Continuous synthesis for zirconium metal-organic frameworks with high quality and productivity via microdroplet flow reaction

Zirconium metal-organic frameworks(Zr-MOFs) represent the most promising candidates among MOFs for industrial utilizations owing to their high porosity and excellent stability. However, the efficient synthesis of Zr-MOFs combining with continuous production, high productivity and good product quality still remains a critical issue for practical applications. Herein, we report an efficient method of synthesizing a series of Zr-MOFs through a microdroplet flow reaction, which is more accommodate the requirements of industrial production. Four types of Zr-based MOFs with different ligands and topologies(MOF-801, MOF-804, DUT-67 and MOF-808) were produced as a pure phase of high quality crystalline with uniform morphologies. Furthermore, this series of Zr-MOFs were obtained in a continuous way and at a space-time yield(STY) highly up to 367.2 kg m~(-3) d~(-1). These MOFs exhibit the similar pore structure and thermal stability with that prepared from conventional solvothermal synthesis. CO_2 sorption studies on these MOFs demonstrate that the hydroxyl groups on ligand can render MOFs with high CO_2/N_2 selectivity.