Tuning the separation properties of zeolitic imidazolate framework core-shell structures via post-synthetic modification

The conversion of ZIF-8 into ZIF-7 via post-synthetic modification with benzimidazole has been monitored by quantifying the liberated 2-methylimidazole by chromatography. The reaction kinetics have been adjusted to the shrinking core model, providing the diffusion coefficient of bIm inside the pores and the reaction kinetic constant (2.86 × 10-7 cm2 s-1 and 1.36 × 10-4 cm s-1, respectively). A wide variety of ZIF-7/8 hybrid core-shell frameworks have been obtained during this reaction. The most promising have been characterized by SEM/TEM, TGA, N2 and CO2 adsorption, FTIR and 13C NMR, showing features of the coexistence of both phases inside the frameworks. Their structures have also been simulated, providing comparable XRD and adsorption results. The hybrid material has been used as a filler for PBI mixed matrix membranes (MMMs) applied to H2/CO2 separation, enhancing the performances of the bare PBI polymer and MMMs containing ZIF-8 or ZIF-7 as a filler, with a maximum H2 permeability value of 1921 Barrer and a H2/CO2 selectivity of 11.8

Entropic Separations of Mixtures of Aromatics by Selective Face-to-Face Molecular Stacking in One-Dimensional Channels of Metal-Organic Frameworks and Zeolites

Separation of challenging mixtures using metal-organic frameworks can be achieved by an entropy-driven mechanism, where one of the components can arrange into a face-to-face stacking, thus reducing its footprint and reaching a higher saturation loading

Controlling Thermal Expansion: A Metal-Organic Frameworks Route

Controlling thermal expansion is an important, not yet resolved, and challenging problem in materials research. A conceptual design is introduced here, for the first time, for the use of metal–organic frameworks (MOFs) as platforms for controlling thermal expansion devices that can operate in the negative, zero, and positive expansion regimes. A detailed computer simulation study, based on molecular dynamics, is presented to support the targeted application. MOF-5 has been selected as model material, along with three molecules of similar size and known differences in terms of the nature of host–guest interactions. It has been shown that adsorbate molecules can control, in a colligative way, the thermal expansion of the solid, so that changing the adsorbate molecules induces the solid to display positive, zero, or negative thermal expansion. We analyze in depth the distortion mechanisms, beyond the ligand metal junction, to cover the ligand distortions, and the energetic and entropic effect on the thermo-structural behavior. We provide an unprecedented atomistic insight on the effect of adsorbates on the thermal expansion of MOFs as a basic tool toward controlling the thermal expansion

White Rabbit: Detection and geometrical analysis of rings and pores in mesoporous materials

The algorithm automatically detects the rings of the structures (CIF, PDB, and CAR files) and performs statistics on them: area, distortions, ellipticities and characteristic distances. Falling down the rabbit hole