Porous zeolitic imidazolate frameworks assembled with highly-flattened tetrahedral copper(II) centres and 2-nitroimidazolates.

Cu(II)-based zeolitic imidazolates (Cu-ZIFs), Cu-ZIF-gis and -rho, formulated as Cu(nIm)2 (nIm = 2-nitroimidazolate) have highly-flattened tetrahedral coordination geometry. Cu-ZIF-gis has 2.4 Å cylindrical pores that can adsorb H2 gas, and Cu-ZIF-rho has 19.8 Å cages with a BET surface area of 1320 m2 g-1.

Gas adsorption properties of highly porous metal-organic frameworks containing functionalized naphthalene dicarboxylate linkers.

Three functionalized metal-organic frameworks (MOFs), MOF-205-NH2, MOF-205-NO2, and MOF-205-OBn, formulated as Zn4O(BTB)4/3(L), where BTB is benzene-1,3,5-tribenzoate and L is 1-aminonaphthalene-3,7-dicarboxylate (NDC-NH2), 1-nitronaphthalene-3,7-dicarboxylate (NDC-NO2) or 1,5-dibenzyloxy-2,6-naphthalenedicarboxylate (NDC-(OBn)2), were synthesized and their gas (H2, CO2, or CH4) adsorption properties were compared to those of the un-functionalized, parent MOF-205. Ordered structural models for MOF-205 and its derivatives were built based on the crystal structures and were subsequently used for predicting porosity properties. Although the Brunauer-Emmett-Teller (BET) surface areas of the three MOF-205 derivatives were reduced (MOF-205, 4460; MOF-205-NH2, 4330; MOF-205-NO2, 3980; MOF-205-OBn, 3470 m(2) g(-1)), all three derivatives were shown to have enhanced H2 adsorption capacities at 77 K and CO2 uptakes at 253, 273, and 298 K respectively at 1 bar in comparison with MOF-205. The results indicate the following trend in H2 adsorption: MOF-205 < MOF-205-NO2 < MOF-205-NH2 < MOF-205-OBn. MOF-205-OBn showed good ideal adsorbed solution theory (IAST) selectivity values of 6.5 for CO2/N2 (15/85 in v/v) and 2.7 for CO2/CH4 (50/50 in v/v) at 298 K. Despite the large reduction (-22%) in the surface area, MOF-205-OBn displayed comparable total volumetric CO2 (at 48 bar) and CH4 (at 35 bar) storage capacities with those of MOF-205 at 298 K: MOF-205-OBn, 305 (CO2) and 112 (CH4) cm(3) cm(-3), and for MOF-205, 307 (CO2) and 120 (CH4) cm(3) cm(-3), respectively.

Poly[bis-(µ4-2,3,5,6-tetra-fluoro-benzene-1,4-di-carboxyl-ato-κ(4) O (1):O (1'):O (4):O (4'))bis-(tetra-hydro-furan-κO)dizinc].

The title compound, [Zn2(C8F4O4)2(C4H8O)2] n , has a three-dimensional metal-organic framework structure. The asymmetric unit consists of two Zn(II) atoms, two tetrahydrofuran ligands, one 2,3,5,6-tetra-fluoro-benzene-1,4-di-carboxyl-ate ligand and two half 2,3,5,6-tetra-fluoro-benzene-1,4-di-carboxyl-ate ligands, which are completed by inversion symmetry. One Zn(II) atom has a distorted trigonal-bipyramidal coordination geometry, while the other has a distorted octa-hedral geometry. Two independent tetra-hydro-furan ligands are each disordered over two sets of sites with occupancy ratios of 0.48 (4):0.52 (4) and 0.469 (17):0.531 (17).

Crystal structure and electronic properties of 2-amino-2-methyl-1-propanol (AMP) carbamate.

A crystal structure of a carbamate of 2-amino-2-methyl-1-propanol (AMP-carbamate) has been elucidated and its structural and electronic properties investigated by density functional theory calculations and natural bond orbital analyses.

Ultrahigh porosity in metal-organic frameworks.

Crystalline solids with extended non-interpenetrating three-dimensional crystal structures were synthesized that support well-defined pores with internal diameters of up to 48 angstroms. The Zn4O(CO2)6 unit was joined with either one or two kinds of organic link, 4,4',4''-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate (BTE), 4,4',44''-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate (BBC), 4,4',44''-benzene-1,3,5-triyl-tribenzoate (BTB)/2,6-naphthalenedicarboxylate (NDC), and BTE/biphenyl-4,4'-dicarboxylate (BPDC), to give four metal-organic frameworks (MOFs), MOF-180, -200, -205, and -210, respectively. Members of this series of MOFs show exceptional porosities and gas (hydrogen, methane, and carbon dioxide) uptake capacities. For example, MOF-210 has Brunauer-Emmett-Teller and Langmuir surface areas of 6240 and 10,400 square meters per gram, respectively, and a total carbon dioxide storage capacity of 2870 milligrams per gram. The volume-specific internal surface area of MOF-210 (2060 square meters per cubic centimeter) is equivalent to the outer surface of nanoparticles (3-nanometer cubes) and near the ultimate adsorption limit for solid materials.

Solvothermal synthesis of Fe-MOF-74 and its catalytic properties in phenol hydroxylation.

A Fe-containing metal-organic framework, Fe-MOF-74, was solvothermally synthesized using FeCl2.4H2O and 2,5-di-hydroxy-1,4-benzenedicarboxylic acid. Characterization was conducted by XRD, BET surface area measurement, FT-IR spectroscopy, TGA, and elemental analysis, which confirmed successful preparation of Fe-MOF-74 having an identical framework structure to that reported for MOF-74. Fe-MOF-74 was found to be an effective heterogeneous catalyst for the hydroxylation of phenol using H2O2 as an oxidant; 60% phenol conversion was achieved at 20 degrees C in water with 68 and 32% selectivity to catechol and hydroquinone, respectively. The effect of temperature, phenol/H2O2 mole ratio, catalyst quantity, and solvent on catalytic performance was discussed, and a reaction mechanism is proposed based upon the experimental results.

Catalytic nickel nanoparticles embedded in a mesoporous metal-organic framework.

Ni nanoparticles embedded in the pores of a mesoporous MOF (MesMOF-1) act as a catalyst for hydrogenolysis of nitrobenzene or hydrogenation of styrene.

Grand canonical Monte Carlo simulation study on the catenation effect on hydrogen adsorption onto the interpenetrating metal-organic frameworks.

Among recently synthesized isoreticular metal-organic frameworks (IRMOFs), interpenetrating IRMOFs show high hydrogen adsorption capacities at low temperature and under ambient pressure. However, little is known about the molecular basis of their hydrogen binding properties. In this work, we performed grand canonical Monte Carlo (GCMC) simulations to investigate the effect of catenation on the interactions between hydrogen molecules and IRMOFs. We identified the adsorption sites and analyzed the adsorption energy distributions. The simulation results show that the small pores generated by catenation can play a role to confine the hydrogen molecules more densely, so that the capacity of the interpenetrating IRMOFs could be higher than that of the non-interpenetrating IRMOFs.