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- Chen, Hong, 1986-
(author)
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Open-framework Structures Built by Inorganic Clusters : Synthesis and Characterization
- 2014
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Doctoral thesis (other academic/artistic)abstract
- Novel open-framework germanates and vanadoborates, which are constructed from typical types of clusters, have been synthesized based on different strategies. The crystal structures are solved by using single crystal X-ray diffraction (SXRD) technique or by combined techniques. Additionally, the structures of two open-framework materials, PKU-3 and PKU-16, are determined from nano-sized crystals by rotation electron diffraction (RED) combined with powder X-ray diffraction (PXRD).This thesis serves as an introduction to synthesis of open-framework germanates and vanadoborates based on different design strategies. Two germanates are obtained; SU-74 is achieved by employing a novel structure directing agent (SDA), SUT-8 is achieved by assembling the novel structure building units (SBUs) of Co@Ge14 with the introduction of cobalt ions in the synthesis. Four strategies are successfully used in construction of open-framework vanadoborates: using metal-oxo polyhedra as the linkages in SUT-6; applying the scale chemistry approach in SUT-7; employing metal-organic complexes as the linkages in SUT-12, SUT-13, SUT-14; and introducing covalent bond organic linkages into SUT-10 and SUT-11. Single crystal X-ray diffraction is used to conduct the structure determination in combination with other techniques.Furthermore, the structures of two open-framework materials, an aluminoborate PKU-3 and a germanosilicate PKU-16, are solved from nano-sized crystals using RED data. The structures are further confirmed by Rietveld refinement against PXRD data. The advantages of the RED techniques are demonstrated in two aspects. In PKU-3, the presence of seriously preferred orientation and light elements in the structure makes it difficult for structure determination by PXRD, but it is easier by RED. In PKU-16, the RED technique is used to determine its structure from the as-synthesized multi-phasic sample containing nano-sized crystals. After the structure of PKU-16 has been solved, the synthesis of this interesting phase can be optimized and pure PKU-16 can be obtained.Keywords: Open-framework, germanates, vanadoborates, aluminoborates, germanosilicates, crystal structure, hydrothermal synthesis, single crystal X-ray diffraction, rotation electron diffraction, powder X-ray diffraction
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| 2. |
- Lin, Junzhong, 1987-
(author)
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Synthesis, characterization and applications of hierarchical porous inorganic materials: a multi-dimensional approach
- 2018
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Doctoral thesis (other academic/artistic)abstract
- Zeolites are a type of microporous crystalline materials that have been widely used in industrial applications including separation, adsorption, and catalysis. However, great limitations on diffusion through these materials can arise due to the small pores present in mircoporous frameworks, and this can impact catalytic reactions in particular. The synthesis of hierarchical zeolites has solved the diffusion problem. In this thesis, various hierarchically porous materials have been synthesized and tested as catalysts.In the first part of this thesis, a titanium-containing hierarchically porous silicate material has been constructed from double-four-ring (D4R) units as building blocks.In the second part of this thesis, hierarchical MWW zeolites were synthesized by swelling and pillaring of a lamellar MWW zeolitic precursor (MCM-22) using D4R building units. The synthesis procedure has been carefully studied by various characterization methods, such as PXRD, TEM, N2 adsorption–desorption etc.In the last part of this thesis, MFI zeolites with controllable hierarchical pore systems have been prepared. Firstly, hierarchical ZSM-5 and TS-1 with open pores were generated using a temperature programmed dissolution–recrystallization post-synthesis treatment and tested as catalysts for benzyl alcohol self-etherification and cyclohexanone ammoximation. Secondly, single-crystalline hierarchical shell-like ZSM-5 has been synthesized via a dissolution–recrystallization post-treatment of mesoporous ZSM-5. The post-treatment increased the catalytic activity of the ZSM-5 zeolite for the aldol condensation of bulky substrates.
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| 3. |
- Wang, Yunchen, 1988-
(author)
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3D Electron Diffraction : Application and Development towards High-quality Structure Determination
- 2017
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Doctoral thesis (other academic/artistic)abstract
- Electron crystallography has been proven to be effective for structure determination of nano- and micron-sized crystals. In the past few years, 3D electron diffraction (3DED) techniques were used for the structure solution of various types of complex structures such as zeolites, metal-organic frameworks (MOF) and pharmaceutical compounds. However, unlike X-ray crystallography, electron diffraction has not yet become an independent technique for a complete structure determination due to relatively poorer diffraction intensities and often powder X-ray diffraction data are used for structure validation and refinement.Electron beam damage to the structures that are sensitive to high energy electrons and dynamical scattering are important factors to lead to the deviation of electron diffraction intensities from the squared amplitudes of the structure factors. In this thesis, we investigate various aspects around the 3D electron diffraction data quality and strategies for obtaining better data and structure models. We combined 3D electron diffraction methods and powder X-ray diffraction to determine the structure of an open-framework material and discussed the difficulties and limitations of electron diffraction for beam sensitive materials. Next, we illustrated the structure determination of a pharmaceutical compound, bismuth subgallate, using 3D electron diffraction. While severe beam damage and diffuse scattering were observed in the dataset collected with the conventional rotation electron diffraction (RED) method, the continuous rotation electron diffraction (cRED) method coupled with sample cooling significantly improved the data quality and made the structure solution possible. In order to better understand the potentials and limitations of the continuous rotation method, we collected multiple datasets from different crystals of a known structure and studied the data quality by evaluating the accuracy of the refined structure models. To tackle dynamical scattering in electron diffraction data, we explored a routine for structure refinement with dynamical intensity calculation using RED data from a known structure and discussed its potentials and limitations.
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