Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature

Metal-organic frameworks (MOFs) show high CO2 storage capacity at room temperature. Gravimetric CO2 isotherms for MOF-2, MOF-505, Cu3(BTC)2, MOF-74, IRMOFs-11, -3, -6, and -1, and MOF-177 are reported up to 42 bar. Type I isotherms are found in all cases except for MOFs based on Zn4O(O2C)6 clusters, which reveal a sigmoidal isotherm (having a step). The various pressures of the isotherm steps correlate with increasing pore size, which indicates potential for gas separations. The amine functionality of the IRMOF-3 pore shows evidence of relatively increased affinity for CO2. Capacities qualitatively scale with surface area and range from 3.2 mmol/g for MOF-2 to 33.5 mmol/g (320 cm3(STP)/cm3, 147 wt %) for MOF-177, the highest CO2 capacity of any porous material reported.     

Strategies for hydrogen storage in metal--organic frameworks

Increased attention is being focused on metal-organic frameworks as candidates for hydrogen storage materials. This is a result of their many favorable attributes, such as high porosity, reproducible and facile syntheses, amenability to scale-up, and chemical modification for targeting desired properties. A discussion of several strategies aimed at improving hydrogen uptake in these materials is presented. These strategies include the optimization of pore size and adsorption energy by linker modification, impregnation, catenation, and the inclusion of open metal sites and lighter metals.     

Characterization of H2 binding sites in prototypical metal-organic frameworks by inelastic neutron scattering

The hindered rotor transitions of H(2) adsorbed in the chemically related and prototypical porous metal-organic frameworks IRMOF-1, IRMOF-8, IRMOF-11, and MOF-177 were studied by inelastic neutron scattering to gain information on the specifics of H(2) binding in this class of adsorbents. Remarkably sharp and complex spectra of these materials signify a diversity of well-defined binding sites. Similarities in the spectral features as a function of H(2) loading and correlations with recent crystallographic studies were used to assign transitions ranging in rotational barrier from <0.04 to 0.6 kcal/mol as corresponding to localized adsorption sites on the organic and inorganic components of these frameworks. We find that binding of H(2) at the inorganic cluster sites is affected by the nature of the organic link and is strongest in IRMOF-11 in accord with our adsorption isotherm data. The sites on the organic link have lower binding energies, but a much greater capacity for increases in H(2) loading, which demonstrates their importance for hydrogen uptake by these materials.     

Amidation,Esterification, and Thioesterification of a Carboxyl‐Functionalized Covalent Organic Framework

Three new post‐synthetic modification reactions, namely amidation, esterification, and thioesterification, were demonstrated on a novel highly crystalline two‐dimensional covalent organic framework (COF), COF‐616, bearing pre‐installed carboxyl groups. The strategy can be used to introduce a large variety of functional groups into COFs and the modifications can be carried out under mild reaction conditions, with high yields, and an easy work‐up protocol. As a proof of concept, various chelating functionalities were successfully incorporated into COF‐616 to yield a family of adsorbents for efficient removal of several contaminants in the water.     

Precise Control of Molecular Self-Diffusion in Isoreticular and Multivariate Metal-Organic Frameworks

Understanding the factors that affect self-diffusion in isoreticular and multivariate (MTV) MOFs is key to their application in drug delivery, separations, and heterogeneous catalysis. Here, we measure the apparent self-diffusion of solvents saturated within the pores of large single crystals of MOF-5, IRMOF-3 (amino-functionalized MOF-5), and 17 MTV-MOF-5/IRMOF-3 materials at various mole fractions. We find that the apparent self-diffusion coefficient of N,N-dimethylformamide (DMF) may be tuned linearly between the diffusion coefficients of MOF-5 and IRMOF-3 as a function of the linker mole fraction. We compare a series of solvents at saturation in MOF-5 and IRMOF-3 to elucidate the mechanism by which the linker amino groups tune molecular diffusion. The ratio of the self-diffusion coefficients for solvents in MOF-5 to those in IRMOF-3 is similar across all solvents tested, regardless of solvent polarity. We conclude that average pore aperture, not solvent-linker chemical interactions, is the primary factor responsible for the different diffusion dynamics upon introduction of an amino group to the linker.