Publications

Rare-earth polynuclear metal–organic frameworks (RE-MOFs) have demonstrated high durability for caustic acid gas adsorption and separation based on gas adsorption to the metal clusters. The metal clusters in the RE-MOFs traditionally contain RE metals bound by μ₃–OH groups connected via organic linkers. Recent studies have suggested that these hydroxyl groups could be replaced by fluorine atoms during synthesis that includes a fluorine-containing modulator. Here, a combined modeling and experimental study was undertaken to elucidate the role of metal cluster fluorination on the thermodynamic stability, structure, and gas adsorption properties of RE-MOFs. Through systematic density-functional theory calculations, fluorinated clusters were found to be thermodynamically more stable than hydroxylated clusters by up to 8–16 kJ/mol per atom for 100% fluorination. The extent of fluorination in the metal clusters was validated through a ¹⁹F NMR characterization of 2,5-dihydroxyterepthalic acid (Y-DOBDC) MOF synthesized with a fluorine-containing modulator. ¹⁹F magic-angle spinning NMR identified two primary peaks in the isotropic chemical shift (δ_iso) spectra located at -64.2 and -69.6 ppm, matching calculated ¹⁹F NMR δ_iso peaks at -63.0 and -70.0 ppm for fluorinated systems. Calculations also indicate that fluorination of the Y-DOBDC MOF had negligible effects on the acid gas (SO₂, NO₂, H₂O) binding energies, which decreased by only ~4 kJ/mol for the 100% fluorinated structure relative to the hydroxylated structure. Additionally, fluorination did not change the relative gas binding strengths (SO₂ > H₂O > NO₂). Therefore, for the first time the presence of fluorine in the metal clusters was found to significantly stabilize RE-MOFs without changing their acid-gas adsorption properties.

Barium titanate (BTO) nanoparticles show great potential for use in electrostatic capacitors with high energy density. This includes both polymer composite and sintered capacitors. However, questions about the nanoparticles' size distribution, amount of agglomeration, and surface ligand effect on performance properties remain. Reducing particle agglomeration is a crucial step to understanding the properties of nanoscale particles, as agglomeration has significant effects on the composite dielectric constant. BTO surface functionalization using phosphonic acids is known reduce BTO nanoparticle agglomeration. We explore solution synthesized 10 nm BTO particles with tert-butylphosphonic acid ligands. Recent methods to quantifying agglomeration using an epoxy matrix before imaging shows that tert-butylphosphonic acid ligands reduce BTO agglomeration by 33%. Thermometric, spectroscopic, and computational methods provide confirmation of ligand binding and provide evidence of multiple ligand binding modes on the BTO particle surface.