Mesoporous Zeolites

Javier Garcia-Martinez is the founder of and chief scientist at Rive Technology, Inc. in Boston, USA, a spin-off from MIT that commercializes mesostructured zeolites to the refining industry. He is also Professor of Inorganic Chemistry and the director of the Molecular Nanotechnology Lab at the University of Alicante, Spain. Since 2011 he is a member of the Bureau of IUPAC and Fellow of the Royal Society of Chemistry. His work has been honored with the European Young Chemist Award in 2006, MIT's Technology Review Award (TR35) in 2007, and by the World Economic Forum, which selected him as a Young Global Leader in 2009. Professor Garcia-Martinez has published extensively in the areas of nanomaterials, catalysis, and energy, and also has over 25 patents to his name. His latest books are "Nanotechnology for the Energy Challenge" (Wiley-VCH, 2014) and "The Chemical Element" (Wiley-VCH, 2011). Kunhao Li is a Project Leader at Rive Technology, Inc. since 2008. He has been heavily involved in the improvement of Rive's core technology in zeolite mesostructuring processes, zeolites and catalysts characterization, testing, and evaluation, as well as extension of application areas of mesostructured zeolites to chemical separations and other catalytic processes. He obtained PhD in chemistry at The George Washington University and did postdoctoral research at Rutgers University. His research work has resulted in many publications in the form of original papers and reviews, book chapters, technical reports, patent applications, and patents.

• Foreword XIIIPreface XVIIList of Contributors XXV1 Strategies to Improve the Accessibility to the Intracrystalline Void of ZeoliteMaterials: Some Chemical Reflections 1Joaquén Pérez-Pariente and Teresa Álvaro-Münoz1.1 Introduction 11.2 Strategies to Obtain New Large-Pore Materials 51.3 Methodologies to Control the Crystallization Process of Zeolite Materials in the Absence of Pore-Forming Agents 91.3.1 Confined Nucleation and Growth 111.3.2 Use of Blocking Agents for Crystal Growth 131.3.2.1 Silanization Methods 131.3.2.2 Use of Surfactants in the Synthesis of Silicoaluminophosphates 161.3.3 Synthesis in the Presence of Pore-Forming Agents 181.4 Postsynthesis Methodologies 211.4.1 Materials with High Structural Anisotropy: Layered Zeolites 211.4.2 Removal/Reorganization of T Atoms in the Crystal Bulk 231.5 Conclusions 24Acknowledgments 25References 252 Zeolite Structures of Nanometer Morphology: Small Dimensions, New Possibilities 31Heloise de Oliveira Pastore and Dilson Cardoso2.1 The Structures of Zeolites 342.1.1 FAU and EMT Structures: Zeolites X and Y 342.1.2 LTA Structure 502.1.3 BEA Structure 522.1.4 Pentasil Zeolites, MFI, and MEL Structures: ZSM-5, ZSM-11, and S-1 562.2 The Structures of Zeotypes: Aluminophosphates and Silicoaluminophosphates 632.3 Lamellar Zeolites 662.4 Conclusions and Perspectives 71References 753 Nanozeolites and Nanoporous Zeolitic Composites: Synthesis and Applications 79Gia-Thanh Vuong and Trong-On Do3.1 Introduction 793.2 Synthesis of Nanozeolites 813.2.1 Principles 813.2.2 Synthesis from Clear Solutions 873.2.2.1 Parameters Affecting the Crystal Size 873.2.3 Synthesis Using Growth Inhibitor 903.2.4 Confined Space Synthesis 913.2.5 Synthesis of Nanozeolites Using Organic Media 953.3 Nanozeolite Composites 983.4 Recent Advances in Application of Nanozeolites 1063.5 Conclusions and Perspectives 109References 1104 Mesostructured and Mesoporous Aluminosilicates with Improved Stability and Catalytic Activities 115Yu Liu4.1 Introduction 1154.2 Zeolite/Mesoporous Composite Aluminosilicates 1164.2.1 Synthesis of Zeolite/Mesoporous Composite Material 1164.2.2 Catalytic Evaluation of Zeolite/Mesoporous Composite Material 1244.3 Posttreatment of Mesostructured Materials 1284.3.1 Posttreatment of Mesoporous Materials by Zeolite Structure-Directing Agents or Zeolite Nanocrystals 1284.3.2 Postsynthesis Grafting of Aluminum Salts on theWalls of Mesostructured Materials 1334.4 Mesostructured and Mesoporous Aluminosilicates Assembled from Digested Zeolite Crystals 1354.5 Mesostructured and Mesoporous Aluminosilicates Assembled from Zeolite Seeds/Nanoclusters 1414.5.1 Assembly of Mesostructured Aluminosilicates from Zeolite Y Seeds 1414.5.2 Assembly of Mesostructured Aluminosilicates from Pentasil Zeolite Seeds 1454.6 Conclusions 152References 1535 Development of Hierarchical Porosity in Zeolites by Using Organosilane-Based Strategies 157David P. Serrano, José M. Escola, and Patricia Pizarro5.1 Introduction 1575.2 Types of Silanization-Based Methods 1595.2.1 Functionalization of Protozeolitic Units with Organosilanes 1595.2.1.1 Fundamentals of the Method 1595.2.1.2 Influence of the Organosilane Type 1635.2.1.3 Application to Different Zeolites 1665.2.1.4 Influence of the Silica Source 1685.2.1.5 Reduction of the Gel Viscosity by Means of Alcohols 1695.2.1.6 State of the Aluminum and Acidity 1715.2.2 Use of Silylated Polymers 1735.2.3 Use of Amphiphile Organosilanes 1755.3 Catalytic Applications 1805.3.1 Fine Chemistry 1805.3.2 Oil Refining and Petrochemistry 1855.3.3 Production of Advanced Fuels 1895.4 Conclusions 1935.5 New Trends and Future Perspectives 195References 1966 Mesoporous Zeolite Templated from Polymers 199Xiangju Meng and Feng-Shou Xiao6.1 Introduction 1996.2 Cationic Polymer Templating 2006.3 Nonionic Polymer Templating 2036.4 Silane-Functionalized Polymer Templating 2086.5 Polymer–Surfactant Complex Templating 2106.6 Morphology Control of Mesoporous Zeolites Using Polymers 2126.7 Zeolites with Oriented Mesoporous Channels 2186.8 Microfluidic Synthesis of Mesoporous Zeolites 2206.9 Nonsurfactant Cationic Polymer as a Dual-Function Template 2206.10 Conclusions 224References 2247 Nanofabrication of Hierarchical Zeolites in Confined Space 227Zhuopeng Wang and Wei Fan7.1 Introduction of Confined Space Synthesis 2277.2 General Principles of Confined Space Synthesis 2287.3 Crystallization Mechanisms of Zeolite under Hydrothermal Conditions 2287.4 Preparation of Synthesis Gel within the Confined Space of Inert Matrices 2307.5 Crystallization of Zeolite within Confined Space 2307.6 Synthesis of Hierarchical Zeolites in Carbon Blacks, Nanotubes, and Nanofibers by SAC Method 2327.7 Synthesis of Hierarchical Zeolites within Ordered Mesoporous Carbons by SAC and VPTMethods 2347.8 Synthesis of Hierarchical Zeolites within Carbon Aerogels, Polymer Aerogels, and other Carbon Materials 2417.9 Synthesis of Hierarchical Zeolites within Carbon Materials Using Seeded Growth Method 2437.10 Confined Synthesis of Zeolites in Polymer and Microemulsions 2487.11 Conclusions 250References 2538 Development of Hierarchical Pore Systems for Zeolite Catalysts 259Masaru Ogura and Masahiko Matsukata8.1 Introduction 2598.2 Alkali Treatment of ZSM-5: Effects of Alkaline Concentration, Treatment Temperature, and Treatment Duration 2608.3 Desilication of ZSM-5: Effects of Temperature and Time 2638.4 Alkali Treatment of ZSM-5 with Various Si/Al Molar Ratios: Effect of Si/Al on Mesopore Formation 2638.5 Desilication of ZSM-5: Effects of Other Descriptors 2728.6 Desilication of Silicalite-1 2738.7 Desilication of Other Zeolites: Multidimensionalization of Low-Dimensional Microstructures 2778.8 Desilicated Zeolites for Applications – Test Reactions 2808.9 Desilicated Zeolites for Applications – Superior Diffusion 2848.10 Desilicated Zeolites for Novel Applications 2898.11 Summary 291References 2929 Design and Catalytic Implementation of Hierarchical Micro–Mesoporous Materials Obtained by Surfactant-Mediated Zeolite Recrystallization 295Irina I. Ivanova, Elena E. Knyazeva, and Angelina A. Maerle9.1 Introduction 2959.2 Mechanism of Zeolite Recrystallization 2969.3 Synthetic Strategies Leading to Different Types of Recrystallized Materials 3019.4 Coated Mesoporous Zeolites (RZEO-1) 3039.5 Micro–Mesoporous Nanocomposites (RZEO-2) 3089.6 Mesoporous Materials with Zeolitic Fragments in theWalls (RZEO-3) 3129.7 Conclusions 316Acknowledgment 318References 31810 Surfactant-Templated Mesostructuring of Zeolites: FromDiscovery to Commercialization 321Kunhao Li,Michael Beaver, Barry Speronello, and Javier García-Martínez10.1 Introduction 32110.2 Surfactant-Templated Mesostructuring of Zeolites 32610.3 Mesostructured Zeolite Y for Fluid Catalytic Cracking Applications 33410.4 Beyond Catalysis: Mesostructured Zeolite X for Adsorptive Separations 34110.5 Concluding Remarks 344References 34511 Physical Adsorption Characterization of Mesoporous Zeolites 349Matthias Thommes, Rémy Guillet-Nicolas, and Katie A. Cychosz11.1 Introduction 34911.2 Experimental Aspects 35211.2.1 General 35211.2.2 Choice of Adsorptive 35411.3 Adsorption Mechanism 35711.4 Surface Area, Pore Volume, and Pore Size Analysis 36311.4.1 Surface Area 36311.4.2 Pore Size Analysis 36711.4.2.1 General Aspects 36711.4.2.2 Pore Size Analysis: Hierarchically Structured Materials 37011.5 Probing Hierarchy and Pore Connectivity in Mesoporous Zeolites 37611.6 Summary and Conclusions 378References 37912 Measuring Mass Transport in Hierarchical Pore Systems 385Jörg Kärger, Rustem Valiullin, Dirk Enke, and Roger Gläser12.1 Types of Pore Space Hierarchies in Nanoporous Host Materials 38512.2 Hierarchy of Mass Transfer Parameters and Options of Their Measurement Techniques 38912.2.1 Diffusion Fundamentals 38912.2.2 Techniques of Diffusion Measurement 39212.2.2.1 Macroscopic Diffusion Studies: Uptake and Release 39212.2.2.2 Microscopic Diffusion Measurement: Molecular Displacements 39612.2.2.3 Microscopic Diffusion Measurement: Transient Concentration Profiles 39912.3 Diffusion Measurement in Various Types of Pore Space Hierarchies 40012.3.1 Macro/Meso 40012.3.2 Macro/Micro 40112.3.3 Meso/Meso 40412.3.4 Meso/Micro 40712.3.4.1 PFG NMR DiffusionMeasurements in Y-Type Zeolites: A Case Study with FCC Catalysts 40712.3.4.2 Mass Transfer in Mesoporous LTA-Type Zeolites: An In-Depth Study of Diffusion Phenomena in Mesoporous Zeolites 40912.3.4.3 Diffusion Studies with Mesoporous Zeolite of Structure-Type CHA: Breakdown of the Fast-Exchange Model 41412.3.4.4 The Impact of Hysteresis 41512.4 Conclusions and Outlook 416References 41713 Structural Characterization of Zeolites and Mesoporous Zeolite Materials by ElectronMicroscopy 425Wei Wan, Changhong Xiao, and Xiaodong Zou13.1 Introduction 42513.2 Characterization of Zeolites by Electron Diffraction 42613.2.1 Geometry of Electron Diffraction 42713.2.2 Conventional Electron Diffraction 42813.2.3 Three-Dimensional (3D) Electron Diffraction 43013.3 Characterization of Zeolite and Mesoporous Materials by High-Resolution Transmission Electron Microscopy 43313.3.1 Introduction to HRTEM 43313.3.2 Working with Electron-Beam-Sensitive Materials 43413.3.3 Structure Projection Reconstruction from Through-Focus HRTEM Images 43513.3.4 3D Reconstruction of HRTEM Images 43713.4 Characterization of Zeolite and Mesoporous Materials by Electron Tomography (ET) 44013.4.1 Basic Principles of Electron Tomography 44013.4.2 Applications of Electron Tomography on Mesoporous Zeolites 44313.4.2.1 Quantification of Mesopores in Zeolite Y 44313.4.2.2 Quantification of Pt Nanoparticles in Mesoporous Zeolite Y 44413.4.2.3 Orientation Relationship between the Intrinsic Micropores of Zeolite Y andMesopore Structures 44513.4.2.4 Single-Crystal Mesoporous Zeolite Beta Studied by Transmission Scanning Electron Microscopy (STEM) 44813.5 Other Types of Mesoporous Zeolites Studied by EM 45013.5.1 Aluminosilicate Zeolite ZSM-5 Single Crystals with b-Axis-Aligned Mesopores 45013.5.2 Mesoporous Zeolite LTA 45113.5.3 Ultrasmall EMT Crystals with Intercrystalline Mesopores from Organic Template-Free Synthesis 45213.5.4 Self-Pillared Zeolites with Interconnected Micropores and Mesopores 45213.6 Future Perspectives 45413.7 Conclusions 455Acknowledgments 456References 45614 Acidic Properties of Hierarchical Zeolites 461Jerzy Datka, Karolina Tarach, and Kinga Góra-Marek14.1 Short Overview of Experimental Methods Employed for Acidity Investigations 46114.2 Hierarchical Zeolites Obtained by Templating and Dealumination of Composite Materials 46314.2.1 Surfactant Templating Approach 46514.2.2 Dealumination 47014.3 Hierarchical Zeolites Obtained by Desilication 47114.3.1 Studies of Desilicated Zeolites Acidity 47114.3.1.1 Analysis of the Hydroxyl Groups Spectra 47114.3.1.2 Concentration of Acid Sites 47414.3.1.3 Studies of Acid Sites Strength 47514.3.1.4 Realumination: Mesopore Surface Enrichment in Al Species 47614.3.1.5 Nature and Origin of Lewis Acid Sites in Desilicated Zeolites 47714.3.2 Accessibility of Acid Sites in Desilicated Zeolites 48114.4 Conclusions and Future Perspectives 487Acknowledgments 489References 48915 Mesoporous Zeolite Catalysts for Biomass Conversion to Fuels and Chemicals 497Kostas S. Triantafyllidis, Eleni F. Iliopoulou, Stamatia A. Karakoulia, Christos K. Nitsos, and Angelos A. Lappas15.1 Introduction to Mesoporous/Hierarchical Zeolites 49715.2 Potential of Hierarchical Zeolites as Catalysts for the Production of Renewable/Biomass-Derived Fuels and Chemicals 50315.3 Catalytic Fast Pyrolysis (CFP) of Lignocellulosic Biomass 50815.4 Catalytic Cracking of Vegetable Oils 51415.5 Hydroprocessing of Biomass-Derived Feeds 51615.6 Methanol to Hydrocarbons 52415.6.1 Methanol to Dimethyl Ether (DME) 52515.6.2 Methanol to Gasoline (MTG)/Methanol to Olefins (MTO) 52715.7 Other Processes 53315.8 Summary and Outlook 535References 53616 Industrial Perspectives for Mesoporous Zeolites 541Roberto Millini and Giuseppe Bellussi16.1 Introduction 54116.2 Enhancing the Effectiveness of the Zeolite Catalysts 54316.2.1 Increasing the Pore Size 54416.2.2 Hierarchical (Mesoporous) Zeolites 54616.3 Industrial Assessment of Mesoporous Zeolite 55516.4 Conclusions 560References 561Index 565

'This book is interesting and very informative. It broadly covers all areas of mesoporous materials: synthesis, characterisation and application.' (Johnson Matthey Process Technology 2016)