Publications

Direct air capture (DAC) of CO₂ is one of the negative emission technologies under development to limit the impacts of climate change. The dilute concentration of CO₂ in the atmosphere (~400 ppm) requires new materials for carbon capture with increased CO₂ selectivity that is not met with current materials. Porous liquids (PLs) are an emerging material that consist of a combination of solvents and porous hosts creating a liquid with permanent porosity. PLs have demonstrated excellent CO₂ selectivity, but the features that control how and why PLs selectively capture CO₂ is unknown. To elucidate these mechanisms, density functional theory (DFT) simulations were used to investigate two different PLs. The first is a ZIF-8 porous host in a water/glycol/2-methylimidazole solvent. The second is the CC13 porous organic cage with multiple bulky solvents. DFT simulations identified that in both systems, CO₂ preferentially bound in the pore window rather than in the internal pore space, identifying that the solvent-porous host interface controls the CO₂ selectivity. Additionally, SNL synthesized ZIF-8 based PL compositions. Evaluation of the long-term stability of the PL identified no change in the ZIF-8 crystallinity after multiple agitation cycles, identifying its potential for use in carbon capture systems. Through this project, SNL has developed a fundamental understanding of solvent-host interactions, as well as how and where CO₂ binds in PLs. Through these results, future efforts will focus not on how CO₂ behaves inside the pore, but on the porous host-solvent interface as the driving force for PL stability and CO₂ selectivity.

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.

Understanding the selectivity of metal–organic frameworks (MOFs) to complex acid gas streams will enable their use in industrial applications. In this study, ab initio molecular dynamic simulations (AIMD) were used to simulate ternary gas mixtures (H₂O-NO₂-SO₂) in rare earth 2,5-dihydroxyterephthalic acid (RE-DOBDC) MOFs. Stronger H₂O gas-metal binding arose from thermal vibrations in the MOF sterically hindering access of SO₂ and NO₂ molecules to the metal sites. Gas-gas and gas-linker interactions within the MOF framework resulted in the formation of multiple secondary gas species including HONO, HNO₂, NOSO, and HNO₃⁻. Four gas adsorption sites were identified along with a new de-protonation reaction mechanism not observable through experiment. This study not only provides valuable information on competitive gas binding energies in the MOF, but it also provides important chemical insights into transient chemical reactions and mechanisms.