MICROPORODS MATERIALS

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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 [5]. 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
Corresponding author. 0927-6513/97/$17.00 1997 Elsevier Science BY All rights reserved. PII S0927-6513(97)00028-X

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 [12]. 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 [13], 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

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F. Di Ren::o et al. ! Microporous Materials 10 ( 1997) 283-286

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bromide (Aldrich) was dissolved in 42 g of ammonia solution (28%). After addition of 9 g of tetraethylorthosilicate (Aldrich), the mixture was stirred at room temperature for 90 min before being heated at 70"C. The solid product was characterized by powder X-ray diffraction and N 2 adsorption at 77 K after calcination, and by transmission electron microscopy (TEM). The X-ray powder diffraction pattern of the solid. after calcination at 550C in an air flow, is reported in Fig. 1(a). The solid features a main peak at 39.3 A and two weaker signals which can be indexed on a hexagonal cell with a=45.3 A. The presence of several well-defined peaks is considered as a test for long-range ordering of the pores in the MCM-41 material. This result is supported by the TEM observation of the precipitation product (Fig. 1(b )), which reveals a neat honeycomb pattern. The N 2 adsorption isotherm at 77 K on the calcined solid is reported in Fig. 1(c). The reversible type-IV isotherm features a sharp step at PI pO = 0.32, indicating a narrow distribution of mesopores centered around a diameter of 32 A. The measured mesopore volume is 0.61 cm 3 g-l, and the t-plot reveals no micropore volume. All these data indicate that the material prepared according to the recipe of Chiola et al. [1] features the characteristic properties of well-ordered MCM-41 hexagonal mesoporous silica [2]. The low-density material of Chiola et al. is not only a forerunner of MCM-41 silica, but also of surfactant-templated materials of different composition [14]. The 1971 patent relates the application of the synthesis method to the manufacture of doped zinc orthosilicate phosphors. The history of micelle-templated mesoporous silica follows a pattern which is not rare in the history of discoveries. Columbus cannot be disavowed as the discoverer of America, although Leif Ericsson preceded him by several centuries. The latter had a priority on the discovery, but he failed to realize, and surely did not claim in widespread reports, the nature and the implications of his finding. As a consequence, the independent research of the second discoverer was needed to spread the knowledge of a new world properly. A similar pattern has often been observed in materials science [15], a recent example being represented

by the history of the VPI-5 aluminophosphate molecular sieve [16]. The presence of forerunners, unknown outside a restricted field of application, 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. Nevertheless, such a situation can seriously affect a research community characterized by solid connections between fundamental and applied science. Do we have to rejoice at the prospect of treasures hidden in old literature, or complain about the risk that claims for priority can be impaired?

Acknowledgment The authors thank D. Plee for useful discussions, and F. Fajula for his constant support.

References
[I] V. Chiola, J.E. Ritsko, e.D. Vanderpool, US Patent 3556725, 1971. [2] J.S. Beck, e.T.-W. Chu. I.D. Johnson, e.T. Kresge. M.E. Leonowicz, W.J. Roth, J.W. Vartuli, WO Patent 91/11390,1991. [3] e.T. Kresge, M.E. Leonowicz, W.J. Roth. J.e. Vartuli, J.S. Beck, Nature 359 (1992) 710. [4] J.S. Beck. J.e. Vartuli, W.J. Roth. M.E. Leonowiz, e.T. Kresge, K.D. Schmitt, e.T.-W. Chu. D.H. Olson. E.W. Sheppard. S.B. McCullen. J.B. Higgins, J.L. Schlenker, J. Am. Chern. Soc. 114 (1992) 10834. [5] D.E.W. Vaughan, in: P.A. Jacobs, R.A. van Santen (Eds.l. Zeolites: Facts. Figures, Future. Studies in Surface Science and Catalysis. vol. 49, part A. Elsevier, Amsterdam, 1989, p. 95. [6] S. Inagaki, Y. Fukushima, K. Kuroda, J. Chern. Soc., Chern. Commun. (1993) 680. [7] e.-Y. Chen, S.L. Burkett, H.-X. Li, M.E. Davis. Microporous Mater. 2 (1993) 27. [8] e.A. Fyfe, G. Fu. J. Am. Chern. Soc. 117 (\995\ 9709. [9] A. Firouzi. D. Kumar, L.M. Bull. T. Besier. P. Sieger. Q. Huo, S.A. Walker, JA. Zasadzinski, e. Glinka. J. Nicol, D. Margolese, G.D. Stucky, B.F. Chmelka, Science 267 (\ 995) 1138. [10] G.D. Stucky. Q. Huo, A. Firouzi, B.F. Chmelka, S. Schacht. I.G. Voigt-Martin, F. Schuth. in: H. Chon, S.-K. Ihm. V.S. Uh (Eds.), Progress in Zeolite and Microporous Materials, Studies in Surface Science and Catalysis. vol. lOS, part A. Elsevier. Amsterdam, 1997. p. 3. [II] B.H. Bijsterbosch. J. Colloid Interface Sci. 51 (1975) 212.

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[12] R.K. Iter, US Patent 2663650, 1953. [13] R.K. IIer, The Chemistry of Silica, Wiley. New York 1971, p. 562. [14] Q. Huo, D.1. Margolese, U. Ciesla, P. Feng, T.E. Gier. P. Sieger, R. Leon. P.M. Petroff, F. Schuth, G.D. Stucky, Nature 368 (1994) 317.

[15] A.I. Ihde, The Development of Modern Chemistry, Dover, New York, 1964. [16] I.-P. Gilson, in: E.G. Derouane, F. Lemos, C. Naccache, F.R. Ribeiro, (Eds.), Zeolite Microporous Solids: Synthesis. Structure, and Reactivity, Kluwer, Dordrecht, 1992. p. 19.