Characterization of crystalline materials by rotation electron diffraction Phase identification and structure determination

University dissertation from Stockholm : Department of Materials and Environmental Chemistry (MMK), Stockholm University

Abstract: Electron crystallography is powerful for determination of complex structures. The newly-developed 3D electron diffraction (ED) methods make structure determination from nano- and micron-sized crystals much easier than using other methods, for example X-ray diffraction. Almost complete 3D ED data can be collected easily and fast from crystals at any arbitrary orientations. Dynamical effects are largely reduced compared to zonal ED patterns. 3D ED is powerful for phase identification and structure solution from individual nano- and micron-sized crystals, while powder X-ray diffraction (PXRD) provides information from all phases present in the samples. 3D ED methods and PXRD are complementary and their combinations are promising for studying multiphasic samples and complicated crystal structures.In this thesis, the feasibility and capability of 3D ED methods, specifically rotation electron diffraction (RED), in phase identification and structure determination of different kinds of crystalline materials with nano- or submicrometer-sized crystals are investigated. Experimental conditions for RED data collection and data processing in relation to data quality, as well as the challenges in the applications of RED are discussed.RED was combined with PXRD to identify phases from as-synthesized samples and to characterize atomic structures of eleven crystalline compounds. It was shown to be possible to identify as many as four distinct compounds within one sample containing submicron-sized crystals in a Ni-Se-O-Cl system. RED was also used to determine unit cell and symmetry of isoreticular metal-organic frameworks (SUMOF-7) and solve five zeolite structures with new frameworks, ITQ-51, ITQ-53, ITQ-54, EMM-23 and EMM-25 and that of a metal-organic framework (MOF), SUMOF-7I. The structure of an open-framework germanate SU-77 was solved by combining RED with PXRD. The structures of the zeolites and SU-77 were confirmed by Rietveld refinement against PXRD. High-resolution transmission electron microscopy was used to confirm the structure models of ITQ-51, EMM-25 and SUMOF-7I.