Recent advances in the synthesis, characterization and applications of mesoporous molecular sieves

Current Opinion in Solid State and Materials Science

Volumn 1, Issue 1, 1996, Pages 76-87

  Beck, Jeffrey S ^a   Vartuli, James C ^a  

^a EXXONMOBIL UPSTREAM RESEARCH COMPANY   (United States)

Author keywords

HDN hydrodenitrogenation; HDS hydrodesulfurization; LCT liquid crystal templating; TP+ 2,4,6 triphenylpyrylium

Indexed keywords

MEMBRANE TECHNOLOGY; SEPARATION; SORPTION;

EID: 0029676390     PISSN: 13590286     EISSN: None     Source Type: Journal    
DOI: 10.1016/S1359-0286(96)80014-3     Document Type: Article

References (55)

1. Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature. 359:1992;710-712.
2. Beck JS, Vartuli JC, Roth WJ, Leonowicz ME, Kresge CT, Schmitt KD, Chu CTW, Olson DH, Sheppard EW, McCullen SB, et al. A new family of mesoporous molecular sieves prepared with liquid crystal templates. J Am Chem Soc. 114:1992;10835. A comprehensive paper detailing the isolation of the initial silicate and aluminosilicate members of the M41S family. Full details on the synthesis methods and physical characterization of M41S materials are presented. A proposed mechanism of formation, liquid-crystal templating (LCT), implicating the formation of surfactant liquid crystal phases in the synthesis is presented. Studies supporting this mechanism, including surfactant chain length variation and the addition of micelle swelling agents to synthesis mixture are reported. The isolation of three silicate phases, (MCM-41 (hexagonal phase), MCM-48 (cubic phase) and lamellar phase), analogous to three of the most prominent surfactant liquid crystal phases, also supports the LCT hypothesis. of outstanding interest.
3. Behrens P. Mesoporous inorganic solids. Adv Mater. 5:1993;127-132.
4. Behrens P, Stucky GD. Ordered molecular arrays as templates: a new approach to the synthesis of mesoporous materials. Int Ed Engl Angew Chem. 32:1993;696-699.
5. Casci JL, Karge HG, Weitkamp J. The preparation and potential application of ultra-large pore molecular sieves: a review. Jansen JC, Stöcker M. Advanced Zeolite Science and Applications, Studies in Surface Science and Catalysis. 85:1994;329-356 Elsevier Science, Amsterdam. An initial review of progress in the study of mesoporous silicates up to 1994. The paper reviews a wide spectrum of materials ranging from zeolites to pillared-layered materials to mesoporous materials, making appropriate synthesis and characterization connections. The review also includes a fairly extensive patent review covering both composition of matter, synthesis techniques, and applications. The question of the extent of crystallinity in M41S materials is examined. Potential uses for mesoporous materials are described. of special interest.
6. Ozin GA. Nanochemistry: synthesis in diminishing dimensions. Adv Mater. 4:(10):1992;612-649.
7. Vartuli JC, Schmitt KD, Kresge CT, Roth WJ, Leonowicz ME, McCullen SB, Hellring SD, Beck JS, Schlenker JL, Olson DH, Sheppard EW. Effect of surfactant/silica molar ratios on the formation of mesoporous molecular sieves: inorganic mimicry of surfactant liquid crystal phases and mechanistic implications. Chem Mater. 6:1994;2317-2326. This paper gives detailed synthesis methodology for the formation of the three most prominent M41S phases: hexagonal, cubic and lamellar. The importance of the surfactant : silica molar ratio is demonstrated in a simple ternary synthesis system containing tetraethylorthosilicate, cetyltrimethyl-ammonium cation and water. It is shown that as the surfactant : silica molar ratio is increased the synthetic product changes from hexagonal to cubic to lamellar. These results are found to be consistent with known liquid-crystal transformations triggered by variation in cation/anion concentrations. xof special interest.
8. Vartuli JC, Schmitt KD, Kresge CT, Roth WJ, Leonowicz ME, McCullen SB, Hellring SD, Beck JS, Schlenker JL, Olson DH, Sheppard EW. Development of a formation mechanism for M41S materials. Weitkamp J, Karge HG, Pfeifer H, Hölderich W. Zeolites and Related Microporous Materials: State of the Art 1994, Stud in Surf Sci and Catal 1994. 84:1994;53-60 Elsevier Science, Amsterdam. Proc 10th Intl Zeolite Conf Garmisch-Partenkirchen Germany 1994.
9. Kresge CT, Vartuli JC, Roth WJ, Leonowicz ME, Beck JS, Schmitt KD, Chu CTW, Olson DH, Sheppard EW, McCullen SB, Higgins JB, Schlenker JL. M41S: a new family of mesoporous molecular sieves prepared with liquid crystal templates. Izumi Y, Arai H, Iwamoto M. tudies in Surface Science and Catalysis 92, Science and Technology in Catalysis 1994. 1994;11-19 Elsevier Science, Amsterdam.
10. Chen CY, Burkett SL, Li HX, Davis ME. Studies on mesoporous materials. II. Synthesis mechanism of MCM-41. Microporous Mater. 2:1993;27-34.
11. Yanagisawa T, Shimizu T, Kuroda K, Kato C. The preparation of alkyltrimethylammonium-kanemite complexes and their conversion to microporous materials. Bull Chem Soc Jpn. 63:1990;988-992.
12. Inagaki S, Fukushima Y, Kuroda K. Synthesis of highly ordered mesoporous materials from a layered polysilicate. J Chem Soc Chem Commun. 1993;680-682. volume.
13. Vartuli JC, Kresge CT, Leonowicz ME, Chu AS, McCullen SB, Johnson ID, Sheppard EW. Synthesis of mesoporous materials: liquid crystal templating versus intercalation of layered silicates. Chem Mater. 6:(11):1994;2070-2077. Two differing route to the formation of mesoporous materials are examined. X-ray diffraction data, transmission electron microscopy (TEM) and sorption capacity measurements are used to establish differences in the mechanistic pathways leading to mesoporous silicates arising from variations in synthesis protocol. In the case of MCM-41 mesoporous silicates, it was demonstrated that surfactant-silicate liquid-crystals arrays are implicated as the templating species. The material could be prepared via a layered silicate (kanemite) with identical surfactant cations shows that this synthesis proceeds with retention of the silicate layer. The materials prepared via the intercalation route are shown to be less ordered, have broader pore-size distributions and exhibit lower sorption capacity than liquid-crystal templated, MCM-41 materials. of special interest.
14. Chen CY, Xiao SQ, Davis ME. Studies on ordered mesoporous materials. III. Comparison of MCM-41 to mesoporous materials derived from kanemite. Microporous Mater. 4:1995;1-20. As in reference 13 mesoporous materials derived from kanemite are contrasted with MCM-41 materials prepared from unstructured silica sources. It was concluded that both routes produce mesoporous materials, but that the kanemite materials have thicker silicate walls enhancing thermal and hydrothermal stability. of special interest.
15. Inagaki S, Fukushima Y, Kuroda K. Synthesis and characterization of highly ordered mesoporous material; FSM-16, from a layered polysilicate. Izumi Y, Arai H, Iwamoto M. Studies in Surface Science and Catalysis 92, Science and Technology in Catalysis 1994. 1994;125-131 Elsevier Science, Amsterdam.
16. Inagaki S, Fukushima Y, Kuroda K. Synthesis and adsorption properties of a new folded sheets mesoporous material (FSM) from a layered polysilicate. Proceedings: Symposium of Synthesis of Zeolites, Layered Compounds and Other Microporous Solids: 209th National Meeting. April 2-7, 1995;American Chemical Society Anaheim, California. The latest in a series of papers dealing with mesoporous materials derived from the layered silicate, kanemite. The mesoporous silicate product is dubbed FSM-16 and appears to have greater hexagonal ordering than previously reported materials prepared via the intercalation route. The 'folded-sheets' mechanism, which involves the transformation of the individual silicate layer about the intercalated surfactant molecules to produce a porous material, provides further explanation of differences between the mechanism of formation of this material and that of MCM-41. of special interest.
17. 13CP/MAS NMR and X-ray powder diffraction data were used to support the role of the surfactant in the formation of the respective material. of outstanding interest.
18. Huo Q, Margolese DI, Ciesla U, Feng P, Gier TE, Sieger P, Leon R, Petroff PM, Schüth F, Stucky GD. Generalized synthesis of periodic surfactant/inorganic composite materials. Nature. 368:1994;317-323. A generalized approach to the synthesis of mesoporous materials via charge density matching is presented. It is shown that by combining the appropriately charge balanced species, a plethora of mesophase materials could be formed. It was demonstrated that mesophases of various metal oxides could be generated by the charge-matching of surfactant and solution phase metal oxide. The work has broad implications for the synthesis of a number of types of mesoporous materials because the concept of charge balancing to direct the synthesis allows one to work with either anionic or cationic surfactants to effect formation of cationic and anionic frameworks, respectively. of outstanding interest.
19. +) in which the surfactant, if positively charged, can be combined with an anionic inorganic species, such as in the formation of M41S materials. The converse may also be applied, in that a egatively charged surfactant can react with positively charged inorganic oxide cluster. The latter methodology was used to prepare Fe oxide (lamellar) and Pb oxide (lamellar and hexagonal) phases. The charge balancing technique leads to endless possibilities for the creation of the basic mesophase structural types, although issues of the exact nature of the framework (simply organic-inorganic salt-pairing, or condensed) and resulting stability issues need further attention. of outstanding interest.
20. Stein A, Fendorf M, Jarvie TE, Mueller KT, Benesi AJ, Mallouk TW. Salt/3-gel synthesis of porous transition-metal oxides. Chem Mater. 7:(2):1995;304-313. Expands on the work of reference 19 showing that many of the mesophase transition metal oxides are not condensed frameworks as in the case of the mesoporous silicates, and this is illustrated in their structural collapse upon template removal. of special interest.
21. 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. Cooperative organization of inorganic-surfactant and biomimetic assemblies. Science. 267:1995;1138-1143. This work suggest a generalized model by which mesostructures may form. This model goes beyond simple concepts of charge-balance to include consideration that nucleation, growth and phase transitions are subject to direction by many variables including charge density, coordination and steric requirements. The organization of silicate mesophases is examined with respect to separation of surfactant self-assembly and interfacial silicate condensation. of special interest.
22. Tanev PT, Pinnavia TJ. A neutral templating route to mesoporous molecular sieves. Science. 267:1995;865-867. An exciting twist on the conventional charge balance mechanisms expounded upon above. In this case, the mesostructure is effected via the use of hydrogen-bonding interactions and self-assembly between neutral primary amine micelles. Important implications for the production of other mesoporous oxides not amenable to electrostatic templating pathways. of outstanding interest.
23. Bagshaw SA, Prozet E, Pinnavia TJ. Templating of mesoporous molecular sieves by nonionic polyethylene oxide surfactants. Science. 209:1995;1242-1245. As in reference 22, it is further demonstrated that neutral surfactant templates may play a role as organizing species. In this case the polyethylene oxide surfactants are also inexpensive and lead towards potentially improved routes in large scale synthesis. of special interest.
24. Huo Q, Leon R, Petroff PM, Stucky GD. Mesostructure design with Gemini surfactants: supercage formation in a three-dimensional hexagonal array. Science. 268:1995;1324-1327. In this work, important advances are made in extending the 'design' of the surfactant template for the production of mesostructures. Gemini surfactants which contain two quaternary ammonium head-groups separated by a variable length methylene chain are used as templates [24]. With this template system, a new hexagonal mesophase containing regular supercages and a large inner surface area was produced. The results suggest that many new types of liquid-crystal structures may be available in the form of mesoporous silicates. of special interest.
25. Sayari A, Karra VR, Sudhaker Reddy J. Synthesis of mesoporous molecular sieves using dialkyl dimethyl ammonium bromide as templates. Symp on Synthesis of Zeolites. Layered Compounds and other Microporous Solids: Division of Petrol Chem 209th National American Chemical Society Meeting: Anaheim, California. 1995;. In press.
26. Perego G, Bellusi G, Corno G, Taramasso M, Buonomo F, Esposito A. Titanium silicalite: a novel derivative in the Pentasil family. tudies in Surface Science And Catalysis. 28:1986;129-136.
27. Corma A, Navarro MT, Pariente JP. Synthesis of an ultralarge pore titanium silicate isomorphous to MCM-41 and its application as a catalyst for selective oxidation of hydrocarbons. J Chem Soc Chem Commun. 1994;147-148. volume.
28. Corma A, Navarro MT, Pérez-Pariente J, Sánchez F. Preparation and properties of Ti-containing MCM-41. Izumi Y, Arai H, Iwamoto M. Zeolites and Related Microporous Materials: State of the Art 1994., Stud in Surf Sci and Catal 1994, Proceedings of the 10th International Zeolite Conference Garmisch-Partenkirchen Germany 1994. 84:1994;69 Elsevier Science, Amsterdsam.
29. Tanev PT, Chibwe M, Pinnavaia TJ. Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds. Nature. 368:1994;321-323. A Ti-containing mesoporous molecular sieve was capable of the shape-selective conversion of 2,6-di-tert-butyl phenol to the corresponding quinone. This example provides promise that mesoporous materials may some day be used in highly shape selective transformations of large molecules. of special interest.
30. Sayari A, Sudhakar Reddy J, Dicko A. Ti-Modified Mesoporous Molecular Sieves. Symposium on Synthesis of Zeolites. Layered Compounds and other Microporous Solids, Division of Petrol Chem 209th National Am Chem Soc Meeting: Anaheim, California. 1995;. In press.
31. Franke O, Rathousky J, Schulz-Ekloff G, Stárek J, Zukal A. New Mesoporous Titanosilicate Molecular Sieve. Weitkamp J, Karge HG, Pfeifer H, Hölderich W. Zeolites and Related Microporous Materials: State of the Art 1994, Stud in Surf Sci and Catal 1994, Proceedings of the 10th International Zeolite Conference Garmisch-Partenkirchen Germany 1994. 84:1994;77 Elsevier Science, Amsterdam.
32. Schulz-Ekloff G, Rathousky J, Zukat A. Titanium species in mesoporous materials. Symposium on Synthesis of Zeolites. Layered Compounds and other Microporous Solids, Division of Petrol Chem 209th National Am Chem Soc Meeting: Anaheim, California. 1995.
33. Reddy KM, Moudrakovski I, Sayari A. Synthesis of mesoporous vanadium silicate molecular sieves. J Chem Soc Chem Commun. 1994;1059-1060. volume.
34. Zhao D, Goldfarb D. Synthesis of mesoporous manganosilicates: Mn-MCM-41, Mn-MCM-48 and Mn-MCM-L. J Chem Soc Chem Commun. 1995;875-876. volume.
35. Yuan ZY, Liu SQ, Chen TH, Wang JZ, Li HX. Synthesis of iron-containing MCM-41. J Chem Soc Chem Commun. 1995;973-974. volume.
36. Sayari A, Danumah C, Moudrakovski IL. Boron-modified MCM-41 mesoporous molecular sieves. Chem Mater. 7:(5):1995;813-815.
37. Borade RB, Clearfield A. Synthesis of aluminum rich MCM-41. Catal Lett. 31:1995;267-272.
38. Kloetstra KR, Zandbergen HW, van Bekkum H. MCM-41 type materials with low Si/Al ratios. Catal Lett. 33:1995;157-163.
39. Branton PJ, Hall PG, Sing KSW, Reichert H, Schüth F, Unger KK. Physisorption of argon, nitrogen and oxygen by MCM-41, a model mesoporous adsorbent. J Chem Soc Faraday Trans. 90:(19):1994;2965-2967. Detailed physisorption of argon, nitrogen and oxygen on mesoporous MCM-41 materials conclusively establish the type IV isotherm behavior for all three gases. The argon and oxygen isotherms exhibit hysteresis loops, whereas the nitrogen isotherm is completely reversible. The latter result was attributed to capillary condensation within a narrow range of tubular pores. of special interest.
40. Rathousky J, Zukal A, Franke O, Schulz-Ekloff G. Adsorption on MCM-41 mesoporous molecular sieves. Part 1. Nitrogen isotherms and parameters of the porous structure. J Chem Soc Faraday Trans. 90:(18):1994;2821-2826.
41. Branton PJ, Hall PG, Sing KSW. Physisorption of nitrogen and oxygen by MCM-41, a model mesoporous adsorbent. J Chem Soc Chem Commun. 1993;1257-1258. volume.
42. Llewellyn PL, Grillet Y, Schüth F, Reichert H, Unger KK. Effect of pore size on adsorbate condensation and hysteresis within a potential model adsorbent: M41S. Microporous Mater. 3:1994;345-349.
43. Schmidt R, Stöcker M, Hansen E, Akporiaye D, Ellestad OH. MCM-41: a model system for adsorption studies on mesoporous materials. Microporous Mater. 3:1995;443-448.
44. Franke O, Schulz-Ekloff G, Rathousky J, Stárek J, Zukal A. Unusual type of adsorption isotherm describing capillary condensation without hysteresis. J Chem Soc Chem Commun. 1993;724-726. volume.
45. 1H NMR. J Phys Chem. 98:(7):1994;1926-1928.
46. Llewellyn PL, Schüth F, Grillet Y, Rouquerol F, Ungel KK. Langmuir. 11:1995;574.
47. Rathousky J, Zukal A, Franke O, Schulz-Ekloff G. Adsorption on MCM-41 mesoporous molecular sieves. Part 2. Cyclopentane isotherms and their temperature dependence. J Chem Soc Faraday Trans. 91:(5):1995;937-940.
48. Armengol E, Cano ML, Corma A, Garcia H, Navarro MT. Mesoporous aluminosilicate MCM-41 as a convenient acid catalyst for Friedel-Crafts alkylation of a bulky aromatic compound with ciunamyl alcohol. J Chem Soc Chem Commun. 1995;519-520. volume.
49. Corma A, Martinez A, Martinez-Soria V, Montón JB. Hydrocracking of vacuum gasoil on the novel mesoporous MCM-41 aluminosilicate catalyst. J Catal. 153:1995;25-31. The large pore character of aluminosilicate MCM-41 is used to prepare a NiMo version for use in several catalytic reactions. In comparison with a zeolitic (USY) and amorphous silica-alumina with the same metal loadings, the NiMo-MCM-41 was shown to give superior desulfurization, denitrogenation and hydrocracking activity. A combination of large surface area, uniform pore-size distribution and reduced diffusion problems, combined with a required mild acidity were determined to be the beneficial characteristics. of special interest.
50. Kozhevnikov IV, Sinnema A, Jansen RJJ, Pamin K, van Bekkum H. New acid catalyst comprising heteropoly acid on a mesoporous molecular sieve MCM-41. Catal Lett. 30:1995;241-252.
51. +) ion incorporated in MCM-41 was used as a highly efficient electron-transfer material for the conversion of cis-stilbene to trans-stilbene. Improved results over zeolitic and amorphous hosts were demonstrated. of special interest.
52. Huber C, Moller K, Bein T. Reactivity of a trimethylstannyl molybdenum complex in mesoporous MCM-41. J Chem Soc Chem Commun. 1994;2619-2620. volume.
53. Wu CG, Bein T. Polyaniline wires in oxidant-containing mesoporous channel hosts. Chem Mater. 6:(8):1994;1109-1112.
54. Wu CG, Bein T. Conducting polyaniline filaments in a mesoporous channel host. Science. 264:1994;1757-1759. A very interesting concept of encapsulating conducting polymers into mesoporous silicates to effect the formation of silicate encased nano-wires is explored. Conducting filaments of polyaniline were prepared by adsorption of aniline vapor into the mesoporous host followed by oxidation with peroxydisulfate. The filaments were demonstrated to have significant conductivity while encapsulated in the channels. of special interest.
55. Llewellyn PL, Ciesla U, Decher H, Stadler R, Schüth F, Unger K, Pfeifer H, Hölderich W. MCM-41 and related materials as media for controlled polymerization processes. Weitkamp J, Karge HG. Zeolites and Related Microporous Materials: State of the Art 1994, Stud in Surf Sci and Catal 1994. Processings of the 10th International Zeolite Conference Garmisch-Partenkirchen Germany 1994. 84:1994;2013 Elsevier Science, Amsterdam. This work demonstrates that mesoporous silicates can be used for the controlled polymerization of styrene, methylmethacrylate and vinyl acetate It was observed that the properties of the polymerized guests varied with the degree of confinement (40 Å versus 25 S̊ pores). An increase in the average molecular mass of polymethylmethacrylate was observed with an increase in confinement on polymerization. It was suggested that the increase in confinement leads to a smaller quantity of growing polymer chains which are unable to interact resulting in the formation of longer chains. The work has substantial implications for the use of mesophase control in the design of polymer structure and molecular weight. It is interesting to note that a mesoporous silicate, which itself has been templated via an organic array, may subsequently serve as an inorganic template for the production of shape/size controlled organic species. of special interest.