Controlling Size, Defectiveness, and Fluorescence in Nanoparticle UiO-66 through Water and Ligand Modulation

Abstract

UiO-66, a zirconium(IV) metal-organic framework (MOF) comprised of six-metal clusters and terephthalic acid ligands, displays excellent thermal and chemical stability and has functions in gas storage, catalysis, selective adsorption, and drug delivery. Though the stability of UiO-66 is highly advantageous, simultaneous synthetic control over particle size and defectiveness of UiO-66 remains difficult to attain. Using an acid-free solvothermal synthesis, we demonstrate that particle size, defectiveness, and inherent fluorescence of UiO-66 can be precisely tuned using the molar ligand to metal ratio, quantified water content, and reaction time during synthesis. These three synthetic handles allow for reproducible modulation of UiO-66 defectiveness between 0 and 12% and particle size between 20 to 120 nm, while maintaining high crystallinity in the nanoparticles that were formed. We also find that particle defectiveness is linked to common over-estimation of particle size measurements obtained via dynamic light scattering (DLS) and propose a model to correct elevated hydrodynamic diameter measurements. Finally, we report inherent fluorescence of non-functionalized UiO-66, which exhibits peak fluorescence at a wavelength of 390 nm following excitation at 280 nm and is maximized in large, defect-free particles. Overall, this synthetic approach and characterization of defect, size, and fluorescence represent new opportunities to tune the physiochemical properties of UiO-66.