Stabilizing the extrinsic porosity in metal-organic cages-based supramolecular framework by in situ catalytic polymerization

Abstract

Porous supramolecular frameworks based on metal-organic cages (MOCs) usually have poor structural stability after activation. This issue narrows the scope of their potential applications, particularly for the inclusion of guest molecules that demand high porosity. Herein, the authors have reported the stabilization of a mesoporous zirconium MOC-based supramolecular framework with an in situ catalytic polymerization strategy. Due to the passivation effect imparted by this strategy, the introduced polymer is primarily distributed on the surface of the crystals, which results in the hybrid material retaining its crystallinity and permanent porosity. A preliminary application of this type of stabilized mesoporous supramolecular framework shows that among MOC-based supramolecular frameworks, it has the highest high-pressure methane uptake. Such a facile strategy may provide a general way to stabilize fragile porous materials and facilitate exploration of their potential applications.