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Joseph Wang

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ANALYTICAL ELECTROCHEMISTRY An accessible and robust text with comprehensive coverage of modern electroanalytical techniques and devices In the newly revised 4th edition of Analytical Electrochemistry, distinguished researcher Dr. Joseph Wang delivers an authoritative and comprehensive discussion of modern electroanalytical techniques and devices. With a strong focus on electroanalysis (as opposed to physical electrochemistry), the book offers readers a thorough grounding in the fundamentals of electrode reactions and the principles of electrochemical methods. It also demonstrates the solving of real-life analytical problems using the techniques discussed within. This latest edition contains extensive updates to the cited literature and its descriptions of various electrochemical processes and techniques. Additional worked examples are included in the text and numerous quantitative questions and exercise problems are found at the end of each chapter. Readers will also find: * A thorough introduction to the fundamental concepts of electroanalysis, including discussions of Faradaic processes, electrical double layers, and the electrocapillary effect * Comprehensive explorations of the study of electrode reactions, interfacial properties, and controlled potential techniques * Practical discussions of the practical considerations of electroanalysis, including electrochemical cells, solvents and supporting electrolytes, and instrumentation * Detailed treatments of potentiometry and electrochemical sensors, including ion selective electrodes, electrochemical biosensors and wearable devices Perfect for graduate students studying electroanalytical chemistry, Analytical Electrochemistry will also benefit advanced undergraduate students taking courses in instrumental analysis, as well as academics and industrial professionals considering the use of electroanalysis in their labs.

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Table of Contents

Cover

Title Page

Copyright Page

Preface

Abbreviations and Symbols

1 Fundamental Concepts

1.1 Why Electroanalysis?

1.2 Faradaic Processes

1.3 Electrical Double Layer

1.4 Electrocapillary Effect

1.5 Supplementary Reading

References

Questions

2 Study of Electrode Reactions and Interfacial Properties

2.1 Cyclic Voltammetry

2.2 Spectroelectrochemistry

2.3 Scanning Probe Microscopy

2.4 Electrochemical Quartz Crystal Microbalance

2.5 Impedance Spectroscopy

References

Examples

Questions

3 Controlled‐Potential Techniques

3.1 Chronoamperometry

3.2 Polarography

3.3 Pulse Voltammetry

3.4 AC Voltammetry

3.5 Stripping Analysis

3.6 Flow Analysis

References

Examples

Questions

4 Practical Considerations

4.1 Electrochemical Cells

4.2 Solvents and Supporting Electrolytes

4.3 Oxygen Removal

4.4 Instrumentation

4.5 Working Electrodes

References

Examples

Questions

5 Potentiometry

5.1 Principles of Potentiometric Measurements

5.2 Ion‐Selective Electrodes

5.3 On‐line, On‐site, In Situ, and In Vivo Potentiometric Measurements

References

Examples

Questions

6 Electrochemical Sensors

6.1 Electrochemical Biosensors

6.2 Gas Sensors

6.3 Solid-State Devices

6.4 Sensor Arrays

6.5 Wearable Electrochemical Sensors

References

Examples

Questions

Index

End User License Agreement

List of Tables

Chapter 1

Table 1.1 Properties of controlled‐potential techniques.

Chapter 2

Table 2.1 Electrochemical mechanisms involving coupled chemical reactions....

Chapter 3

Table 3.1 Functional groups reducible at the DME.

Table 3.2 Common adsorptive stripping schemes for measurements of trace met...

Table 3.3 Representative applications of stripping analysis.

Table 3.4 The limiting‐current response of various flow‐through electrodes....

Chapter 4

Table 4.1 Current suppliers of voltammetric analyzers.

Table 4.2 Commonly used membrane barriers.

Chapter 5

Table 5.1 Characteristics of solid‐state crystalline electrodes.

a

Chapter 6

Table 6.1 Some common enzyme electrodes.

Table 6.2 Potentiometric gas sensors.

List of Illustrations

Chapter 1

Figure 1.1 The three modes of mass transport.

Figure 1.2 Concentration profiles for different times after the start of a p...

Figure 1.3 Planar (a) and spherical (b) diffusional fields at spherical elec...

Figure 1.4 Concentration profiles (left) for different potentials during a l...

Figure 1.5 Concentration profiles for two rates of convection transport: low...

Figure 1.6 Current–potential curve for the system O + ne ↔ R, assuming that ...

Figure 1.7 Tafel plots for the cathodic and anodic branches of the current–p...

Figure 1.8 Free energy curve for a redox process at a potential more positiv...

Figure 1.9 Effect of a change in the applied potential on the free energies ...

Figure 1.10 Schematic representation of the electrical double layer. The ill...

Figure 1.11 Variation of the potential across the electrical double layer.

Figure 1.12 Double‐layer capacitance of a mercury drop electrode in NaF solu...

Figure 1.13 Electrocapillary curve (surface tension γ vs. potential).

Figure 1.14 Electrocapillary curves for different electrolytes showing the r...

Figure 1.15 Electrocapillary curves of background (◾), ethynylestradiol (⦁),...

Chapter 2

Figure 2.1 Potential‐time excitation signal in cyclic voltammetric experimen...

Figure 2.2 Typical cyclic voltammogram for a reversible O + ne

 ⇌ R re...

Figure 2.3 Concentration distribution of the oxidized and reduced forms of t...

Figure 2.4 Cyclic voltammetry of C

60

(a) and C

70

(b) in an acetonitrile/tolu...

Figure 2.5 Cyclic voltammograms for irreversible (a) and quasi‐reversible (b...

Figure 2.6 Cyclic voltammograms for a reversible electron transfer followed ...

Figure 2.7 Repetitive cyclic voltammograms for 1 × 10

−6

M riboflavin i...

Figure 2.8 Ideal cyclic voltammetric behavior for a surface layer on an elec...

Figure 2.9 Repetitive cyclic voltammograms illustrating the continuous growt...

Figure 2.10 Time‐potential waveform of fast‐scan cyclic voltammetry (FSCV): ...

Figure 2.11 Thin‐layer spectroelectrochemical cell.

Figure 2.12 Spectra for a series of applied potentials (mV vs. Ag/AgCl) duri...

Figure 2.13 Plot of vs. E for 1.55 × 10

−3

M methyl viologen at tin o...

Figure 2.14 Electrochemiluminescence (ECL) reaction sequence, based on a Ru(...

Figure 2.15 STM image of an electrochemically activated glassy carbon surfac...

Figure 2.16 STM image of 7.7 × 7.7 nm (a) and 2.65 × 2.65 nm (b) sections of...

Figure 2.17 Design of a system for in situ electrochemical scanning tunnelin...

Figure 2.18 Design of a scanning electrochemical microscope.

Figure 2.19 Principles of SECM: (a) tip far from the substrate surface – dif...

Figure 2.20 SECM image of a gold minigrid surface.

Figure 2.21 Single‐molecule detection with SECM. Molecule A trapped between ...

Figure 2.22 Use of SECM to visualize the oxygen consumption of single living...

Figure 2.23 The quartz crystal microbalance: (a) the quartz crystal, (b) the...

Figure 2.24 EQCM (bottom) and cyclic voltammetry (top) profiles at an ion‐ex...

Figure 2.25 (a) Randles equivalent circuit of the electrified interface and ...

Figure 2.26 EIS immunosensing of increasing myoglobin concentrations over th...

Chapter 3

Figure 3.1 Chronoamperometric experiment: (a) potential‐time waveform, (b) c...

Figure 3.2 Chronocoulometric experiment: Anson plot of Q vs. t

1/2

.

Figure 3.3 Polarograms for 1 M hydrochloric acid (a) and 4 × 10

−4

 M Cd

Figure 3.4 Variation of the charging and diffusion currents (a and b, respec...

Figure 3.5 Excitation signal for normal‐pulse voltammetry.

Figure 3.6 Excitation signal for differential‐pulse voltammetry.

Figure 3.7 Differential pulse (a) and DC (b) polarograms for a 1.3 × 10

−5

...

Figure 3.8 Normal‐pulse (a) and differential‐pulse (b) polarograms for a mix...

Figure 3.9 Square‐wave waveform showing the amplitude, E

sw

; step height,

Δ

...

Figure 3.10 Square‐wave voltammograms for reversible electron transfer: (a) ...

Figure 3.11 Square‐wave voltammograms for TNT solutions of increasing concen...

Figure 3.12 Cyclic square‐wave voltammogram of multivitamin tablet at a SWCN...

Figure 3.13 Potential‐time waveform used in staircase voltammetry.

Figure 3.14 Potential–time waveform used in alternating current (AC) voltamm...

Figure 3.15 Anodic stripping voltammetry combining accumulation and measurem...

Figure 3.16 Concentration gradient of the metal in the mercury film electrod...

Figure 3.17 Response of Bi film electrode to 10 successive additions of Zn(I...

Figure 3.18 Stripping potentiograms for a solution containing 100 μg/l ...

Figure 3.19 Accumulation and stripping steps in adsorptive stripping measure...

Figure 3.20 (a) Adsorptive stripping potentiograms for 0.5 ppm calf‐thymus D...

Figure 3.21 Stripping voltammograms for trace iodide in seawater.

Figure 3.22 Elements measured by conventional ASV , and adsorptive strippin...

Figure 3.23 Adsorptive stripping voltammograms of chromium in groundwater (t...

Figure 3.24 Typical amperometric readout during automated flow injection ass...

Figure 3.25 Capillary‐electrophoresis/amperometric response of a Bud Light b...

Figure 3.26 Common configurations of electrochemical flow detectors: thin‐la...

Figure 3.27 Schematic of a carbon‐fiber amperometric detector for capillary ...

Figure 3.28 Electrophoretic separation of catechols with an end‐column detec...

Figure 3.29 Common configurations of electrochemical detectors for CE microc...

Figure 3.30 Triple‐pulse amperometric waveform.

Figure 3.31 Dual‐electrode thin‐layer detector configurations for operation ...

Figure 3.32 Three‐dimensional chromatogram for oxidizable biological compoun...

Chapter 4

Figure 4.1 Schematic diagram of a cell for voltammetric measurements: w.e., ...

Figure 4.2 A complete cell stand.

Figure 4.3 Schematic diagram of a three‐electrode potentiostat.

Figure 4.4 Modern electrochemical instrumentation from (a) bench‐top analyze...

Figure 4.5 (a) Smartphone as an electrochemical analyzer, which is incorpora...

Figure 4.6 Ring‐based electrochemical devices for rapid field detection of c...

Figure 4.7 Accessible potential window of platinum, mercury, and carbon elec...

Figure 4.8 The dropping mercury electrode.

Figure 4.9 Construction of a typical disk electrode.

Figure 4.10 Rotating disk (a) and ring‐disk (b) electrodes.

Figure 4.11 The open‐pore structure of reticulated vitreous carbon.

Figure 4.12 Scanning electron image of a carbon‐fiber electrode.

Figure 4.13 Current–potential curve for platinum surface oxide formation and...

Figure 4.14 Steps involved in the screen‐printing process: (a) deposit the g...

Figure 4.15 Structure of common polymeric coatings: (a) Nafion, (b) polyviny...

Figure 4.16 Formation of a self‐assembled monolayer at a gold substrate.

Figure 4.17 Nanoforest of vertically aligned CNT “trees” acting as molecular...

Figure 4.18 Cyclic voltammograms for 1.5 × 10

−3

M ribose (a), glucose ...

Figure 4.19 Electrocatalytic detection of NADH.

Figure 4.20 Preconcentrating surfaces based on covalent binding of the ligan...

Figure 4.21 Permselective coatings: flow injection response of a poly (1,2‐d...

Figure 4.22 Scanning electron micrograph of a polyaniline‐coated electrode....

Figure 4.23 Use of negatively charged polymeric films for excluding anionic ...

Figure 4.24 Conductivity range of common conducting polymers, along with the...

Figure 4.25 Typical response of polypyrrole detector to carbonate: S

1

, 1 × 1...

Figure 4.26 Use of electropolymerization for preparing molecularly imprinted...

Figure 4.27 Experimental setup for monitoring dopamine release by exocytosis...

Figure 4.28 Cyclic voltammograms for the oxidation of ferrocene at a 6‐μm pl...

Figure 4.29 Normalized calculated concentration profiles for disk electrodes...

Figure 4.30 Common configurations of microelectrodes: microdisk (a), microri...

Figure 4.31 Classification of composite electrodes used in controlled potent...

Figure 4.32 Schematic representation of an interdigitated microarray electro...

Figure 4.33 Cottrell plot of the chronoamperometric response for 1 × 10

−3

...

Figure 4.34 Cyclic voltammogram for ferrocene at a 3‐μm width, 2‐μm gap inte...

Figure 4.35 Microneedle electrochemical sensors: (a) Schematic of pyramidal ...

Chapter 5

Figure 5.1 Schematic diagram of an electrochemical cell for potentiometric m...

Figure 5.2 Membrane potential reflects the gradient of activity of the analy...

Figure 5.3 Typical calibration plot for a monovalent ion.

Figure 5.4 The potential response of an ion‐selective electrode vs. activity...

Figure 5.5 Determination of the detection limit of ion‐selective electrodes....

Figure 5.6 A glass pH electrode.

Figure 5.7 The alkaline and acid errors of several glass pH electrodes. A, C...

Figure 5.8 A modern microprocessor‐controlled pH meter.

Figure 5.9 Elimination of primary ion leaching from the inner filling soluti...

Figure 5.10 Schematic diagram of a calcium ion‐selective electrode.

Figure 5.11 Quaternary alkyl ammonium chloride.

Figure 5.12 The recognition process occurring at the TDMAC/PVC membrane–samp...

Figure 5.13 Valinomycin: highly selective potassium ionophore.

Figure 5.14 Structure of neutral carriers used in liquid‐membrane ion‐select...

Figure 5.15 Direct potentiometric speciation of lead ion in Zurich tap water...

Figure 5.16 Structures of some chemical species useful for devising anion‐se...

Figure 5.17 Migration of the fluoride ion through the LaF

3

lattice (doped wi...

Figure 5.18 Response mechanisms for the SC‐ISEs (a): schematic representatio...

Figure 5.19 Schematic representation of a CNT‐based solid‐contact ISE. It sh...

Figure 5.20 Coated‐wire ion‐selective electrode.

Figure 5.21 Flow injection potentiometric determination of potassium in seru...

Figure 5.22 Flow‐through potentiometric cell‐cap design. a, reference electr...

Figure 5.23 Top: placement of the two pH and two potassium flexible potentio...

Figure 5.24 Image of solid‐contact chloride and sodium potentiometric sensor...

Figure 5.25 Textile‐based array of ion‐selective electrodes, for real‐time h...

Chapter 6

Figure 6.1 Enzyme electrode based on a biocatalytic layer immobilized on an el...

Figure 6.2 Methods for immobilizing enzymes onto electrode surfaces.

Figure 6.3 Steps in the preparation of an amperometric enzyme electrode, with ...

Figure 6.4 Dependence of the velocity of an enzyme-catalyzed reaction upon the...

Figure 6.5 Three generations of amperometric enzyme electrodes based on the us...

Figure 6.6 Schematic of a “first-generation” glucose biosensor.

Figure 6.7 “Second-generation” enzyme electrode: sequence of events that occur...

Figure 6.8 Chemical structure of some common redox mediators: (a) dimethyl fer...

Figure 6.9 Schematic representation of a disposable glucose sensor strip.

Figure 6.10 (a) Composition of an electron-relaying redox polymer and (b) its ...

Figure 6.11 Electrical contacting of a flavoenzyme by its reconstitution with ...

Figure 6.12 A reagentless ethanol biosensor based on the coimmobilization of A...

Figure 6.13 Urea potentiometric biosensor based on the immobilization of ureas...

Figure 6.14 Enzyme immunosensors based on the competitive or sandwich modes of...

Figure 6.15 Dual analyte immunosensor chip, coupling sandwich immunoassay of i...

Figure 6.16 E-AB sensing platform using a surface-bound, redox-reporter-modifi...

Figure 6.17 Steps involved in the detection of a specific DNA sequence using a...

Figure 6.18 Differential pulse voltammograms for the ferrocenyl naphthalene di...

Figure 6.19 Schematic representation of guanine oxidation mediated by a ruthen...

Figure 6.20 Molecular imprinting process: the template molecule, cross-linker,...

Figure 6.21 Schematic of the potentiometric sensor for carbon dioxide.

Figure 6.22 Membrane-covered oxygen probe based on the Clark electrode.

Figure 6.23 An ion-selective field effect transistor.

Figure 6.24 Configuration of a penicillin sensor based on a microarray electro...

Figure 6.25 A silicon-based sensor array for monitoring various blood electrol...

Figure 6.27 Fully integrated on-chip electrochemical detection for capillary e...

Figure 6.28 Picture of three electrode paper-based microfluidic device. The hy...

Figure 6.29 Response pattern of an amperometric sensor array for various carbo...

Figure 6.30 The information of flow in the array-based artificial nose.

Figure 6.31 Epidermal multichannel multielectrode multiplexed fluidic system o...

Figure 6.32 Wearable electrochemical biosensors based on immobilized GOx for a...

Guide

Cover Page

Title Page

Copyright Page

Preface

Abbreviations and Symbols

Table of Contents

Begin Reading

Index

Wiley End User License Agreement

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Analytical Electrochemistry

Fourth Edition

Joseph Wang

University of California San Diego, La Jolla, CA, USA

This fourth edition first published 2023© 2023 John Wiley & Sons, Inc.

Edition HistoryJohn Wiley & Sons, Inc. (3e, 2006; 2e, 2000; 1e, 1994)

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions.

The right of Joseph Wang to be identified as the author of this work has been asserted in accordance with law.

Registered OfficeJohn Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA

For details of our global editorial offices, customer services, and more information about Wiley products visit us at www.wiley.com.

Wiley also publishes its books in a variety of electronic formats and by print‐on‐demand. Some content that appears in standard print versions of this book may not be available in other formats.

Trademarks: Wiley and the Wiley logo are trademarks or registered trademarks of John Wiley & Sons, Inc. and/or its affiliates in the United States and other countries and may not be used without written permission. All other trademarks are the property of their respective owners. John Wiley & Sons, Inc. is not associated with any product or vendor mentioned in this book.

Limit of Liability/Disclaimer of WarrantyIn view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. While the publisher and authors have used their best efforts in preparing this work, they make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives, written sales materials or promotional statements for this work. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further information does not mean that the publisher and authors endorse the information or services the organization, website, or product may provide or recommendations it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.

Library of Congress Cataloging‐in‐Publication DataNames: Wang, Joseph, 1948– author.Title: Analytical electrochemistry / Joseph Wang, Arizona State University, Tempe, USA.Description: Fourth edition. | Hoboken, NJ, USA : John Wiley & Sons, Inc., 2023. | Includes bibliographical references and index.Identifiers: LCCN 2022051894 (print) | LCCN 2022051895 (ebook) | ISBN 9781119787693 (Hb) | ISBN 9781119787709 (ePDF) | ISBN 9781119787716 (epub)Subjects: LCSH: Electrochemical analysis.Classification: LCC QD115 .W33 2023 (print) | LCC QD115 (ebook) | DDC 543/.4–dc23/eng20230126LC record available at https://lccn.loc.gov/2022051894LC ebook record available at https://lccn.loc.gov/2022051895

Cover image: Courtesy of the AuthorCover design: Wiley

Preface

The goal of this textbook is to cover the full scope of modern electroanalytical techniques and devices. The objective is to provide a sound understanding of the fundamentals of electrode reactions and of the principles of different electrochemical methods and sensing tools, and to demonstrate their potential for solving real‐life analytical problems. This fourth edition of Analytical Electrochemistry has been extensively revised to reflect the rapid growth of electroanalytical chemistry over the past two decades. Since the publication of the third edition of Analytical Electrochemistry in 2006, the field of electroanalytical chemistry has witnessed a major progress and tremendous growth. Such dramatic changes reflect major technological advances in materials, mobile and wearable devices, microfabrication and miniaturization, biotechnology and nanotechnology, along with a variety of societal changes and new trends (toward digital health, personalized nutrition, or wellness). The recent COVID‐19 pandemic has accelerated the digital revolution and emphasized the crucial role of electrochemical biosensors for fighting such outbreaks. Electrochemical sensors are currently playing an important role in the digital revolution and have been widely integrated into wearable devices toward continuous on‐body monitoring of major chemical markers. As a result of the development of wearable electrochemical biosensors, millions of diabetes patients can now track their blood glucose levels continuously in a minimally invasive fashion. Electrochemical sensors are also widely used as key components of automated clinical analyzers and for the monitoring of brain neurochemical processes, singe‐cell activities, or environmental effluents.

The fourth edition of Analytical Electrochemistry has been extensively updated to cover new directions and tools of electroanalytical chemistry introduced over the past two decades. The entire text has been revised to cover new topics and the very latest developments and trends in electroanalytical chemistry. This includes new sections describing new topics such as fast‐scan cyclic voltammetry, solid‐contact potentiometric sensors, wearable electrochemical platforms, scanning electrochemical probes, paper‐based devices, new electrode materials (e.g. graphene and bismuth), new receptors (such as reusable aptamers or molecularly imprinted polymers), single‐use sensing strips and 3D‐printed electrochemical devices, multiplexed bioelectronic assays, hand‐held electrochemical analyzers, and smartphone‐based electrochemical sensing. The fundamental aspects of different electrochemical processes and techniques have been expanded throughout the text. Coverage of the literature has been updated by over 50% and numerous new figures have been added. Additional worked‐out examples and a variety of quantitative questions and exercise problems have been added at the end of each chapter to provide students with the necessary problem‐solving experience and skills related closely to advanced electroanalytical research and practical applications.

The book is suitable as a text for graduate‐level and high‐level undergraduate courses in electroanalytical chemistry, and as Supplement to “Analytical Chemistry” and “Sensors and Biosensors” classes. By covering the basic principles of modern electroanalytical techniques and addressing the modern practice of electroanalytical chemistry, the book bridges the gap between traditional general textbooks on analytical chemistry and the modern research literature. It should also be extremely useful as a self‐contained starting point to those considering the use of electrochemical sensors and systems in their laboratories, and to researchers in the areas of electroanalytical chemistry, biosensors, clinical diagnostics, or environmental or security monitoring, and to analytical chemistry and electrochemistry, in general.

Finally, I wish to thank my wife, Ruth, and my daughter, Sharon, for their love, patience, and support, Kuldeep Mahato and Shichao Ding for their technical assistance, and the numerous electrochemists across the globe who led to the exciting advances and new tools and capabilities described in this textbook. Thank you all!

Joseph Wang

UCSD, San Diego, CA, USA

August 2022

Abbreviations and Symbols

a

Activity

A

Area of electrode

A

Absorbance

Ab

Antibody

AdSV

Adsorptive stripping voltammetry

AFM

Atomic force microscopy

AI

Artificial intelligence

ALP

Alkaline phosphatase

Ag

Antigen

ASV

Anodic stripping voltammetry

B

Adsorption coefficient

BiFE

Bismuth film electrode

BSA

Bovine serum albumin

BDD

Boron‐doped diamond

C

Concentration

C

dl

Differential capacitance

CGM

Continuous glucose monitoring

CNT

Carbon nanotubes

CSV

Cathodic stripping voltammetry

CV

Cyclic voltammetry

C‐SWV

Cyclic square‐wave voltammetry

CZE

Capillary zone electrophoresis

D

Diffusion coefficient

DET

Direct electron transfer

DNA

Deoxyribonucleic acid

DME

Dropping mercury electrode

DNNS

Dinonylnaphthalenesulfonic acid

DPV

Differential pulse voltammetry

E

Potential (V)

ΔE

Pulse amplitude

E‐AB

Electronic aptamer based

Standard electrode potential

E

1/2

Half‐wave potential

E

p

Peak potential

E

pzc

Potential of zero charge

EC

Electrode process involving electrochemical followed by chemical step

ECL

Electrochemiluminescence

EIS

Electrochemical impedance spectroscopy

EQCM

Electrochemical quartz crystal microbalance

ePAD

Electrochemical paper‐based analytical devices

F

Faraday constant

FAD

Flavin adenine dinucleotide

FSCV

Fast‐scan cyclic voltammetry

FET

Field effect transistor

FIA

Flow injection analysis

f

i

Activity coefficient

ΔG

Free energy of activation

GOx

Glucose oxidase

HER

Hydrogen evolution

HMDE

Hanging mercury drop electrode

HRP

Horseradish peroxidase

i

Electric current

i

c

Charging current

i

t

Tunneling current

IDE

Interdigitated electrodes

ISM

Ion‐selective membrane

IHP

Inner Helmholtz plant

IRS

Internal reflectance spectroscopy

ISE

Ion‐selective electrode

ISF

Interstitial fluid

J

Flux

Potentiometric selectivity coefficient

Standard rate constant

K

m

Michaelis–Menten constant

Km

Mass‐transport coefficient

LCEC

Liquid chromatography/Electrochemistry

LEED

Low‐energy electron diffraction

LIG

Laser‐induced graphene

LOC

Laboratory‐on‐a Chip

m

Mercury flow rate (in polarography)

Δm

Mass charge (in EQCM)

MFE

Mercury film electrode

MIP

Molecularly imprinted polymers

N

Collection efficiency

n

Number of electrons transferred

NADH

Reduced nicotinamide adenine dinucleotide

NPG

Nanoporous gold

O

The oxidized species

OHP

Outer Helmholtz plane

ORR

Oxygen reduction

OTE

Optically transparent electrode

PAD

Pulsed amperometric detection

Pan

Polyaniline

PVC

Poly(vinyl chloride)

PSA

Potentiometric stripping analysis

q

Charge

QCM

Quartz crystal microbalance

R

(a) Resistance (b) Gas constant

R

ct

Charge transfer resistance

RDE

Rotating disk electrode

Re

Reynolds number

RRDE

Rotating ring disk electrode

RVC

Reticulated vitreous carbon

S

Barrier width (in STM)

SAM

Self‐assembled monolayers

SC

Solid contact

SECM

Scanning electrochemical microscopy

SELEX

Systematic evolution of ligands by exponential enrichment

SPE

Screen‐printed electrode

STM

Scanning tunneling microscopy

SWV

Square‐wave voltammetry

SWASV

Square‐wave anodic stripping voltammetry

T

Temperature

TMB

Tetramethylbenzidine

TNT

2,4,6‐trinitrotoluene

t

Time

t

m

Transition time (in PSA)

U

Flow rate

v

Potential scan rate

V

Hg

Volume of mercury electrode

W

1/2

Peak width (at half height)

WJD

Wall‐jet detector

α

Transfer coefficient

ε

Molar absorptivity

ε

Dielectric constant

Γ

Surface coverage

γ

Surface tension

δ

Thickness of the diffusion layer

δ

H

Thickness of the hydrodynamic boundary layer

η

Overvoltage

ν

Kinematic viscosity

ω

Angular velocity

ϕ

Barrier height