Solid-State Synthesis of Defect-Rich Zr-UiO-66 Metal–Organic Framework Nanoparticles for the Catalytic Ring Opening of Epoxides with Alcohols

Perfect crystals do not exist; however, the introduction of defects can tailor the physical and chemical properties of materials. Defects in metal–organic frameworks (MOFs) have been demonstrated to be important in many applications, including but not limited to catalysis, gas separation, and energy storage. While a few liquid-phase synthesis methods have been reported to prepare defect-rich UiO-66, the heavy use of organic solvents may cause irreversible environmental problems. Here, we present a green, rapid, and facile solid-state synthesis approach to prepare UiO-66. All UiO-66 crystals remain in the nanometer size due to the limited diffusivity of growth species in solid-state synthesis without a large quantity of the solvent. The defect concentrations can be fine-tuned by the content of ethanol addition. Defect-rich UiO-66 shows excellent catalytic activity to the ring opening of epoxides with alcohols. This work provides insights into the large-scale production of defect-rich MOFs.