Metal-organic frameworks (MOFs) have been utilized for a number of applications ranging from gas storage to biomedicine. Tunability of the ligand and metal source has created a library of non-toxic carrier systems whose particle size can be adjusted through various synthetic conditions. For certain biomedical applications, such as targeting delivery to the lungs, particle size control is key. One potentially non-toxic framework whose particle size has been studied is UiO-66. In this material, particle size control can be achieved through the use of acid modulation. However, utilization of acids, such as hydrochloric or formic, typically induces defects into the structure. To address this, we targeted modulator free synthesis of UiO-66, using rigorous control of water and ligand to metal ratio in the reaction mixture to simultaneously tune particle size and defectiveness. This modulator free synthesis has shown to yield extremely crystalline material, as confirmed by powder X-ray diffraction. Gas adsorption, TGA methods, and NMR spectroscopy indicate this route can be used to afford defect-free nanoparticle materials. SEM imaging indicates the presence of ~ 20 to 125 nm particles. A correlation between particle size and porosity has been established as observed by DLS. Furthermore, formation kinetics experiments shed light on changes in defectiveness and particle size as a function of reaction time.

Particle size and defect control in nanoparticulate UiO-66 via modulator-free synthetic conditions

2019 Fall National Meeting

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