Micro-Mesoporous Metallosilicates

Peng Wu, PhD, is a Professor in School of Chemistry and Molecular Engineering at East China Normal University. His research interests focus on design, functionalization, and catalytic applications of novel zeolites. Hao Xu, PhD, is a Professor in School of Chemistry and Molecular Engineering at East China Normal University. Her research interests focus on the design and synthesis of novel zeolite catalysts via post modifications

• Preface xv1 Synthesis of Titanosilicates 1Xinqing Lu1.1 Introduction 11.2 Synthesis of Medium-Pore Titanosilicates 51.2.1 TS-1 Synthesis 51.2.2 Ti-MWW Synthesis 61.2.3 TS-2 Synthesis 81.2.4 Synthesis of Other Medium-Pore Titanosilicates 91.3 Synthesis of Large-Pore Titanosilicates 91.3.1 Ti-Beta Synthesis 91.3.2 Ti-MOR Synthesis 101.3.3 Ti-MSE Synthesis 121.3.4 Synthesis of Other Large-Pore Titanosilicates 131.4 Synthesis of Extra-Large-Pore Titanosilicates 141.5 Synthesis of Mesoporous Titanosilicates 151.6 Synthesis of ETSs 171.7 Conclusions 18References 182 Layered Heteroatom-Containing Zeolites 31Hao Xu and Peng Wu2.1 Introduction 312.2 Traditional Layered Heteroatom-Containing Zeolites 322.2.1 Heteroatom-Containing MWW-Type Layered Zeolites and Their Derivative Zeolitic Materials 322.2.2 Heteroatom-Containing Layered Zeolites Built from fer-Layers 362.3 Novel Layered Heteroatom-Containing Zeolites 412.3.1 Heteroatom-Containing MFI-Type Layered Zeolites 412.3.2 Germanosilicate-Derived Heteroatom-Containing Zeolites 442.4 Conclusions 45Acknowledgments 46References 463 Synthesis and Catalytic Applications of Sn- and Zr-Zeolites 53Zhiguo Zhu3.1 Introduction 533.2 Synthesis of Sn- and Zr-Zeolites 553.2.1 Bottom-up Approaches 563.2.2 Top-Down Approaches 633.3 General Remarks 663.4 Catalytic Applications of Sn- and Zr-Zeolites 673.4.1 Redox Catalysis 683.4.2 Lewis Acid Catalysis 713.4.3 Biomass Conversion 733.5 General Remarks 78References 794 Synthesis of Germanosilicates 87Jiuxing Jiang4.1 Introduction 874.1.1 General Property of Ge/Si Oxides 874.1.2 Germanosilicate Glass 884.2 Isomorphous Substitution in Germanosilicates 894.2.1 Isomorphous Substitution Si in Germanate 894.2.2 Isomorphous Substitution Ge in Silicates 924.3 Inorganic Structure-Directing Effects 934.3.1 Structure-Directing Effects of Ge 934.3.2 Structure-Directing Effects of F− 944.4 Organic Structure-Directing Agents in Germanosilicate Synthesis 944.4.1 Organic Structure-Directing Agent Types and Revolutions 944.4.2 Two Important Families of OSDA 954.5 Structure Diversity of Germanosilicates/Silicogermanates 1064.5.1 Relationship Between Composition and Structure 1064.5.2 Pore Opening 1064.6 Possibility of Elimination of Ge and Catalytic Research of Germanosilicates 1084.6.1 The Price Concern of Ge 1084.6.2 Removal of Ge in Zeolite Synthesis 1084.6.3 Removal of Ge with Post-synthesis 1094.6.4 Catalytic Research of Germanosilicates 1124.7 Conclusions and Outlook 112References 1125 Structural Modifications on Germanosilicates 119Ondřej Veselý, Maksym Opanasenko, and Jǐrí Čejka5.1 Introduction 1195.2 Germanosilicates to Layered Precursors 1215.2.1 UTL to IPC-1P 1215.3 ADOR Strategy for Developing New Zeolite Structures 1255.3.1 Assembly 1265.3.2 Disassembly 1275.3.3 Organization 1275.3.4 Reassembly 1275.3.5 Liquid-phase ADOR 1285.3.6 Vapor-phase ADOR 1355.3.7 Reductive Degermanation 1365.3.8 Solid-state Transformations 1375.4 Structure Stabilization 1395.4.1 Degermanation 1395.4.2 Functionalization With Catalytic Sites 1405.4.3 Slow Disassembly 1415.4.4 Reverse ADOR 1415.5 Germanosilicate-Derived Catalysts 1425.5.1 Summary and Perspectives 144Acknowledgements 146References 1466 Heteroatom-Containing Dendritic Mesoporous Silica Nanoparticles 153Bo Peng, Jia-Feng Zhou, Meng Ding, Laurent Bonneviot, and Kun Zhang6.1 Introduction 1536.2 Main Synthetic Methods and Formation Mechanism of Pure Silica-Based Dendritic Mesoporous Silica Nanoparticles (DMSNs) 1556.2.1 Main Synthetic Methods of Dendritic Mesoporous Silica Nanoparticles (DMSNs) 1556.2.2 Unified Formation Mechanism of Dendritic Mesoporous Silica Nanoparticles 1556.3 Synthesis of Heteroatom-Containing DMSNs and Their Catalytic Applications 1646.3.1 One-Pot Doping Strategy for DMSNs Containing Heteroatoms (Al/Ti/V/Sn/Mn/Fe/Co) 1656.3.2 Post-grafting for Surface Metal Complexes 1676.3.3 Loading of Metal and/or Metal Oxide Nanoparticles Within the Nanopores 1696.4 Summary and Perspectives 173Acknowledgments 173References 1737 Chemical Post-Modifications of Titanosilicates 181Fang Nan, Liu Dongxu, Yu Yunkai, and Liu Yueming7.1 Introduction 1817.2 Diffusion and Adsorption/Desorption 1827.2.1 Hierarchical Titanosilicates 1827.2.2 Surface Hydrophilicity and Hydrophobicity 1837.3 Surface Reaction 1847.3.1 Ti Active Sites Content 1847.3.2 Ti Active Sites Distribution 1867.3.3 Ti Active Sites Properties 1877.4 Solvent Effect 1967.4.1 Effect of Solvent on Diffusion 1977.4.2 Effect of Solvent on Adsorption/Desorption 1997.4.3 Effect of Solvent on Surface Reactions 2007.5 Conclusions and Prospects 204References 2048 Spectroscopic Characterization of Heteroatom-Containing Zeolites 217Guodong Qi, Jun Xu, and Feng Deng8.1 X-Ray Technique 2178.1.1 XRD Determination of Framework Structure and Heteroatoms in Zeolites 2178.1.2 XAS Characterization of Metals in Zeolite 2198.1.3 XPS Analysis of the Chemical State of Metal Species 2228.2 Ultraviolet–Visible-Near Infrared (UV–VIS–NIR) Spectroscopy 2248.2.1 UV–VIS–NIR Characterization of Framework and Non-Framework Metal Species 2248.2.2 UV–VIS–NIR Characterization of Metal Species on Ion Exchange Sites of Zeolites 2268.3 Raman Spectroscopy 2278.3.1 Raman Study of Synthesis Mechanism and Assembly of Metal-Zeolites 2288.3.2 Raman Characterization of Active Metal-Oxygen Species in Zeolites 2288.4 Solid-State NMR Spectroscopy 2308.4.1 Solid-State NMR Characterization of Metal Elements in Zeolites 2318.4.2 Solid-State Correlation NMR Measurement of Active Site Proximity and Host–Guest Interactions 2338.4.3 In Situ Solid-State NMR for the Study of Reaction Mechanisms 2358.5 Conclusions 238Acknowledgments 239References 2399 Theoretical Calculations of Heteroatom Substituted Zeolites 253Xin Yu, Wenjun Dong, Wei Chen, and Anmin Zheng9.1 Introduction 2539.2 Ti-Doped Zeolites 2549.2.1 Preferred Tetrahedral (T) Sites for Substitution 2559.2.2 Lewis Acid 2579.2.3 Active Site with H2O2 2589.2.4 Reaction Mechanism 2619.3 Sn-Doped Zeolites 2679.3.1 Preferred Substitution T Sites and Acidity 2679.3.2 Reaction Mechanism 2689.3.3 Other Catalytic Reactions 2729.4 Other Metal-Substituted Zeolites 2739.5 Summary and Outlook 276Acknowledgments 276References 27710 Catalytic Ammoximation of Ketones or Aldehydes Using Titanosilicates 283Rusi Peng, Hao Xu, Chengwei Zhai, Mingyuan He, and Peng Wu10.1 Introduction 28310.2 The Development of Titanosilicates in Ammoximation of Ketones and Aldehydes 28410.3 Ammoximation Mechanism and Product Distributions of Representative Ketones and Aldehydes 28810.3.1 Titanosilicate-Catalyzed Ammoximation Mechanism 28810.3.2 Product Distributions for Ammoximation of Representative Carbonyl Compounds 29010.4 Enhancing Ammoximation Performances in Titanosilicate/H2O2 System 29510.4.1 Improvement of Catalytic Ammoximation Activity 29610.4.2 Improvement of Catalytic Ammoximation Stability 30010.5 Ketone Ammoximation Technology for Industrial Processes 30210.6 Titanosilicate-Based Bifunctional Catalysts for Process Intensified or Tandem Ammoximation Reactions 30610.7 Conclusions and Perspectives 310Acknowledgments 311References 31111 Titanosilicate-Based Alkene Epoxidation Catalysis 323Changjiu Xia and Xiang Feng11.1 Introduction 32311.2 Reaction Chemistry of Alkene Epoxidation Catalyzed by Titanosilicate Zeolites 32611.3 Typical Alkene Epoxidation Cases 32911.3.1 Propylene Epoxidation for PO Production 32911.3.2 Propylene Chloride Epoxidation 33111.3.3 Ethylene Epoxidation to EO, EG, and Ethers 33411.4 Industrial Propylene Epoxidation Techniques and Processes 33611.5 Conclusion and Outlook 339Acknowledgments 339References 34012 Propylene Epoxidation with Cumene Hydroperoxide/Titanosilicates 345Le Xu and Hailang Liu12.1 Introduction 34512.2 Traditional Route for PO Production (Chlorohydrin Process) 34712.3 Co-production Route for PO Production (PO/TBA and PO/SM Processes) 34712.4 PO-Only Production Routes (HPPO and CMHPPO Routes) 34912.5 Catalyst Design for PO-Only Routes 35012.5.1 Mesoporous Ti-Doped Catalysts for CMHPPO Process 35212.5.2 Hierarchical Titanosilicates for CMHPPO Process 35712.6 Industrial CMHPPO Process 36212.7 Conclusions and Outlooks 363References 36413 Hydroxylation of Benzene and Phenol on Zeolite Catalysts 367Shiying Li, Shanhui Zhu, Sen Wang, Mei Dong, and Weibin Fan13.1 Introduction 36713.2 Hydroxylation of Benzene to Phenol 36813.2.1 Gas-Phase Reactions 36813.2.2 Liquid-Phase Reactions 37813.3 Hydroxylation of Phenol to DHB 38113.3.1 Fe-Containing Molecular Sieves as Catalysts 38213.3.2 Titanosilicate Molecular Sieves as Catalysts 38713.3.3 Transition Metal Complexes Encapsulated in Zeolite Y as Catalysts 39313.4 Summary 394Acknowledgments 395References 39514 Bifunctional Titanosilicate Systems for the Gas-Phase Catalytic Propylene Epoxidation with Hydrogen and Oxygen 403Gang Wang, Qianhong Wang, Zhihua Zhang, Xuezhi Duan, and Xinggui Zhou14.1 Introduction 40314.2 Advances in the Catalytic Propylene Epoxidation with H2 and O2 40414.2.1 Mechanistic Insights into Au-Ti Synergy 40414.2.2 Effects of Au Particle Properties 40614.2.3 Effects of Materials’ Properties for Immobilizing Au Particles 40814.2.4 Effect of Promoters 41314.3 Conclusions and Outlook 415Conflicts of Interest 416References 41615 Zeolites Containing Heteroatoms/Metal Nanoparticles for Catalytic Conversion of Light Alkanes 423Hang Zhou, Liang Wang, and Feng-Shou Xiao15.1 Introduction 42315.2 Metal Nanoclusters and Heteroatoms in Zeolite for Propane Dehydrogenation 42415.2.1 Zeolite-Based Catalysts for Non-Oxidative PDH 42515.2.2 Zeolite-Based Catalysts for Oxidative PDH 42615.3 Metallosilicates for Ethane Dehydrogenation 43015.3.1 Metallosilicates for Non-Oxidative Dehydrogenation of Ethane 43015.3.2 Metallosilicates for Oxidative Dehydrogenation of Ethane 43115.4 Zeolite Catalysts for Selective Oxidation of Methane 43215.4.1 Bionic Catalysis of Methane to Methanol Using Metallosilicates 43415.4.2 In situ Synthesizing Hydrogen Peroxide for Low-Temperature Methane Oxidation Using Metal@zeolite 43515.4.3 Direct Metal Oxidation with Oxygen by Zeolite-Supported Nanoparticle Catalysts 43615.5 Summary and Outlook 439Acknowledgments 440References 44016 Design and Applications of Single-Site Photocatalysis Using Metallosilicates 447Priyanka Verma and Hiromi Yamashita16.1 Introduction 44716.2 Ti-Based Single-Site Photocatalysis Within Zeolites and Mesoporous Silica 44916.3 Single-Site Photocatalysis Based Thin Films 45016.3.1 Thin Films with Ti-Oxide Species 45016.3.2 Thin Films with Various Metal Oxide Species (Mo, V, Cr, and W) 45216.4 Visible-Light Sensitive Single-Site Photocatalysis 45416.5 Nano-Sized Metal Preparation Using Single-Site Photocatalyst 45616.5.1 Preparation of Monometallic NPs 45616.5.2 Preparation of Bimetallic Metal NPs 45716.6 Conclusions 458Acknowledgments 461References 461Index 465