Zeolites are crystalline aluminosilicates that are widely used as shape-selective catalysts in the refinery and petrochemical industries. By synthesizing a series of structurally related zeolite catalyst and applying them in the industrially relevant conversion of methanol to hydrocarbons, new and extended understanding of the concept of shape selectivity has been reached. We have analyzed the relationship between particle morphology and pore system for catalysts having both small- and medium-sized pores using microscopy and diffraction, as well as performing extensive standard characterization. Two instances of preferential exposure of certain crystal facets, favoring access to one pore system over the other, have been found. Zeolites ZSM-57 (MFS) and SUZ-4 (SZR) both have both 8- and 10-ring channels. MFS prefers a plate-like or nanosheet-type morphology, where the 10-ring channels are perpendicular to the plates/sheets. This leads to favorable diffusion properties and a pronounced deactivation resistance. For SZR, needle-like crystals with high aspect ratio are preferred. In this instance, the sides of the needles are covered by the 8-ring pore openings, whereas the 10-ring pore openings are only exposed at the ends of the needles. This leads to unexpected product selectivity, as the material behaves essentially as an 8-ring catalyst. We argue that it should be possible to tune the shape selectivity of zeolite catalysts having pore systems of different dimensions by controlling the crystal morphology.
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