. Chem. Soc., Chem. Commun. 1994, 921-922. Armengol, E.; Cano, M. L.; Corma, A.; Garcıá, H.; Navarro, M. T. Mesoporous Aluminosilicate MCM-41 as A Convenient Acid Catalyst for Friedel-Crafts Alkylation of a Bulky Aromatic Compound with Cinnamyl Alcohol. J. Chem. Soc., Chem. Commun. 1995, 519-520. Armor, J. N. Environmental Catalysis. Appl. Catal. 1992, B1, 221256. Beck, J. S.; Vartuli, C.; Roth, W. J.; Leonowicz, M. E.; Kresge, C. T.; Schmitt, K. D.; Chu, C. T-W.; Olson, D. H.; Sheppard, E. W.; McCullen, S. B.; Higgins, J. B.; Schlenker, J. L. A New Family of Mesoporous Molecular Sieves Prepared with Liquid Crystal Templates. J. Am. Chem. Soc. 1992a, 114, 1083410843.

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Zhao, X. S.; Lu, G. Q.; Millar, G. J.; Li, X. S. Synthesis of Mesoporous Molecular Sieves MCM-41 from an Alkali-Free System and its Catalytic Activity. Catal. Lett. 1995a, in press. Zhao, X. S.; Lu, G. Q.; Millar, G. J. Encapsulation of Transition Metal Species into Zeolites and Molecular Sieves as Redox Catalysts. Part 2. J. Porous Mater. 1995b, in preparation.

Received for review November 21, 1995 Revised manuscript received March 25, 1996 Accepted March 27, 1996X IE950702A X Abstract published in Advance ACS Abstracts, June 1, 1996.

Advances in Mesoporous Molecular Sieve MCM-41 - Industrial

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