Structure determination of zeolites is of great significance for understanding their fascinating properties. In this study, we successfully solve one of polymorphic structures (polymorph A) of zeolite EMM-17, which can only crystallize in sub-micron-sized crystals while containing complex stacking disorders, from the three-dimensional (3D) electron diffraction (ED) data. This is the first time that the atomic structure of this polymorph has been ab initio solved, and the result reveals a unique 10(12) X 10(12) X 11-ring channel system. Moreover, we acquire the first atomic-resolution images of EMM-17 using integrated differential phase-contrast scanning transmission electron microscopy. The images allow us to directly observe polymorphs B and C and discover a large number of local structural defects. Based on structural features unraveled from the reciprocal-space 3D ED data and real-space images, we propose a series of energetically feasible local structures in EMM-17. In addition, we demonstrate that the unique porous structure of EMM-17 enables efficient kinetic separation of C6 alkane isomers.
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