Structure Determination and P r e diction of Z e o l i t e s - A Combined Study by Electron Diffraction, Powder X - Ray Diffraction and Database M i n i n g Peng Guo Structure Determination and Prediction of Zeolites -- A Combined Study by Electron Diffraction, Powder X-Ray Diffraction and Database Mining Peng Guo 郭鹏 Doctoral Thesis 2016 Department of Materials and Environmental Chemistry Arrhenius Laboratory, Stockholm University SE-106 91 Stockholm, Sweden Cover: An old zeolite ZSM-25 is woke up by an alarm Faculty opponent: Prof. Christine Kirschhock Center for Surface Chemistry and Catalysis KU Leuven Belgium Evaluation committee: Dr. Johanne Mouzon Department of Civil, Environmental and Natural Resources Engineering Luleå University of Technology Prof. Vadim Kassler Department of Chemistry and Biotechnology Swedish University of Agricultural Sciences Dr. German Salazar Alvarez Department of Materials and Environmental Chemistry Stockholm University Substitute: Dr. Mårten Ahlquist Theoretical Chemistry and Biology KTH Royal Institute of Technology ©Peng Guo, Stockholm University 2016 ISBN 978-91-7649-384-7 Printed by Holmbergs, Malmö 2016 Distributor: Department of Materials and Environmental Chemistry A shrewd and ambitious life needs no explanation. ---Yong-hao Luo (罗永浩) To my family Abstract Zeolites are crystalline microporous aluminosilicates with well-defined cavi- ties or channels of molecular dimensions. They are widely used for applica- tions such as gas adsorption, gas storage, ion exchange and catalysis. The size of the pore opening allows zeolites to be categorized into small, medium, large and extra-large pore zeolites. A typical zeolite is the small pore sili- coaluminophosphate SAPO-34, which is an important catalyst in the MTO (methanol-to-olefin) process. The properties of zeolite catalysts are deter- mined mainly by their structures, and it is therefore important to know the structures of these materials to understand their properties and explore new applications. Single crystal X-ray diffraction has been the main technique used to de- termine the structures of unknown crystalline materials such as zeolites. This technique, however, can be used only if crystals larger than several micro- metres are available. Powder X-ray diffraction (PXRD) is an alternative technique to determine the structures if only small crystals are available. However, peak overlap, poor crystallinity and the presence of impurities hinder the solution of structures from PXRD data. Electron crystallography can overcome these problems. We have developed a new method, which we have called “rotation electron diffraction” (RED), for the automated collec- tion and processing of three-dimensional electron diffraction data. This the- sis describes how the RED method has been applied to determine the struc- tures of several zeolites and zeolite-related materials. These include two interlayer expanded silicates (COE-3 and COE-4), a new layered zeolitic fluoroaluminophosphate (EMM-9), a new borosilicate (EMM-26), and an aluminosilicate (ZSM-25). We have developed a new approach based on strong reflections, and used it to determine the structure of ZSM-25, and to predict the structures of a series of complex zeolites in the RHO family. We propose a new structural principle that describes a series of structurally relat- ed zeolites known as “embedded isoreticular zeolite structures”, which have expanding unit cells. The thesis also summarizes several common structural features of zeolites in the Database of Zeolite Structures. Key words: zeolites, rotation electron diffraction, structure determination, structure prediction, strong reflections approach List of papers Paper I: Ab initio structure determination of interlayer expanded zeolites by single crystal rotation electron diffraction Peng Guo, Leifeng Liu, Yifeng Yun, Jie Su, Wei Wan, Hermann Gies, Hai- yan Zhang, Feng-Shou Xiao and Xiaodong Zou. Dalton Trans., 2014, 43, 10593–10601. Scientific contributions: I conducted the TEM work, carried out the structure solution, made the Rietveld refinement, wrote and corrected the manuscript. Paper II: Synthesis and structure determination of a layered zeolitic fluoroalumi- nophosphate and its transformation to a three-dimensional zeolite framework Peng Guo, Guang Cao, Mobae Afeworki, YifengYun, Junliang Sun, Jie Su, Wei Wan and Xiaodong Zou. In manuscript Scientific contributions: I conducted the TEM work, carried out the structure solution, made the Rietveld refinement, and wrote the manuscript. Paper III: EMM-26: a two-dimensional medium pore borosilicate zeolite with 10×10 ring channels solved by rotation electron diffraction Peng Guo, Karl Strohmaier, Hilda Vroman, Mobae Afeworki, Peter I. Ra- vikovitch, Charanjit S. Paur, Junliang Sun, Allen Burton and Xiaodong Zou. In manuscript Scientific contributions: I conducted the TEM work, carried out the structure solution, made the Rietveld refinement, and wrote the manuscript. Paper IV: A zeolite family with expanding structural complexity and embedded isoreticular structures Peng Guo#, Jiho Shin#, Alex G. Greenaway, Jung Gi Min, Jie Su, Hyun June Choi, Leifeng Liu, Paul A. Cox, Suk Bong Hong, Paul A. Wright and Xiaodong Zou. Nature, 2015, 524, 74–78. (# Equal contribution) Scientific contributions: I conducted the TEM work, carried out the structure solution and structure prediction work, made the Rietveld refinements, wrote and corrected the manuscript. Paper V: Targeted Synthesis of Two Super-Complex Zeolites with Embedded Isoreticular Structures Jiho Shin, Hongyi Xu, Seungwan Seo, Peng Guo, Jung Gi Min,Jung Cho, Paul A. Wright, Xiaodong Zou and Suk Bong Hong. Angew. Chem. Int. Ed., 2016, DOI: 10.1002/anie.201510726. Scientific contributions: I predicted structural models and wrote the struc- ture prediction part of the manuscript. Paper VI: On the relationship between unit cells and channel systems in high silica zeolites with the "butterfly" projection Peng Guo, Wei Wan, Lynne McCusker, Christian Baerlocher and Xiaodong Zou. Z. Kristallogr., 2015, 230, 5, 301–309. Scientific contributions: I identified the related structures, analyzed them, wrote and corrected the manuscript. Papers not included in the thesis Paper VII: The Use of Porous Palladium(II)-polyimine in Cooperatively- catalyzed Highly Enantioselective Cascade Transformations Chao Xu, Luca Deiana, Samson Afewerki, Celia Incerti-Pradillos, Oscar Córdova, Peng Guo, Armando Córdova, and Niklas Hedin. Adv. Synth. Catal., 2015, 357, 2150–2156 Scientific contributions: I conducted the TEM work. Paper VIII: Fabrication of novel g-C3N4/nanocage ZnS composites with enhanced photocatalytic activities under visible light irradiation Jing Wang, Peng Guo, Qiangsheng Guo, Pär G. Jönsson and Zhe Zhao. CrystEngComm, 2014, 16, 4485–4492. Scientific contributions: I conducted the TEM work and corrected the manu- script. Paper IX: Visible light-driven g-C3N4/m-Ag2Mo2O7 composite photocatalysts: syn- thesis, enhanced activity and photocatalytic mechanism Jing Wang, Peng Guo, Maofeng Dou, Jing Wang, Yajuan Cheng, Pär G. Jönsson and Zhe Zhao. RSC Adv., 2014, 4, 51008–51015. Scientific contributions: I conducted the TEM work and corrected the manu- script. Paper X: Rapid sintering of silicon nitride foams decorated with one-dimensional nanostructures by intense thermal radiation Duan Li, Elisângela Guzi de Moraes, Peng Guo, Ji Zou, Junzhan Zhang, Paolo Colombo and Zhijian Shen. Sci. Technol. Adv. Mater., 2014, 15, 045003–04509. Scientific contributions: I conducted the TEM work and corrected the manu- script. Paper XI: One-pot Synthesis of Metal-Organic Frameworks with Encapsulated Target Molecules and Their Applications for Controlled Drug Delivery Haoquan Zheng, Yuning Zhang, Leifeng Liu, Wei Wan, Peng Guo, Andreas M. Nyström and Xiaodong Zou. J. Am. Chem. Soc., 2016, 138, 962–968 Scientific contributions: Haoquan and I identified this unique material. Paper XII: Two ligand-length-tunable interpenetrating coordination networks with stable Zn2 unit as three-connected uninode and supramolecular topolo- gies Guohai Xu, Jianyi Lv, Peng Guo, Zhonggao Zhou, Ziyi Dua and Yongrong Xie. CrystEngComm, 2013, 15, 4473–4482. Scientific contributions: I did structure and topology analysis and cor- rected the manuscript. Contents 1. Introduction ............................................................................................... 15 2. Zeolites ...................................................................................................... 19 2.1 Zeolite structure .................................................................................. 19 2.1.1 Building units ............................................................................. 20 2.1.2 Pore system ................................................................................. 23 2.1.3 Non-framework species .............................................................. 23 2.2 Properties of zeolites .......................................................................... 25 2.2.1 Small pore zeolites ...................................................................... 25 2.2.2 Medium pore zeolites ................................................................. 25 2.2.3 Large pore zeolites ...................................................................... 26 3. Structure determination of zeolites ........................................................... 27 3.1 Basic crystallography ......................................................................... 27 3.1.1 Crystals