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on larger crystals. Recently, MFI-type zeolite containing aluminum and gallium within its framework (GaAlMFI) was coated with silicalite-1 and applied in propane aromatization reaction [270]. Thereby, the para-selectivity was increased to 80% in comparison to para-selectivity of 57% for the GaAlMFI catalyst without the silicalite-1 coating, remaining however lower than the respective para-selectivity in toluene alkylation over silicalite-1/H-ZSM-5 reported above. Going one step further, the same working group evaluated the effect of the synthesis conditions in terms of alkali concentration in the synthesis solution and proton-exchange procedure on the preparation of silicalite-1 coated GaAlMFI [271]. In this context, low TPAOH concentration was reported to improve the para-selectivity due to decreased number of acid sites on the external surface of the catalyst. On the other hand, the para-selectivity was significantly decreased by repeating the proton-exchanged procedure since Ga and Al species were removed from the framework leading to the formation of non-selective sites on the catalyst surface. Interestingly, during n-butane and propane aromatization, the silicalite-1/GaAlMFI performed better in the former case attributed by the authors to the higher formation of naphthalene and its derivatives during the propane aromatization. Very recently, Zhou et al. [272] examined the oriented growth of MFI zeolite shells on ZSM-5 crystals. Ammonia as surface modifier was applied for the pretreatment of the catalyst core in order to facile the formation of b-oriented MFI film. The shape-selective core-shell catalyst was evaluated in toluene methylation experiments, demonstrating optimized selectivity and stability against the common ZSM-5 zeolite. However, due to incorporation of small amount of aluminum in the framework near the external surface of the shell, the obtained para-selectivity was lower than that in the previous reports [245,246]. Silicalite zeolite membrane was also employed as membrane coating over Pd-Co/activated carbon catalysts for the hydroformylation of 1-hexene with syngas [248]. The silicalite membrane decreased the 1-hexene conversion, while higher n- to i-heptanal ratios were reported due to the spatial confinement of the zeolite membrane pore channels limiting the diffusion of the i-heptanal out of the core. By increasing the membrane thickness via second hydrothermal synthesis, and thus complicating the diffusion of the reactants into the core catalyst, a further decrease in the 1-hexene conversion was observed. However, the ratio of the aldehyde products experienced sharp increase due to the rise in the n-heptanal selectivity predominated by the membrane thickness. 6.2. Application as Catalytic Membranes A further extensively studied area for application of encapsulated catalysts with zeolite membrane as a shell possessing catalytic properties represent the Fischer-Tropsch synthesis reactions. The Fischer-Tropsch synthesis converts syngas 49PDF Image | Zeolite Catalysis
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