Do-Young Hong1, Young Kyu Hwang2, You-Kyung Seo2, Sung Hwa Jhung3, Christian Serre4, Gerard Ferey4, and Jong-San Chang2. (1) School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive NW, Atlanta, GA 30332, (2) Catalysis Center for Molecular Engineering, Korea Research Institute of Chemical Technology, Yuseong, 305-600, Daejon, South Korea, (3) Department of Chemistry, Kyungpook National University, 1370 Sankyuk-dong, Buk-gu, Daegu, South Korea, (4) Institut Lavoisier (UMR 8180), Université de Versailles Saint Quentin-en-Yvelines, 45 avenue des Etats-Unis, 78035, Versailles Cedex, France
In porous hybrid materials, the existence of coordinatively unsaturated metal sites (CUS) is very beneficial since these sites can strongly interact with guest molecules such as gases and organic molecules in adsorption and catalysis. The CUS in MIL-101, the chromium(III) terephthalate with zeotypic giant pores, can be selectively functionalized, in a way differing from the functionalization of mesoporous silica and porous hybrids reported so far. This work reports catalytic activities in MOF, grafted with ethylene diamine (ED) and diethylene triamine (DETA) on the CUS Cr(III) of MIL-101. They exhibit remarkably high activities in the Knoevenagel condensation compared to that of the mesophase. ED-grafted MIL-101, a size-selective molecular sieve catalyst, is also able to encapsulate noble metals (Pd, Pt, and Au). In particular, the Pd-loaded MIL-101 catalyses the Heck coupling reaction, with a high activity comparable with that of a commercial Pd/C catalyst.