A series of metalloporphyrin dimers were modularly prepared and shown to catalyze the methanolysis of a phosphate triester, yielding rates that are large compared to the rate of the uncatalyzed reaction. Up to 1300-fold rate acceleration can be achieved via a combination of cavity-localized Lewis-acid activation and methoxide-induced methanolysis.

Experimental results in the literature show that two metal-organic frameworks (MOFs) containing copper and cobalt nodes are active for hydroperoxide decomposition, which is an important reaction in auto-oxidation processes. Density functional theory (DFT) calculations reported here for these systems suggest that the metal sites in the interior of these MOFs are not the active sites for this type of reaction due to the steric effects of the adjacent linkers. This implies that the experimental catalysis observed may occur on the exterior surface of the MOF crystals. Additional calculations with a copper paddlewheel node show that, despite being able to form complexes with hydroperoxides, the metal sites in copper paddlewheels do not catalyze hydroperoxide decomposition. Preliminary calculations involving undercoordinated metal atoms as a model for metal sites on the MOF exterior crystal surface suggest that these sites could be catalytically active.

A variety of metal-organic frameworks (MOFs) with varying linkers, topologies, pore sizes, and metal atoms were screened for xenon/krypton separation using grand canonical Monte Carlo (GCMC) simulations. The results indicate that small pores with strong adsorption sites are desired to preferentially adsorb xenon over krypton in multicomponent adsorption. However, if the pore size is too small, it can significantly limit overall gas uptake, which is undesirable. Based on our simulations, MOF-505 was identified as a promising material due to its increased xenon selectivity over a wider pressure range compared with other MOFs investigated. (C) 2010 American Institute of Chemical Engineers AIChE J, 57: 1759-1766, 2011

Experimental results in the literature show that some metal-organic frameworks (MOFs) are active for hydroperoxide decomposition, which is an important reaction in autooxidation processes. Using density functional theory (DFT), we suggest that the metal sites in the interior of these MOFs are not the active sites for this type of reaction. Instead, we hypothesize the experimental catalysis observed may occur on the surface of the MOF crystals, which could contain undercoordinated metal sites.

Grand canonical Monte Carlo (GCMC) simulations demonstrate that catenation can be beneficial for improving hydrogen storage in metal-organic frameworks at cryogenic temperatures and low pressures but not necessarily at room temperature.

The adsorption of CO2 and CH4 in a mixed-ligand metal-organic framework (MOF) Zn 2(NDC) 2(DPNI) [NDC = 2,6-naphthalenedicarboxylate, DPNI = N, N'-di-(4-pyridyl)-1,4,5,8-naphthalene tetracarboxydiimide] was investigated using volumetric adsorption measurements and grand canonical Monte Carlo (GCMC) simulations. The MOF was synthesized by two routes: first at 80 degrees C for two days with conventional heating, and second at 120 degrees C for 1 h using microwave heating. The two as-synthesized samples exhibit very similar powder X-ray diffraction patterns, but the evacuated samples show differences in nitrogen uptake. From the single-component CO2 and CH4 isotherms, mixture adsorption was predicted using the ideal adsorbed solution theory (IAST). The microwave sample shows a selectivity of approximately 30 for CO2 over CH4, which is among the highest selectivities reported for this separation. The applicability of IAST to this system was demonstrated by performing GCMC simulations for both single-component and mixture adsorption.