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Silicalite-1 core/Al-ZSM-5 shell zeolite crystals were prepared in various sizes for use as catalysts in methane dehydroaromatization (MDA), and the growth kinetics and corresponding physicochemical properties of this core–shell zeolite were investigated. Al-ZSM-5 was grown on silicalite-1 seeds at various Si/Al ratios. Core–shell catalysts of all size variations exhibited similar deactivation trends in the MDA reaction, with minor changes in aromatic yields despite clear differences in reaction channel lengths and acid-site properties. This outcome was shown to originate from the unique growth kinetics of the Al-ZSM-5 layer on silicalite-1 seeds, in which the Al species in the sol used in the synthesis were consumed quickly during the early aggregative growth period. This led to an interesting spatial distribution of Al in the Al-ZSM-5 layer, in that the inner layer was relatively Al-rich. This distribution is advantageous because it can inhibit coke deactivation, which often occurs at the catalyst surface during MDA. However, a substantial quantity of Si–OH nests, which inhibit the effective loading of Mo species at the acid sites of the crystals, were detected in the microstructural analysis of large crystals. Therefore, this study shows that silicalite-1 core/Al-ZSM-5 shell zeolites can be prepared for use as coke-resistant catalysts for the MDA reaction. Further work is required, however, to design a synthesis method which reduces the number of Si–OH nests formed.

Surface-templated evaporation driven (STED) method is a promising method to fabricate supraparticles with various sizes, porosities, and shapes by drying colloidal dispersion drops on liquid repellent surfaces. Until now, for the method, only spherical shaped colloidal particles have been used as primary colloids. Here, we introduce six different shapes of nano-colloidal dispersions for the STED method: nanocubics, nanoplates, nanosheets, coffin-shaped nanoparticles (NPs), spherical NPs, and aggregates of NPs. It is confirmed that the shape and size of the primary colloids have little effect for drying the dispersion drop when a single component colloidal dispersion is dried. For heterogeneous supraparticles with composite material assembly, still the shape of the colloids has no influences, while the size and dispersity play roles for tuning the morphology of the supraparticles. From the results, we propose a way to fabricate homogeneous mixture, core/shell, and Janus core/shell structures of the supraparticles depending on the size and dispersity of the mixture colloidal dispersion. Indeed, knowledge on the effects of types of colloids would be of great importance for tailoring supraparticles.

Mixed matrix membranes (MMMs) containing zeolitic imidazolite framework-8 (ZIF-8) and UiO-66 as microporous fillers were prepared and evaluated their potential for the separation of a gas mixture produced by a methane reforming process. Hydrothermal synthesis was performed to prepare both the ZIF-8 and UiO-66 crystals, with crystal sizes ranging from 50 to 70 nm for ZIF-8 and from 200 to 300 nm for UiO-66. MMMs were prepared with 15% filler loading for both MMM (ZIF-8) and MMM (UiO-66). MMM (UiO-66) exhibited H2 permeability of 64.4 barrer and H2/CH4 selectivity of 153.3 for single gas permeation, which are more than twice the values that were exhibited by a neat polymer membrane. MMM (ZIF-8) also showed better separation properties than that of a neat polymer membrane with H2 permeability of 27.1 barrer and H2/CH4 selectivity of 123.2. When a gas mixture consisting of 78% Ar/18% H2/4% CH4 flowed into the membranes at 5 bar, the H2 purity increased to as high as 93%. However, no improvement in the mixture gas separation performance was achieved by the MMMs as compared to that of a neat polymer membrane.