Analytical Electrochemistry

Joseph Wang, PhD, is Distinguished Professor, SAIC Endowed Chair and Chair in the Department of Nanoengineering at University of California, San Diego (UCSD). He is the Director of the UCSD Center of Wearable Sensors and Founding Editor of Electroanalysis. He is a Fellow of the ECS, Royal Society of Chemistry, and the American Institute of Medical and Biological Engineering.

• Preface ixAbbreviations and Symbols xi1 Fundamental Concepts 11.1 Why Electroanalysis? 11.2 Faradaic Processes 21.2.1 Mass-Transport-Controlled Reactions 41.2.1.1 Potential-Step Experiment 61.2.1.2 Potential Sweep Experiments 71.2.2 Reactions Controlled by the Rate of Electron Transfer 91.2.2.1 Activated Complex Theory 121.3 Electrical Double Layer 141.4 Electrocapillary Effect 181.5 Supplementary Reading 19References 20Questions 212 Study of Electrode Reactions and Interfacial Properties 222.1 Cyclic Voltammetry 222.1.1 Data Interpretation 242.1.1.1 Reversible Systems 242.1.1.2 Irreversible and Quasi-reversible Systems 252.1.2 Study of Reaction Mechanisms 262.1.3 Study of Adsorption Processes 292.1.4 Quantitative Applications – Fast-Scan Cyclic Voltammetry 302.2 Spectroelectrochemistry 322.2.1 Experimental Arrangement 322.2.2 Principles and Applications 332.2.3 Electrochemiluminescence 352.2.4 Optical Probing of Electrode/Solution Interfaces 362.3 Scanning Probe Microscopy 372.3.1 Scanning Tunneling Microscopy 372.3.2 Atomic Force Microscopy 382.3.3 Scanning Electrochemical Microscopy 402.4 Electrochemical Quartz Crystal Microbalance 432.5 Impedance Spectroscopy 45References 47Examples 50Questions 523 Controlled-Potential Techniques 543.1 Chronoamperometry 543.2 Polarography 563.3 Pulse Voltammetry 593.3.1 Normal-Pulse Voltammetry 593.3.2 Differential-Pulse Voltammetry 603.3.3 Square-Wave Voltammetry 623.3.4 Staircase Voltammetry 653.4 AC Voltammetry 663.5 Stripping Analysis 673.5.1 Anodic Stripping Voltammetry 683.5.2 Potentiometric Stripping Analysis 713.5.3 Adsorptive Stripping Voltammetry and Potentiometry 723.5.4 Cathodic Stripping Voltammetry 743.5.5 Abrasive Stripping Voltammetry 753.5.6 Applications 753.6 Flow Analysis 753.6.1 Principles 773.6.2 Cell Design 793.6.3 Mass Transport and Current Response 813.6.4 Detection Modes 83References 85Examples 88Questions 904 Practical Considerations 934.1 Electrochemical Cells 934.2 Solvents and Supporting Electrolytes 954.3 Oxygen Removal 954.4 Instrumentation 964.5 Working Electrodes 1014.5.1 Mercury Electrodes 1024.5.2 Solid Electrodes 1034.5.2.1 Rotating Disk and Ring-Disk Electrodes 1044.5.2.2 Carbon Electrodes 1064.5.2.3 Metal Electrodes 1094.5.3 Printed Electrodes and Devices 1104.5.3.1 Planar Screen-Printed Electrodes 1104.5.3.2 3D-Printed Electrochemical Cells and Electrodes 1124.5.4 Chemically Modified Electrodes 1134.5.4.1 Self-Assembled Monolayers 1144.5.4.2 Carbon-Nanotube-Modified Electrodes 1154.5.4.3 Graphene-Based Electrodes 1164.5.4.4 Sol–Gel Encapsulation of Reactive Species 1174.5.4.5 Electrocatalytic Modified Electrodes 1174.5.4.6 Preconcentrating Electrodes 1184.5.4.7 Permselective Coatings 1194.5.4.8 Conducting Polymers 1224.5.5 Microscale and Nanoscale Electrodes 1244.5.5.1 Diffusion at Microelectrodes 1264.5.5.2 Configurations of Microelectrodes 1264.5.5.3 Composite Electrodes 1284.5.6 Microneedle Electrodes and Arrays 130References 132Examples 137Questions 1375 Potentiometry 1395.1 Principles of Potentiometric Measurements 1395.2 Ion-Selective Electrodes 1455.2.1 Glass Electrodes 1455.2.1.1 pH Electrodes 1455.2.1.2 Glass Electrodes for Other Cations 1485.2.2 Liquid Membrane Electrodes 1485.2.2.1 Ion-Exchanger Electrodes 1505.2.2.2 Neutral Carrier Electrodes 1515.2.3 Solid-State Electrodes 1545.2.4 Solid-Contact ISE: Eliminating the Internal Filling Solution 1575.3 On-line, On-site, In Situ, and In Vivo Potentiometric Measurements 160References 164Examples 167Questions 1686 Electrochemical Sensors 1706.1 Electrochemical Biosensors 1716.1.1 Enzyme‐Based Electrodes 1716.1.1.1 Practical and Theoretical Considerations 1716.1.1.2 Enzyme Electrodes of Analytical Significance 1756.1.2 Affinity Biosensors 1826.1.2.1 Immunosensors 1826.1.2.2 Aptamer‐Based Electrochemical Biosensors 1856.1.2.3 DNA Hybridization Biosensors 1866.1.2.4 Electrochemical Sensors Based on Molecularly Imprinted Polymers 1896.2 Gas Sensors 1896.2.1 Carbon Dioxide Sensors 1906.2.2 Oxygen Electrodes 1916.3 Solid-State Devices 1926.3.1 Ion‐Selective Field Effect Transistors 1926.3.2 Microfabrication of Solid‐State Sensor Assemblies 1946.3.3 Photolithographic Sensor Fabrication Techniques 1946.3.4 Micromachined Analytical Microsystems 1956.3.5 Paper‐Based Electroanalytical Devices 1966.4 Sensor Arrays 1976.5 Wearable Electrochemical Sensors 200References 203Examples 210Questions 211Index 213