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Mixed-linker zeolitic imidazolate frameworks (ZIFs) with the sodalite (sod) topology type and based on ZIF-7 have been prepared by direct synthesis from the mixtures of benzimidazole (BzIm) and 4,5-dichloroimidazole (dcIm). Incorporation of dcIm into the ZIF-7 structure gives ZIF-7/COK-17 hybrids with rhombohedral symmetry that do not show the “open-to-closed form” structural transition upon solvent removal exhibited by ZIF-7. They show Type I isotherms for low molecular weight gases and high affinity for CO2even at low partial pressures. Synthesis under mild conditions gives ZIF nanoparticles (250–400 nm) suitable for incorporation into mixed matrix membranes (MMMs): these were prepared with both glassy (Matrimid) and rubbery (PEBAX 1657) polymers. Permeation tests at 298 K and 1.2 bar reveal that the incorporation of Zn(BzIm0.55dcIm0.45)2nanoparticles at up to ca. 12 wt % gives defect-free membranes with enhanced CO2permeability in both polymer matrices, with retention of selectivity (Matrimid) or with an enhancement in selectivity that is most pronounced for the smaller nanoparticles (PEBAX). The membrane with the best performance exhibits a selectivity of ca. 200 for CO2/N2(a 4-fold increase compared to the pure polymer) and a CO2permeability of 64 Barrer. At the relatively low loadings investigated, the MMMs’ performance obeys the Maxwell model, and the intrinsic property of diffusivity of the ZIFs can be extracted as a result.

The lithium-exchanged form of a merlinoite zeolite (MER) with Si/Al = 4.2 (unit cell composition Li6.2Al6.2Si25.8O64) possesses a strongly contracted framework when dehydrated (the unit cell volume decreases by 12.9% from the hydrated “wide-pore” form to the dehydrated “narrow-pore” form). It shows cooperative adsorption behavior for CO2, leading to two-step isotherms with the second step at elevated pressure (>2.5 bar at 298 K). Partially exchanging Na and K cations to give single-phase Li,Na- and Li,K-MER materials reduces the pressure of this second adsorption step because the transition from narrow- to wide-pore forms upon CO2adsorption occurs at lower partial pressures compared to that in Li-MER: partial exchange with Cs does not reduce the pressure of this transition. Exsolution effects are also seen at K cation contents >2.2 per unit cell. The phase transitions proceed via intermediate structures by complex phase behavior rarely seen for zeolitic materials. The strongly distorted narrow-pore structures adopted upon dehydration give one-dimensional channel structures in which the percolation of CO2through the material requires cation migration from their locations in stesites. This is slow in Li3.4Cs2.8-MER where Cs cations occupy these critical stecavities in the channels, causing very slow adsorption kinetics. As the partial pressure of CO2increases, a threshold pressure is reached where cooperative adsorption and Cs cation migration occur and the wide-pore form results, with a three-dimensionally connected pore system, leading to a sharp increase in uptake. This is far in excess of the increase of unit cell volume because more of the pore space becomes accessible. Strong hysteretic effects occur upon desorption, leading to CO2encapsulation. CO2remaining within the material after repeated adsorption/desorption cycles without heated activation improves sorption kinetics and modifies the stepped isotherms.

The adsorption of CO2on zeolite Li-Rho (unit cell composition Li9.8Al9.8Si38.2O96) has been investigated by the measurement of adsorption isotherms (273–300 K), breakthrough curves with a CO2/CH4/He mixture (308 K), and in situsynchrotron X-ray powder diffraction in CO2(298 K). The Rho framework distorts when in the Li-form to give a shape selective adsorbent for CO2over CH4, although breakthrough curves reveal diffusional limitations. In situsynchrotron powder XRD follows the expansion of the Li-Rho unit cell upon adsorption, which remains single phase to a CO2pressure of ca. 0.6 bar. Partial cation exchange of Li-Rho by Na+or Cs+gives two series of M,Li-Rho zeolites (M = Na, Cs). Where the occupancy of window sites (8R, D8R) between ltacages is less than 50%, hysteresis is not observed in CO2isotherms at 298 K. For Cs1.8Li8-Rho, which has a larger unit cell and a wider window than zeolite Li-Rho due to the presence of large Cs+cations in double 8-ring sites, breakthrough curves indicate faster CO2diffusion without significant loss of selectivity. We propose this control of adsorption kinetics of the flexible zeolite Rho via modification of cation content as a mechanism for cation controlled molecular sieving.

We have studied the adsorption of n-butane and isobutane in the mesoporous silica SBA-2. Our work has two purposes: (i) to better understand the structure of the material, and in particular the impact of calcination on the evolution of the pore network, and (ii) to investigate our ability to tune the structure of SBA-2 to separate normal and isoalkanes by molecular sieving. By a combination of experimental adsorption measurements, molecular simulation, and percolation analysis, we determined the evolution of the sizes of the pores and the connectivity of the pore network as the calcination temperature increases. For a certain range of calcination temperatures, the pore network drops below its percolation threshold for isobutane, while allowing the percolation of n-butane, giving an extremely high selectivity for n-butane over isobutane. This suggests that tuning the window size of SBA-2 and other structured mesoporous materials of this general type has the potential to generate optimized adsorbents for particular applications.

SBA-2 and STAC-1 are two related periodic mesoporous silicas (PMSs) that have regular networks of spherical, interconnected pores; the pores are similar in the two materials but the networks differ in their symmetry. The nature of the interconnected network of pores in these materials gives rise to interesting properties related to their potential use in separation processes. In this work, we extend a kinetic Monte Carlo (kMC) technique, originally derived for MCM-41, a simpler PMS, and apply it to mimic the condensation, aggregation, deformation, and calcination stages of the synthesis of SBA-2 and STAC-1. Our simulated synthesis results suggest that the pores are connected through windows formed during micelle aggregation because of the close packing of the spherical micelles and the presence of water molecules at the silica–micelle interface. The simulated materials were validated by comparing properties such as unit cell size, pore size, pore shape, and wall density to results from experimental X-ray diffraction (XRD), transmission electron microscopy (TEM), density measurements, and 29Si NMR. Quantitative agreement between simulated and experimental nitrogen isotherms was achieved demonstrating the realism of the pore models obtained by the kMC simulations. Our results highlight the importance of a realistic, rough pore surface for the prediction of adsorption at low pressures in these materials.