Chemically modified electrodes / edited by Richard C. Alkire ... [and others]

Includes bibliographical references and index

Contents Preface IX List of Contributors XI 1 Nanostructured Electrodes with Unique Properties for Biological and Other Applications 1 J. Justin Gooding, Leo M.H. Lai, and Ian Y. Goon 1.1 Introduction 1 1.2 High Surface Area Electrodes 2 1.2.1 Attachment of Nanoparticles onto Electrodes 3 1.2.2 Templating using Membranes 12 1.2.3 Templating using Lyotropic Liquid Crystals 19 1.2.4 Colloidal Templates 22 1.3 Catalytic Properties 23 1.4 Exploiting Nanoscale Control to Interface Electrodes with Biomolecules 27 1.4.1 Plugging Nanomaterials into Proteins – Nanoparticles 27 1.4.2 Plugging Nanomaterials into Proteins – Carbon Nanotubes 29 1.4.3 Plugging Nanomaterials into Proteins – Molecular Wires 31 1.4.3.1 Nanostructuring Electrodes to Achieve Intimate Connectivity with Biomolecules 32 1.4.3.2 Nanostructuring Electrodes using Rigid Molecules 32 1.4.3.3 The use of Molecular Wires in Electrochemistry such that Long-Distance Electron Transfer can be Exploited for a Variety of Applications 35 1.5 Switchable Surfaces 39 1.5.1 Switching Properties of Monolayer Systems 39 1.5.2 Control and Enhancement of Electrochemical Reactions using Magnetic Nanostructures on Electrodes 43 1.6 Conclusions 50 References 50 Advances in Electrochemical Science and Engineering: Vol. 11 Chemically Modified Electrodes. Edited by Richard C. Alkire, Dieter M. Kolb, Jacek Lipkowski and Philip N. Ross 2 Electrochemically Active Polyelectrolyte-Modified Electrodes 57 Mario Tagliazucchi and Ernesto J. Calvo 2.1 Introduction 57 2.1.1 Chemically Modified Electrodes 58 2.1.2 Redox Hydrogels 59 2.1.3 Redox Polyelectrolyte Monolayers 60 2.1.4 Redox Polymer Brushes and Grafted DNA 61 2.1.5 Layer-by-Layer Polyelectrolyte Multilayers 62 2.2 Structure 64 2.2.1 Polyelectrolye Interpenetration 66 2.2.2 Compensation of Polyelectrolyte Charges 66 2.2.3 Film Inner Structure 66 2.2.4 Effect of the Assembly pH 67 2.2.5 Theoretical Description 68 2.3 Electrochemical Response 72 2.3.1 Ideal Response 72 2.3.2 Peak Position and Donnan Potential 73 2.3.3 Coupling Between the Acid–Base and Redox Equilibria 78 2.3.4 Peak Width 79 2.3.5 Nonreversible Electrochemistry: Charge Transport 81 2.4 Dynamics of Solvent and Ion Exchange 84 2.4.1 Ion Exchange 84 2.4.2 Solvent Exchange 86 2.4.3 Specific Ionic Effects 86 2.4.4 Break-In 88 2.5 Molecular Description of Redox Polyelectrolyte-Modified Electrodes 89 2.5.1 Formulation of the Molecular Theory 89 2.5.2 Comparison with Phenomenological Models, Advantages and Limitations 96 2.6 Applications 97 2.6.1 Amperometric Enzymatic Electrodes 97 2.6.2 Electrochromic Devices 105 2.7 Conclusions 106 References 109 3 Electrochemistry on Carbon-Nanotube-Modified Surfaces 117 María José Esplandiu 3.1 Introduction 117 3.2 Structure and Properties of Carbon Nanotubes 118 3.2.1 Structure and Electronic Properties 118 3.2.2 Chemical Properties 121 3.2.3 Electrochemical Properties 123 3.3 Towards the Design of CNT-Modified Electrodes 128 3.3.1 Synthesis of CNTs 128 3.3.2 CNT Purification Methods 129 3.3.3 Chemical and Biochemical Functionalization 130 3.3.3.1 Covalent Modification 131 3.3.3.2 Noncovalent Modification 133 3.3.3.3 Chemical Modification for CNT Sorting 133 3.3.3.4 Chemical Doping, Intercalation and Artificial Defects 135 3.3.4 CNT Deposition on Electrode Surfaces 135 3.3.4.1 Randomly Dispersed CNTs 135 3.3.4.2 Oriented CNT Electrodes 141 3.3.4.3 Individual CNT Electrodes 144 3.3.5 CNT-Modified Electrode Pretreatments 146 3.4 Electrochemical Applications of CNT Electrodes 147 3.4.1 Biosensors 147 3.4.1.1 Enzymatic and Redox Protein Biosensors 148 3.4.1.2 CNT/DNA and Genosensors 151 3.4.1.3 Immunosensors 156 3.4.2 Electrochemical Actuators 157 3.4.3 Electrochemical Energy-Harvesting Devices 157 3.5 Conclusions and Future Prospects 160 References 162 4 Electrochemistry of Electroactive Surface-Immobilized Nanoparticles 169 Daniel A. Buttry 4.1 Introduction 169 4.2 Synthetic Approaches and Characterization 171 4.3 Immobilization Schemes 174 4.4 Metal Oxides 178 4.4.1 TiOx 178 4.4.2 MnOx 180 4.4.3 FeOx 184 4.4.4 NiOx and CoOx 185 4.5 Other Metal Oxides and Metal Sulfides 186 4.6 Prussian Blue and Its Derivatives 187 4.7 Concluding Remarks 192 References 193 5 Structure, Electrochemistry and Applications of Self-Assembled Monolayers of Thiols 197 Manfred Buck 5.1 Introduction 197 5.2 Structural Aspects of Thiol-Like SAMs 200 5.3 Reductive Desorption of SAMs 209 5.4 Metal Deposition on SAM-Modified Electrodes 218 5.4.1 General Remarks 218 5.4.2 On-Top Deposition 220 5.4.3 Underpotential Deposition 228 5.4.4 Bulk-Metal Deposition 239 5.5 Summary and Outlook 245 References 247 Index 257

"With contributions from an international group of expert authors, this book includes the latest trends in tailoring interfacial properties electrochemically. The chapters cover various organic and inorganic compounds, with applications ranging from electrochemistry to nanotechnology and biology."--pub. desc