Stable polyoxometalate insertion within the mesoporous metal organic framework MIL-100(Fe)

Romain Canioni; Catherine Roch-Marchal; Francis Sécheresse; Patricia Horcajada; Christian Serre; Menaschi Hardi-Dan; Gérard Férey; Jean-Marc Grenèche; Frédéric Lefebvre; Jong-San Chang; Young-Kyu Hwang; Oleg Lebedev; Stuart Turner; Gustaaf Van Tendeloo

doi:10.1039/C0JM02381G

Stable polyoxometalate insertion within the mesoporous metal organic framework MIL-100(Fe)†

Romain Canioni,^a Catherine Roch-Marchal,*^a Francis Sécheresse,^a Patricia Horcajada,*^a Christian Serre,^a Menaschi Hardi-Dan,^a Gérard Férey,^a Jean-Marc Grenèche,^b Frédéric Lefebvre,^c Jong-San Chang,^d Young-Kyu Hwang,^d Oleg Lebedev,^e Stuart Turner^f and Gustaaf Van Tendeloo^f

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* Corresponding authors

^a I.L.V., Institut Lavoisier de Versailles, UMR 8180, Université de Versailles-St Quentin en Yvelines, 45 Avenue des États-Unis, Versailles Cedex, France
E-mail: Roch@chimie.uvsq.fr, horcajada@chimie.uvsq.fr.
Fax: +33(1)39254388
Tel: +33(1)39254381

^b Laboratoire de Physique de l'Etat Condensé LPEC, UMR CNRS 6087, Université du Maine, Avenue Olivier Messiaen, LE MANS Cedex France

^c Laboratoire C2P2, Equipe de Chimie Organométallique de Surface, LCOMS, UMR 526, CPE Lyon, 43 Bd du 11 Novembre 1918, Villeurbanne cedex, France

^d Catalysis Center for Molecular Engineering, Korea Research Institute of Chemical Technology (KRICT), P.O. Box 107, Yuseong, Daejeon, Republic of Korea

^e Laboratoire CRISMAT, UMR 6508 CNRS/ENSICAEN, 6 bd du Maréchal Juin, CAEN, Cedex 4 - France

^f Electron Microscopy for Materials Research (EMAT), University of Antwerp, Groenenborgerlaan 171, Antwerpen, Belgium

Abstract

Successful encapsulation of polyoxometalate (POM) within the framework of a mesoporous iron trimesate MIL-100(Fe) sample has been achieved by direct hydrothermal synthesis in the absence of fluorine. XRPD, ³¹P MAS NMR, IR, EELS, TEM and ⁵⁷Fe Mössbauer spectrometry corroborate the insertion of POM within the cavities of the MOF. The experimental Mo/Fe ratio is 0.95, in agreement with the maximum theoretical amount of POM loaded within the pores of MIL-100(Fe), based on steric hindrance considerations. The POM-MIL-100(Fe) sample exhibits a pore volume of 0.373 cm³ g⁻¹ and a BET surface area close to 1000 m² g⁻¹, indicating that small gas molecules can easily diffuse inside the cavities despite the presence of heavy phosphomolybdates. These latter contribute to the decrease in the overall surface area, due to the increase in molar weight, by 65%. Moreover, the resulting Keggin containing MIL-100(Fe) solid is stable in aqueous solution with no POM leaching even after more than 2 months. In addition, no exchange of the Keggin anions by tetrabutylammonium perchlorate in organic media has been observed.

Journal of Materials Chemistry

Stable polyoxometalate insertion within the mesoporous metal organic framework MIL-100(Fe)†

Abstract

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Stable polyoxometalate insertion within the mesoporous metal organic framework MIL-100(Fe)

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