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Microporous Materials 10 (1997) 283-286
A 28-year-old synthesis of micelle-templated mesoporous silica
Francesco Di Renzo *, Helene Cambon, Roger Dutartre
Laboratoire de Materiaux Catalytiques et Catalyse en Chimie Organique. UMR 5618 CNRS, ENSCM, 8 rue de i'Ecole Normale, 34296 Montpellier, Cedex 5. France
Received 11 March 1997; accepted 17 March 1997
Abstract A procedure for the preparation of low-density silica described in a patent filed in 1969 [V. Chiola, J.E. Ritsko, CD. Vanderpool, US Patent 3556725, 1971] leads to the formation of solids having all the properties of MCM-41, the ordered mesoporous silica disclosed in 1991 [J.S. Beck, CT.-W. Chu, I.D. Johnson, CT. Kresge, M.E. Leonowicz. W.J. Roth. J.W. Vartuli, WO Patent 91/11390, 1991].~' 1997 Elsevier Science B.V.
Keywords: Cetyltrimethylammonium; MCM-41; Mesopores; Silica; Synthesis
M41 mesoporous silicas present pores of uniform size obtained by the self-assembly of a soluble silicate and surfactant micelles. The disclosure of their properties by the scientists of Mobil [3,4] fullfilled a long-term expectation of researchers in catalysis and adsorption, and extended to the mesopore range the applications of molecular sieving, formerly limited to microporous zeolites . The importance of this breakthrough is evidenced by the wave of research activities on the selfassembly of inorganic materials and micelles which it initiated [6-10]. Recent literature reports indicate that MCM-4L the hexagonal member of the micelle-templated mesoporous silica group, can be synthesized in a wide range of experimental conditions. Interactions between silica and cationic surfactants have been studied intensively in recent decades [II], and we wondered why no MCM-41 forerunner
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had been formed in early experiments. In several early studies, the strong adsorption of surfactant micelles on the surface of silica particles was applied to control of the flocculation of colloidal silica . If the surfactant is added to a soluble silicate instead of being adsorbed on the surface of pre-formed grains, MCM-41 is the more likely condensation product. We looked for a description of such a process in the early literature, and found that lIer, in his classical book on silica , reports on a patent of 1971 of V. Chiola et al. [I] assigned to Sylvania Electric Products Inc., in which tetraethylorthosilicate is hydrolyzed and condensed in the presence of a cationic surfactant to form "Iowbulk density silica". The patent does not report on the characterization of the precipitation product beyond its bulk density, and we prepared a solid according to the specifications of the patent in order to evaluate its properties. In a reproduction of example I of the patent of Chiola et al., 8.3 g of cetyltrimethylammonium
3 121.-(j 00 E OJ 45121 400 350 :a: ..B Relative pressure. "0 £ 300 250 '" OJ '" ~ E 200 15121 11~0 5121 0 0..0 ----+ 4 5 6 b 600 550 500 c .5 111. 1 QI.6 111.. ! Microporous Materials 10 ( 1997) 283-286 a f .0 ~I. Di Ren::o et al. 1. transmission electron microscopy (b). Powder X-ray diffraction (a).284 F. [I].7 I1I. ..4 121.. and nitrogen adsorption isotherm (c) of the micelletemplated mesoporous silica prepared according to the patent of Chiola et a1.--~----------2 3 degree 20. P/P o Fig.0 .
3 A and two weaker signals which can be indexed on a hexagonal cell with a=45. Firouzi.A. W. although Leif Ericsson preceded him by several centuries. Huo. Beck. The solid features a main peak at 39.W. Schlenker. part A. e. e. Stucky. Am. the mixture was stirred at room temperature for 90 min before being heated at 70"C. unknown outside a restricted field of application. and F.E. Nevertheless. The X-ray powder diffraction pattern of the solid.W. Beck. Chern.T.F. I. Science 267 (\ 995) 1138.G. McCullen. Glinka. Bull.e. A similar pattern has often been observed in materials science . T.l. in: P.-W. 1(b )). S. and by transmission electron microscopy (TEM). Vanderpool.-X. Nature 359 (1992) 710. 114 (1992) 10834. Voigt-Martin.S. S. Schmitt. Studies in Surface Science and Catalysis.A. Leonowiz. the independent research of the second discoverer was needed to spread the knowledge of a new world properly. [II] B. E. Q.M. 1971. Kuroda. Sheppard. Chiola.61 cm 3 g-l.J. S.-K. Am.  features the characteristic properties of well-ordered MCM-41 hexagonal mesoporous silica . 1997. 1(c). Leonowicz. M. J. Colloid Interface Sci..D. G. L. WO Patent 91/11390. Chern.H. Zasadzinski.). Fyfe. Progress in Zeolite and Microporous Materials. 95. Fajula for his constant support. vol. 3. Kumar. The solid product was characterized by powder X-ray diffraction and N 2 adsorption at 77 K after calcination.T.S. The history of micelle-templated mesoporous silica follows a pattern which is not rare in the history of discoveries. J. e. Leonowicz. I.J. Kresge. is not only a forerunner of MCM-41 silica. in: H.  J. Walker. Plee for useful discussions. e.T.A. .E. Besier. J. S. Fu. The presence of several well-defined peaks is considered as a test for long-range ordering of the pores in the MCM-41 material. Nicol. The measured mesopore volume is 0. 1(a).32. P.E. Y. Vartuli. Chmelka. R. K. Jacobs.-W.E. Microporous Mater.B.  G. by no means decreases the value of the characterization and modelling which make the results available to a wider community and fertile for further research. or complain about the risk that claims for priority can be impaired? Acknowledgment The authors thank D. Ritsko. J. 1989. Chern. Elsevier.e. J. Chon. Firouzi.L. Davis. and surely did not claim in widespread reports. Commun. Future. Chmelka. Roth.B.F Di Ren::o et at. (1993) 680. the nature and the implications of his finding. After addition of 9 g of tetraethylorthosilicate (Aldrich). 51 (1975) 212. a recent example being represented by the history of the VPI-5 aluminophosphate molecular sieve . D. Zeolites: Facts. e. 117 (\995\ 9709. Chu.E. Amsterdam.T. but also of surfactant-templated materials of different composition . M.S. The presence of forerunners. Soc. Figures. Inagaki.3 A. Li. A. and the t-plot reveals no micropore volume. J. Uh (Eds.J. lOS. Higgins. JA. B. Burkett. J. Beck. J. Chern.D.  e. such a situation can seriously affect a research community characterized by solid connections between fundamental and applied science. vol. Chen. Q.E.  S. K. D. Ihm.W. Margolese. / Microporous Materials 10 ( 1997) 283-286 285 bromide (Aldrich) was dissolved in 42 g of ammonia solution (28%). The N 2 adsorption isotherm at 77 K on the calcined solid is reported in Fig. Johnson.1991. 2 (1993) 27. Roth. part A.A. Huo. Soc. The reversible type-IV isotherm features a sharp step at PI pO = 0.D. Columbus cannot be disavowed as the discoverer of America. References [I] V.  J. Schuth. All these data indicate that the material prepared according to the recipe of Chiola et al. after calcination at 550°C in an air flow. p.  D. This result is supported by the TEM observation of the precipitation product (Fig. Roth. B.-Y. is reported in Fig. Elsevier. J. Bijsterbosch. Kresge. Amsterdam. Stucky.  e. D.D. indicating a narrow distribution of mesopores centered around a diameter of 32 A. J. V. van Santen (Eds. 49.H. W. F.  A. J. M.S. H. Sieger. e. Schacht. Olson.T. S. Vartuli. which reveals a neat honeycomb pattern.F. W. Soc. Fukushima.D. Chu. J. Do we have to rejoice at the prospect of treasures hidden in old literature. Vartuli. but he failed to realize. G. Vaughan. p.  e. Kresge. US Patent 3556725. The 1971 patent relates the application of the synthesis method to the manufacture of doped zinc orthosilicate phosphors. Studies in Surface Science and Catalysis.L. M. The latter had a priority on the discovery. As a consequence. The low-density material of Chiola et al.
Sieger. Feng. Margolese. Gier. New York 1971. 1953. Huo. (Eds. Stucky. Wiley.1.D. Naccache. The Chemistry of Silica. Ribeiro. Schuth. IIer. 19. R. The Development of Modern Chemistry. ! Microporous Materials 10 ( 1997) 283-286  R. C. G. Kluwer. Nature 368 (1994) 317. D. US Patent 2663650.-P. New York. Gilson. Ciesla.  I. T. 562.  Q.).  A.K. Leon. Derouane. . 1964. P. F.E. Lemos. P.286 F Di Renzo et al. Petroff.K. Zeolite Microporous Solids: Synthesis.I. in: E. U.M. P. Ihde. Dordrecht. Dover.G. 1992.  R. and Reactivity. p. p. F. Iter. Structure. F.R.
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