Armored MOFs: Enforcing Soft Microporous MOF Nanocrystals with Hard Mesoporous Silica

Metal-organic frameworks (MOFs) are a class of fascinating supramolecular soft matters but with relatively weak mechanical strength. To enforce MOF materials for practical applications, one possible way seems to be transforming them into harder composites with a stronger secondary phase. Apparently, such a reinforcing phase must possess larger porosity for ionic or molecular species to travel into or out of MOFs without altering their pristine physicochemical properties. Herein we report a general synthetic approach to coat microporous MOFs and their derivatives with an enforcing shell of mesoporous silica (mSiO2). Four well-known MOFs (ZIF-8, ZIF-7, UiO-66, and HKUST-1), representing two important families of MOFs, have served as a core phase in nanocomposite products. We show that significant enhancement in mechanical properties (hardness and toughness) can indeed be achieved with this "armoring approach". Excellent accessibility of the mSiO2-wrapped MOFs and their metal-containing nanocomposites has also been demonstrated with catalytic reduction of 4-nitrophenol.