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Investigating the effect of randomly methylated β-cyclodextrin/block copolymer molar ratio on the template-directed preparation of mesoporous alumina with tailored porosity

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Abstract

Supramolecular assemblies formed between cyclodextrins and block copolymers can be efficiently used as templates for the preparation of mesoporous materials with controlled porosity. In this work, we use dynamic light scattering (DLS) and viscosity measurements to follow the variations occurring in the size and morphology of the triblock copolymer poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (P123) micelles in the presence of various amounts of randomly methylated β-cyclodextrin (RAMEB). The results obtained with a series of solution compositions reveal that the cyclodextrin-to-copolymer (RAMEB/P123) molar ratio plays a crucial role in the growth rate of the micelles. At low RAMEB/P123 molar ratios (below ~7.5), a swelling effect of the cyclodextrin in the P123 micelles is noticed together with a modification of the micellar curvature from spherical to ellipsoidal. At high molar ratios (~7.5 and above), an abrupt transition toward large supramolecular assemblies, which no longer resemble micelles, occurs. When the RAMEB-swollen P123 micelles are used as templates to direct the self-assembly of colloidal boehmite nanoparticles, mesoporous γ-Al2O3 materials with high surface areas (360–400 m2/g), tunable pore sizes (10–20 nm), large pore volumes (1.3–2.0 cm3/g) and fiberlike morphologies are obtained under mild conditions. The composition of the mixed micellar solution, in particular the cyclodextrin-to-copolymer molar ratio, appears to be a key factor in controlling the porosity of alumina.

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Acknowledgments

The TEM facility in Lille (France) is supported by the Conseil Regional du Nord-Pas de Calais and the European Regional Development Fund (ERDF). The ERDF, CNRS, Région Nord Pas-de-Calais and Ministère de l’Education Nationale de l’Enseignement Supérieur et de la Recherche are acknowledged for fundings of the X-ray diffractometer. We thank Laurence Burylo (UCCS, University of Lille) as well as Dominique Prevost (UCCS, Artois) for technical assistance in XRD measurements and gravimetric analyses respectively.

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Authors and Affiliations

  1. Université Lille Nord de France, 59000, Lille, France

    Rudina Bleta, Cécile Machut, Bastien Léger, Eric Monflier & Anne Ponchel

  2. UArtois, UCCS, Faculté des Sciences Jean Perrin, Rue Jean Souvraz, SP 18, 62307, Lens, France

    Rudina Bleta, Cécile Machut, Bastien Léger, Eric Monflier & Anne Ponchel

  3. CNRS, UMR 8181, 59650, Villeneuve d’Ascq, France

    Rudina Bleta, Cécile Machut, Bastien Léger, Eric Monflier & Anne Ponchel

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  1. Rudina Bleta
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Correspondence to Rudina Bleta.

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Bleta, R., Machut, C., Léger, B. et al. Investigating the effect of randomly methylated β-cyclodextrin/block copolymer molar ratio on the template-directed preparation of mesoporous alumina with tailored porosity. J Incl Phenom Macrocycl Chem 80, 323–335 (2014). https://doi.org/10.1007/s10847-014-0405-7

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