Synthesis and photochemical modification of monolayer thin MOF flakes for incorporation in defect free polymer composites

Metal-organic frameworks (MOFs) with benzophenone linker molecules are characterized by their ability to undergo photochemical postsynthetic modification. While this approach opens up almost unlimited possibilities for tailoring materials to specific applications, the processability of the large particles is still lacking. In this work, we present a new approach to fabricate micro flakes of the stable Zr-bzpdc-MOF (bzpdc = benzophenone-4-4 & PRIME;-dicarboxylate) with a thickness of only a few monolayers. The crystalline and nanoporous flakes form dispersions in acetone that are stable for months. Embedding the flakes in polymer composites was investigated as one of many possible applications. Zr-bzpdc-MOF micro flakes were decorated with poly(dimethylsiloxane) (PDMS) via a photochemical postsynthetic modification and incorporated into silicon elastomers. The PDMS functionalization allows covalent cross-linking between the MOF and the polymer while maintaining the porosity of the MOF. The resulting hybrid materials provide defect-free interfaces and show preferential adsorption of CO2 over CH4, making them attractive for gas separation or sensing applications. The work should serve as a basis for bringing bzpdc-MOFs into real-world applications - in polymeric membranes, but also beyond. Monolayer thin flakes of a photoreactive Zr-based MOF with benzophenone linker molecules are synthesized. Subsequent photochemical modification allows the incorporation into defect-free polymer composites showing preferred adsorption of CO2 over CH4.