PROFESSOR DUNCAN BRUCE graduated from the University of Liverpool (UK), where he also gained his PhD. In 1984, he took up a Temporary Lectureship in Inorganic Chemistry at the University of Sheffield and was awarded a Royal Society Warren Research Fellowship. He was then appointed Lecturer in Chemistry and was promoted Senior Lecturer in 1994, in which year he became co-director of the Sheffield Centre for Molecular Materials. In 1995, he was appointed Professor of Inorganic Chemistry at the University of Exeter. Following the closure of Exeter's chemistry department in 2005, Professor Bruce took up his present position as Professor of Materials Chemistry in York. He is currently Chair of the Royal Society of Chemistry Materials Chemistry Forum. His current research interests include liquid crystals and nanoparticle-doped, nanostructured, mesoporous silicates. His work has been recognized by various awards including the British Liquid Crystal Society's first Young Scientist prize and the RSC's Sir Edward Frankland Fellowship and Corday-Morgan Medal and Prize. He has held visiting positions in Australia, France, Japan and Italy. DR. RICHARD WALTON, who was also formerly based in the Department of Chemistry at the University of Exeter, now works in the Department of Chemistry at the University of Warwick. His research group works in the area of solid-state materials chemistry and has a number of projects focusing upon the synthesis, structural characterization and properties of inorganic materials.DERMOT O'HARE is Professor in the Chemistry Research Laboratory at the University of Oxford. is research group has a wide range of research interests. They all involve synthetic chemistry ranging from organometallic chemistry to the synthesis of new microporous solids. Duncan Bruce and Dermot O'Hare have edited several editions of Inorganic Materials published by John Wiley & Sons Ltd.

• Inorganic Materials Series Preface ix Preface xiList of Contributors xiii1 Metal-Organic Framework Materials 1Cameron J. Kepert1.1 Introduction 11.2 Porosity 31.2.1 Framework Structures and Properties 31.2.2 Storage and Release 181.2.3 Selective Guest Adsorption and Separation 211.2.4 Heterogeneous Catalysis 271.3 Incorporation of Other Properties 311.3.1 Magnetic Ordering 321.3.2 Electronic and Optical Properties 411.3.3 Structural and Mechanical Properties 511.4 Concluding Remarks 54Acknowledgements 56References 562 Mesoporous Silicates 69Karen J. Edler2.1 Introduction 692.2 Nomenclature 702.3 Methods of Preparation 712.4 Surfactant Aggregation 722.5 Silica Source 752.6 Template Removal 792.7 Synthetic Routes and Formation Mechanisms 832.7.1 True Liquid Crystal Templating 832.7.2 Cooperative Self-Assembly 872.7.3 Evaporation-Induced Self-Assembly 992.8 Properties and Characterisation 1082.9 Macroscopic Structures 1172.10 Applications 124References 1283 Ordered Porous Crystalline Transition Metal Oxides 147Masahiro Sadakane and Wataru Ueda3.1 Introduction 1473.2 Scope and Limitations of this Review 1483.3 Microporous Transition Metal Oxide Materials 1493.4 Mesoporous Transition Metal Oxide Materials 1533.4.1 Soft Template Method 1543.4.2 Hard Template Method 1553.4.3 MesoporousOxides ofGroup 4 Elements (Ti,Zr) 1573.4.4 MesoporousOxidesofGroup5Elements (Nb,Ta) 1703.4.5 Mesoporous Oxides of Group 6 Elements (Cr, Mo, W) 1723.4.6 Mesoporous Oxides of Group 7 Elements (Mn) 1723.4.7 Mesoporous Oxides of Elements of Groups 8–11 (Fe, Co, Ni, Cu) 1733.4.8 Mesoporous Oxides of Lanthanide Elements (Ce) 1743.5 Macroporous Materials 1743.5.1 Macroporous Monometal Oxides 1773.5.2 MacroporousOxidesofGroup4Elements (Ti,Zr) 1913.5.3 MacroporousOxidesofGroup5Elements(V,Nb) 1913.5.4 MacroporousOxidesofGroup6Elements(Cr,W) 1923.5.5 Macroporous Oxides of Elements of Groups 7–11 (Mn, Fe, Co, Ni, Cu) 1933.5.6 Macroporous Oxides of Lanthanide Elements (La, Ce, Nd, Sm, Eu) 1943.5.7 Macroporous Multi-Component Metal Oxides 1943.5.8 Two-Step Templating Method 2073.5.9 Applications 2073.6 Conclusion 209References 2094 Templated Porous Carbon Materials: Recent Developments 217Yongde Xia, Zhuxian Yang and Robert Mokaya4.1 Introduction 2174.2 Microporous Carbon Materials 2214.2.1 Zeolites as Hard Template 2214.2.2 Clays as Hard Template 2294.2.3 Other Microporous Materials as Hard Template 2314.3 Mesoporous Carbon Materials 2314.3.1 Conventional Hard Template Synthesis Strategy 2324.3.2 Cost-Effective Strategies for the Synthesis of Mesoporous Carbons 2404.3.3 Soft-Template Synthesis Strategy for Ordered Mesoporous Carbons 2414.3.4 Ordered Mesoporous Carbons with Graphitic Pore Wall 2444.3.5 Mesopore Size Control 2464.3.6 Morphology Control 2474.4 Macroporous Carbon Materials 2524.4.1 Silica Colloidal Crystals as Hard Template 2524.4.2 Polymer Microspheres as Template 2544.4.3 Dual Template Method 255References 2585 Synthetic Silicate Zeolites: Diverse Materials Accessible Through Geoinspiration 265Miguel A. Camblor and Suk Bong Hong5.1 Introduction 2655.2 Zeolites: Some Definitions 2675.3 Zeolite Structures 2695.4 Chemical Composition of Silicate Zeolites 2705.4.1 Naming Zeolites 2725.4.2 Loewenstein’s Rule 2735.5 Zeolite Properties 2745.6 Zeolite Applications 2755.7 Zeolite Synthesis 2795.7.1 The Synthetic Zeolites as Geoinspired Materials 2795.7.2 Thermochemistry of Zeolite Synthesis 2815.7.3 Organic Structure-Directing Agents 2845.7.4 Structure-Direction by Flexible, Hydrophilic OSDAs 2895.7.5 Double OSDA Strategies 2955.7.6 Structure-Direction by T-Atoms 2975.7.7 Zeolite Synthesis from Nonaqueous Solvents 3075.7.8 The Fluoride Route to Zeolites 3085.7.9 Structure-Direction Issues in the Fluoride Route to Pure-Silica Zeolites 3125.7.10 Topotactic Condensation of Layered Silicates 3155.8 Concluding Remarks 316Acknowledgements 316References 317Index 327

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PROFESSOR DUNCAN BRUCE graduated from the University of Liverpool (UK), where he also gained his PhD. In 1984, he took up a Temporary Lectureship in Inorganic Chemistry at the University of Sheffield and was awarded a Royal Society Warren Research Fellowship. He was then appointed Lecturer in Chemistry and was promoted Senior Lecturer in 1994, in which year he became co-director of the Sheffield Centre for Molecular Materials. In 1995, he was appointed Professor of Inorganic Chemistry at the University of Exeter. Following the closure of Exeter's chemistry department in 2005, Professor Bruce took up his present position as Professor of Materials Chemistry in York. He is currently Chair of the Royal Society of Chemistry Materials Chemistry Forum. His current research interests include liquid crystals and nanoparticle-doped, nanostructured, mesoporous silicates. His work has been recognized by various awards including the British Liquid Crystal Society's first Young Scientist prize and the RSC's Sir Edward Frankland Fellowship and Corday-Morgan Medal and Prize. He has held visiting positions in Australia, France, Japan and Italy. DR. RICHARD WALTON, who was also formerly based in the Department of Chemistry at the University of Exeter, now works in the Department of Chemistry at the University of Warwick. His research group works in the area of solid-state materials chemistry and has a number of projects focusing upon the synthesis, structural characterization and properties of inorganic materials.DERMOT O'HARE is Professor in the Chemistry Research Laboratory at the University of Oxford. is research group has a wide range of research interests. They all involve synthetic chemistry ranging from organometallic chemistry to the synthesis of new microporous solids. Duncan Bruce and Dermot O'Hare have edited several editions of Inorganic Materials published by John Wiley & Sons Ltd.

• Inorganic Materials Series Preface ix Preface xiList of Contributors xiii1 Metal-Organic Framework Materials 1Cameron J. Kepert1.1 Introduction 11.2 Porosity 31.2.1 Framework Structures and Properties 31.2.2 Storage and Release 181.2.3 Selective Guest Adsorption and Separation 211.2.4 Heterogeneous Catalysis 271.3 Incorporation of Other Properties 311.3.1 Magnetic Ordering 321.3.2 Electronic and Optical Properties 411.3.3 Structural and Mechanical Properties 511.4 Concluding Remarks 54Acknowledgements 56References 562 Mesoporous Silicates 69Karen J. Edler2.1 Introduction 692.2 Nomenclature 702.3 Methods of Preparation 712.4 Surfactant Aggregation 722.5 Silica Source 752.6 Template Removal 792.7 Synthetic Routes and Formation Mechanisms 832.7.1 True Liquid Crystal Templating 832.7.2 Cooperative Self-Assembly 872.7.3 Evaporation-Induced Self-Assembly 992.8 Properties and Characterisation 1082.9 Macroscopic Structures 1172.10 Applications 124References 1283 Ordered Porous Crystalline Transition Metal Oxides 147Masahiro Sadakane and Wataru Ueda3.1 Introduction 1473.2 Scope and Limitations of this Review 1483.3 Microporous Transition Metal Oxide Materials 1493.4 Mesoporous Transition Metal Oxide Materials 1533.4.1 Soft Template Method 1543.4.2 Hard Template Method 1553.4.3 MesoporousOxides ofGroup 4 Elements (Ti,Zr) 1573.4.4 MesoporousOxidesofGroup5Elements (Nb,Ta) 1703.4.5 Mesoporous Oxides of Group 6 Elements (Cr, Mo, W) 1723.4.6 Mesoporous Oxides of Group 7 Elements (Mn) 1723.4.7 Mesoporous Oxides of Elements of Groups 8–11 (Fe, Co, Ni, Cu) 1733.4.8 Mesoporous Oxides of Lanthanide Elements (Ce) 1743.5 Macroporous Materials 1743.5.1 Macroporous Monometal Oxides 1773.5.2 MacroporousOxidesofGroup4Elements (Ti,Zr) 1913.5.3 MacroporousOxidesofGroup5Elements(V,Nb) 1913.5.4 MacroporousOxidesofGroup6Elements(Cr,W) 1923.5.5 Macroporous Oxides of Elements of Groups 7–11 (Mn, Fe, Co, Ni, Cu) 1933.5.6 Macroporous Oxides of Lanthanide Elements (La, Ce, Nd, Sm, Eu) 1943.5.7 Macroporous Multi-Component Metal Oxides 1943.5.8 Two-Step Templating Method 2073.5.9 Applications 2073.6 Conclusion 209References 2094 Templated Porous Carbon Materials: Recent Developments 217Yongde Xia, Zhuxian Yang and Robert Mokaya4.1 Introduction 2174.2 Microporous Carbon Materials 2214.2.1 Zeolites as Hard Template 2214.2.2 Clays as Hard Template 2294.2.3 Other Microporous Materials as Hard Template 2314.3 Mesoporous Carbon Materials 2314.3.1 Conventional Hard Template Synthesis Strategy 2324.3.2 Cost-Effective Strategies for the Synthesis of Mesoporous Carbons 2404.3.3 Soft-Template Synthesis Strategy for Ordered Mesoporous Carbons 2414.3.4 Ordered Mesoporous Carbons with Graphitic Pore Wall 2444.3.5 Mesopore Size Control 2464.3.6 Morphology Control 2474.4 Macroporous Carbon Materials 2524.4.1 Silica Colloidal Crystals as Hard Template 2524.4.2 Polymer Microspheres as Template 2544.4.3 Dual Template Method 255References 2585 Synthetic Silicate Zeolites: Diverse Materials Accessible Through Geoinspiration 265Miguel A. Camblor and Suk Bong Hong5.1 Introduction 2655.2 Zeolites: Some Definitions 2675.3 Zeolite Structures 2695.4 Chemical Composition of Silicate Zeolites 2705.4.1 Naming Zeolites 2725.4.2 Loewenstein’s Rule 2735.5 Zeolite Properties 2745.6 Zeolite Applications 2755.7 Zeolite Synthesis 2795.7.1 The Synthetic Zeolites as Geoinspired Materials 2795.7.2 Thermochemistry of Zeolite Synthesis 2815.7.3 Organic Structure-Directing Agents 2845.7.4 Structure-Direction by Flexible, Hydrophilic OSDAs 2895.7.5 Double OSDA Strategies 2955.7.6 Structure-Direction by T-Atoms 2975.7.7 Zeolite Synthesis from Nonaqueous Solvents 3075.7.8 The Fluoride Route to Zeolites 3085.7.9 Structure-Direction Issues in the Fluoride Route to Pure-Silica Zeolites 3125.7.10 Topotactic Condensation of Layered Silicates 3155.8 Concluding Remarks 316Acknowledgements 316References 317Index 327

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PROFESSOR DUNCAN BRUCE graduated from the University of Liverpool (UK), where he also gained his PhD. In 1984, he took up a Temporary Lectureship in Inorganic Chemistry at the University of Sheffield and was awarded a Royal Society Warren Research Fellowship. He was then appointed Lecturer in Chemistry and was promoted Senior Lecturer in 1994, in which year he became co-director of the Sheffield Centre for Molecular Materials. In 1995, he was appointed Professor of Inorganic Chemistry at the University of Exeter. Following the closure of Exeter's chemistry department in 2005, Professor Bruce took up his present position as Professor of Materials Chemistry in York. He is currently Chair of the Royal Society of Chemistry Materials Chemistry Forum. His current research interests include liquid crystals and nanoparticle-doped, nanostructured, mesoporous silicates. His work has been recognized by various awards including the British Liquid Crystal Society's first Young Scientist prize and the RSC's Sir Edward Frankland Fellowship and Corday-Morgan Medal and Prize. He has held visiting positions in Australia, France, Japan and Italy. DR. RICHARD WALTON, who was also formerly based in the Department of Chemistry at the University of Exeter, now works in the Department of Chemistry at the University of Warwick. His research group works in the area of solid-state materials chemistry and has a number of projects focusing upon the synthesis, structural characterization and properties of inorganic materials.DERMOT O'HARE is Professor in the Chemistry Research Laboratory at the University of Oxford. is research group has a wide range of research interests. They all involve synthetic chemistry ranging from organometallic chemistry to the synthesis of new microporous solids. Duncan Bruce and Dermot O'Hare have edited several editions of Inorganic Materials published by John Wiley & Sons Ltd.

• Inorganic Materials Series Preface ix Preface xiList of Contributors xiii1 Metal-Organic Framework Materials 1Cameron J. Kepert1.1 Introduction 11.2 Porosity 31.2.1 Framework Structures and Properties 31.2.2 Storage and Release 181.2.3 Selective Guest Adsorption and Separation 211.2.4 Heterogeneous Catalysis 271.3 Incorporation of Other Properties 311.3.1 Magnetic Ordering 321.3.2 Electronic and Optical Properties 411.3.3 Structural and Mechanical Properties 511.4 Concluding Remarks 54Acknowledgements 56References 562 Mesoporous Silicates 69Karen J. Edler2.1 Introduction 692.2 Nomenclature 702.3 Methods of Preparation 712.4 Surfactant Aggregation 722.5 Silica Source 752.6 Template Removal 792.7 Synthetic Routes and Formation Mechanisms 832.7.1 True Liquid Crystal Templating 832.7.2 Cooperative Self-Assembly 872.7.3 Evaporation-Induced Self-Assembly 992.8 Properties and Characterisation 1082.9 Macroscopic Structures 1172.10 Applications 124References 1283 Ordered Porous Crystalline Transition Metal Oxides 147Masahiro Sadakane and Wataru Ueda3.1 Introduction 1473.2 Scope and Limitations of this Review 1483.3 Microporous Transition Metal Oxide Materials 1493.4 Mesoporous Transition Metal Oxide Materials 1533.4.1 Soft Template Method 1543.4.2 Hard Template Method 1553.4.3 MesoporousOxides ofGroup 4 Elements (Ti,Zr) 1573.4.4 MesoporousOxidesofGroup5Elements (Nb,Ta) 1703.4.5 Mesoporous Oxides of Group 6 Elements (Cr, Mo, W) 1723.4.6 Mesoporous Oxides of Group 7 Elements (Mn) 1723.4.7 Mesoporous Oxides of Elements of Groups 8–11 (Fe, Co, Ni, Cu) 1733.4.8 Mesoporous Oxides of Lanthanide Elements (Ce) 1743.5 Macroporous Materials 1743.5.1 Macroporous Monometal Oxides 1773.5.2 MacroporousOxidesofGroup4Elements (Ti,Zr) 1913.5.3 MacroporousOxidesofGroup5Elements(V,Nb) 1913.5.4 MacroporousOxidesofGroup6Elements(Cr,W) 1923.5.5 Macroporous Oxides of Elements of Groups 7–11 (Mn, Fe, Co, Ni, Cu) 1933.5.6 Macroporous Oxides of Lanthanide Elements (La, Ce, Nd, Sm, Eu) 1943.5.7 Macroporous Multi-Component Metal Oxides 1943.5.8 Two-Step Templating Method 2073.5.9 Applications 2073.6 Conclusion 209References 2094 Templated Porous Carbon Materials: Recent Developments 217Yongde Xia, Zhuxian Yang and Robert Mokaya4.1 Introduction 2174.2 Microporous Carbon Materials 2214.2.1 Zeolites as Hard Template 2214.2.2 Clays as Hard Template 2294.2.3 Other Microporous Materials as Hard Template 2314.3 Mesoporous Carbon Materials 2314.3.1 Conventional Hard Template Synthesis Strategy 2324.3.2 Cost-Effective Strategies for the Synthesis of Mesoporous Carbons 2404.3.3 Soft-Template Synthesis Strategy for Ordered Mesoporous Carbons 2414.3.4 Ordered Mesoporous Carbons with Graphitic Pore Wall 2444.3.5 Mesopore Size Control 2464.3.6 Morphology Control 2474.4 Macroporous Carbon Materials 2524.4.1 Silica Colloidal Crystals as Hard Template 2524.4.2 Polymer Microspheres as Template 2544.4.3 Dual Template Method 255References 2585 Synthetic Silicate Zeolites: Diverse Materials Accessible Through Geoinspiration 265Miguel A. Camblor and Suk Bong Hong5.1 Introduction 2655.2 Zeolites: Some Definitions 2675.3 Zeolite Structures 2695.4 Chemical Composition of Silicate Zeolites 2705.4.1 Naming Zeolites 2725.4.2 Loewenstein’s Rule 2735.5 Zeolite Properties 2745.6 Zeolite Applications 2755.7 Zeolite Synthesis 2795.7.1 The Synthetic Zeolites as Geoinspired Materials 2795.7.2 Thermochemistry of Zeolite Synthesis 2815.7.3 Organic Structure-Directing Agents 2845.7.4 Structure-Direction by Flexible, Hydrophilic OSDAs 2895.7.5 Double OSDA Strategies 2955.7.6 Structure-Direction by T-Atoms 2975.7.7 Zeolite Synthesis from Nonaqueous Solvents 3075.7.8 The Fluoride Route to Zeolites 3085.7.9 Structure-Direction Issues in the Fluoride Route to Pure-Silica Zeolites 3125.7.10 Topotactic Condensation of Layered Silicates 3155.8 Concluding Remarks 316Acknowledgements 316References 317Index 327

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