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纳米科学与技术大全5:自组装与纳米化学（导读版）

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印刷时间：2012年07月01日
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国际标准书号ISBN：9787030346605
丛书名：纳米科学与技术大全：5

作者:(英)安德鲁斯出版社:科学出版社出版时间:2012年07月

内容简介

纳米科学与技术大全5：自组装与纳米化学（导读版）作者将生态学不同领域的理论和实验进展与新方法相结合，在个体层次与群落结构、生态系统功能间，微观世界与宏观生态间的融合做了很好的尝试，为我们理解生态现象、生态过程以及生态功能展示了一个很好的途径。
纳米科学与技术大全5：自组装与纳米化学（导读版）可作为研究生生态课程的参考书，对于从事生态学教学和研究的教师和科研人员及生态学者有非常高的参考价值。

作者简介

Gregory D.Scholes、Frank Caruso

目　　录

5.01 多孔金属有机骨架
5.01.1 Introduction
5.01.2 Inorganic SBUs and Organic Linkers
5.01.3 Architecture of the Networks
5.01.4 Porous Structures
5.01.4.1 0D Cage
5.01.4.2 1D Channels
5.01.4.3 2D Layers
5.01.4.4 3D Channels
5.01.5 Synthesis of MOFs
5.01.5.1 Influencing Factors
5.01.5.2 Solvent-Evaporation Synthesis
5.01.5.3 Diffusion Synthesis
5.01.5.4 Hydrothermal (or Solvothermal) Synthesis

5.01 多孔金属有机骨架 5.01.1 Introduction 5.01.2 Inorganic SBUs and Organic Linkers 5.01.3 Architecture of the Networks 5.01.4 Porous Structures 5.01.4.1 0D Cage 5.01.4.2 1D Channels 5.01.4.3 2D Layers 5.01.4.4 3D Channels 5.01.5 Synthesis of MOFs 5.01.5.1 Influencing Factors 5.01.5.2 Solvent-Evaporation Synthesis 5.01.5.3 Diffusion Synthesis 5.01.5.4 Hydrothermal (or Solvothermal) Synthesis 5.01.5.5 Microwave-Reaction Synthesis 5.01.5.6 Ionothermal Synthesis 5.01.5.7 Electrochemical Synthesis 5.01.5.8 High-Throughput Synthesis 5.01.6 Functions of MOFs 5.01.6.1 Gas Storage 5.01.6.1.1 Hydrogen Storage 5.01.6.1.2 Methane Storage 5.01.6.1.3 Carbon Dioxide Storage 5.01.6.2 Selective Gas Adsorptions and Separations 5.01.6.3 Catalysis 5.01.6.4 Magnetism 5.01.6.5 Optics 5.01.6.6 Sensor 5.01.6.7 Drug Delivery 5.01.7 Summary and Outlook References 5.02 纳米粒子配体 5.02.1 Introduction 5.02.2 Ligands, Chief Cook, and Bottle Washer 5.02.2.1 Ligands Control the Synthesis of NPs 5.02.2.2 A Brief Introduction to Classical Nucleation Theory 5.02.2.3 Ligands Stabilize NP Suspensions 5.02.2.4 Ligands and the Shape of NPs 5.02.2.5 Ligands Give NPs Physicochemical Functionality 5.02.3 What to Expect,Ab Initio Calculations 5.02.4 Experimental Observation of NP Ligands 5.02.4.1 Indirect Probing of Ligand Exchange 5.02.4.2 Direct Probing of Ligands 5.02.5 Observing NP Ligands with Solution NMR Spectroscopy 5.02.5.1 Solution NMR Techniques for Observing QD Ligands 5.02.5.1.1 A brief introduction in solution NMR spectroscopy 5.02.5.1.2 Pulsed field gradient NMR spectroscopy 5.02.5.1.3 Nuclear Overhauser effect NMR spectroscopy 5.02.5.2 The Tightly Bound Ligand 5.02.5.2.1 What to expect? 5.02.5.2.2 The basic experiment:1D 1H NMR 5.02.5.2.3 Tracing down the ligand resonances by diffusion NMR 5.02.5.2.4 Identifying ligands, proton-carbon correlations 5.02.5.2.5 A note on relaxation rates and peak broadening 5.02.5.3 Adsorption-Desorption Equilibria,1H NMR as a Quantitative Technique 5.02.5.3.1 Quantitative NMR 5.02.5.3.2 Observing adsorption-desorption equilibria by NMR 5.02.5.3.3 Understanding the adsorption isotherm 5.02.5.4 Adsorption-Desorption Kinetics,Exploiting the NOE 5.02.5.4.1 Dodecylamine stabilized Q-CdTe,does the tightly bound ligand model work? 5.02.5.4.2 Observed NMR resonances,a story of timescales 5.02.5.4.3 Tightly bound ligands have strongly negative NOEs 5.02.5.4.4 Rapidly exchanging ligands show strongly negative transfer NoEs 5.02.5.5 In Situ Monitoring of NP Synthesis References 5.03 纳米粒子组装 5.03.1 Introduction 5.03.2 Assembly Methods for 1D NPs 5.03.2.1 Assembly of NPs for Nanorod and Nanowire Formation 5.03.2.2 Assembly of 1D NPs on Polymer Templates 5.03.3 Assembly of NPs to Form 2D Nanocomposites 5.03.4 Biomolecules as Templates for Assembling NPs in 1D and 2D Architectures 5.03.5 Modulation of the Properties of 1D and 2D Structures 5.03.5.1 Optical Response 5.03.5.2 Electronic Behavior 5.03.5.3 Magnetic Properties 5.03.6 Summary and Outlook References 5.04 周期的介孔材料:充满机遇的孔道 5.04.1 Introduction 5.04.2 Hierarchical Organization of Mesoporous Materials 5.04.2.1 Self-Assembly of Sol-Gel Precursors and Templates-From Micro to Meso 5.04.2.2 Growing Complexity:Powder,Films,and the Importance of Form 5.04.3 Bringing Function into Voids 5.04.3.1 Grafting 5.04.3.2 Co-Condensation 5.04.3.3 Periodic Mesoporous Organosilicates 5.04.4 Nonsiliceous Mesoporous Materials 5.04.4.1 Mesoporous Metal Oxides and Phosphates 5.04.4.1.1 Synthesis strategies and objectives 5.04.4.1.2 Realized compositions 5.04.4.1.3 Perspectives I:Toward crystallized mesoporous oxides 5.04.4.1.4 Perspectives II:Form and function 5.04.4.2 Mesoporous Metals and Semiconductors 5.04.4.2.1 Mesoporous semiconductors 5.04.4.2.2 Mesoporous metals 5.04.4.3 Mesoporous Carbon 5.04.4.3.1 OMCs obtained by hard templating 5.04.4.3.2 OMCs obtained by soft templating 5.04.4.4 Mesoporous Ceramic Materials 5.04.4.4.1 Silicon-based mesoporous ceramics 5.04.4.4.2 Mesoporous carbon and boron-based ceramics 5.04.5 Mesoscience to Mesotechnology-Why Meso? 5.04.5.1 Sorbents and Separation Science 5.04.5.2 Catalysis 5.04.5.3 Drug Delivery 5.04.5.4 Sensing 5.04.5.5 Low-k Materials 5.04.5.6 Photovoltaics 5.04.6 Conclusion and Outlook References 5.05 单层自组装 5.05.1 Molecular Self-Assembly and Nanoscience 5.05.2 Driving Forces for Molecular Assembly:Molecular Interactions in Self-Assembled Monolayers 5.05.3 Overview of Previous Studies of Molecular Self-Assembled Monolayers 5.05.4 Brief Summary of Synthetic Methods of 2D Self-Assembled Monolayers and the Main Techniques to Study them 5.05.5 Molecular Self-Assembly on Au(111) 5.05.5.1 CH3(CH2)nSH 5.05.5.2 CH3(CH2)nCS2H 5.05.5.3 C6H5(CH2)nSH 5.05.5.4 CH3-(C6H4)2-(CH2)n-SH 5.05.5.5 CF3(CH2)nSH 5.05.5.6 Diamidothiol 5.05.6 Organic Monolayers on Ag(111) 5.05.7 Self-assembly of Organic Molecules on Cu,Al,Hg,Al2O3,and SiOx/Si Substrates 5.05.8 Molecular Self-Assembly on Highly Oriented Pyrolytic Graphite 5.05.8.1 Single-Component Long-Chain Molecules:Linear Packing and Molecular Distortion 5.05.8.1.1 Molecular parallel packing 5.05.8.1.2 Molecular distortion 5.05.8.2 Multicomponent Self-Assembly and Formation of Nanostructures 5.05.8.3 Molecular Chirality upon Self-Assembly 5.05.9 Summary References 5.06 纳米晶体合成 5.06.1 Introduction 5.06.1.1 Milestones of Progress in Nanocrystal Synthesis 5.06.1.2 Synthetic Methods 5.06.1.2.1 High-temperature organo-metallic method 5.06.1.2.2 Single-source molecular precursor method 5.06.1.2.3 Solvothermal/hydrothermal method 5.06.1.2.4 Water-phase synthesis 5.06.1.2.5 Template-assisted growth methods 5.06.1.2.6 Synthesis of semiconductor nanocrystals in microfluidic reactors 5.06.2 Size Tuneability of Nanocrystals 5.06.2.1 Introduction 5.06.2.2 Mechanisms of Size Control 5.06.2.2.1 Nucleation and growth of nanocrystal 5.06.2.2.2 Concepts in size control 5.06.3 Shape,Phase,and Composition Control of Nanocrystals 5.06.3.1 Shape Control of Nanocrystals 5.06.3.1.1 Dynamic-induced anisotropic growth 5.06.3.1.2 Seed-mediated growth 5.06.3.1.3 The Oriented attached method 5.06.3.2 Composition Control 5.06.4 Overview of the Nanocrystal Synthesis by Material 5.06.4.1 II-VI Semiconductor Nanocrystals 5.06.4.2 III-V Semiconductor Nanocrystals 5.06.4.3 IV-VI Semiconductor Nanocrystals 5.06.4.4 IV Semiconductor Nanocrystals 5.06.4.5 III-VI and I-III-V Nanocrystals 5.06.4.6 Metal Oxides 5.06.4.6.1 Sol-gel method 5.06.4.6.2 Nonhydrolytic route 5.06.5 New-Generation Semiconductor Nanocrystals 5.06.5.1 Nanocrystal Heterostructures 5.06.5.1.1 Synthetic techniques for the preparation of nanocrystal heterostructures 5.06.5.1.2 Synthesis of 0D core-shell Nanocrystal heterostructures 5.06.5.1.3 Synthesis of anisotropic and more complex nanocrystal heterostructures 5.06.5.2 Doped Nanocrystals 5.06.5.2.1 Synthesis of doped nanocrystals 5.06.6 Summary References 5.07 纳米粒子自组装基元 5.07.1 Introduction 5.07.1.1 Self-Assembly Principle 5.07.1.2 NBB Classification 5.07.2 NBB Self-Assembly Approaches 5.07.2.1 Self-Assembly on a Substrate 5.07.2.2 Interfacial Assembly 5.07.2.3 Template-Assisted Assembly 5.07.3 Self-Assembly of Complex-Shaped NBBs:Tetrapods 5.07.4 Computational Approach to Nanoparticle Self-Assembly 5.07.4.1 Computational Framework for Nanoparticle Self-Assembly 5.07.4.2 Computational Studies on the Self-Assembly of NBBs on a Substrate 5.07.4.3 Computational Studies on the Interfacial Assembly of NBBs 5.07.4.4 Computational Studies on NBB Self-Assembly on a Templated Surface 5.07.4.5 A Proposed Approach for Modeling Tetrapod Self-Assembly 5.07.5 Summary References 5.08 组装嵌段共聚物的化学过程 5.08.1 Introduction 5.08.2 Work Prior to 1992 on Chemical Processing of Self-Assembled Block Copolymers 5.08.3 Our Research Program and Activities 5.08.4 Architectures from Chemically Processing Assembled Block Copolymers 5.08.4.1 Cyclic Polymers 5.08.4.2 Thin Films Containing Nanochannels 5.08.4.3 Cell-Like Microspheres 5.08.5 Block Copolymer Nanofibers and Nanotubes 5.08.5.1 Nanofiber Preparation 5.08.5.2 Nanotube Preparation 5.08.5.3 Dilute Solution Properties 5.08.5.4 Chemical Reactions 5.08.5.4.1 Backbone modification 5.08.5.4.2 Surface grafting 5.08.5.4.3 End functionalization 5.08.6 Concluding Remarks References 5.09 生物模版制备半导体纳米晶体 5.09.1 Introduction 5.09.2 Living Cells as Semiconductor Nanocrystal Factories 5.09.3 Peptides and Proteins as Templates for Semiconductor-Based Nanomaterials 5.09.4 Nucleic Acids as Templates for Semiconductor-Based Nanomaterials 5.09.4.1 Monomeric Nucleotides as Semiconductor Nanocrystal Ligands:Roles of Base and Backbone 5.09.4.2 Oligomeric Nucleotides as Semiconductor Nanocrystal Ligands:Roles of Length and Sequence 5.09.4.3 Studies of Nucleic Acids with 3D Structure as Semiconductor Nanocrystal Ligands:Control of Nanomaterials Properties with Biomolecular Structure 5.09.4.4 One-Step Synthesis of Biofunctionalized Semiconductor Nanocrystals Using Nucleic Acids Ligands 5.09.5 Summary and Outlook References 5.10 高分子层状硅酸盐纳米复合物 5.10.1 Introduction and Historical Perspective 5.10.2 Basic Structures of Layered Silicates and Polymers 5.10.2.1 Layered Silicate Structure 5.10.2.2 PLSN Structure: Degree of Silicate Layer Dispersion 5.10.2.3 Polymers Used in PLSNs 5.10.3 Synthetic Methods 5.10.3.1 In Situ Polymerization 5.10.3.2 Solution Intercalation/Exfoliation 5.10.3.3 Melt Processing 5.10.4 Characterization and Properties of PLSN Structures 5.10.4.1 Structure of Modified Silicates 5.10.4.1.1 XRD and TEM 5.10.4.2 Thermal and Mechanical Properties of PLSNs 5.10.4.2.1 Mechanical properties 5.10.4.2.2 Thermal and flame-retardant properties 5.10.4.3 Other Properties 5.10.4.3.1 Gas-barrier properties 5.10.4.3.2 Electrical properties 5.10.4.3.3 Compatibilization of polymer blends 5.10.5 Conclusions References 5.11 介晶和介相 5.11.1 Introduction 5.11.1.1 Classification of Thermotropic Mesophases 5.11.1.2 Classification of Mesogens 5.11.1.3 Self-Assembly of Mesogens to Mesophases 5.11.1.4 Alignment,Self-Healing,and Fixation 5.11.1.5 Length Scales 5.11.2 Thermotropic Mesophases 5.11.2.1 Carbon Allotropes-from Conventional Mesogens based on Polycondensed Aromatics to Hybrid Systems of Carbon Nanoparticles 5.11.2.1.1 Molecular structure of graphenes,synthetic strategies and interaction motifs 5.11.2.1.2 The supramolecular self-assembling of discotic or sanidic mesogens 5.11.2.1.3 Applications of graphene LCs 5.11.2.1.4 Macrocycles 5.11.2.1.5 CNTs-mesogens from enrolled graphenes 5.11.2.1.6 LCs and fullerenes 5.11.2.1.7 Miscellaneous carbon mesogens 5.11.2.2 Supramolecular Mesogens 5.11.2.2.1 Hydrogen-bonded systems 5.11.2.2.2 Mesogens formed by halogen bonds 5.11.2.2.3 Metallomesogens 5.11.2.2.4 Ionic liquid crystals 5.11.2.2.5 Donor?acceptor interactions,charge transfer,and polytopic interactions 5.11.2.3 Bolaamphiphiles and Facial Amphiphiles-Nanostructured Mesophases by Multicolor Tiling 5.11.2.4 Star-Shaped Mesogens 5.11.2.5 Dendrons and Dendrimers 5.11.2.5.1 Supramolecular dendromesogens 5.11.2.5.2 Side-chain liquid-crystalline dendrimers 5.11.2.5.3 Main-chain liquid-crystalline dendrimers 5.11.3 Lyotropic Mesophases 5.11.3.1 Lyotropic Phases-Templates for the Synthesis of Nanomaterials 5.11.3.2 Cubosomes,Hexosomes,Lamellarsomes:Nanostructured Reverse Phases Stable in Excess Solvent 5.11.3.3 From Mineral LCs to LCs of Nanobiomolecules 5.11.3.3.1 Introduction 5.11.3.3.2 Colloidal suspensions: The Derjaguin?Landau?Verwey?Overbeek theory,steric stabilization,and Onsager theory 5.11.3.3.3 Mineral LCs 5.11.3.3.4 Applications 5.11.3.3.5 From nanobiomolecules toward viruses 5.11.4 Nanoparticles and LCs 5.11.4.1 Synthesis of Nanoparticles from LC phases 5.11.4.2 LC Phases from Nanoparticles 5.11.4.3 Nanoparticle Doped LCs References 5.12 层层自组装胶囊在生物医药的应用 5.12.1 Introduction 5.12.2 LbL Assembly:Background 5.12.3 Engineering the Capsule Layers 5.12.3.1 pH-Responsive Capsules 5.12.3.2 Redox-Responsive Capsules 5.12.3.3 Light-Responsive Capsules 5.12.3.4 Temperature-Responsive Capsules 5.12.3.5 Enzyme-Responsive Capsules 5.12.3.6 Chemically Responsive Capsules 5.12.3.7 Other Stimuli-Responsive Capsules 5.12.4 Engineering the Capsule Surface 5.12.5 Encapsulating Cargo 5.12.6 Applications of LbL Capsules 5.12.6.1 Glucose-Responsive Systems-Delivery and Sensing 5.12.6.2 LbL Drug Delivery Systems 5.12.6.3 Bioreactors 5.12.7 Conclusion References 5.13 功能化石墨烯:合成和性能 5.13.1 Introduction 5.13.2 Chemical Functionalization of Fullerenes 5.13.2.1 Nucleophilic Additions to Fullerenes 5.13.2.2 Nucleophilic Addition?Elimination Mechanism:The Bingel-Hirsch Reaction with Fullerenes 5.13.2.3 Cycloaddition Reactions to Fullerenes 5.13.2.4 1,3-Dipolar Cycloaddition of Azomethine Ylides to Fullerenes 5.13.2.5 Diels-Alder Cycloaddition Reactions with Fullerenes 5.13.3 Molecular Machines 5.13.4 Molecular Charge-Transfer Conjugates 5.13.5 Molecular Wires 5.13.6 Conclusion and Outlook References 5.14 微乳化制备方法(综述) 5.14.1 Introduction 5.14.1.1 Basic Concepts:Micelles and Microemulsions 5.14.1.2 Properties and Applications 5.14.2 Synthesis of Nanoparticles(NPs)Microemulsion 5.14.2.1 Synthesis of Metal and Mixed-Metal NPs 5.14.2.2 Synthesis of Semiconductor NPs 5.14.2.3 Synthesis of Magnetic NPs 5.14.2.4 Synthesis of Oxide NPs in Microemulsion 5.14.3 Synthesis of Rare Earth(RE)Nanocrystals(NCs)in Microemulsion 5.14.3.1 Synthesis of Regular RE NCs with Well-Defined Facets 5.14.3.2 Synthesis of 1D RE NCs 5.14.3.3 Synthesis of RE Super Nanostructures 5.14.4 Silica Coating of NPs 5.14.4.1 Hydrophilic Metallic NPs 5.14.4.2 Hydrophilic Semiconductor NPs 5.14.4.3 Hydrophilic Magnetic NPs 5.14.4.4 Miscellaneous Hydrophilic NPs 5.14.4.5 Hydrophobic Metallic NPs 5.14.4.6 Hydrophobic Magnetic NPs 5.14.5 Direct Coating of Hydrophobic Semiconductor QDs 5.14.5.1 Hydrophobic Multifunctional NCs 5.14.5.2 Silica Coating of RE NCs 5.14.6 Conclusions and Outlook References 5.15 纳米技术、社会和环境 5.15.1 Introduction 5.15.2 Twenty-first Century Relationships between Science,Technology,Society,and the Environment 5.15.3 Economy 5.15.3.1 Technoscience and Business 5.15.3.2 Nanoproducts and Society 5.15.3.3 Patenting Nanoproducts 5.15.3.4 Military Applications 5.15.4 Ecology 5.15.4.1 Nanotechnology and the Environment 5.15.4.2 Nature,Technology,and Public Discourse 5.15.4.3 NGOs and Local Communities 5.15.5 Health 5.15.5.1 Nanotechnology and Health 5.15.5.2 Nanotoxicity 5.15.6 Equity 5.15.6.1 Global Equity and Rights:Implications for Developing Countries 5.15.6.2 Power 5.15.6.3 Identity 5.15.6.4 Gender 5.15.6.5 Privacy 5.15.7 Governance 5.15.7.1 Science and Technology Policy:Funding Nanotechnology Research and Development 5.15.7.2 Nanotechnology Regulatory Capacity 5.15.7.3 Public Attitudes and Media Coverage 5.15.7.4 Nanotechnology Public Engagement and Democracy 5.15.8 Imagined Futures 5.15.8.1 Fact and Fiction:Social and Cultural Influences 5.15.8.2 The Construction of Utopias and Dystopias 5.15.8.3 Scenario Planning 5.15.9 Conclusion: Nature and Nanotechnology References

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5.01 Porous Metal-Organic Frameworks
Q Fang, J Sculley, and H-C J Zhou, Texas A&M University, College Station, TX, USA G Zhu, Jilin University, Changchun, P.R. China a 2011 Elsevier B.V. All rights reserved.
5.01.1 Introduction 1 5.01.2 Inorganic SBUs and Organic Linkers 2 5.01.3 Architecture of the Networks 2 5.01.4 Porous Structures 3 5.01.4.1 0D Cage 3 5.01.4.2 1D Channels 3 5.01.4.3 2D Layers 4 5.01.4.4 3D Channels 5 5.01.5 Synthesis of MOFs 5 5.01.5.1 Influencing Factors 5 5.01.5.2 Solvent-Evaporation Synthesis 5 5.01.5.3 Diffusion Synthesis 5 5.01.5.4 Hydrothermal (or Solvothermal) Synthesis 6 5.01.5.5 Microwave-Reaction Synthesis 6 5.01.5.6 Ionothermal Synthesis 6 5.01.5.7 Electrochemical Synthesis 6 5.01.5.8 High-Throughput Synthesis 6 5.01.6 Functions of MOFs 7 5.01.6.1 Gas Storage 7 5.01.6.1.1 Hydrogen Storage 7 5.01.6.1.2 Methane Storage 8 5.01.6.1.3 Carbon Dioxide Storage 8 5.01.6.2 Selective Gas Adsorptions and Separations 10 5.01.6.3 Catalysis 11 5.01.6.4 Magnetism 13 5.01.6.5 Optics 13 5.01.6.6 Sensor 14 5.01.6.7 Drug Delivery 15 5.01.7 Summary and Outlook 15 References 16
5.01.1 Introduction
Porousmaterials,eithernaturalorartificial,havelongattractedtheattentionofchemists,physicists,andmate-rialsscientists,muchofthisinterestowingtothepotentialpropertiesoflargepores.Basedontheircom-position,theseporousmaterialscanbeclassifiedastwotypes:inorganicandcarbon-basedmaterials[1-5].
Recently,anewclassofporousmaterials,metal-organicframeworks(MOFs,alsoreferredtoaspor-ouscoordinationpolymers(PCPs)),hasundergonerapiddevelopmentandbeguntobridgethegap
betweenthetwopreviouslymentionedclassesofporousmaterials[6-26].MOFsarebuiltupofmetalionsormetalionclustersconnectedtoorganicligandspossessingmultidentategroupsbystrongionocovalentordativebonds.ThereareexamplesofMOFscontainingmetalsrangingfromalkalineearthtotransitiontop-blockmetalsandlanthanides.MOFsattractedagreatdealofattentioninthe1990s,asisapparentfromtheremarkableincreaseinthenumberofpaperspublishedinthisareaduringthistime.TheattentionstemsfromthesynthesisofMOFs,whichcanexhibitcompletelyregularlarge

5.01 Porous Metal-Organic Frameworks 
 Q Fang, J Sculley, and H-C J Zhou, Texas A&M University, College Station, TX, USA G Zhu, Jilin University, Changchun, P.R. China a 2011 Elsevier B.V. All rights reserved. 
 5.01.1 Introduction 1 5.01.2 Inorganic SBUs and Organic Linkers 2 5.01.3 Architecture of the Networks 2 5.01.4 Porous Structures 3 5.01.4.1 0D Cage 3 5.01.4.2 1D Channels 3 5.01.4.3 2D Layers 4 5.01.4.4 3D Channels 5 5.01.5 Synthesis of MOFs 5 5.01.5.1 Influencing Factors 5 5.01.5.2 Solvent-Evaporation Synthesis 5 5.01.5.3 Diffusion Synthesis 5 5.01.5.4 Hydrothermal (or Solvothermal) Synthesis 6 5.01.5.5 Microwave-Reaction Synthesis 6 5.01.5.6 Ionothermal Synthesis 6 5.01.5.7 Electrochemical Synthesis 6 5.01.5.8 High-Throughput Synthesis 6 5.01.6 Functions of MOFs 7 5.01.6.1 Gas Storage 7 5.01.6.1.1 Hydrogen Storage 7 5.01.6.1.2 Methane Storage 8 5.01.6.1.3 Carbon Dioxide Storage 8 5.01.6.2 Selective Gas Adsorptions and Separations 10 5.01.6.3 Catalysis 11 5.01.6.4 Magnetism 13 5.01.6.5 Optics 13 5.01.6.6 Sensor 14 5.01.6.7 Drug Delivery 15 5.01.7 Summary and Outlook 15 References 16 
 5.01.1 Introduction 
 Porousmaterials,eithernaturalorartificial,havelongattractedtheattentionofchemists,physicists,andmate-rialsscientists,muchofthisinterestowingtothepotentialpropertiesoflargepores.Basedontheircom-position,theseporousmaterialscanbeclassifiedastwotypes:inorganicandcarbon-basedmaterials[1-5].
 Recently,anewclassofporousmaterials,metal-organicframeworks(MOFs,alsoreferredtoaspor-ouscoordinationpolymers(PCPs)),hasundergonerapiddevelopmentandbeguntobridgethegap
 betweenthetwopreviouslymentionedclassesofporousmaterials[6-26].MOFsarebuiltupofmetalionsormetalionclustersconnectedtoorganicligandspossessingmultidentategroupsbystrongionocovalentordativebonds.ThereareexamplesofMOFscontainingmetalsrangingfromalkalineearthtotransitiontop-blockmetalsandlanthanides.MOFsattractedagreatdealofattentioninthe1990s,asisapparentfromtheremarkableincreaseinthenumberofpaperspublishedinthisareaduringthistime.TheattentionstemsfromthesynthesisofMOFs,whichcanexhibitcompletelyregularlarge
 
 
 (a) (b) 
 Figure 1 View of the structures of (a) MOF-5 and (b) HKUST-1. 
 cavitiesand/oropenchannels.TopicalexamplesareHKUST-1andMOF-5,whichresultinlargeporesizesandBrunauer,Emmett,andTeller(BET)sur-faceareasof1800and3800m2 g 1 respectively(Figure1)[21,24].Theatomsthatcomposethewallsoftheseporescreateanastonishinglylargesurfaceareaonwhichinteractionsandreactionscanoccur.ThesynthesisofsuchMOFsoccursundermildconditionsandtheselectionofacertaincombi-nationofdiscretemolecularunitsleadstothedesiredextendednetwork.Asalreadymentioned,researchintoMOFsisgainingmomentumbecauseMOFspossesstheadvantagesofbothorganicandinorganicmaterialsincludingfunctionalgroupsandopen-metalsites[27].ThesefeaturesofMOFsgiverisetoagreatnumberofpotentialandrealizedapplica-tions,suchasgasseparationsandstorage,catalysis,drugdelivery,aswellasnewfunctionalmaterialsbasedonpost-syntheticmodification[28-33].
 MOFshavegreatlyexpandedthescopeofporousmaterials,eventhoughtheyarelargelyrestrictedtothemicroporousdomain(poreslessthan2nm).Recently,somemesoporousMOFswithporesizesrangingfrom2to50nmhavebeenreported.ThesecompoundsexpandthepotentialapplicationsofMOFsintoareassuchasmacromolecularcatalysisandseparation[34-44].Forexample,Yaghietal.preparedthefirst(3D)mesoporousMOF,isoreticularmetal-organicframe-work(IRMOF)-16,bysuccessfullyusingalonglinker,[1,19:49,10-terphenyl]-4,40-dicarboxylate(TPDC)[34].ThisMOFhastheexpectedtopologyofCaB6adaptedbytheprototypeIRMOF-1(alsodesignatedasMOF-5)inwhichanoxide-centeredZn4Otetrahedronisedge-bridgedbysixcarboxylategroupstogivetheoctahedron-shapedsecondarybuildingunit(SBU)thatreticulatesintoa3Dcubicporousnetwork.Inthisstructure,thefree-andfixed-diametervaluesare19.1and28.8A. ,respectively. 
 
 
 5.01.2 Inorganic SBUs and Organic Linkers 
 Inadditiontothetwocentralcomponentswithwhichtheprincipalframeworkisconstructed,metalionsandligands,thereareauxiliarycomponents,suchascounteranions,nonbondingguests,andtemplatemolecules,whichmayallinfluencethefinalstructure.DuetothecomplexanddynamicconditionsunderwhichMOFsaresynthesized,itisdifficulttopredicttheresultingstructureofaMOFbasedsolelyonthestartingmaterialsandconditions.
 Theimportantcharacteristicsofmetalionsandligandsaretheircoordinationnumbersandcoordinationgeometries.Asmetalcentershavetoomanybindingsitesfortheorganicligandsandcontainlittledirectionalinformation,itisdifficulttopredictthestructuresthatwillresultfromanycombinationofsimplemetalsaltsandorganiclinkers.Recently,YaghiandcoworkershavedefinedmetalcentersofMOFsasSBUsandillustratedthepossibleinorganicSBUs(Figure2).ThedesignofMOFsbasedontheseinorganicSBUsfacilitatesframe-worksynthesis[13].Themostcommonlinkersaremultidentateorganicligandssuchascarboxylates,4,49-bipyridine,andimidazolederivatives.Theseorganiclinkersaffordawidevarietyoflinkingsiteswithtunedbindingstrengthanddirectionality.Theseligandscanbeselectedforthenodesinthetargetnetworkandtheycanbealsosynthesizedandmodifiedbyorganicsynthesis.
 
 
 5.01.3 Architecture of the Networks 
 Figure3showssomesimplearchitecturesofthenet-worksassembledfrommetalionsandorganicligands[11].However,morecomplicated3Dframeworkscanbeobtainedbymimickingthetopologiesofthetradi-tionalinorganicsolids[25,26].Theapproachisbased
 
 Inorganic units SBUs Inorganic units SBUs 
 (a) 
 
 (b) 
 
 (c) 
 
 
 
 
 Figure 2 Examples of inorganic SBUs: (a) triangle, (b) square planar, (c) tetrahedron, (d) octahedron, and (e) trigonal prism. Reprinted by permission from Macmillan Publishers Ltd: Nature (Yaghi OM, O’Keeffe M, Ockwig NW, Chae HK, Eddaoudi M, and Kim J (2003) Reticular synthesis and the design of new materials. Nature 423: 705-714), Copyright (2003). 
 
 (a) (b) (c) (d) (e) (f) 
 Figure3Schematicrepresentationsofsomeofthesimplenetworkarchitectures:(a)2Dhoneycomb,(b)1Dladder,
 (c) 3Doctahedral,(d)3Dhexagonaldiamondoid,(e)2Dsquaregrid,and(f)1Dzigzagchain.ReproducedfromMoultonBandZaworotkoMJ(2001)Frommoleculestocrystalengineering:Supramolecularisomerismandpolymorphisminnetworksolids.
 Chemical Reviews 101: 1629-1658. 
 ontheideaofnets,whicharetheabstractmathema-ticalentitiesincludingacollectionofpointsornodeswithdefinedconnectivity[45].Yaghietal.haveexplainedthetopologyoftheorderednetworksbysimplifyingthemathematicalexpressions[25].WhenallverticesarelinkedtoNneighbors,thetopologyisreferredtoasanN-connectednet.Whensomever-ticesareconnectedtoNneighborsandsometoMneighbors,itisa(N,M)-connectednet.Figure4showsexamplesoftopologicalnets.
 
 
 5.01.4 Porous Structures 
 5.01.4.1 0D Cage 
 MOFswith(0D)cagesareframeworkswhicharetoosmalltopermittheguestmoleculestopassthroughandmaybedefinedaseithersolidswithoutwindowsorsolidswithnarrowwindows.Forinstance,Robsonetal.reportedaninterpenetrated3Dnetwork[Zn(CN)(NO3)(tpt)2/3]?(C2H2Cl4)3/4?(CH3OH)3/4(tpt.2,4,6-tri(4-pyridyl)-1,3,5-triazine)thatprovidesabarrierimpenetrabletoeventhesmallestmolecules,whicheffectivelyisolateseachporefromitsneighborsandfromtheoutsidespace[46].Inthisstructure,eachcageiswideopenandcanaccommodateapproximatelynine1,1,2,2-tetrachloroethanemoleculesandninemethanolmolecules,allofwhicharehighlydisordered.ThedistanceacrosstheinnershellofthecagefromoneZn4squaretotheoppositeandparallelZn4squareis23.448(4)A. . However, due to narrow windows, guest molecules are unable to pass out of these cages. 
 
 
 5.01.4.2 1D Channels 
 AccordingtotheInternationalUnionofPureandAppliedChemistry(IUPAC)definition,aporethatisinfinitelyextendedinonedimensionandislargeenoughtoallowguestspeciestodiffusealongitslengthiscalledachannel[47].SeveralMOFswithregular1Dchannelshavebeensynthesizedandcrystallographi-callycharacterized.Forexample,Qiuetal.describedthesynthesisandstructureofamesoporousMOF,JUC-48,fromarigidandlinearorganicO-donorligand,4,49-biphenyldicarboxylate(bpdc)[36].InthisMOF,Cd(II)centersarelinkedtogetherbycarboxylategroupsofbpdctoconstruct1DCd-O-Cchainsthatareinter-connectedthroughthebiphenylgroupsofbpdcto
 
 
 Figure4Examplesoftopologicalnets:(a)SrSi2net,(b)ThSi2net,(c)diamondnet,(d)CdSO4net,(e)NbOnet,(f)PtS(cooperite)net,(g)Pt3O4net(filledcirclesarePt),(h)boracitenet,(i)BNnet,(j)BCTnet,(k)body-centeredcubicnet,and(l)ReO3arrangementofcorner-sharingoctahedral.ReproducedfromO’KeeffeM,EddaoudiM,LiHL,ReinekeT,andYaghiOM(2000)Frameworksforextendedsolids:Geometricaldesignprinciples.JournalofSolidStateChemistry152:3-20,withpermissionfromElsevier.
 
 (a) (b) 
 
 Figure 5 Representation of a hexagonal nanotube-like channel of JUC-48 of dimensions 24.5 . 27.9A. 2 viewed along the (a) 
 [001] and(b)[100]directions.ReprintedfromFangQR,ZhuGS,JinZ,etal.(2007)Mesoporousmetal-organicframeworkwithrareetbtopologyforhydrogenstorageanddyeassembly.AngewandteChemieInternationalEdition46:6638-6642.Copyright2007AmericanChemicalSociety.
 generatea3Dnoninterpenetratingextendednetworkincorporatedbetweenthelayers.Kitagawaetal.havewith1Dhexagonalchannelsof24.527.9A. 2 viewedsynthesizedaseriesoflayeredintercalationMOFs,alongthe[001]direction(Figure5).Eachhexagonal[M(CA)(H2O)2](G)(M.Fe2t,Co2t,orMn2t; channel of JUC-48 can be viewed as a nanotube-like H2CA . chloranilic acid; G . H2Oorphenazine),architecture.whicharesupportedbyhydrogen-bondinginter-
 actions[48].Thehostlayersareclassifiedintotwo
 groups:thefirsttypeofsheetisformedbyzigzag
 
 
 5.01.4.3 2D Layers 
 
 chains,andthesecondoneisconstructedfromWhilethereareseveralMOFswith2Dlayers,fewstraightchains.Inthisstructure,themolecularhavebeenreportedinwhichseveralguestscanbeassembliesofmetal(II)-CA2chainsandguestmoleculesrevealthreekeyfactorsthatcontrolthecrystalstructures.Thefirstfactoristheconstructionofahydrogen-bond-supported2Dsheet,whichisflexibleandamenabletointercalationofvariouskindsofmoleculesusingthehydrogen-bondinginteraction.Thesecondaspectisthattheintercalatedguestmoleculesaffectthesheetstructureanditsdynamics.Thehydrogenbondingincreasesthedimensionalityofthesystemandthusprovidesstruc-turalvarietiesinthecrystalstructure.Thethirdfeaturecontrollingthecrystalstructureistheselec-tionofthemetalthatmediatesthefine-tuningofthesheet’sstructureandtheconformationoftheguestmolecules.
 
 5.01.4.4 3D Channels 
 3Dintersectingchannels,whichfrequentlyoccurinzeolites,areconstructedbytheinterconnectionof1Dchannelsfromthreedirections.SomeMOFswithhighporosityassociatedwithsuch3Dchannelshaverecentlybeenpresented.Forinstance,ZhouandcoworkersreportedanoninterpenetratedmesoporousMOF,mesoMOF-1[35].Inthisstructure,twocopperatomsarebridgedbyfourcarboxylategroupstoformthewell-knownpaddlewheelSBUwithaxialaqualigands.EachSBUconnectsfour4,49,40-s-triazine-1,3,5-triyltri-p-aminobenzoate(TATAB),andeachTATABbindsthreeSBUstoformaTdoctahedron,inwhichallsixverticesareoccupiedbytheSBUs,andfouroftheeightfacesarespannedbyTATABligands.EightsuchTdoctahedraoccupytheeightverticesofacubetoformacuboctahedronthroughcornersharing.Thesecuboctahedrapropagatetoa3Dframeworkwithatwistedboracitenettopology.Openchannelsfromallthreeorthogonaldirectionsareidenticalinsizeandcanbeaslargeas22.526.1A. 2 (Figure6).
 
 (a) (b) 
 Figure6(a)ApaddlewheelstructuralunitofmesoMOF-1.
 (b) A view of packing of mesoMOF-1 with 22.5 . 26.1A. 2 fromthe[001]direction.ReproducedfromWangXS,MaSQ,SunDF,ParkinS,andZhouHC(2006)Amesoporousmetal-organicframeworkwithpermanentporosity.JournaloftheAmericanChemicalSociety128:16474-16475.
 
 
 5.01.5 Synthesis of MOFs 
 5.01.5.1 InfluencingFactors
 Theself-assemblyofMOFsisinfluencedbymanyfactors,suchasthestructuralcharacteristicsoftheligands,coordinationnatureofmetalions,thesolventsystem,anytemplatemolecules,thepHvalueofthesolution,stericrequirementofthecounterion,reactiontemperature,andtheratioofmetaltoligand[49-54].SomestudiesoftheinfluenceofthetemperatureandpHhavebeensurveyed[55-57].TheyindicatedthathigherpHandtemperatureproducemorecondensedphases.Inthecaseofthecobalt(II)/succinatesystem,thedimensionalityofboththeframeworkandtheinorganicchainshasincreasedwithtemperature.Morerecently,aseriesofMOFshavebeensynthe-sizedbyQiuetal.usingdifferentorganicaminesastemplates[58].Thesystematicanalysisofthenon-bondinginteractionenergiesofthesecompounds,includingH-bondingandvanderWaals,showedthattheorganicaminecationsresideintheinterlayerorchannelspacewheretheyplayimportantrolesastemplating,space-filling,andcharge-balancingagents.
 
 5.01.5.2 Solvent-EvaporationSynthesis
 Solvent-evaporationsynthesisproducescrystalsbyslowlyincreasingtheconcentrationofthemotherliquor.Crystalscanslowlygrowasthesolutionbecomessaturatedbyeithercoolingofthesolutionorbyevaporationofexcesssolvent.Forinstance,Chenetal.dissolved2-hydroxymethyl-1-methylimidazole(Hmmi)andtwodifferentkindsofmetalionsinmethanol,andthenthemixturewasstoredatroomtemperature.Threediscretedinuclearcopper(II)-lanthanide(III)MOFsweresynthesizedbyslowsolventevaporationafterabout10days[59].
 
 5.01.5.3 Diffusion Synthesis 
 Theadvantageofdiffusionsynthesisisthatthistechniqueslowlybringsthedifferentsolventsintocontact[36].Oneapproachissolvent-liquiddiffu-sion,whichinvolvestheformationofthreediscretelayers.Onelayercontainstheproductinthesolvent,anotheristheprecipitantsolvent,andthethirdlayerservestoseparatetheothertwolayerstherebyallow-ingfordiffusiontooccurataslowerrate.Astheprecipitantsolventandtheproductsolutionslowlydiffuseintothemiddlelayer,crystalgrowthcanoccurattheinterface.Theotherapproachistheslowdiffusionofreactantsandtheavoidanceofpre-cipitationofbulkmaterialbytheseparationofphysicalbarriers,suchasgels.DiffusionmethodsareusefulforisolatingsinglecrystalssuitableforX-raydiffractionanalysisinsteadofprecipitatingpolycrystallineproducts.
 
 5.01.5.4 Hydrothermal(orSolvothermal)Synthesis
 Hydrothermal(orsolvothermal)synthesisfacilitatestheself-assemblyofproductsbyexploitingthesolubilityofprecursorsinhotwater(ororganicsolvent)underhighpressure.Thecrystalgrowthoccursinasteelpressurevessel,alsocalledanautoclave,atrunningtemperaturesrangingfrom60Cto260 C.Atemperaturegradientismaintainedattheoppositeendsofthegrowthchambersothatthehotterenddissolvesthenutrientandthecoolerendcausesseedstocontinuetogrow.Thismethodwasoriginallyusedforthesynthesisofzeolites,buthasbeenwidelyadaptedforthesynthesisofMOFs,suchasthehighlyporousMIL-101(Figure7)[39].
 
 5.01.5.5 Microwave-ReactionSynthesis
 Microwave-reactionsynthesishasbeenusedtopro-ducesmallmetalandoxideparticles.Nanosizedcrystalsofmetalcanbeproducedbyheatingasolutionwithmicrowavesforaperiodofanhourormore.SuchprocesseswererecentlyemployedinthesynthesisofsomeMOFs,suchasIRMOFs,anickelglutarate,MIL-101,oranickeltrimesate[60-63].Theproper-tiesofthecrystalsmadebythemicrowavereactionareofthesamequalityasthoseproducedbythestandardsolvothermalprocesswiththeaddedbonusofmuch
 
 (a) (b) 
 Figure7(a)Thesupertetrahedronconstructedformtrimericbuildingblockandbdcligands.(b)StructuralrepresentationsofMIL-101withlargercavitiesof34A..ReproducedfromHorcajadaP,SerreC,Vallet-RegiM,SebbanM,TaulelleF,andFe′reyG(2006)Metal-organicframeworksasefficientmaterialsfordrugdelivery.AngewandteChemieInternationalEdition45:5974-5978.
 morerapidcrystalgrowth.Sincethepropertiesofthemicrowavesynthesizedcrystalsareanalogoustothoseobtainedbytraditionalmethods,therangeofpracticalapplicationsisdramaticallyincreased.
 
 5.01.5.6 IonothermalSynthesis
 Thismethodwasusedforthefirsttimeintraditionalporousmaterials,suchaszeolitesandphosphates,andonlyrecentlyutilizedinMOFs[64,65].IonicliquidshavebeenappliedasexcellentandsafemediainthesynthesisofMOFsbecauseoftheirhighthermalsta-bility,avaporpressureclosetozero,andpoorcoordinationability.InthecaseofanioncontrolintheionothermalsynthesisoffourkindsofMOFs,itwasshownthatitispossibletocontroltheframeworksoftheresultingcompoundsbyusingdifferentanions[66].AnotherinterestingresultwasthesynthesisofachiralMOFwiththeuseofchiralionicliquid[67].
 
 5.01.5.7 ElectrochemicalSynthesis
 Differentfromconventionalsolvothermalsynthesis,Muelleretal.haverecentlydevelopedanelectroche-micalmethodtosynthesizeHKUST-1constructedfromCu(II)and1,3,5-benzenetricarboxylate(btc)ligand[22].Inanelectrochemicalcell,copperplatesarearrangedastheanodeandcathodewithbtcdis-solvedinmethanol.Theproduct,agreenishblueprecipitate,wasformedinabout150minatavoltageof12-19Vandacurrentof1.3A.Thebenefitofthismethodliesinitsspeedanditshigherpurity,duetotheabsenceofcounterionsfromthemetalsaltsother-wiseusedduringthepreparation.
 
 5.01.5.8 High-ThroughputSynthesis
 High-throughputsynthesisisroutinelyusedinscreen-ingforactivityofdrugmoleculesandcatalysts.Recently,high-throughputtechniqueswereappliedinthesynth-esisofMOFs,thusreducingthetime-consumingprocessofphasediscoveryandshininglightontothehighversa-tilityofsuchsystems.Stocketal.haveperformed48synthesesonasmallscale(volumeofthecontaineris
 0.25ml)byasemi-automatedsystem(reagentweighing, productrecovery,andcharacterization)whilesimulta-neouslyvaryingthereactionparameters(stoichiometry,concentration,pH,andsoon)inasystematicfashion[68].Inaddition,ahigh-throughputmethodwaspro-posedbyYaghietal.forthesynthesisofnovelmetal-organiccompounds,zeoliticimidazolateframeworks(ZIFs).Twenty-fivedifferentZIFswereobtainedfromonly9600microreactionsofeitherzinc(II)orcobalt(II)andimidazolate-typelinkers[69].
 
 
 
 5.01.6 Functions of MOFs 
 
 5.01.6.1 Gas Storage 
 Amajoradvantageinusingporousmaterialsasanaidingasstorageisthatthesematerialsallowthepressureinagiventanktobelowerthanthatinanidenticaltankwithoutanadsorbent.Anumberofrecentstudieshavebeendevotedtotheadsorptionofhydrogen,methane,andcarbondioxideonMOFsbecausetheyhaveadsorp-tioncapacitiesthatareequivalenttoorbetterthanthecurrentzeoliteoractivatedcarbonsamples[70].
 
 5.01.6.1.1 Hydrogen Storage 
 Hydrogenisanidealenergycarrierbecauseitiscarbonfreeandthemainproductafterenergyreleaseiswater.Anotherbenefitisthatthegravimetricheatofcombustionofhydrogenisalmosttriplethatofgasoline(120MJkg1 vs. 44.5 MJ kg1)[71].Thegravimetricandvolumetricstoragetargets,setbytheUSDepartmentofEnergy,foron-boardhydro-genstorageare6wt%,45gl1 for 2010 and 9 wt%, 81gl1 for 2015 [72]. 
 SinceRosietal.presentedthefirstMOF-basedhydrogenstoragestudy[73],approximately150MOFshavebeentestedfortheirhydrogenuptakecapacity,andseveralreviewsfocusingonthistopichavebeenpublished[31,74-80].ItiswellknownthathydrogenstorageofMOFsisbasedonphysisorption.Thecontactbetweenhydrogenandtheadsorbentcanthereforebeincreasedbyincreasingthesurfacearea.Asurveyofpublisheddatarevealstheappropriate
 (a) 
 
 
 positivecorrelationbetweentheuptakeofhydrogen
 at77Kandthesurfacearea[81].Itisbelievedthat
 increasingthesurfaceareaenhancesthecontact
 betweenhydrogenandtheadsorbentresultinginan
 increasedhydrogenuptake.Forexample,MOF-177,
 whichhasaBETsurfaceareaof4500m2 g 1,ranks 
 highestforgravimetrichydrogenuptakes,withavalue
 of7.5wt.%at70bar,77K(Figure8)[81,82].Another
 waytoincreasetheinteractionbetweenhydrogenand
 MOF’ssurfaceistotailortheporesizeintheMOF.
 Theoreticalandexperimentalresultssupportthatthe
 optimalporesizeisaround6A. ,abouttwicetheeffec-
 tivekineticdiameterofthehydrogenmolecule[83].A
 methodtoaltertheporesizeofaMOFistocreate
 catenated(orinterpenetrated)frameworks.Maetal.
 preparedapairofcatenatedandnoncatenatedMOFs,
 PCN-6andPCN-69[84].Theresultinghydrogen
 uptakestudyathigherpressureandambienttempera-
 tureshowedpromisingresults.ThecatenatedPCN-6
 hadahigherhydrogenadsorbtionof6.7wt%at77K/
 50bar(0.92wt.%at298K/50bar)comparedto4.0
 wt.%at77K/50bar(0.40wt.%at298K/50bar)for
 PCN-69(Figure9).
 Unsaturatedmetalcenters(UMCs),another
 viableoptiontoincreasethehydrogen-uptakecapa-
 citiesinMOFs,canbegeneratedbytheremovalof
 thecoordinatedsolventmolecules.Leeetal.reported
 isostructural MOFs with and without UMCs and 
 comparedtheirhydrogen-sorptioncapacities[85].
 Higherhydrogenuptakeatbothlowpressure
 (2.87 wt%vs.2.07wt%at77K/1atm)andhighpressure(5.22wt%vs.3.70wt%at77K/50bar)wasreportedfortheMOFswithUMCs.
 Amethoddenotedashydrogenspillover,toincreasethehydrogenuptake,hasbeenreported
 
 (b) 
 Amount N2 sorbed (mg g-1)
 1500 1200 900 600 300 0 
 
 0 0.2 0.4 0.6 0.8 1 P/P0 
 
 Figure8(a)Crystalstructureand(b)nitrogengassorptionisothermat78KforMOF-177.ReprintedbypermissionfromMacmillanPublishersLtd:Nature(ChaeHK,Siberio-Pe′rezDY,KimJ,etal.(2004)Aroutetohighsurfacearea,porosityandinclusionoflargemoleculesincrystals.Nature427:523-527),Copyright(2004).
 (a) (b) 
 (c) 
 
 
 Amount absorbed (mg g-1)
 80 60 40 20 0 0 10 20 30 40 50 01234567 
 
 
 P (bar) H2 Uptake (m mol) 
 Figure9(a)TheframeworkofcatenatedPCN-6.(b)TheframeworkofnoncatenatedPCN-69.(c)ExcesshydrogensorptionisothermsofPCN-6andPCN-69at77(red)and298K(black).(d)IsostericheatsofadsorptionforPCN-6andPCN-69.ReproducedfromMaSQ,SunDF,AmbrogioM,FillingerJA,ParkinS,andZhouHC(2007)Framework-catenationisomerisminmetal-organicframeworksanditsimpactonhydrogenuptake.JournaloftheAmericanChemicalSociety129:1858-1859.
 byYangetal.ItconsistsofmixingaPt/CcatalystwiththeMOF,thusallowingboththedissociativechemisorptionofhydrogenontothemetalsurfaceandthephysisorptionofH2intheporesoftheMOF.Remarkably,theresultingframeworkledtoastrongenhancement,asmuchaseightfold,ofthehydrogenadsorptionofMOF-5(orIRMOF-8)[86-88].
 
 
 5.01.6.1.2 Methane Storage 
 Asaresultofmethane’savailabilityanditsgravimetricheatofcombustioncomparabletothatofgasoline
 (50.0 MJ kg1 vs.44.5MJkg1)[71],itrankswithhydrogenintermsofbeingagoodcandidateforon-boardfuel.Intermsofavailability,methaneisthemaincomponentofnaturalgasatslightlyover95%[89].Theheatofadsorptionformethaneisapproxi-mately20kJmol1,whichisalreadywithintheidealscopeforpracticalusage.Theonlyrealdownsideofmethaneisthatwecurrentlydonothaveaneffectivestoragetechnology.TheDepartmentofEnergy(DOE)hassetamethanestoragetarget:180v/v(v/v.volumeofadsorbate/volumeofadsorbent)atambienttemperatureand35bar[90].
 SinceKondoetal.reportedthefirstMOF-basedmethane-sorptionstudy[91],severalstudieshavebeenpresented.Table1summarizesthemethane-uptakedataforselectedMOFs.Forinstance,amicro-porousMOF,PCN-14,basedonapredesignedanthracenederivativeligandthatwassynthesizedbyZhouetal.containsnanoscopiccagessuitableformethaneuptake[92].High-pressuremethane-adsorptionstudiesshowthatPCN-14exhibitsanabso-lutemethane-adsorptioncapacityof230v/v(28%higherthantheDOEtargetof180v/vatambienttemperature)andheatofadsorptionofmethanearound30kJmol1,bothrecordhighsamongthosereportedformethane-storagematerials(Figure10).
 
 
 5.01.6.1.3 Carbon Dioxide Storage 
 TheDOEhassettargetsforcarbondioxide-storagesystemsat56wt.%[93].Besideszeolitesandcarbon-basedadsorbents,porousMOFsarecurrentlybeingconsideredasanalternative.ThisattentionisdrawnfromanumberofstudiesthathavereportedtheadsorptioncapacitiesofcarbondioxidetobehigherincertainMOFsthantheadsorptioncapacitiesinzeoliteoractivatedcarbonsamples(Table2)[94].
 Forexample,Yaghietal.haveinvestigatedthestoragecapacityofCO2inMOF-177[95].MOF-177showsahighcarbondioxidecapacitywith
 
 Table 1 Methane uptake data for selected MOFs 
 Material Conditions Max loading (wt.%) Max loading (v/v) Reference 
 Co2(4,49-bipy)3(NO3)4 3.04 MPa/RT 3.6 71 91 
 Cu2(pzdc)2(pyz) 3.14 MPa/RT 1.3 32 139 
 Cu2(pzdc)2(4,49-bipy) 3.14 MPa/RT 3.9 139 
 Cu2(pzdc)2(pia) 3.14 MPa/RT 4.4 139 
 CuSiF6(4,49-bipy)2 3.65 MPa/RT 9.4 124 140 
 IRMOF-6 3.65 MPa/RT 14.7 155 34 
 MIL-53(Al) 3.5 MPa/RT 10.2 155 141 
 MIL-53(Cr) 3.5 MPa/RT 10.2 165 141 
 PCN-14 3.5 MPa/RT 16.0 220 92 
 PCN-11 3.5 MPa/RT 14.1 171 142 
 HKUST-1 15.0 MPa/RT 15.7 228 143 
 Zn2(bdc)2(dabco) 7.5 MPa/RT 14.3 202 143 
 MIL-101 12.5 MPa/RT 14.2 72 143 
 
 (a) 
 (b) 
 
 (c) 
 
 
 
 500 
 
 
 Uptake (v(STP)/v)
 
 
 
 400 
 300 
 200 
 100 400 
 300 
 200 
 100 
 0
 0 
 
 0 1020304050 0 1020304050 P (bar) P (bar) 
 Figure10(a)TheadipligandandpaddlewheelSBU.(b)NanoscopiccageinPCN-14.High-pressuremethanesorptionisothermsatvarioustemperatures:(c)excessadsorptionand(d)absoluteadsorption.ReproducedfromMaSQ,SunDF,SimmonsJM,CollierCD,YuanDQ,andZhouHC(2008)Metal-organicframeworkfromananthracenederivativecontainingnanoscopiccagesexhibitinghighmethaneuptake.JournaloftheAmericanChemicalSociety130:1012-1016.
 33.5mmolg1 at298Kand42bar,whichtranslatesintoanimmensevalueof320v/v.Astonishingly,acontainerfilledwithMOF-177under35barcancaptureninetimestheamountofCO2comparedtoacontainerwithoutadsorbent,andabouttwicetheamountcomparedtothebenchmarkmaterials(zeolite13XandMAXSORB).Ataslightlyhighertemperatureandpressureof303Kand50bar,MIL-101,reportedbyFe′reyetal.,possessesanenormouscarbondioxidecapacitywith40mmolg1,whichisequivalenttothehighcapacityof390v/v[96].Comparedtozeolites,saturationinlarge-poreMOFsoccursatmuchhigherpressures,whichcouldbeanimportantfactorfortherecoveryofCO2fromgasstreams.Furthermore,comparedwithzeolitesoractivecarbons,itisaclearadvantagethattheregenerationofMOFsisgenerallypossibleundermildconditions.
 
 Table 2 Carbon dioxide adsorption capacities for various adsorbents 
 Adsorbent Conditions Maxloading(mmolg1) Maxloading(cm3cm3) Reference 
 Silicalite 302 K/3.0 MPa 2.5 123 144 
 Zeolite NaX 302 K/3.0 MPa 7.8 147 145 
 SBA-16 300 K/3 MPa Nongrafted 6 N/A 146 
 Grafted 3-4 N/A 
 Active carbon NORIT R1 298 K/3.0 MPa 10 96 94 
 Active carbon Maxsorb 298 K/3.5 MPa 25 162 94 
 Cu(bpy)(BF4)2 273 K/3.0 MPa 4 153 147 
 MIL53(Al, Cr) 302 K/2.5 MPa 10 225 141 
 HKUST-1 298 K/4.2 MPa 10.7 210 95,148 
 MIL-47(V) 302 K/2.0 MPa 11 250 141 
 IRMOF-1 298 K/3.5 MPa 21.7 290 95 
 MOF-177 298 K/4.2 MPa 33.5 320 95 
 MIL-100(Cr) 304 K/5.0 MPa 18 280 96 
 MIL-101(Cr) 304 K/5.0 MPa 40 390 96 
 
 ReprintedwithpermissionfromLlewellynPL,BourrellyS,SerreC,etal.(2008)HighuptakesofCO2andCH4inmesoporousmetal-organicframeworksMIL-100andMIL-101.Langmuir24:7245-7250.Copyright2008AmericanChemicalSociety.
 
 
 5.01.6.2 SelectiveGasAdsorptionsandSeparations
 MOFshaverecentlyattractedmuchattentionforselectivegasadsorption,whichleadstogassepara-tion.MOFsforselectivegasadsorptionarechosenbasedontwomaincriteria:theadsorptioncapacityoftheadsorbentandtheselectivityoftheadsorbentforanadsorbate[33].ThesepropertiesofMOFsaredependentonthechemicalcompositionandstruc-tureoftheadsorbent,aswellastheequilibriumpressureandtemperatureduringtheadsorption.
 TheprincipalmechanismsofselectivegasadsorptioninMOFsincludeadsorbate-surfaceinteractions,whichinvolvethechemicaland/orphysicalinteractionbetweentheadsorbentandsize-exclusion(alsoreferredtoasmolecularsievingeffect)thatdependsonthedimensionandshapeoftheframeworkpores.Itisnotedthatthesetwoeffectsarecapableofworkingindependentlyorcooperatively.Forinstance,Zhouetal.reportedaninterestingMOF,PCN-13,whichexhibitsselectivegasadsorptionbasedonthesize-exclusionprinciple.PCN-13containsasquarehydrophobicchannelof
 3.5 . 3.5A. 2 and a pore volume of 0.3 cm3 g 1 [97].TheresultsofgasadsorptionsofPCN-13showthatitcancompletelypreventN2(kineticdiameterof3.64A. )fromenteringtheaperturewhileallowingO2(kineticdiameterof3.46A. )topassthroughthepore.AnotherexampleofaMOFwithaporeopeningof3.46-3.64A. ,Mg3(ndc)3,showsalmostnoN2uptake,whereasabout3.5mmolg1 ofO2isadsorbedat77Kand880Torr[98].
 Recently,theseparationofalkaneisomersthroughgaschromatographictechniqueshasbeendemonstratedbyMOF-508[99].Inthisstructure,reportedbyChenetal.,the3Dpillaredlayerpro-videsthenecessaryframeworktoselectivelyseparatelinearandbranchedalkanes.Thediffer-enceinvanderWaalsinteractionsbetweentheisomersandtheporesoftheframeworkisrespon-siblefortheadsorptionofthelinearalkaneswhileallowingthebranchedonestopass.Interestingly,MOFshavealsobeenincorporatedintothinfilmtoaidingasseparation.Qiuetal.preparedHKUST-1supportedbyathinfilmcoppernet,whichdemon-stratedthesuccessfulseparationofH2fromH2/N2,H2/CO2,andH2/CH4mixtures(Figure11)[100].TheresultsshowthatthisfilmpossessesexcellentpermeationselectivityforH2andexhibitssepara-tionfactorsmuchhigherthantraditionalzeolites.Inaddition,therecyclabilityofthisfilmfurtherenhancesitspotentialuseinH2separationandpurification.
 Itisnotedthatoneofthemostpromisingmate-rialsforselectivegasadsorptionistheMOF-basedmesh-adjustablemolecularsieve(MAMS)[101].Differentfromthepreviouslymentionedrigidstruc-tures,theporesizesofMAMScanbetunedacrossawiderangebyadjustingthetemperature.Zhouetal.haverecentlyreportedsuchacompound,designatedMAMS-1,whichisalayeredstructurewithhydrophilicchannelsandhydrophobicchambersinterconnectedthroughasize-adjustablegate(Figure12)[101].Thegateisconstructedoftwo5-tert-butyl-1,3-benzenedicarboxylate(bbdc)
 
 
 H2/ N2 
 7 
 
 
 
 H2/CO2 
 6
 Separation factor 
 
 
 
 
 
 
 
 H2/CH4 
 5 
 
 Sweep rate = 150 ml/min Feed flow rate = 50 ml/min 4 Feed presure = 1.0 × 105 Pa Permeance temperature = 25 °C 
 3 0 5 10 15 2025 Test time (h) 
 
 experiment 
 
 
 InternationalEdition46:2458-2462.
 ligands,positionedbetweenthehydrophilicchan-nelsandthehydrophobicchambers,whichcanbeopenedorclosedbyincreasingordecreasingthetemperature.Bychangingthetemperaturefrom60to300KthegatesizeofMAMS-1canbeadjustedbetween2.9and5.0A. .Gas-separationexperimentsofMAMS-1havebeenconductedandithasdis-playedselectiveadsorptionofH2overCO,O2,andN2at77K;O2overCOandN2at87K;N2overCOandCH4at113K;CH4overC2H4at143K;C2H4overC3H6at196K;andC3H6overiso-C4H10at241K.Likewise,isostructuralMAMSs,whichwerepreparedwithdifferentmetalcenters,alsodemon-stratedtemperature-dependentmolecularsievingeffects[102].
 
 
 5.01.6.3 Catalysis 
 Theexploitationofpracticalcatalystsforefficientsynthesisisofkeyimportancetothechemicalindustry[103,104].Homogeneouscatalystsusuallyshowadvantagesofhighactivityandselectivityinabroadrangeofsyntheticreactions[105].However,theirpracticalapplicationsremainlimitedduetodifficultyincatalyst/productseparationaswellascatalystinstability.RecentresultsshowingtheuseofMOFsassolidcatalystsareparticularlyinterestingbecausetheporesizeandfunctionalityoftheframe-workcanbeadjustedoverawiderangetoaccommodateavarietyofcatalyticreactions.MOFsareinsolubleintheconventionalreactionmediaandthushavepotentialtobeusefulinheterogeneouscatalysis[106].
 Someexamplesofselectivecatalysishavebeenpublished[107,108].Forinstance,Kitagawaetal.reporteda3DMOFfunctionalizedwithamidegroups,whichshowsgoodselectivecatalysis.Theselectivecatalysishasbeenattributedtotheuniformdistributionoftheamidegroupsonthechannelsurfaces[107].Thecatalyticprocessstu-diedwasthereactionofbenzaldehydewitheachoftheactivemethylenecompounds(malononi-trile,ethylcyanoacetate,orcyanoaceticacidtert-butylester),alsoknownastheKnoevenagelcondensation.Interestingly,mostofthesubstratesshowedverylittleconversiontotheadduct,whereas98%ofthemalononitrilewasconverted.Thisselectivitydependsontherelationshipbetweenthesizeofthereactantsandtheporewindowofthehost.
 Bybeingdopedwiththelargecatalyticallyactivemolecules,metalloporphyrins,Eddaoudiandco-workersfoundanenhancementofcatalyticactivityofarho-MOF[109].Theyfirstassembledthefree-baseporphyrinintorho-ZMOF,followedbythemettalationoftheframeworkandpostsyntheticmod-ificationbyseveraltransitionmetalions.Inthisway,theywereabletoproducepreviouslyunknownencapsulatedmetalloporphyrinsinasystematicfash-ion.Toassesscatalyticactivity,hydrocarbon(specificallycyclohexane)oxidationwasperformed
 on Mn-doped MOF. 
 (a) (b) 
 100 
 80 
 
 Fe′reyandcoworkershaverecentlystudiedthecatalyticpropertiesofMIL-101bypostsynthesizeddecoration[110].Theyfoundthatthepresenceoftrinuclearchromium(III)UMCsinMIL-101canleadtotheformationofthethermallystableaminespeciesgraftedtothesurface.Thiswouldbeaccomplishedwiththehelpofelectron-richfunctionalgroups.SeveralcatalyticallyactiveMOFswerereportedalongwiththesedata.Thenovelamine-graftedMIL-101showedhighactivitiesintheKnoevenagelcondensationwhenusingethylenediamine(ED)ordiethylenetriamineasthegraftingagents.TwootherMOFs,APS-MIL-101(APS.3-aminopropyltrialk-oxysilane)andED-MIL-101,resultedinhighactivitiesduringtheHeckreactionuponfurtherloadingofpalladium.
 Kimetal.forthefirsttimeshowedthatenantio-selectivetransesterificationispossibleinaMOFbyusingachiralporousMOF,D-POST-1(Figure13)[111].Thecatalytictransesterificationofethanolwasreportedata77%yield

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