A journey towards complete structure determination of zeolites by electron crystallography methods

Electron crystallography has recently become very successful for structural studies of materials with sub-micrometer sized crystals. In this thesis two major techniques have been applied for structure elucidation – 3-dimensional electron diffraction (3D ED) and high-resolution transmission electron microscopy (HRTEM) imaging. Both can provide information about the structure at the atomic level and have been used for structure determination. During the last decade, two 3D ED methods have been used in our group; the stepwise rotation electron diffraction (RED) method developed in our lab and continuous rotation electron diffraction (cRED) where improvements on the already existing RED method were implemented. Both 3D ED methods can be used for fast structure determination of ordered crystalline materials. HRTEM imaging is very useful for structure determination of more complex and severely disordered materials. For complex structures it is often necessary to combine several methods including powder X-ray diffraction (PXRD).    Zeolites are microporous crystalline materials. They have complex structures and often synthesized as polycrystalline powders. The aforementioned electron crystallography methods have unique advantages in elucidation of atomic structures of such zeolites. In this thesis, the development of 3D ED methods, especially from RED to cRED, is described through the journey of structure determination of four zeolites; a known pure silicate silicalite-1 for testing the RED method, and three new zeolites. The new zeolites include two extra-large pore germanosilicates ITQ-56 and SYSU-3 and one small-pore aluminosilicate EMM-37. The thesis shows the limitations and advantages of the RED and cRED methods and how different challenges in the structure determination of zeolites are tackled by the advances of 3D ED methods. Finally the thesis presents a detailed structural study of disorders in an aluminosilicate zeolite ITQ-39 by combining HRTEM, RED with sample preparation by ultramicrotomy. The structure of ITQ-39 was determined in 2012 by our group. Here three new zeolite polytypes of ITQ-39 were identified from the HRTEM images and their structure models are proposed.    A complete structure determination of zeolites includes elucidation of the framework structure, guest species such as structure directing agent (SDA) molecules and ions in the pores, and any structural disorder in the crystal. This thesis reflects to all of these structural characteristics of zeolites, presenting the power of electron crystallography.At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Manuscript.</p

Detailed Structural Survey of the Zeolite ITQ-39 by Electron Crystallography

The structure of the highly faulted zeolite ITQ-39 was previously determined by electron crystallography, revealing the presence of stacking disorders and twinning. Structural models of three polytypes were proposed, providing a basic description of the ITQ-39 material. Here, a more comprehensive description of the complex structure of the ITQ-39 zeolite is presented based on a one-dimensional periodic building unit. The study includes a detailed description of the structural defects in the material based on the analysis of high resolution transmission electron microscopy images and information on how the defects influence the pore system. A new structure arrangement with alternating twinning was found in the material, and structural models of three twinned end-members are presented. The geometry of the different structural models is evaluated to understand the formation of the crystals

Gas sorption properties and kinetics of porous bismuth-based metal-organic frameworks and the selective CO2 and SF6 sorption on a new bismuth trimesate-based structure UU-200

Bismuth-based metal-organic frameworks (Bi-MOFs) such as bismuth subgallate are important for applications ranging from medicine to gas separation and catalysis. Due to the porous nature of such Bi-MOFs, it would be valuable to understand their gas sorption and separation properties. Here, we present the gas sorption properties of three microporous Bi-MOFs, namely, CAU-17, CAU-33, and SU-101, along with a new trimesate-based structure, UU-200. We perform a detailed analysis of the sorption properties and kinetics of these Bi-MOFs. UU-200 shows good uptake capacities for CO2 (45.81 cm3 g-1 STP) and SF6 (24.69 cm3 g-1 STP) with CO2/N2 and SF6/N2 selectivities over 35 and 44, respectively at 293 K, 100 kPa. The structure of UU-200 is investigated using continuous rotation electron diffraction, and is found to be constructed with a 3D porous framework containing pores with diameters of 3.4-3.5 Å.  Bi-MOFs as a group of relatively under-investigated type of MOFs, have interesting sorption properties that render them promising for greenhouse gas adsorbents with good gas uptake capacities and high selectivities

Structure analysis of zeolites by rotation electron diffraction (RED)

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Synthesis and Structure of a 22 × 12 × 12 Extra-Large Pore Zeolite ITQ-56 Determined by 3D Electron Diffraction

A multidimensional extra-large pore germanosilicate, denoted ITQ-56, has been synthesized by using modified memantine as an organic structure-directing agent. ITQ-56 crystallizes as plate-like nanocrystals. Its structure was determined by 3D electron diffraction/MicroED. The structure of ITQ-56 contains extra-large 22-ring channels intersecting with straight 12-ring channels. ITQ-56 is the first zeolite with 22-ring pores, which is a result of ordered vacancies of double 4-ring (d4r) units in a fully connected zeolite framework. The framework density is as low as 12.4 T atoms/1000 Å3. The discovery of the ITQ-56 structure not only fills the missing member of extra-large pore zeolite with 22-ring channels but also creates a new approach of making extra-large pore zeolites by introducing ordered vacancies in zeolite frameworks.This work has been supported by the European Union through ERC-AdG-2014-671093 (SynCatMatch), by the Spanish Government-MINECO through “Severo Ochoa” (SEV-2016-0683), the Swedish Research Council (VR, 2017-04321, 2019-05465), and the Knut & Alice Wallenberg Foundation through the project grant 3DEM-NATUR (KAW, 2012-0112). The EM facility was supported by the Knut and Alice Wallenberg Foundation. J.J. thanks the National Natural Science Foundation 21971259

Synthesis and Structure of a 22 12 12 Extra-Large Pore Zeolite ITQ-56 Determined by 3D Electron Diffraction

[Image: see text] A multidimensional extra-large pore germanosilicate, denoted ITQ-56, has been synthesized by using modified memantine as an organic structure-directing agent. ITQ-56 crystallizes as plate-like nanocrystals. Its structure was determined by 3D electron diffraction/MicroED. The structure of ITQ-56 contains extra-large 22-ring channels intersecting with straight 12-ring channels. ITQ-56 is the first zeolite with 22-ring pores, which is a result of ordered vacancies of double 4-ring (d4r) units in a fully connected zeolite framework. The framework density is as low as 12.4 T atoms/1000 Å(3). The discovery of the ITQ-56 structure not only fills the missing member of extra-large pore zeolite with 22-ring channels but also creates a new approach of making extra-large pore zeolites by introducing ordered vacancies in zeolite frameworks