265 research outputs found
Interplay of Linker Functionalization and Hydrogen Adsorption in the Metal–Organic Framework MIL-101
Functionalization of metal–organic frameworks results in higher hydrogen uptakes owing to stronger hydrogen–host interactions. However, it has not been studied whether a given functional group acts on existing adsorption sites (linker or metal) or introduces new ones. In this work, the effect of two types of functional groups on MIL-101 (Cr) is analyzed. Thermal-desorption spectroscopy reveals that the −Br ligand increases the secondary building unit’s hydrogen affinity, while the −NH2 functional group introduces new hydrogen adsorption sites. In addition, a subsequent introduction of −Br and −NH2 ligands on the linker results in the highest hydrogen-store interaction energy on the cationic nodes. The latter is attributed to a push-and-pull effect of the linkers
Stability and Hydrolyzation of Metal Organic Frameworks with Paddle-Wheel SBUs upon Hydration
Instability of most prototypical metal organic frameworks (MOFs) in the
presence of moisture is always a limita- tion for industrial scale development.
In this work, we examine the dissociation mechanism of microporous paddle wheel
frameworks M(bdc)(ted)0.5 [M=Cu, Zn, Ni, Co; bdc= 1,4-benzenedicarboxylate;
ted= triethylenediamine] in controlled humidity environments. Combined in-situ
IR spectroscopy, Raman, and Powder x-ray diffraction measurements show that the
stability and modification of isostructual M(bdc)(ted)0.5 compounds upon
exposure to water vapor critically depend on the central metal ion. A
hydrolysis reaction of water molecules with Cu-O-C is observed in the case of
Cu(bdc)(ted)0.5. Displacement reactions of ted linkers by water molecules are
identified with Zn(bdc)(ted)0.5 and Co(bdc)(ted)0.5. In contrast,.
Ni(bdc)(ted)0.5 is less suscept- ible to reaction with water vapors than the
other three compounds. In addition, the condensation of water vapors into the
framework is necessary to initiate the dissociation reaction. These findings,
supported by supported by first principles theoretical van der Waals density
functional (vdW-DF) calculations of overall reaction enthalpies, provide the
necessary information for de- termining operation conditions of this class of
MOFs with paddle wheel secondary building units and guidance for developing
more robust units
Geometry analysis and systematic synthesis of highly porous isoreticular frameworks with a unique topology
Porous coordination polymers are well known for their easily tailored framework structures and corresponding properties. Although systematic modulations of pore sizes of binary prototypes have gained great success, simultaneous adjustment of both pore size and shape of ternary prototypes remains unexplored, owing to the difficulty in controlling the self-assembly of multiple molecular building blocks. Here we show that simple geometry analysis can be used to estimate the influence of the linker lengths and length ratios on the synthesis/construction difficulties and framework stabilities of a highly symmetric, ternary prototype composed of a typical trinuclear metal cluster and two types of bridging carboxylate ligands. As predicted, systematic syntheses with 5×5 ligand combinations produced 13 highly porous isoreticular frameworks, which show not only systematic adjustment of pore volumes (0.49–2.04 cm3 g−1) and sizes (7.8–13.0 Å; 5.2–12.0 Å; 7.4–17.4 Å), but also anisotropic modulation of the pore shapes
Metal-organic replica of fluorite built with an eight-connecting tetranuclear cadmium cluster and a tetrahedral four-connecting ligand
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CCDC 1423720: Experimental Crystal Structure Determination
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures
CCDC 1423719: Experimental Crystal Structure Determination
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures
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