Aryl Diazonium Salts and Related Compounds: Surface Chemistry and Applications (Physical Chemistry in Action)

This volume provides the latest developments in the field of surface science and technology based on diazonium coupling agents as well as their precursors (e.g. aromatic amines). It presents new concepts of surface chemistry of diazonium salts and discusses their novel and challenging applications. The latest advances on surface modification with diazonium salts are discussed and various promising alternative surface modifiers such as iodonium salts are examined. This book demonstrates the universality of diazonium salts in the surface treatment of classical and emergent materials and it will be a great tool for researcher and graduates working in this field. Preface Contents Contributors Principle, General Features and Scope of the Reaction, Recent Advances, Future Prospects 1 Introduction 2 The Principles of the Reaction 3 Electrografting 4 Non-electrochemical Grafting 5 Bonding of the Organic Film 6 The Grafting Mechanism 7 The Structure of the Films, Monolayers, Multilayers, Multifunctional Films 7.1 Monolayers 7.2 Multilayers 8 Surface Functional Groups 8.1 Mixed Layers 9 New Substrates 10 Indirect Grafting 11 Conclusion References Structures, Stability, and Safety of Diazonium Salts 1 Influence of the Nature of Counterions 2 Influence of the Structure of Aryl and Heteroaryl Radicals 2.1 Triazenes as Safe Surrogates for Diazonium Salts 2.2 Unconventional Methods for Synthesis of Diazonium Salts References Kinetics and Mechanisms of Aryldiazonium Ions in Aqueous Solutions 1 Introduction 2 A Brief Survey of the Chemistry of Arenediazonium Ions in Aqueous Solutions 3 Kinetics and Mechanisms of Spontaneous Decomposition of ArN2+ in Aqueous Solution and in Alcohol-Water Mixtures 3.1 Dediazoniations Under Acidic (pH 9) Aqueous Solutions 4 Analytical Chemistry of Diazonium Salts and Their Degradation Products 5 Conclusions and Future Perspectives References Iodonium Salts as Reagents for Surface Modification: From Preparation to Reactivity in Surface-Assisted Transformations 1 Introduction 2 Iodonium Salts: Preparation and Reactivity 3 Surface Modification via Decomposition of Iodonium Salts 3.1 Iodonium Salts as Modification Agent: General Insight 3.2 Electrochemical Modification 3.3 Nucleophilic Substitution—A Straight Way for Modification of Carbon Allotropes 3.4 Iodonium Salts—Spontaneous Modification? 3.5 Light as a New Stimulus for ISs Grafting 4 Conclusion and Outlook References Control of the Aryl Layer Growth 1 Introduction 2 How to Characterize the Growth of Organic Layers? 3 Impact of Grafting Conditions on the Layer Growth 4 Limiting the Grafting to a Monolayer 4.1 Degradation of an Existing Multilayer 4.2 Modulation of the Deposition Conditions 4.3 Blocking of Reactive Positions 4.4 Lowering the Local Concentration of Reactive Radicals 5 Concluding Remarks References Grafting of Aryl Radicals onto Surfaces—A DFT Study 1 Introduction 2 The Adsorption/Grafting of the Diazonium Salts 2.1 Metallic Systems 2.2 Au-C Bond Characterization 2.3 Evidence of Au–N Bond 2.4 Carbon Based Materials 3 The Activation Energy of the Grafting Reaction 3.1 Carbon Based Nanomaterials 3.2 Phosphorus and Silicone Based Materials 4 Spectroscopic Studies References Modification of sp2 Carbon Allotropes with Diazonium Salts—Focus on Carbon Nanotubes Functionalization 1 Introduction 2 Functionalization of the CNTs by Diazonium Chemistry. An Overview 2.1 Electrochemical Grafting of CNT 2.2 Other Methods of CNTs Functionalization via Diazonium Chemistry 3 Properties of the CNT Induced by the Functionalization via Diazonium Chemistry 3.1 Solubilization—Application to the Separation of Metallic to Semiconducting SWCNT 3.2 Influence of the Surfactant on the Selectivity of the Functionalization via Diazonium Chemistry 3.3 Optical Properties Focus on Photoluminescence (PL) 3.4 Electrical and Thermoelectric Properties 4 Characterization of the Functionalized CNT 5 Applications of the Functionalized CNT 5.1 Catalytic Applications 5.2 Nanocomposites 5.3 Energy Conversion 5.4 Sensors and Biosensors 6 Conclusion References Covalent Modification of Graphite and Graphene Using Diazonium Chemistry 1 Functionalization of Graphite—Graphene 2 Aryl Diazonium Salts as Modifiers of sp2 Materials 3 Functionalization of Graphite Surfaces 4 On-Surface Functionalization of Graphene 5 Control in Thickness. From Multilayers to Monolayers 6 Control in Spatial Distribution—Patterning 7 From Surfaces to Bulk 8 Aryl Linkers to Build Complex Architectures. Toward the Application of Grafted Surfaces 9 Conclusions References Aryldiazonium Tetrachloroaurate(III) Salts: Synthesis, Structure, and Fundamental Applications 1 Introduction 2 Synthesis and X-Ray Structure of Diazonium Gold(III) Salts 3 Electrochemistry of Aryldiazonium Tetrachloroaurate(III) Salts 4 Forensic Science Applications 5 Medical Applications 6 Fabrication of Alloy and Core–Shell Structures 7 Miscellaneous Applications 8 Conclusions References Modification and Uses of Synthetic and Biobased Polymeric Materials 1 Introduction 1.1 Polymers 1.2 Biomass 2 Conclusion References Surface Modification of Plasmonic Nanomaterials with Aryl Diazonium Salts 1 Properties of Plasmonic Nanoparticles 2 Common Strategies for Surface Functionalization of Plasmonic NPs 3 Surface Functionalization of Plasmonic NPs with Aryl Diazonium Salts 3.1 Electrografting 3.2 Spontaneous Grafting or Chemical Reduction 3.3 Plasmon-Mediated Grafting 4 Surface Immobilization of Small Molecules, Polymer Films, and Biomolecules at the Surface of Plasmonic Nanoparticles 4.1 Surface Immobilization of Small Molecules 4.2 Surface Immobilization of Polymers 4.3 Surface Immobilization of Biomolecules 5 Targeted Applications 5.1 Biomedical Science 5.2 Environmental Protection 5.3 Forensic Science 5.4 Catalysis 6 Conclusion References Diazonium Electroreduction and Molecular Electronics 1 Introduction 2 Advantages of Diazonium Electroreduction for Generating Molecular Junctions 3 Various Electronic Functions Demonstrated in Large-Area Diazonium-Based Mjs 4 Conclusion References Modification of Surfaces with Calix[4]arene Diazonium Salts 1 Introduction 2 Synthesis of Calix[4]arene Tetradiazonium Derivatives 3 Surface Modification and Characterization 3.1 Formation of True Monolayers 3.2 Formation of Mixed Monolayers of Controlled Composition 3.3 Post-functionalization of Calixarene-Based Monolayers 3.4 Robustness of the Calixarene-Based Coatings 4 Applications of Calix[4]arene Tetradiazonium-Based Coatings 4.1 Hydrophobicity 4.2 Antifouling 4.3 Sensing 4.4 Electrocatalysis 5 Conclusions and Future Perspectives References Diazonium Salts and Related Compounds for Biomedical Applications 1 Introduction 2 Implantable Materials 2.1 Using Diazonium Modification to Bind Intermediate Linkers 2.2 Using Diazonium Modification to Change Surface Properties Directly 3 Scaffolds for Tissue Engineering 3.1 Bone Tissue Engineering 3.2 ECM Mimetics 3.3 Immune Response Modulation 4 Drug Delivery 4.1 Carbon-Based Nanomaterials as Drug Carriers Modified by Diazonium Chemistry 4.2 Protein-Based Drug Delivery Systems 4.3 Other Substrates Modified by Diazonium Chemistry for Drug Delivery Applications 5 Summary and Perspective References On the Use of Diazonium Salts in the Design of Catalytic Hybrid Materials and Coatings 1 Introduction 2 Immobilization of Catalysts on Arylated Surfaces 3 Diazonium Modification of Catalysts 4 Conclusion References Aryldiazonium Salts as Photoinitiators for Cationic and Free Radical Polymerizations 1 Introduction 2 Cationic Polymerization 2.1 Direct Photolysis 2.2 Indirect Acting Photoinitiating Systems 3 Free Radical Polymerization 4 Conclusions References Polymer Surface Science and Adhesion Using Diazonium Chemistry 1 Introduction and Scope 2 Earlier Developments (1997–2011) 3 Recent Progress in Polymer Grafting to Arylated Surfaces: 2012–2021 3.1 Surface-Initiated ATRP 3.2 RAFT and (Photo)iniferter 3.3 Radical Photopolymerization Using Type II Photoinitiators 3.4 Concurrent Radical Photopolymerization and Metal Nanoparticle Formation 3.5 Azide-Alkyne Click Polymerization 3.6 Oxidative Polymerization of Conjugated Monomers 3.7 New Trends 4 Conclusion References Diazonium-Modification of Plasmonic Surfaces Formed by Laser Ablation 1 Surface Enhanced Raman Spectroscopy 2 Functional SERS Substrates Based on Diazonium Surface Modification 3 Diazonium Grafted SERS Substrates for Selective Entrapping and Detection 3.1 Heavy Metal Ions and Radicals SERS Detection 3.2 MOF-Based Surface Functionalization for Pollutants and Drug SERS Detection 3.3 Enantiospecific and Large Biomolecules SERS Detection 4 Conclusion and Outlook References Diazonium Salts and the Related Compounds for the Design of Biosensors 1 Introduction 2 Strategies for Generation of the Aryldiazonium Salt Chemistry Decorated Substrates 2.1 Preparation of Aryldiazonium Salts 2.2 Compatible Substrates for Aryldiazonium Salt Chemistry 2.3 Methods for Modification of Substrates Using Aryldiazonium Salts 3 Applications of Aryl Diazonium Salts and Related Compounds in Biosensing Applications 3.1 Single Aryl Layer-Based Sensors 3.2 Mixed Aryl Layer-Based Sensors 4 Conclusions References Reinforced Polymers: The Emerging Role of Diazonium Modification of Fillers 1 Introduction 2 Fillers: Definition, Features and Properties Imparted to Polymer Matrices 3 Case Studies of Diazonium Modification of Fillers and Uses Thereof 3.1 Diazonium Modification of Nanosilicas and Zeolites 3.2 Clay Modification with Aryldiazonium Salts 3.3 Modification of Carbon Allotropes 4 Summary of Shortlisted Polymeric Systems Reinforced with Diazonium-Modified Fillers 5 Conclusion: What Have We Learned So Far from Diazonium Filler Modification for Polymer Composites References Diazonium Salts for the Preparation of Carbon Composites with a Focus on Applications of Carbon Fibers 1 Introduction: With a Focus on Application 1.1 Production 1.2 Introduce Interphase/Interface Region 2 Analysis of Functionalised Carbon Fiber 2.1 IFSS and Micro Bond Test 2.2 Chemical Analysis of Carbon Fiber 3 Diazonium Salts—A Method to Functionalize Carbon Fiber 3.1 Chemically Grafted Approach 3.2 ElectroChemically Grafted Approach 3.3 Combining Grafting Methods 3.4 Examining the Use of Diazonium Salt Functionalisation 3.5 One-Pot Functionalisation of Polymers to Carbon Fiber 4 Conclusion References Diazonium Salts and Related Compounds in Electrochemical Energy Storage and Conversion 1 Introduction 2 Batteries 2.1 Basic Concepts 2.2 Anode 2.3 Cathode 2.4 Carbon Additive 3 Electrochemical Capacitors 3.1 Basic Concepts 3.2 Grafting of Redox Active Molecules 3.3 Two-Electrode Systems 3.4 Immobilization of Metal Oxide on Grafted Materials 3.5 Grafting Electrochemically Inert Species 4 Fuel Cells 4.1 Basic Concepts 4.2 Functionalization of Carbon Supports 4.3 Functionalization of Metal Particles 4.4 Functionalization of Carbon as Support for Nonprecious Metal Catalyst 5 Biofuel and Microbial Fuel Cells 5.1 Basic Concepts 5.2 Immobilization of Enzyme on Aryl-Modified Electrode 5.3 Biofuel Cell 5.4 Microbial Fuel Cell 6 Conclusion References Recent Patents and Industrial Applications 1 Supporting Intraocular Lenses: The GraftFast® Process 1.1 Introduction 1.2 Summary of the Graftfast® Process 1.3 Heparin-Like Coatings 1.4 Synthetic Heparin to Eradicate Secondary Cataracts 2 GraftFast® to Improve the Robustness of pH Sensors 2.1 Introduction 2.2 Optode 2.3 Neutral Red 2.4 Neutral Red Grafting 2.5 Thickening of the Grafted Layer 3 Treatment of the Aerospace Alloy Al2024 3.1 Introduction 3.2 Diazonium Coating as Adhesion Primer 3.3 Anodization Under Coating 4 Conclusion 5 Chapter Conclusion References Index