Electrochemical Methods: For Biosensors, MEMS, Nanotechnology, Neuroscience, Renewable Energy, Batteries

Cover
Half Title
Also of Interest
Electrochemical Methods: For Biosensors, MEMS, Nanotechnology, Neuroscience, Renewable Energy, Batteries
Copyright
Dedication
Preface
Preface to the second edition
About the book
Contents
Part I: Fundamentals
	1. Introduction
		1.1 Short history of electrochemistry
			1.1.1 Luigi Galvani – animal electricity
			1.1.2 Allesandro Volta – pile to disprove animal electricity
			1.1.3 John Daniell – early battery
			1.1.4 William Grove – early fuel cell
			1.1.5 Robert Bunsen – economic electrode material
			1.1.6 Michael Faraday – quantitative experiments
			1.1.7 Walther Nernst – thermodynamics
		1.2 Fields of applications
			1.2.1 Biomedical sensors and point-of-care systems
			1.2.2 Neuroscience, neurotechnology, and auditory nerve stimulation
			1.2.3 Microelectronics
			1.2.4 Energy applications
		1.3 Electrochemical cells
			1.3.1 Primary and secondary cells
			1.3.2 Half-cell
			1.3.3 Electrochemical cell in equilibrium
	2. Electrochemical theory
		2.1 Conventions
			Potential vs. energy
			Current vs. current density and charge vs. charge density
			Flux vs. flux density
			Concentration
		2.2 Faradaic processes
			2.2.1 Faraday’s law
			2.2.2 Electron transfer
			2.2.3 Faradaic processes in equilibrium – Nernst equation
			2.2.4 General electrode reaction
		2.3 Faradaic processes: kinetic control – electron transfer
			2.3.1 Activated complex theory
			2.3.2 Butler–Volmer equation
			2.3.3 Charge-transfer close to equilibrium: linearization
			2.3.4 Charge-transfer far from equilibrium: Tafel plot
		2.4 Faradaic processes: mass transfer control
			2.4.1 Diffusion
			2.4.2 Migration
			2.4.3 Convection
			2.4.4 Nernst–Planck equation
			2.4.5 Diffusion: constant polarization
			2.4.6 Diffusion: potential step experiment – Cottrell equation
				Infinite planar electrode
				Hemispherical electrode
				Disk-shaped electrode
		2.5 Faradaic processes: combined kinetic and mass transfer control
			2.5.1 Reversibility
				Electrochemical reversible systems
				Electrochemical irreversible systems
			2.5.2 Overpotential
				Concentration overpotential
				Activation overpotential
				Resistive overpotential
		2.6 Interfacial region
			2.6.1 Electrical double layer
			2.6.2 Zeta potential – electrokinetic effects
		2.7 Non-faradaic processes
			2.7.1 Capacitive currents
				Linear scan experiment
				Potential step experiment
			2.7.2 Pseudo-capacitive effects
		2.8 Potential scales
			2.8.1 Influence of pH
			2.8.2 Stability of water
			2.8.3 Pourbaix diagrams
				Horizontal boundary line
				Vertical boundary line
				Sloped boundary lines
	3. Instrumentation
		3.1 Three-electrode setup
		3.2 Potentiostat
			3.2.1 Adder potentiostat
			3.2.2 Signal generation and data acquisition
			3.2.3 Stability, noise, and compliance voltage
				Stability
				Noise
				Compliance voltage
			3.2.4 Potential drop (IR drop) and its compensation
				Measurement of the uncompensated resistance
				Potential drop compensation
			3.2.5 Potential of the counter electrode
			3.2.6 Commercial devices
			3.2.7 Integrated circuits, embedded potentiostats
				Texas Instruments LMP91000
				Analog Devices AD5940/AD5941
				ADuCM355
		3.3 Galvanostat
		3.4 Potential measurement
		3.5 Electrical shielding
	4. Electrochemical laboratory
		4.1 Classification of electrodes
			4.1.1 Classes of electrodes
			4.1.2 Polarizability and potential window
		4.2 Reference electrodes
			4.2.1 Hydrogen reference electrodes
				Standard hydrogen electrode, normal hydrogen electrode
				Reversible hydrogen electrode
			4.2.2 Silver/silver chloride electrode
				Temperature dependency
			4.2.3 Silver/silver bromide electrode
			4.2.4 Calomel electrode
			4.2.5 Diffusion potential, liquid junction potentials
				Minimizing liquid junction potentials
		4.3 Working and counter electrodes
			4.3.1 Metal electrodes
			4.3.2 Mercury electrodes
			4.3.3 Carbon electrodes
				Graphite
				Glassy carbon (glass-like carbon)
				Diamond
			4.3.4 Metal oxide electrodes
			4.3.5 Counter electrodes
			4.3.6 Ultramicroelectrodes
			4.3.7 Microfabricated electrodes
			4.3.8 Gas-diffusion electrodes
			4.3.9 Electrode polishing
		4.4 Electrochemical cells – labware
			4.4.1 Flat sample cell
			4.4.2 Electrolyte droplets on the electrode chip
		4.5 Electrolytes
			4.5.1 Aqueous electrolytes
			4.5.2 Nonaqueous liquid electrolytes
			4.5.3 Solid electrolytes
		4.6 Redox couples
			4.6.1 Ruthenium hexamine
			4.6.2 Ferrocene
			4.6.3 Ferrocyanide/ferricyanide
			4.6.4 Inner-sphere versus outer-sphere electron transfer
Part II: Methods
	5. Classical methods
		5.1 Potentiometry
			5.1.1 Open circuit potential
			5.1.2 Donnan potential, membrane potential
			5.1.3 Ion-selective electrode
				Nikolsky–Eisenman equation
				Selectivity: separate solutions method
				Selectivity: fixed interference method
				Limit of detection
			5.1.4 pH glass electrode
			5.1.5 Active potentiometry
		5.2 Amperometry
			5.2.1 Single-potential amperometry
			5.2.2 Step-response amperometry
				Diffusion constant measurement
			5.2.3 Chronoamperometry
				Double-step chronoamperometry
				Oxygen monitoring
			5.2.4 Pulsed-amperometric detection
			5.2.5 Chronocoulometry
				Platinum: surface oxidation
		5.3 Voltammetry
			5.3.1 Sign conventions
			5.3.2 Cyclic voltammetry and linear scan voltammetry
			5.3.3 Cyclic voltammetry of metal electrodes
				Influence of scanrate and turning points
				First cycles to trace the electrode’s history
				Combination with redox-active substances in the electrolyte
			5.3.4 Cyclic voltammetry of electroactive substances in the electrolyt
				Reversible systems (Nernstian systems)
				Influence of the turning point
				Irreversible systems
				Reversibility
				Multistep reactions
				Multicomponent systems
				Reaction mechanism including chemical reactions
				Adsorption
				Nonidealities
				Microelectrodes
			5.3.5 Polarography
			5.3.6 Pulse voltammetry
				Normal pulse voltammetry
				Differential pulse voltammetry
				Staircase voltammetry
				Data analysis
			5.3.7 Square-wave voltammetry
			5.3.8 AC voltammetry
			5.3.9 Stripping voltammetry
				Anodic stripping voltammetry
				Cathodic stripping voltammetry
				Adsorptive stripping voltammetry
			5.3.10 Fast-scan cyclic voltammetry
		5.4 Current-controlled techniques
			5.4.1 Chronopotentiometry
				5.4.1.1 Reciprocal derivative chronopotentiometry
	6. Combined methods
		6.1 Hydrodynamic methods
			6.1.1 Rotating disk electrode
				Levich study – mass transport limitation
				Koutecký–Levich analysis
				Experimental considerations
			6.1.2 Rotating ring disk electrode
				Measurement of reaction products
				Example: oxygen reduction reaction
				Measurement of reaction products’ stability
			6.1.3 Flow cells
			6.1.4 Zeta potential measurement
		6.2 Scanning methods
			6.2.1 Scanning electrochemical microscopy
			6.2.2 Electrochemical atomic force microscopy
			6.2.3 Electrochemical scanning tunneling microscope
		6.3 Other measurement methods
			6.3.1 Electrochemical quartz crystal microbalance
				Viscoelastic properties of the deposited material
			6.3.2 Sensor access to the microenvironment of an electrode
				Respirometry
			6.3.3 Electrochemical noise analysis
			6.3.4 Spectroelectrochemistry
	7. Electrochemical impedance spectroscopy
		7.1 Fundamentals
			7.1.1 Mathematical formulation and assumptions
				Linearity
				Time-invariance or steady state
				Causality
			7.1.2 Measurement methods
			7.1.3 Multisine approach
			7.1.4 Data presentation
				Nyquist plot
				Bode plot
				Lissajous figures
		7.2 Circuit elements and equivalent networks
			7.2.1 Basic elements
				Resistor: R
				Capacitor: C
				Constant phase element: Q
				Inductor: L
			7.2.2 Charge transfer resistance
			7.2.3 Randles circuit
			7.2.4 Mass transport control – Warburg impedance
			7.2.5 Coatings
		7.3 Toolbox
			7.3.1 Kramer–Kronig test
			7.3.2 Software
			7.3.3 Challenges in modeling
Part III: Applications
	8. Selected aspects: material science
		8.1 Corrosion
			8.1.1 Fundamentals
				Local element
			8.1.2 Types of corrosion
				Uniform corrosion
				Pitting corrosion
				Crevice corrosion
				Galvanic corrosion
				Waterline corrosion
				Microbiologically influenced corrosion
			8.1.3 Thermodynamics: Pourbaix diagram
			8.1.4 Kinetics: Evans diagram, Tafel plot
				Mixed potential
				External polarization
				Mass transport control
			8.1.5 Passivation and transpassivity
		8.2 Methods to analyze corrosion
			8.2.1 Corrosion potential measurement
			8.2.2 Linear sweep voltammetry
				Polarization resistance
				Tafel analysis
				Large range linear sweep voltammetry
			8.2.3 Electrochemical impedance spectroscopy
				Polarization resistance
				Coating
			8.2.4 Short-circuit current measurement
			8.2.5 Critical pitting temperature measurement
			8.2.6 Combined research methods
		8.3 Methods to prevent corrosion
			8.3.1 Cathodic protection
			8.3.2 Anodic protection
			8.3.3 Corrosion inhibitors
			8.3.4 Protective barriers
		8.4 Platinum electrochemistry
			8.4.1 Platinum surface reactions
				EQCM measurement
			8.4.2 Electrode roughness
			8.4.3 Degradation of platinum
			8.4.4 Volcano plots
	9. Selected aspects: microfabrication and nanotechnology
		9.1 Electroless metal deposition
			9.1.1 Nickel-phosphorus plating
			9.1.2 Other electroless plating processes
			9.1.3 Immersion plating
		9.2 Electrodeposition
			9.2.1 Electroplating of metals
				Nickel plating
				Copper plating
				Damascene process
				Silver plating
			9.2.2 Platinum black and hierarchical platinum structures
				Platinum nanostructures
				Hierarchical platinum micro/nanostructures
			9.2.3 Anodically electrodeposited iridium oxide films
			9.2.4 Unterpotential deposition
			9.2.5 Nanofilm deposition: electrochemical atomic layer deposition
				Combination of UPDs
				Combination of UPD and SLRR
			9.2.6 Electrophoretic deposition
			9.2.7 Electropolymerization
		9.3 Subtractive electrochemical techniques
			9.3.1 Electrochemical machining
			9.3.2 Electrochemical etching
			9.3.3 Electropolishing
		9.4 Nanoelectrodes, nanomaterials
			9.4.1 Carbon nanomaterials
				Carbon nanotubes
				Carbon nanofibers
	10. Selected aspects: microsystems and nanosystems
		10.1 Sensors
			10.1.1 Potentiometric ion-selective sensors
				Metaloxide pH sensors
			10.1.2 Microsensors with gas-permeable membrane
				Clark-type oxygen sensor
				Severinghaus carbon dioxide sensor
			10.1.3 Biosensors
			10.1.4 Enzymatic biosensors
				Michaelis–Menten kinetics
				Biosensors with oxygen as cosubstrate (“first generation”)
				Biosensors with mediator (“second generation”)
				Biosensors with direct electron transfer (“third generation”)
			10.1.5 Glucose meter
			10.1.6 Immunoassay, immunosensor
			10.1.7 Redox cycling
			10.1.8 Sensortechnology for different applications
				Sensing Sell Culture Flask
				Microphysiometry in a lab-on-chip
				Metabolic monitoring in organ-on-chip systems
				Flexible microsensor for in vivo applications
				Process monitoring in microreactors
		10.2 Actuators
			10.2.1 Release due to membrane corrosion
			10.2.2 Electrolysis actuators and pumps
			10.2.3 Bending beam actuators
		10.3 Neurotechnology
			10.3.1 Neural activation: action potential
			10.3.2 Neural recording by electrodes
			10.3.3 Neural stimulation by electrodes
			10.3.4 Neurotransmitter monitoring
				Dopamine detection
				FSCV for other substances
				Instrumentation
			10.3.5 Sensing by electrodes from neural implants
	11. Selected aspects: energy applications
		11.1 Energy conversion
			11.1.1 Fuel cells
				Proton-exchange membrane fuel cell
				Alkaline fuel cell
				Liquid fuels
				Microbial fuel cell
			11.1.2 Electrolysis
				Water splitting
				CO2 electrolysis
		11.2 Energy storage
			11.2.1 Batteries
				Primary cells
				Secondary cells
				Lithium-ion batteries
				Sodium-ion batteries
				Anode-free sodium batteries
				Sodium-sulfur batteries
			11.2.2 Redox flow batteries
			11.2.3 Supercapacitors
			11.2.4 Ragone plot
A. Reference data
	A.1 Standard reduction potentials
		A.1.1 Alphabetically sorted
		A.1.2 Sorted by potential
	A.2 Dissolved gases
		A.2.1 Solubility
		A.2.2 Salting-out effect
B. Instrumentation
	B.1 Operational amplifier primer
		Open-loop amplifier and voltage follower
		Inverting amplifier and inverting adder
		Current follower
		Integrator
	B.2 Ground and virtual ground
Bibliography
Index
Nomenclature
	Acronyms
	Symbols (greek letters)
	Symbols (latin letters)
List of tasks
Acknowledgment