Steric stabilization of colloidal UiO-66 nanocrystals with oleylammonium octadecylphosphonate.

We report the synthesis and characterization of octahedral UiO-66 nanocrystals (d = 17-25 nm) terminated with amine, oleate, and octadecylphosphonate ligands. Acetate capped UiO-66 nanocrystals were dispersed in toluene using oleic acid and oleylamine. Ligand exchange with octadecylphosphonic acid produces ammonium octadecylphosphonate terminated nanocrystals with coverages of 2.6-3.2 chains per nm2 that stabilize colloidal dispersions in nonpolar solvents. Liquid phase 1H and 31P nuclear magnetic resonance (NMR) spectra of the linkers and surface ligands display line shapes that are broadened by slow tumbling of the nanocrystals. Octadecylphosphonate functionalized MOFs have up to ∼30% carbon dioxide absorption capacities compared to bulk UiO-66 after correcting for the ligand mass. These results illustrate the intriguing perspective that MOF nanocrystals can be characterized and manipulated like a macromolecular complex and represent an important milestone in the nascent field of MOF surface science.