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Nanocarbon Electrochemistry
Nanocarbon Chemistry and Interfaces
Series Editor
Nianjun Yang, Institute of Materials Engineering, University of Siegen, Germany
Titles in the Series
Nanocarbons for Electroanalysis

Sabine Szunerits, Rabah Boukherroub, Alison Downard, Jun-Jie Zhu
Carbon Nanomaterials for Bioimaging, Bioanalysis andTherapy

Huan-Cheng Chang, Yuen Yung Hui, Haifeng Dong, Xueji Zhang
Novel Carbon Materials and Composites: Synthesis, Properties and Applications

Xin Jiang, Zhenhui Kang, Xiaoning Guo, Hao Zhuang
Nianjun Yang, Guohua Zhao, John S. Foord
Forthcoming Titles
Nanocarbons and their Hybrids

Jean-Charles Arnault, Dominik Eder
Edited by
Nianjun Yang
Institute of Materials Engineering
University of Siegen
Germany
Guohua Zhao
School of Chemical Science & Engineering
Tongji University
Shanghai, China
John S. Foord
Department of Chemistry
University of Oxford
UK
This edition first published 2020
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v
Contents
List of Contributors xi
Series Preface xv
Preface xvii
1 Nanoelectrochemistry of Adsorption-Coupled Electron Transfer at

Carbon Electrodes 1
Shigeru Amemiya
1.1 Introduction 1
1.2 Overview of Adsorption-Coupled ET 2
1.3 Clean Carbon Electrodes 4
1.4 SECM-Based Nanogap Voltammetry 7
1.5 Adsorption-Coupled Outer-Sphere ET 13
1.6 Self-Inhibition of Outer-Sphere ET 16
1.7 Coupling Between Outer- and Inner-Sphere ET 19
1.8 Resolving Outer- and Inner-Sphere ET 23
1.9 Summary and Perspectives 26
Acknowledgments 26
References 26
2 The Capacitance of Graphene: From Model Systems to Large-Scale

Devices 33
Pawin Iamprasertkun and Robert A.W. Dryfe
2.1 Graphene Overview 33
2.2 Introduction to Capacitance 34
2.2.1 Capacitance Model 34
2.2.2 Space Charge Capacitance 36
2.2.3 Quantum Capacitance 37
2.3 Capacitance of Graphene 39
2.4 Formation of Heterostructures: Graphene and Other 2D Materials 43
2.4.1 Transition Metal Dichalcogenides (TMDCs) 43
2.4.2 2D Nanocrystal or MXenes 44
2.4.3 Hexagonal Boron Nitride (h-BN) 46
2.4.4 Phosphorene 47
2.5 Formulation of 3D Graphene Architectures 49
vi Contents
2.5.1 Graphene Sponges 49

2.5.2 Template-Assisted Graphene 49
2.5.3 Graphene Aerogels 51
2.5.4 Pillared Graphene Frameworks (PGFs) 54
2.5.5 Carbon Composites 56
2.6 The Influence of Heteroatom Doping on Graphene 56
2.6.1 Oxygen-Doped Graphene 57
2.6.2 Nitrogen-Doped Graphene 58
2.6.3 Boron-Doped Graphene 61
2.6.4 Use of Other Elements to Dope Graphene 61
2.6.5 Co-doped Graphene 63
2.6.6 Multi-element Doping of Graphene 64
2.7 Application of Graphene in Large-Scale Devices 65
2.7.1 General Principles of Supercapacitors 65
2.7.2 Graphene-Based Supercapacitors and Novel Cell Design 68
2.7.3 Li/Na Ion Capacitors 70
2.8 Summary and Future Outlook 71
References 75
3 Graphene and Related Materials as Anode Materials in Li Ion Batteries:

Science and Practicality 85
Sandeep Kumar Marka, Veera Venkata Harish Peruswamula, and Venkata Satya Siva
Srikanth Vadali
3.1 Introduction 85
3.2 Graphite as an Anode Material in Li Ion Batteries 86
3.3 Graphene and Related Materials as Anode Material in Li Ion Batteries 89
3.3.1 Graphene and Related Materials as Anode Material in LIBs-Science and
Practicality 90
3.3.2 Intercalation-based 91
3.3.2.1 rGO-TiO2 System 91
3.3.2.2 rGO-Li4 Ti5 O12 System 91
3.3.2.3 rGO-Vanadium Oxides System 92
3.3.3 Conversion-based 92
3.3.3.1 MMoO4 (i.e., M = Fe, Co, Ni, Ca, Mn, Zn, and Cu) 92
3.3.3.2 Mo-Cluster Oxysalts (i.e., A2 Mo3 O8 Type, A = Fe, Co, Mn, and Zn or
LiHoMo3 O8 ) 95
3.3.4 Alloying-based 97
3.3.4.1 rGO-Si System 97
3.3.4.2 rGO-Ge System 99
3.3.4.3 rGO-SnO2 System 110
References 114
4 Nanocarbon Materials Toward Textile-Based Electrochemical Energy

Storage Devices 123
Qiyao Huang, Dongrui Wang, and Zijian Zheng
4.1 Introduction 123
4.2 Nanocarbon Materials for TEESDs 125
Contents vii
4.2.1 Nanocarbon as Active Material for SCs 125

4.2.2 Nanocarbon as Functional Material for LIBs 127
4.3 Fabrication of Nanocarbon-Based Electrodes for TEESDs 127
4.3.1 Direct Coating on Existing Textile Fibers, Yarns and Fabrics 128
4.4 In-Situ Growth on Textile Surfaces 130
4.4.1 Direct Spinning of Nanocarbon Fibers 133
4.5 Conclusion and Perspective 136
References 137
5 1D and 2D Flexible Carbon Matrix Materials for Lithium–Sulfur

Batteries 145
Tianyi Wang, Yushu Liu, Dawei Su, and Guoxiu Wang
5.2 The Working Mechanism and Challenges of Li–S Batteries 145
5.3 Flexible Cathode Hosts for Lithium–Sulfur Batteries 146
5.4 Electrolyte Membranes for Flexible Li–S Batteries 155
5.5 Solid Polymer Electrolytes for Flexible Li–S Batteries 157
5.6 Gel Polymer Electrolytes for Flexible Li–S Batteries 159
5.7 Composite Polymer Electrolytes for Flexible Li–S Batteries 159
5.8 Separator for Flexible Li–S Batteries 161
5.9 Summary 165
References 165
6 Conductive Diamond for Electrochemical Energy Applications 171

Siyu Yu, Nianjun Yang, Xin Jiang, Wenjun Zhang, and Shetian Liu
6.2 Electrochemical Energy Storage 172
6.2.1 Supercapacitor 172
6.2.1.1 Diamond EDLCs 173
6.2.1.2 Diamond PC 177
6.2.1.3 Supercapacitor Device 179
6.2.2 Battery 180
6.3 Electrochemical Energy Conversion 183
6.3.1 Fuel Cell 183
6.3.2 Solar Cell 186
6.4 Electrocatalysis for CO2 Conversion 187
6.5 Summary and Outlook 191
Acknowledgments 192
References 192
7 Electrocatalysis at Nanocarbons: Model Systems and Applications in

Energy Conversion 201
Carlota Domínguez, James A. Behan, and Paula E. Colavita
7.2 High-Performing Nanocarbon Electrocatalysts 203
7.2.1 Zero-Dimensional (0D) Carbon Materials 204
7.2.1.1 Carbon Dots 205
viii Contents
7.2.1.2 Carbon Nano-Onions 205

7.2.1.3 Carbon Blacks and Activated Carbons 207
7.2.2 High Aspect Ratio (1D) Nanocarbons 208
7.2.2.1 Nanohorns 209
7.2.2.2 Carbon Nanotubes and Nanofibers 211
7.2.3 Two-Dimensional (2D) Carbon Materials 216
7.2.3.1 Graphene and Graphene Nanoribbons 216
7.2.3.2 Carbon Nanobelts and Thin Films 221
7.2.4 Three-Dimensional (3D) Carbon Materials 221
7.2.4.1 Bottom-Up Synthesis of 3D Networks 222
7.2.4.2 Templated 3D Superstructures 224
7.3 Carbon Model Systems 225
7.3.1 HOPG 229
7.3.2 Graphene 233
7.3.3 Amorphous Carbon 236
7.4 Concluding Remarks and Outlook 239
Acknowledgments 240
References 240
8 Metal-Organic Frameworks Based Porous Carbons for Oxygen

Reduction Reaction Electrocatalysts for Fuel Cell Applications 251
Shaofang Fu, Junhua Song, Chengzhou Zhu, Dan Du, and Yuehe Lin
8.2 MOF-Derived Porous Carbon Catalysts 253
8.2.1 Heteroatoms Dopant Effects on MOF-Based Porous Carbon Catalysts 254
8.2.2 MOF-Derived Carbon Composites 257
8.3 Metal Incorporated MOF-Derived Porous Carbon Catalysts 259
8.3.1 Impact of Metallic Composition on ORR Activity 260
8.3.2 Heteroatom Dopant Effect on Incorporated Metal and Single Atoms 266
8.3.3 Morphological Influence on the Catalytic Activity 268
8.4 Challenges and Perspective 274
References 276
9 Diamond Electrodes for Electrogenerated Chemiluminescence 285

Andrea Fiorani, Irkham, Giovanni Valenti, Yasuaki Einaga, and Francesco Paolucci
9.2 Fundamentals of Electrogenerated Chemiluminescence 285
9.3 Coreactants 287
9.4 ECL Luminophores 289
9.5 Electrochemiluminescence at Diamond Electrodes 289
9.6 TPrA 290
9.7 Oxalate 295
9.8 Hydroxyl Radical 299
9.9 Persulfate 303
9.10 Luminol 306
9.11 Conclusions 312
References 312
Contents ix
10 Decoration of Advanced Carbon Materials with Metal Oxides for

Photoelectrochemical Applications 323
Ya-nan Zhang, Huijie Shi, Yuqing Chen, Rongrong Cui, and Guohua Zhao
10.2 BDD and its Application in Electro-Analysis, EC, and PEC Oxidation of
Environmental Pollutants 324
10.2.1 Detection of Pollutants on BDD 324
10.2.2 EC Oxidation of Pollutants on BDD 330
10.2.3 PEC Oxidation of Pollutants on BDD 333
10.3 Decoration of CA with Metal Oxides and their Photoelectrochemical
Applications 337
10.3.1 Fabrication and Structures of CA 337
10.3.2 Decoration of CA with Metal Oxides for Environmental Application 341
10.3.2.1 Enhanced Electrocatalytic Oxidation of Organic Pollutants 341
10.3.2.2 Electro-Fenton and Photo–Electro–Fenton Oxidation of Pollutants 342
10.3.2.3 Efficient Electrosorption-Promoted Photoelectrochemical Oxidation of
Wastewater 344
10.4 Summary 346
Acknowledgments 347
References 347
Index 357
xi
List of Contributors
Shigeru Amemiya Carlota Domínguez

Department of Chemistry School of Chemistry, CRANN and
University of Pittsburgh AMBER Research Centres
Pennsylvania, USA Trinity College Dublin
Ireland
James A. Behan
School of Chemistry, CRANN and Robert A.W. Dryfe
AMBER Research Centres School of Chemistry
Trinity College Dublin University of Manchester
Ireland United Kingdom
Yuqing Chen Dan Du

School of Chemical Science and School of Mechanical and Materials
Engineering, Shanghai Key Lab of Engineering
Chemical Assessment and Sustainability Washington State University
Tongji University WA, USA
Shanghai, China
Yasuaki Einaga
Paula E. Colavita Department of Chemistry
School of Chemistry, CRANN and Keio University
AMBER Research Centres Yokohama, Japan
Trinity College Dublin
Ireland Andrea Fiorani
Department of Chemistry
Rongrong Cui Keio University
School of Chemical Science and Yokohama
Engineering, Shanghai Key Lab of Japan
Chemical Assessment and Sustainability
Tongji University Shaofang Fu
Shanghai, China School of Mechanical and Materials
Engineering
Washington State University
WA, USA
xii List of Contributors
Qiyao Huang Sandeep Kumar Marka

Laboratory for Advanced Interfacial School of Engineering Sciences and
Materials and Devices, Institute of Technology (SEST)
Textiles and Clothing University of Hyderabad
The Hong Kong Polytechnic University Telangana, India
China
Francesco Paolucci
Pawin Iamprasertkun Department of Chemistry “G. Ciamician”
School of Chemistry University of Bologna
University of Manchester Italy
United Kingdom
Veera Venkata Harish Peruswamula
Irkham School of Engineering Sciences and
Department of Chemistry Technology (SEST)
Keio University University of Hyderabad
Yokohama Telangana, India
Japan
Huijie Shi
Xin Jiang School of Chemical Science and
Institute of Materials Engineering Engineering, Shanghai Key Lab of
University of Siegen Chemical Assessment and Sustainability
Germany Tongji University
Shanghai, China
Yuehe Lin
School of Mechanical and Materials Junhua Song
Engineering School of Mechanical and Materials
Washington State University Engineering
WA, USA Washington State University
WA, USA
Shetian Liu
School of Chemistry and Chemical Dawei Su
Engineering University of Technology Sydney
Southwest University School of Mathematical and Physical
Chongqing, P. R. China Sciences, Research Centre for Clean
Energy Technology
Yushu Liu Ultimo, NSW
University of Technology Sydney, School Australia
of Mathematical and Physical Sciences
Research Centre for Clean Energy Venkata Satya Siva Srikanth Vadali
Technology School of Engineering Sciences and
Ultimo, NSW Technology (SEST)
Australia University of Hyderabad
Telangana, India
List of Contributors xiii
Giovanni Valenti Wenjun Zhang

Department of Chemistry “G. Ciamician” Department of Materials Science and
University of Bologna Engineering
Italy City University of Hong Kong
China
Guoxiu Wang
University of Technology Sydney Ya-nan Zhang
School of Mathematical and Physical School of Chemical Science and
Sciences, Research Centre for Clean Engineering, Shanghai Key Lab of
Energy Technology Chemical Assessment and Sustainability
Ultimo, NSW Tongji University
Australia Shanghai, China
Tianyi Wang Guohua Zhao

University of Technology Sydney School of Chemical Science and
School of Mathematical and Physical Engineering, Shanghai Key Lab of
Sciences, Research Centre for Clean Chemical Assessment and Sustainability
Energy Technology Tongji University
Ultimo, NSW Shanghai, China
Australia
Zijian Zheng
Nianjun Yang Laboratory for Advanced Interfacial
Institute of Materials Engineering Materials and Devices, Institute of
University of Siegen Textiles and Clothing
Germany The Hong Kong Polytechnic University
China
Siyu Yu
School of Chemistry and Chemical Chengzhou Zhu
Engineering School of Mechanical and Materials
Southwest University Engineering
Chongqing, P. R. China Washington State University
WA, USA
xv
Series Preface
Carbon, the 6th element in the periodic table, is extraordinary. It forms a variety of mate-
rials because of its ability to covalently bond with different orbital hybridizations. For
millennia, there were only two known substances of pure carbon atoms: graphite and
diamond. In the mid-1980s, a soccer-ball-shaped buckminsterfullerene, namely a new
carbon allotrope C60, was discovered. Together with fullerene-structures (C70, C84)
found later, the nanocarbon researcher was spawned. In the early 1990s, carbon nan-
otubes were discovered. They are direct descendants of fullerenes and capped structures
composed of 5- and 6-membered rings. This was the next major advance in nanocarbon
research. Due to their ground-breaking work on these fullerene materials, Curl, Kroto,
and Smalley were awarded the 1996 Nobel Prize in Chemistry. In the beginning of the
2000s, graphene was prepared using Scotch tape. It is a single sheet of carbon atoms
packed into a hexagonal lattice with a bond distance of 0.142 nm. For their seminal work
with this new nanocarbon material, Geim and Novoselov were awarded the 2010 Nobel
Prize in Physics.
As new members, carbon nanoparticles, such as diamond nanoparticles, carbon dots,
and graphene (quantum) dots, have emerged in the family of nanocarbon materials.
Although all these materials only consist of the same carbon atoms, their physical,
chemical, and engineering features are different, which are fully dependent on their
structures.
The purpose of this series is to bring together up-to-date accounts of recent develop-
ments and new findings in the field of nanocarbon chemistry and interfaces, one of the
most important aspects of nanocarbon research. The carbon materials covered in this
series include diamond, diamond nanoparticles, graphene, graphene-oxide, graphene
(quantum) dots, carbon nanotubes, carbon fibers, fullerenes, carbon dots, carbon com-
posites, and their hybrids. The formation, structure, properties, and applications of these
carbon materials are summarized. Their relevant applications in the fields of electroanal-
ysis, biosensing, catalysis, electrosynthesis, energy storage and conversion, environment
sensing and protection, biology, and medicine are highlighted in different books.
I certainly want to express my sincere thanks to Miss Sarah Higginbotham, Jenny
Cossham, Emma Strickland, and Lesley Jebaraj from Wiley’s Oxford office. Without their
efficient help or valuable suggestions during this book project, the publication of this
book series would not be possible. Last, but not least, I want to thank my family, espe-
cially my wife, Dr. Xiaoxia Wang, and my children Zimo and Chuqian Luisa, for their
xvi Series Preface
constant and strong support as well as for their patience in letting me finalize such a
book series.
Nianjun Yang
April 2019 Siegen, Germany
xvii
Preface
Electrochemistry is an extensively utilized field of chemistry that integrates chemicals

and electric fields. A well-designed electrode material is the key of electrochemistry.
The connection of electrochemistry with carbon materials such as graphite, diamond,
and carbon fibers has had a long history. The discoveries of new carbon materials such
as fullerene, graphene, carbon nanotubes, graphene nanoribbon, carbon dots, and
graphdiyne in past decades have triggered more research advances with respect to their
electrochemical preparation, characterization, and applications.
The purpose of this volume is thus to bring together up-to-date accounts of recent
progress, developments, and achievements in the electrochemistry of different carbon
materials, focusing on their unique properties and various applications. We begin with
a chapter concerning the studies of heterogeneous electron transfer at various carbon
electrodes when redox-active molecules are reversibly and specifically adsorbed on the
carbon electrode surfaces, followed by electrochemical energy storage applications of
various carbon materials, particularly the construction and performance of superca-
pacitors and batteries by use of graphene and related materials. The third part of this
volume is concentrated on electrochemical energy conversion applications where elec-
trocatalysis at 0D, 1D, 2D, and 3D carbon materials nanocarbon materials is highlighted.
This volume is then closed with consideration of electrogenerated chemiluminescence
and photoelectrochemical pollutant degradation by use of diamond and related carbon
materials.
It is the invaluable efforts of distinguished researchers from nine different countries
with thirteen different affiliations that have helped us build such a comprehensive vol-
ume covering the various perspectives of nanocarbon electrochemistry. The chapters
cover the fundamental properties of different carbon materials and their applications
across a wide range of areas. Sufficient background regarding different applications has
been provided in each chapter. By including information with such a wide range, we
hope this volume can contribute to the understanding of non-specialists and special-
ists alike. Thus it should be of interest and use to students, researchers, and industrial
partners working on many diverse fields of electrochemistry, whether they already make
frequent use of carbon electrodes in one form or another or whether they are looking
for electrodes for new applications.
xviii Preface
We certainly want to express our sincere thanks to all colleagues from our publisher,
Wiley, especially to Lesley Jebaraj and Emma Strickland. Their efficient help and valuable
suggestions made this volume proceed smoothly to publication. Last, but not least, we
want to thank our family members for their constant and strong support in letting us
finalize such a volume.
Nianjun Yang
Siegen, Germany
Guohua Zhao
Shanghai, China
John S. Foord
Oxford, United Kingdom
1
Nanoelectrochemistry of Adsorption-Coupled Electron Transfer

at Carbon Electrodes
Shigeru Amemiya
Department of Chemistry, University of Pittsburgh, USA
1.1 Introduction
This chapter is concerned with studies of heterogeneous electron transfer (ET) at carbon
electrodes when redox-active molecules can be reversibly and specifically adsorbed on
the electrode surfaces [1]. These studies of adsorption-coupled ET complement sem-
inal studies of redox-active molecules irreversibly attached to the electrode surfaces
[2, 3]. Adsorption-coupled ET is ubiquitous in applied electrochemistry and plays cru-
cial roles in electrocatalysis [4], photocatalysis [4], electrodeposition [5], electropoly-
merization [6], electrochemical remediation [7], and electroanalysis [8]. For these appli-
cations, carbon materials are highly attractive owing to their well-known propensity
to adsorb molecules [9, 10]. In fact, significant attention has been given not only to
traditional carbon materials, but also to emerging carbon nanomaterials as important
electrode materials [11] for diverse applications, especially in energy conversion and
storage, e.g. fuel cells [12], batteries [13], solar cells [14], and supercapacitors [15]. This
propensity, however, hampers a fundamental understanding of adsorption-coupled ET
at carbon electrodes, which are readily contaminated [9, 16, 17]. The adventitious con-
tamination of carbon surfaces has been well recognized [16, 18], but has not been pre-
vented effectively despite a huge body of work on carbon electrochemistry [11, 19]. It
has been difficult to reliably characterize the intrinsic electrochemical reactivity and
adsorption properties of carbon electrodes [20].
In this chapter, we introduce recent progress in theory of adsorption-coupled
ET and its experimental assessment at carbon electrodes. Theoretical progress
was made recently by Amatore and coworkers [21, 22], who refined a quantitative
model of adsorption-coupled ET developed by Laviron [1, 23] by considering outer-
and inner-sphere ET and surface adsorption as elementary electrode steps [24].
Experimental progress were made by the development and nanoelectrochemical char-
acterization of clean carbon electrodes as requisites to reliably examine theories for
adsorption-coupled ET. In particular, nanoscale scanning electrochemical microscopy
(SECM) [25, 26] serves as an emerging powerful method to quantitatively investigate
carbon electrochemistry [27] and beyond.
Nanocarbon Electrochemistry, First Edition. Edited by Nianjun Yang, Guohua Zhao, and John S. Foord.
© 2020 John Wiley & Sons Ltd. Published 2020 by John Wiley & Sons Ltd.
2 Nanocarbon Electrochemistry
1.2 Overview of Adsorption-Coupled ET

The specific and reversible adsorption of a redox molecule from the solution to the elec-
trode surface couples heterogeneous outer- and inner-sphere ET as modeled by Laviron
[23] and Amatore [24]. In their model (Figure 1.1), a redox molecule, O, is transported
from the solution to the outer Helmholtz plane (OHP) [28] near the electrode surface
to participate in outer-sphere ET, i.e.
Osol + e ⇌ Rsol (1.1)
where the transported molecule, Osol , and the product of outer-sphere ET, Rsol , can be
adsorbed at the inner Helmholtz plane (IHP) [28] of the electrode surface, i.e.
Osol ⇌ Oads (1.2)
Rsol ⇌ Rads (1.3)

When both forms of the redox couple are adsorbed, inner-sphere ET can be mediated,
i.e.
Oads + e ⇌ Rads (1.4)
In addition, a heterogeneous self-exchange ET reaction is possible as given by
Oads + Rsol ⇌ Rads + Osol (1.5)
A quantitative understanding of the Laviron–Amatore model requires the knowledge
of time-dependent concentrations of four species including Oads , Rads , Osol , and Rsol in
addition to time- and distance-dependent concentrations of O and R in a diffusion layer
near the electrode surface, where the respective concentrations are given by ΓO , ΓR ,
C O (0, t), C R (0, t), C O (x, t), C R (x, t) (Figure 1.1). Mathematically, adsorption-coupled
ET can be modeled by solving two Fickian diffusion equations with four independent
equations at the electrode surface as boundary conditions. For instance, the equilib-
rium adsorption of oxidized and reduced forms of a redox couple is described by two
isotherms for competitive adsorption. In addition, two Nernst equations are obtained
to describe the equilibrium of outer- and inner-sphere ET. Adsorption isotherms and
Nernst equations must be substituted by the corresponding kinetic expressions when
equilibrium adsorption or reversible ET is not maintained, respectively.
Historically, the coupling between outer- and inner-sphere ET of a redox couple
through specific adsorption and heterogeneous self-exchange ET was proposed by
Figure 1.1 The reaction scheme of outer- and

O CO(0,t) CO(x,t) inner-sphere ET of non-adsorbed and adsorbed redox
Oads Osol O molecules, respectively. Dashed arrows indicate
heterogeneous self-exchange ET.
electrode
Rads Rsol R
R CR(0,t) CR(x,t)
Nanoelectrochemistry of Adsorption-Coupled Electron Transfer at Carbon Electrodes 3
Anson in 1961 [29] to account for the anomalous non-linear concentration-dependence

of exchange current based on the Fe3+/2+ couple at the Pt electrode [30]. Anson’s work
[29] is theoretically pioneering and insightful, but seems overshadowed by the erro-
neous assignment of a thin-layer effect to an adsorption effect [29], and is well known
rather for the following development of thin-layer electrochemistry [31–33]. Prior
to Anson, Laitinen and Randels proposed a model based on inner-sphere ET of
tris(ethylenediamine) complexes of Co3+ and Co2+ adsorbed on the mercury electrode
without considering an outer-sphere pathway [34]. Similarly, others also considered
only the inner-sphere pathway [35, 36]. Later, Anson attempted to kinetically dis-
tinguish between outer- and inner-sphere ET using the Marcus theory [37] and also
experimentally identify the electrode reaction mechanism of a redox couple as either
outer or inner sphere [38, 39]. More recently, Laviron [23, 40–42] and Amatore [21]
theoretically demonstrated conditions where outer- and inner-sphere ET of a redox
couple are not distinguishable electrochemically, which will be discussed through this
chapter. A redox couple, however, is still considered either as an outer- or inner-sphere
couple [4], even controversially [43, 44], despite the possibility that both outer- and
inner-sphere pathways can be mediated simultaneously and indistinguishably by the
same redox couple.
A quantitative understanding of adsorption-coupled ET is highly challenging
even under diffusion-controlled conditions owing to the requirement of adsorption
isotherms with multiple parameters. For instance, four parameters are introduced when
the adsorption of each form of a redox couple is represented by the simple Langmuir
isotherm for competitive adsorption of both forms of the redox couple, to yield [45]
𝛽O ΓO,s CO (0, t)
ΓO = (1.6)
1 + 𝛽O CO (0, t) + 𝛽R CR (0, t)
𝛽R ΓR,s CR (0, t)
ΓR = (1.7)
1 + 𝛽O CO (0, t) + 𝛽R CR (0, t)
where Γi,s is the saturated surface concentration of species i and 𝛽 i is a parameter char-
acterizing the magnitude of adsorbate–substrate interaction. In addition, two Nernst
equations must be considered to describe diffusion-controlled outer- and inner-sphere
ET. A conventional Nernst equation is given for outer-sphere ET by [46]
RT C (0, t)
ln R
′
0
E = EOS − (1.8)
nF CO (0, t)
′
0
where n is the number of transferred electrons and EOS is the formal potential of
outer-sphere ET. Equation (1.8) can be combined with Langmuir isotherms, Eqs. (1.6)
and (1.7), to yield a Nernst equation for inner-sphere ET as [47]
RT Γ
ln R
′
0
E = EIS − (1.9)
nF ΓO
with
0′
0 ′ RT ΓO,s 𝛽O
EIS = EOS − ln (1.10)
nF ΓR,s 𝛽R
Equation (1.10) indicates that the equilibrium of inner-sphere ET is controlled by the

equilibrium of outer-sphere ET and surface adsorption, thereby introducing no addi-
tional parameter. It should be noted that a formal potential is defined for non-adsorbed
redox couples in the electrochemistry literature [48] to represent outer-sphere ET, i.e.
0′
EOS . By contrast, interactions between redox molecules and electrodes were considered
in a recent theoretical study to calculate formal potentials [49], which should be more
0′
directly relevant to inner-sphere ET, i.e. EIS , rather than outer-sphere ET.
A comparison of Nernst equations for outer- and inner-sphere ET predicts that
these two pathways are thermodynamically coupled or decoupled depending on the
adsorptivities of a redox couple. Specifically, outer- and inner-sphere ET are coupled
and driven simultaneously when both forms of a redox couple are adsorbed similarly, i.e.
ΓO,s 𝛽 O = ΓR,s 𝛽 R , to yield EIS
0′ 0′ ′
= EOS = E0 in Eq. (1.10). In this case, reduction (or oxida-
tion) is driven through both outer- and inner-sphere pathways simultaneously at E < E0
′
(or E > E0 ), thereby yielding an electrochemical response based on the convolution

′
of both pathways. By contrast, outer- and inner-sphere ET are decoupled when O

(or R) is adsorbed more strongly than the other, i.e. ΓO,s 𝛽 O >> ΓR,s 𝛽 R (or ΓO,s 𝛽 O << ΓR,s
𝛽 R ), to yield EIS0′
<< EOS0′ 0′
(or EIS >> EOS
0′
). Specifically, the stronger adsorption of a
reactant, O (or R), thermodynamically hampers inner-sphere reduction (or oxidation),
which requires more negative (or positive) potentials than required for the outer-sphere
counterpart. By contrast, inner-sphere ET is thermodynamically facilitated to require
less extreme potentials when a product is more strongly adsorbed on the electrode
surface. This thermodynamic assessment reveals a misconception in a recent study
that the adsorption of hard-to-reduce metal ions, e.g. Ca2+ , on the electrode surface
facilitates their inner-sphere reduction to yield voltammetric responses within the
potential window [50].
1.3 Clean Carbon Electrodes

Experimentally, a clean carbon surface is required to reliably study adsorption-coupled
ET, because both heterogeneous ET [51–54] and surface adsorption [55] can be
affected by adventitious surface contamination. Historically, methods have been
well established to obtain, maintain, and ensure clean surfaces of metal electrodes,
especially Pt [56]. A flame-annealing method was pioneered by Clavilier [57] and is
widely used to reproducibly yield clean surfaces of single-crystal metal electrodes. This
method, however, is not applicable to carbon materials, which are cleaned by solvents,
laser illumination, (vacuum) heat treatment, electrochemical polarization, mechanical
polishing, plasma treatment, and chemical oxidation [58]. These methods, however,
can be destructive for graphitic materials, especially nanomaterials [58]. Moreover,
a flame-annealed metal electrode must be immediately immersed in ultrapure water
to prevent airborne contamination, which quickly occurs also on carbon surfaces
[17, 59–61]. The ultrapure water must be free from organic, surface-active impurities,
which was originally achieved by pyrocatalytic distillation [62] to lower a total organic
carbon (TOC) to 3 ppb [63]. Currently, ultrapure water with TOC at the level of 1 ppb
is obtainable by UV photooxidation of organic contaminants [64] using commercial
water purifiers [65]. Finally, the in-situ cleanliness of a Pt surface in an electrolyte
solution can be quantitatively evaluated by studying the electrosorption of hydrogen
[56]. There is, however, no established method to validate the in-situ cleanliness of a
carbon electrode surface in an electrolyte solution.
Recent studies showed that the prevention of adventitious organic contamination on
the surface of a carbon electrode is still highly challenging. The surface of highly oriented
pyrolytic graphite (HOPG) and graphene is quickly contaminated by airborne hydrocar-
bons, as confirmed by water contact angle (WCA) measurement, attenuated total inter-
nal reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and ellipsometry
[17, 60]. The heterogeneous distribution of disordered adsorbates on the graphene sur-
face was also observed by atomic force microscopy (AFM) [66]. Traditionally, a freshly
exposed HOPG surface was electrochemically characterized as quickly as possible to
minimize airborne contamination [67–69]. These studies, however, reported very dif-
ferent ET kinetics [20, 68]. Moreover, the contamination of a freshly HOPG surface
in water was revealed by SECM–AFM [70, 71], but not by scanning electrochemical
cell microscopy (SECCM) [68, 72], where the surface of a target substrate was always
exposed to ambient air.
Recently, we demonstrated that the clean surfaces of sp2 carbons, i.e. HOPG and
graphene, can be protected from airborne contamination simply by condensing a
nanometer-thick adlayer of water on the surfaces in humidified air [61] (Figure 1.2a).
The WCA of an unprotected HOPG surface quickly increased from ∼60∘ to ∼90∘ in
ambient air at room temperature until the surface was saturated with hydrophobic
contaminants (Figure 1.2b [61]) as detected by ATR-FTIR. By contrast, the WCA of a
HOPG surface increased only to ∼70∘ in ∼20 minutes when exfoliated and stored in
humidified air at −20 ∘ C to condense a water adlayer, thereby estimating the maximum
surface coverage of ∼33% with airborne contaminants. The water-protected HOPG
surface showed no damage, as confirmed by X-ray photoelectron spectroscopy (XPS).
Moreover, ATR-FTIR of the protected HOPG surface showed OH bond stretching at a
lower frequency, which indicates the formation of an ice-like structure. The quantitative
analysis of ellipsometry data indicated the formation of submonolayer water with a
thickness of 0.08 nm on the HOPG surface.
More recently, we developed a new method to protect the pristine surface of
electron-beam-deposited carbon (eC) by using a KCl layer (Figure 1.3). The amorphous
eC film consists of a mixture of sp2 and sp3 hybridized carbon [74] in contrast to
HOPG and graphene. The thin eC film was deposited on a metal support to yield
sufficient conductivity for electrochemistry as well as molecular electronics [75–78].
Earlier studies showed that the low background current and sufficient transparency of
the thin eC film are advantageous for conventional electrochemistry [74] and optical
spectroscopy [79, 80], respectively. Technically, we deposited all layers of electrode
materials including a KCl layer in vacuum to obtain the pristine eC surface, which
was exposed for the first time when the protective KCl layer was dissolved in the
aqueous electrolyte solution of redox molecules. The exposed eC surface was extremely
flat, as represented by average and root-mean-square roughness of 0.34 ± 0.01 and
0.43 ± 0.02 nm, respectively, based on AFM measurements. Raman and X-ray pho-
toelectron spectroscopies were employed [76] to determine an approximately 70 : 30
ratio of sp2 and sp3 hybridized carbon. Advantageously, KCl-protected electrodes are
storable and transportable in ambient air without compromising surface cleanliness. In
fact, KCl-coated eC samples were prepared in Edmonton and exposed to ambient air
during shipment to Pittsburgh to maintain the cleanliness of the underlying eC surface
2O
H
ith
w
w
ith
ou
t H2
O
(a)
stored at room temperature

stored at low temperature
100
90
WCA(°)
80
70
60
0 10 20 30 40 50 60 120
Time (min)
(b)
Figure 1.2 (a) Scheme of graphite surface protected from airborne hydrocarbon contaminants by a
water adlayer. Yellow, red, white, and gray balls represent sp2 carbon, oxygen, hydrogen, and sp3
carbon atoms. (b) Temporal evolution of the WCA measured on freshly exfoliated HOPG stored at
room temperature and low temperature. For the sample stored at low temperature, it was only
exposed to room temperature during the WCA measurement. Source: Reprinted with permission from
Li et al. [61]. Copyright 2016 American Chemical Society.
as ensured by SECM-based nanogap voltammetry (NV) (see below). Potentially, the

KCl-based protection method will be applicable to a variety of clean electrode materials
prepared in vacuum.
The cleanliness of a macroscopic electrode is maintainable in ultrapure water with low
TOC of 2–3 ppb containing high-purity inorganic electrolytes, because of slow linear
diffusion of organic impurities to the large electrode surface, as predicted theoretically
and confirmed experimentally using HOPG in our recent work [51]. Specifically, we
applied a model based on the diffusion-limited and irreversible adsorption of organic
1 μm KCI
10 nm eC
3 nm TiC
30 nm Au
30 nm Cr
Si/SiOx (300 nm)
1.0
c m
Figure 1.3 Schematic illustration of deposited layers with indicated thicknesses on Si/SiOx substrate.
Source: Reprinted with permission from Morteza Najarian et al. [73]. Copyright 2017 American
Chemical Society.
impurities [65] to a planar macroscopic surface to estimate the surface coverage of con-
taminants, 𝜃 c , as given by [51]
√
2cc Dc t
𝜃c = (1.11)
𝜃sat 𝜌c 𝜋
where cc and Dc are the concentration and diffusion coefficient of organic impurities,
respectively, t is the duration of contamination, 𝜃 sat is a saturation coverage of the HOPG
surface (= 0.14 for benzene [81] as a model for the sake of generality [65]), and 𝜌c is the
density of carbon atom at the graphite surface (= 6.3 × 10−9 mol cm−2 ). Equation (1.11)
predicts that ultrapure water with TOC values of 2–3 ppb (e.g. 28–42 nM benzene)
gives extremely low 𝜃 values of 0.0066–0.0099 with t = 1 hour. A substantial 𝜃 value of
0.066, however, is expected from Eq. (1.11) with t = 1 hour when the HOPG surface
is immersed in ultrapure water with a TOC value of 20 ppb (cc = 0.28 μM for ben-
zene), which is typically obtained using only filters to remove organic impurities [63]. By
contrast, the original model was developed to predict that nanoelectrodes are quickly
contaminated even in ultrapure water with a TOC value of 1 ppb owing to fast mass
transport of organic impurities to compromise the electroactivity of nanoelectrodes
[65], e.g. oxygen reduction at Pt nanoelectrodes [82].
1.4 SECM-Based Nanogap Voltammetry

In-situ cleanliness of a carbon electrode surface was checked experimentally by NV
based on SECM. Originally, SECM-based NV was developed to reliably measure
fast kinetics of nearly reversible ET by monitoring both oxidation and reduction of
a redox couple at quasi-steady states under high mass-transport conditions across a
nanometer-wide gap between an ultramicroelectrode (UME) tip and a macroscopic
substrate electrode [83]. When an only reduced form of a redox couple, R, is initially
present in the solution, the SECM feedback mode is employed to investigate the
reduction of the redox couple on the substrate (e.g. eC in Figure 1.4a). Specifically, the
(a) (c) glass

R Pt tip glass R
R R O R
R R
kred
e-beam carbon (10 nm)
platinum 1μm
Au (30 nm) TiC (3 nm)
(b) 2rg (d)

R 2a R
R O d R O R O
krox
1μm
Figure 1.4 Scheme of (a) feedback and (b) SG/TC modes of SECM for NV at an eC electrode.
Heterogeneous reduction and oxidation rate constants are represented by kred and kox , respectively.
Source: Reprinted with permission from Morteza Najarian et al. [73]. Copyright 2017 American
Chemical Society. SEM images of a borosilicate-sealed Pt UME (c) before and (d) after electrowstatic
damage. Source: Reprinted with permission from Nioradze et al. [84]. Copyright 2013 American
Chemical Society.
diffusion-limited oxidation of the reductant at the SECM tip yields an amperometric tip
current, which varies with the substrate potential. The tip current is enhanced at suffi-
ciently negative potentials, where the reductant is regenerated from the tip-generated
oxidant, O, to complete efficient redox cycling across a narrow gap between the tip
and the substrate. This positive feedback effect is reduced to eventually diminish
the tip current at positive potentials, where the reductant is oxidatively consumed
at the substrate, i.e. a shielding effect [85]. By contrast, the oxidation of the reductant
at the substrate surface is monitored in the substrate generation/tip collection (SG/TC)
mode by detecting the substrate-generated species, O, at the tip (Figure 1.4b). Overall,
a pair of NVs is obtained by plotting the amperometric tip current against the substrate
potential in feedback and SG/TC modes. The resultant voltammograms are obtained
under quasi-steady states to yield a sigmoidal shape when the tip–substrate distance
is sufficiently narrow. The NV approach based on complementary operation modes
is more reliable than the measurement of single steady-state voltammograms based
on either oxidation or reduction of a redox couple, as originally demonstrated for
ion-transfer nanopipet voltammetry [86, 87]. It should be noted that SECM-based NV
enabled the determination of high k 0 values of up to 25 cm s−1 [52] by scanning the
potential of a macroscopic substrate around the formal potential of a redox couple
under quasi-steady-state conditions [83]. By contrast, macroscopic substrates have
been studied by the feedback mode of SECM to predict measurable ET rate constants
of up to 20 cm s−1 [88], which were recently misrepresented as measurable k 0 values
[89], i.e., ET rate constants at the formal potential. The measurable ET rate constants
correspond to lower k 0 values of up to ∼2 cm s−1 even with nanogap configurations

[90], because the substrate potential is usually far from the formal potential in the
feedback mode of SECM to irreversibly electrolyze the tip-generated species at the
substrate, which is required to achieve steady states.
Technologically, the development of SECM-based NV revealed and overcame
challenges that were unrecognized previously [25]. The formation of a nanogap
requires a flat region of a substrate under a small tip with well-defined flat geometry
(Figure 1.4c), which was found compromised by electrostatic damage from an experi-
menter (Figure 1.4d) and a (bi-)potentiostat [84, 91, 92]. Moreover, it was found that the
maintenance of a nanogap with a fixed width required the elimination of the nanoscale
thermal drift of tip position [92, 93]. The importance of preventing tip damage and
thermal drift was overlooked in earlier studies [94, 95], where only the feedback mode
was employed in SECM-based NV of tip reactions to obtain unreliable ET kinetics as
revealed in a recent study [96]. It should be emphasized that the finding of electrostatic
damage of submicrometer- and nanometer-sized electrodes is new and significant,
because the possibility of ill-defined geometry of nanometer-sized electrodes had been
pointed out, but attributed to imperfect electrode fabrication [97–100] rather than the
damage of well-fabricated electrodes. Moreover, the damage of nanoelectrodes was
unseen previously [101, 102], but was noticed [103] after the problem was reported
[84].
SECM-based NV was used to ensure the cleanliness of KCl-protected eC surface
[73]. Both SG/TC and feedback modes of SECM were employed to investigate the
oxidation and reduction of the FcTMA2+/+ couple, respectively, at KCl-protected and
non-protected eC electrodes (Figure 1.5a,b, respectively). When the eC surface was pro-
tected by a KCl layer, symmetric pairs of reversible NVs were obtained at tip–substrate
distances of down to 49 nm. The shortest tip–substrate distance was used to estimate
0.4 0.4
KCl-Protected eC Non-Protected eC
0.2 0.2
Tip Current (nA)
Tip Current (nA)
SG/TC Mode SG/TC Mode

0.0 0.0
–0.2 –0.2
Feedback Mode Feedback Mode

–0.4 –0.4
0.1 0.2 0.3 0.4 0.5 0.6 0.1 0.2 0.3 0.4 0.5 0.6
(a) Substrate Potential (V vs Ag/AgCl) (b) Substrate Potential (V vs Ag/AgCl)
Figure 1.5 Nanogap voltammograms of 0.3 mM FcTMA+ in 1 M KCl at eC electrodes prepared without
(a) and with (b) a protective KCl layer obtained using 1.01 and 1.04 μm-diameter Pt tips, respectively.
Forward and reverse waves are represented by solid and dotted lines, respectively. Tip potentials, 0.55
and 0.15 V vs Ag/AgCl in feedback and SG/TC modes, respectively. Potential sweep rate, 0.05 V s−1 .
′
Circles represent theoretical curves with E 0 = 0.371 V vs Ag/AgCl and gap widths of 44–275 nm.
Dashed lines in panel B represent theoretical reversible curves at the shortest tip−substrate distance
of 49 nm. Source: Reprinted with permission from Morteza Najarian et al. [73]. Copyright 2017
American Chemical Society.
the diffusion-limited minimum k 0 value of 14 cm s−1 , which is equivalent to k 0 a/D = 10

with a tip radius, a, of 0.52 μm and a diffusion coefficient, D, of 6.0 × 106 cm2 s−1 . The
minimum k 0 value is one of the highest k 0 values estimated for a ferrocene derivative
at carbon and metal electrodes (Table 1.1) as discussed further below. By contrast,
NVs at non-protected eC surfaces were kinetically limited to yield a finite k 0 value of
1.45 cm s−1 , which is at least 10 times lower than the k 0 value at the KCl-protected eC
surface. Importantly, the high k 0 value at the clean eC surface is attributed to a standard
0
rate constant of outer-sphere ET, kOS , because the eC surface adsorbs FcTMA+ , but
not FcTMA , i.e. ΓR,s 𝛽 R > > ΓO,s 𝛽 O , to thermodynamically decouple inner-sphere
2+
oxidation of adsorbed FcTMA+ to much more positive potentials. The minimum

0 0
kOS value of 14 cm s−1 is still lower than a kOS value of 100 cm s−1 predicted for the
2+/+
FcTMA couple [104] by Marcus theory [108]
0
kOS = Zhet (kex ∕Zbi )1∕2 (1.12)
where k ex is a homogeneous self-exchange rate constant, and Zhet (∼104 cm s−1 )
and Zbi (∼1011 M−1 sec−1 ) are heterogeneous and bimolecular collision frequencies,
respectively. Equation (1.12) assumes adiabatic conditions, where outer-sphere ET is
controlled by the reorganization of the redox couple and surrounding solvents to yield
0 0
the highest possible kOS value. The adiabatic kOS value of 100 cm s−1 for FcTMA+ is
0
nearly identical to the highest k value that can be measured by SECM, which is limited
by electron tunneling across a narrow gap between the tip and the substrate [109].
We employed SECM-based NV also to study a clean surface of HOPG [104], which
was protected by a nanometer-thick water adlayer condensed on the HOPG surface
freshly peeled in humidified air [61]. The in-situ cleanliness of water-protected HOPG
was ensured by a symmetric pair of NVs for the FcTMA2+/+ couple in feedback and
Table 1.1 Standard ET rate constants of FcTMA+ and FcCH2 OH at carbons and Pt.
Electrode Ferrocene k0 (cm s−1 ) Method Ref.
— FcTMA+ 100a) — [104]

eC (KCl protection) FcTMA +
≥14 SECMb) [73]
eC FcTMA+ 1.45 ± 0.06 SECMb) [73]
HOPG (water protection) FcTMA+ ≥12 SECMb) [104]
HOPG FcTMA+ ≥17, ≥13 SECMb) [51]
+
HOPG FcTMA 1.7 ± 0.3, 0.7 ± 0.3 SECM [51]
HOPG FcTMA+ ≥0.1–1.0 SECCMc) [105]
SWCNT FcTMA+ 9±2 SECCMc) [106]
SWCNT (metallic) FcTMA+ 7±2 SECCMc) [107]
SWCNT (semi-conductive) FcTMA+ 4±2 SECCMc) [107]
Pt nanoelectrode FcCH2 OH >20 SECMb) [96]
FcCH2 OH 6.8 ± 0.7 SECM [94]
a) Marcus theory (Eq. (1.12)).

b) low-TOC water.
c) ambient air.
0.3
Water-Protected HOPG Non-Protected HOPG
0.4
0.2
Tip Current (nA)
Tip Current (nA)

0.1 0.2
SG/TC Mode SG/TC Mode
0.0 0.0
–0.1 –0.2
–0.2
–0.4
Feedback Mode Feedback Mode
–0.3
0.2 0.4 0.6 0.2 0.4 0.6
HOPG Potential (V vs. Ag/AgCl) HOPG Potential (V vs. Ag/AgCl)
(a) (b)
Figure 1.6 (a) Symmetric and (b) asymmetric pairs of nanogap voltammograms of 0.3 mM FcTMA+ at
water-protected and non-unprotected HOPG surfaces, respectively, as obtained using
1.0 μm-diameter Pt tips in 50 mM KCl. Forward and reverse waves are represented by solid and dashed
lines, respectively. Dots represent reversible voltammograms without any adsorption effect simulated
′
with E 0 = 0.340 V and gap widths of (a) 52–270 nm and (b) 45–309 and 36–271 nm in feedback and
SG/TC modes, respectively. Tip potentials, 0.5 and 0.15 V vs Ag/AgCl in the respective modes. Potential
sweep rate, 0.05 V s−1 . Source: Reprinted with permission from (a) Nioradze et al. [51] (Copyright 2015
American Chemical Society) and (b) Chen et al. [104] (Copyright 2016 American Chemical Society).
SG/TC modes (Figure 1.6a). This result also confirmed that the anomalous asymme-
try of a pair of NVs for the FcTMA2+/+ couple at non-protected HOPG (Figure 1.6b)
was due to airborne contamination [51]. More quantitatively, symmetric pairs of NVs
at water-protected HOPG were reversible to yield diffusion-limited minimum k 0 val-
ues of up to 12 cm s−1 consistently in both feedback and SG/TC modes at the shortest
tip–substrate distance of 55 nm. Asymmetric pairs of NVs at non-protected HOPG were
also reversible, but inconsistent in their heights to yield different minimum k 0 values
of 17 and 13 cm s−1 in SG/TC and feedback modes, respectively. The lower limiting
current in the feedback mode was attributed to the lower permeability of a hydropho-
bic contaminant layer to FcTMA2+ , which is reduced at the underlying HOPG surface
in the feedback mode. By contrast, the contaminant layer is more permeable to more
hydrophobic FcTMA+ , which is oxidized in the SG/TC mode to yield a higher limit-
ing current and, subsequently, an apparently larger k 0 value. It should be noted that
the asymmetry of NVs was misattributed to surface adsorption and self-exchange reac-
tions of the FcTMA2+/+ couple by others [110]. We demonstrated that the adsorption
of FcTMA+ on HOPG was seen as hysteresis of each NV during the potential cycle
(Figure 1.6), but was too weak to simulate the asymmetry of NVs between feedback
and SG/TC modes [104]. Moreover, we found [111] that incorrect parameters for the
adsorption of FcTMA+ on HOPG were determined in the previous studies [55, 110] and
inappropriately used to argue very small effects of surface adsorption on SECM-based
NV [89, 110]. We also proved that a heterogeneous self-exchange reaction was not rele-
vant, because only FcTMA+ or FcTMA2+ was adsorbed on HOPG or the glass sheath of
an SECM tip, respectively [112]. Accordingly, the minimum k 0 values were determined
for outer-sphere ET of the FcTMA2+/+ couple at the HOPG surface, which adsorbs only
FcTMA+ to prevent inner-sphere and self-exchange ET [104, 112].
The SECM-based NV study of clean eC and HOPG surfaces revealed the importance
of surface cleanliness in kinetic measurements, where contamination not only from the
air but also from water should be prevented. The latter effect was manifested by lower
k 0 values of 1.7 and 0.7 cm s−1 determined for the FcTMA2+/+ couple from asymmet-
ric pairs of SECM-based NVs when HOPG was immersed in standard ultrapure water
purified only by filters (Table 1.1). More recently it was reported that the k 0 value of
FcCH2 OH at Pt nanoelectrodes was much lower in standard ultrapure water (6.8 cm s−1
[94]) than in low TOC water (>20 cm s−1 [96]) (Table 1.1). The k 0 values measured for
FcTMA+ and FcCH2 OH at HOPG and Pt in low-TOC water are higher than k 0 val-
ues of <10 cm s−1 measured for FcTMA+ at single-wall carbon nanotubes (SWCNTs)
[106, 107] and HOPG [105] by using SECCM. Problematically, SECCM measurements
expose a substrate surface to ambient air without any prevention of adventitious air-
borne contamination of not only the substrate surface, but also a submicrometer-sized
water droplet formed at the tip of a nanopipet. The TOC of the water droplet was not
reported, but is likely compromised by airborne contamination. Such contaminations
may be a reason why lower k 0 values of 7 cm s−1 were obtained for FcTMA+ even with
metallic SWCNTs by SECCM [107]. It should be noted that low k 0 values measured
by SECCM at HOPG [105] are diffusion-limited minimum values [89], which mani-
fests that slow mass transport in tapered pipets [113, 114] lowers measurable k 0 values
for SECCM in comparison with SECM under high mass-transport conditions across
tip–substrate nanogaps.
It should be emphasized that diffusion-limited minimum k 0 values are informative,
but are inaccurate. For instance, diffusion-limited minimum k 0 values of 0.1–1.0 cm s−1
for FcTMA+ at HOPG were determined by SECCM to imply the possibility that a true k 0
value can be 0.1–12 cm s−1 or higher. The former possibility, however, was excluded by
our recent study, which yielded a minimum k 0 value of 12 cm s−1 at clean HOPG surfaces
by using SECM-based NV [104]. This higher minimum value is still lower than predicted
0
for adiabatic outer-sphere ET of FcTMA+ (kOS = 100 cm s−1 ) by Marcus theory and will
be likely exceeded in a future SECM study by using a narrower gap. Nanoscale SECM
will be useful also to more accurately assess the fast ET kinetics of various redox couples
at HOPG, where even lower k 0 values of ∼0.5 cm s−1 were estimated as diffusion-limited
minimum values from reversible cyclic voltammetry (CVs) [69].
SECM-based NV was also employed [52] to reveal that the electrochemical reactivity
of cleaner monolayer graphene was much higher than that of contaminated monolayer
graphene reported previously (Table 1.2). In previous studies [115–118], graphene elec-
trodes were prepared by a polymer-mediated transfer method [119], where graphene
was grown on a metal film (Ni or Cu) by chemical vapor deposition (CVD) and coated
with a polymer film, e.g. poly(methyl methacrylate) (PMMA), to etch away the support-
ing metal film and transfer polymer-coated graphene on a solid support. Problemati-
cally, the removal of the polymer film yielded the graphene surface that was damaged
and also contaminated with polymer residues [115], which were difficult to remove
without further damage [120]. Graphene electrodes prepared by this method yielded
consistently low k 0 values of 0.01–0.037 cm s−1 for FcCH2 OH as measured by CV [115]
and SECM [116, 117] as well as 0.03–0.2 cm s−1 for FcTMA+ by SECCM [118]. By con-
trast, much higher k 0 values of 1.6 cm s−1 were obtained for FcCH2 OH at the graphene
surface that was freshly exposed by etching the copper film just before SECM-based NV,
Table 1.2 Standard ET rate constants of FcTMA+ and FcCH2 OH at monolayer graphene.
Electrode Ferrocene k0 (cm s−1 ) Method Ref.
CVD graphenea) FcCH2 OH 0.037 CV [115]

CVD graphenea) FcCH2 OH 0.020 ± 0.004 SECM [116]
CVD graphenea) FcCH2 OH 0.010 ± 0.002 SECM [117]
CVD grapheneb) FcCH2 OH 1.6 ± 0.5, 0.5 ± 0.2 SECMc) [52]
CVD graphened) FcCH2 OH ≥25 SECMc) [52]
CVD graphenea) FcTMA+ 0.03–0.2 SECCMe) [118]
exfoliated graphene FcCH2 OH ≥0.5 CV [115]
a) PMMA-mediated transfer.
b) PMMA-supported.
c) low-TOC water.
d) PS-supported.
e) ambient air.
where a PMMA film served only as a support [52]. These higher k 0 values were consistent
with diffusion-limited minimum values determined by CV of FcCH2 OH at graphene
exfoliated from HOPG [115]. Interestingly, even higher k 0 values of up to 25 cm s−1
were determined for the oxidation of FcCH2 OH at graphene supported by a non-polar
polystyrene (PS) film. This result suggests the electrochemical transparency of graphene
[52], i.e. the electrochemical reactivity of graphene was affected by the underlying poly-
mer film owing to the atomic thickness of graphene. Electrochemical transparency can
be important to understand the electrochemical reactivity of multilayer graphene (even-
tually equivalent to HOPG), which was studied by SECCM to observe an increase in k 0
values with an increase in the number of graphene layers [118]. None of previous studies,
however, measured the electrochemical reactivity of unambiguously pristine graphene,
which was exposed to ambient air during SECCM measurements [118] and also during
electrode fabrication for CV and SECM as demonstrated by asymmetric pairs of NVs
[52], thereby requiring the protection of graphene from airborne contamination, e.g. by
the water-based protection method [61]. In addition, CVD-grown graphene must be
protected from contamination with silicon oxide nanoparticles deposited from quartz
furnaces [121, 122].
1.5 Adsorption-Coupled Outer-Sphere ET

Heterogeneous ET must be mediated through an outer-sphere pathway when only one
form of a redox couple is adsorbed on the electrode surface to prevent inner-sphere and
self-exchange ET, as we claimed for the first time in recent studies of ferrocene deriva-
tives at HOPG [104, 111]. In this case, only the reduced form of ferrocene derivatives
is adsorbed on the HOPG surface (ΓO,s 𝛽 O < < ΓR,s 𝛽 R ) to thermodynamically decouple
outer-sphere oxidation of the reduced form and suppress its inner-sphere oxidation
0′
(EIS >> EOS
0′
in Eq. (1.10)). Coupling of surface adsorption with outer-sphere oxidation
was clearly demonstrated by CV, where a forward peak was enhanced much more at a
30
FcTMA+ at 10 V/s FcCH2OH at 0.05 V/s
0.4
HOPG Current (mA)
HOPG Current (μA)

15
0.2
0.0 0
–0.2
–15
0.2 0.4 0.6 0.0 0.2 0.4
HOPG Potential (V vs Ag/AgCl) HOPG Potential (V vs Ag/AgCl)
(a) (b)
Figure 1.7 Background-subtracted experimental CVs (solid lines) of 0.3 mM (a) FcTMA+ at 10 V s−1 and
(b) FcCH2 OH at 0.05 V s−1 with water-protected HOPG in 1 M KCl. Theoretical CVs were simulated with
the best fit (circles), no adsorption (dashed lines), and previously reported parameters [110] (dotted
line only in part A). Source: Reprinted with permission from Kurapati et al. [111]. Copyright 2018
American Chemical Society.
faster scan rate than the reverse peak (e.g. FcTMA+ at 10 V s−1 in Figure 1.7a [111]). The
enhancement of the forward peak proves that the reduced form of ferrocene derivatives
was desorbed from the HOPG surface to participate in outer-sphere oxidation. A lower
reverse peak indicates the lack of adsorption of the oxidized form of ferrocene deriva-
tives, e.g. FcTMA2+ . In fact, experimental CV was fitted very well with CV simulated by
considering only outer-sphere ET coupled with surface adsorption of the reduced form
of ferrocene derivatives (Figure 1.7a). The best fit required the consideration of inter-
molecular interactions among adsorbed ferrocene derivatives, which was implemented
by employing the Frumkin isotherm based on Bragg–Williams approximation [123] to
yield [124]
( )
Γi Γ
𝛽i Ci (0, t) = exp −gi′ i (1.13)
Γi,s − Γi Γi,s
where only one species, i, is adsorbed and gi′ represents interactions among adsorbates
on the electrode surface. Weak electrostatic repulsion among adsorbed FcTMA+
yielded a small negative gi′ value of −0.3 ± 0.2, which corresponds to a wider forward
peak than expected from the Langmuir isotherm (gi′ = 0). Experimental CVs at various
scan rates consistently fitted with CVs simulated by using the Frumkin isotherm with
log𝛽 i (l mol−1 ) = 3.6 ± 0.3 and Γi,s = (1.8 ± 0.5) × 10−10 mol cm−2 . A good fit was not
obtained with CV simulated by using previously reported parameters, i.e. the Langmuir
isotherm with log𝛽 i (l mol−1 ) = 2.9 and Γi,s = 5.0 × 10−10 mol cm−2 [110], which was
overestimated by incorrectly assuming that the cyclopentadienyl ring of FcTMA+ was
closely packed on the HOPG surface despite the substituent.
Interestingly, FcCH2 OH was adsorbed strongly on the water-protected HOPG
surface in low TOC ultrapure water to yield a pair of adsorption-based post peaks
(Figure 1.7b). Such a pair of post peaks was not reported in previous CV studies
[55, 115, 125], perhaps because HOPG was not protected from organic contamination
in ambient air or ultrapure water. Importantly, the post peaks are attributed to the
coupling between outer-sphere ET and surface adsorption of FcCH2 OH, not to

inner-sphere ET of adsorbed forms of the FcCH2 OH+/0 couple. In fact, CVs simulated
with adsorption-coupled outer-sphere ET yielded good fits with experimental CVs
at up to 10 V s−1 , where post peaks merged with diffusional peaks. The resultant CV
with a much higher forward peak characteristically indicates that only FcCH2 OH was
adsorbed on the HOPG surface to mediate only outer-sphere ET. The weak dependence
of reverse peak on scan rate is inconsistent with inner-sphere ET of an adsorbed redox
couple [47], where both forward and reverse peaks vary proportionally with the scan
rate. It should be emphasized that a pair of post (or pre) peaks coupled with a pair of
diffusional peaks was simulated by Wopschall and Shain [126], who considered only
outer-sphere ET and the adsorption of a reactant (or a product), although their work
was cited recently to attribute a pair of pre peaks to inner-sphere ET of an adsorbed
redox couple [127]. Similarly, Speiser and coworkers considered only outer-sphere
ET coupled with Langmuir [128] or Frumkin [129] adsorption of a redox couple to
simulate a pair of adsorption-based peaks preceding or following a pair of diffusional
peaks. We are unaware of any theoretical work that yielded a pair of diffusional peaks
preceded or followed by a pair of peaks based on inner-sphere ET.
The strong adsorption of FcCH2 OH on the HOPG surface is attributed to strong
intermolecular interactions among adsorbed FcCH2 OH as demonstrated by the
highly positive gi′ value of +3.2 ± 0.3 determined by the finite element analysis of
CV. The strong intermolecular interactions are attributed to hydrogen bonding and
qualitatively represented by the narrow widths of not only post peaks at low scan
rate (Figure 1.7b), but also higher forward peaks at faster scan rates. By contrast,
Γi,s = (3.0 ± 0.6) × 10−10 mol cm−2 and log𝛽 i (l mol−1 ) = 3.7 ± 0.1 for FcCH2 OH are
similar to those of FcTMA+ (see above). Overall, free energy changes for the entire
adsorption step, ΔG0 , of FcCH2 OH (−30 ± 1 kJ mol−1 ) is more negative than those of
FcTMA+ (−21 ± 2 kJ mol−1 ), because free energy changes for intermolecular interac-
tions among adsorbed FcCH2 OH (−8.0 ± 0.7 kJ mol−1 ) are more negative than FcTMA+
(+0.7 ± 0.4 kJ mol−1 ), i.e. −RTgi′ at saturation (Γi /Γi,s = 1), as given by [124]
ΔG0 = −RT ln 𝛽i − RTgi′ (Γi ∕Γi,s ) (1.14)
where free energy changes for interactions with HOPG, i.e. −RTln𝛽 i , are similar
between FcCH2 OH (−21.5 ± 0.8 kJ mol−1 ) and FcTMA+ (−21 ± 2 kJ mol−1 ). Moreover,
adsorption isotherms can be plotted using adsorption parameters determined from
CVs to find adsorption strength in the order of FcCH2 OH > 1,1′ -ferrocenedimethanol,
Fc(CH2 OH)2 , >FcTMA+ (Figure 1.8a). The adsorption of FcTMA+ is underestimated
by using a Langmuir isotherm with an overestimated Γi,s value and an underestimated
log𝛽 i value, as reported previously [110].
Adsorption parameters are obtainable by CV, which represents the adsorption
isotherm as illustrated by simulating concentrations of redox couples at OHP and IHP
of HOPG against its potential (e.g. FcCH2 OH in Figure 1.8b). At the initial potential
of −0.05 V, the HOPG surface is nearly saturated with FcCH2 OH (solid red line). As
the potential is scanned to >0.1 V, FcCH2 OH at the OHP (solid blue line) is oxidatively
consumed to generate FcCH2 OH+ at the OHP (solid black line). The HOPG surface,
however, is still nearly saturated with FcCH2 OH, which is strongly adsorbed even
when the concentration of FcCH2 OH at the OHP is lowered to ∼40% of the bulk
concentration at 0.2 V. More positive potentials of >0.3 V are required to significantly
1.0 2
, surface coverage
Normalized Concentration
Normalized Concentration
Surface Coverage, Γi/Γi,s
, FcCH2OH+
0.8 , FcCH2OH
4
, Isotherm
0.6
1
0.4
FcCH2OH 2
Fc(CH2OH2)
0.2
FcTMA+
FcTMA+
0.0 0 0
–6 –4 –2 0 0.0 0.2 0.4
logcFcXY HOPG Potential (V vs Ag/AgCl)
(a) (b)
Figure 1.8 (a) Adsorption isotherms (solid lines) for ferrocene derivatives on HOPG in 1 M KCl as
calculated by using 𝛽 i and g′i values determined from CVs (e.g. Figure 1.7). Dashed line represents the
adsorption isotherm of FcTMA+ misestimated in the previous study. Vertical dotted line indicates the
concentration of 0.3 mM ferrocene derivatives used for CV. (b) Normalized concentrations of the
FcCH2 OH+/0 couple at HOPG as simulated for 0.3 mM FcCH2 OH in 1 M KCl by employing a scan rate of
10 V s−1 and parameters determined from the corresponding CV. Solid lines and closed circles
represent the forward scan. Dashed lines and open circles correspond to the reverse scan. Source:
Reprinted with permission from Kurapati et al. [111]. Copyright 2018 American Chemical Society.
desorb FcCH2 OH from the HOPG surface to significantly enhance the current response
based on the oxidation of desorbed FcCH2 OH at the OHP, where the concentration of
FcCH2 OH+ exceeds the bulk concentration of FcCH2 OH by a factor of ∼5. Eventually,
the switching potential of 0.45 V is positive enough to completely deplete FcCH2 OH at
both OHP and IHP, but still maintain a high concentration of FcCH2 OH+ at the OHP.
The concentration of FcCH2 OH adsorbed on the IHP is nearly recovered to saturation
during the reverse scan, where FcCH2 OH at the OHP is still largely depleted owing to
the strong and fast adsorption of FcCH2 OH on the IHP. The equilibrium adsorption
of FcCH2 OH is maintained during the entire potential scan, as demonstrated by the
good agreement between the simulated FcCH2 OH concentration at the OHP and the
concentration of FcCH2 OH at the OHP calculated using the Frumkin isotherm with
the simulated concentration of FcCH2 OH on the IHP (circles in Figure 1.8b).
1.6 Self-Inhibition of Outer-Sphere ET

A redox-active molecule can be adsorbed on the electrode surface to self-inhibit
outer-sphere ET, as revealed by SECM-based NV in our recent study [130]. Specifically,
a self-inhibitory effect was observed by SECM-based NV of Co(phen)3 2+ , which was
adsorbed on the eC surface to electrostatically block the access of non-adsorbed
Co(phen)3 2+ and Co(phen)3 3+ to the OHP (Figure 1.9a). Heterogeneous ET of
the Co(phen)3 3+/2+ couple at the eC surface was mediated unambiguously by an
outer-sphere pathway, because only Co(phen)3 2+ was adsorbed on the eC surface as
confirmed by CV and SECM-based NV. The self-inhibitory effect was less serious in the
SG/TC mode, where Co(phen)3 2+ was oxidatively consumed at the OHP to desorb the
blocking adsorbates. Moreover, weak electrostatic repulsion was exerted on the access
Figure 1.9 (a) Self-inhibition of

Co(phen)3 2+ oxidation by Co(phen)3 2+
adsorbed on the eC surface. (b)
Experimental (lines) and simulated
(circles) nanogap voltammograms of
0.1 mM (= c0 ) Co(phen)3 2+ at an eC
electrode in 1 M KCl as obtained by using
a 0.80 μm-diameter Pt tip in SG/TC (top)
and feedback (bottom) modes. Potential
sweep rate, 0.05 V s−1 . A tip–eC distance,
d, 88 nm. Open and closed circles are
forward and reverse scans, respectively.
Solid and dashed lines are the respective
(a)
scans. Source: Reprinted with permission
from Chen et al. [130]. Copyright 2018 50
American Chemical Society. SG/TC mode
Tip Current (pA)
c0 = 0.1 mM
d = 88 nm
0
Feedback mode
, experiment
, best fit
, reversible
–50
–0.2 0.0 0.2
eC Potential (V vs E0′)
(b)
of less charged Co(phen)3 2+ to the OHP in the SG/TC mode. The resultant SECM-based
NV was fitted well with simulated NV to yield a k 0 value (0.217 cm s−1 with 0.1 mM
Co(phen)3 2+ in the top panel of Figure 1.9b) and a 𝛼 value of 0.5 as expected from the
Marcus theory. The adsorption of only Co(phen)3 2+ at the IHP of the eC surface was
ensured by the hysteresis of the NV, where the tip current was enhanced only during the
forward scan by the oxidation of Co(phen)3 2+ desorbed from the eC surface to yield no
enhancement during the reverse scan. A good fit of experimental and simulated hyste-
resis yielded Γi,s = 3.8 × 10−11 mol cm−2 and log𝛽 i (l mol−1 ) = 5.2 in addition to a large
negative gi′ value of −4.6, which indicates strong electrostatic repulsion among adsorbed
Co(phen)3 2+ molecules. By contrast, a good fit was not obtainable for SECM-based
NV in the feedback mode (the bottom panel of Figure 1.9b), where Co(phen)3 2+ was
generated and adsorbed on the eC surface to seriously self-inhibit the access of highly
charged Co(phen)3 3+ to the OHP for outer-sphere reduction. SECM-based NVs in
the feedback mode were too board to fit with NVs simulated by using optimized
parameters for the SG/TC branches or any set of parameters including a 𝛼 value of
0.5 as expected for outer-sphere ET. Advantageously, the self-inhibitory oxidation of
Co(phen)3 2+ was irreversible under high mass-transport conditions across nanogaps
to yield NVs without an effect of seriously self-inhibitory reduction of Co(phen)3 3+ ,
thereby following the Marcus theory as evidenced by an 𝛼 value of 0.5.
A self-inhibitory effect on Co(phen)3 2+ oxidation was quantitatively characterized and

explained by extending the Amatore model of partially blocked electrodes [131–133].
Adsorbed Co(phen)3 2+ molecules blocked the eC surface to reduce a fraction of the bare
eC surface to 1 − 𝜃 i , where 𝜃 i = Γi /Γi,s . In addition, the access of Co(phen)3 2+ to the OHP
of the bare eC surface was electrostatically inhibited by adsorbates to yield an effective
fraction of 1 − 𝜃 i 𝛾, where 𝛾 represents the electrostatic blocking effect from adsorbates
to extend the Amatore model to self-inhibitory ET, i.e.
k 0 = kOS
0
[1 − 𝜃i 𝛾] (1.15)
This relationship was quantitatively ensured by plotting k 0 against 𝜃 i at E0 for
′
Co(phen)3 2+ oxidation at the eC surface as determined by the finite element analysis

of SECM-based NV. Experimentally, the bulk concentration of Co(phen)3 2+ in 1 M
KCl was increased from 0.05 to 1 mM to increase 𝜃 i at E0 from ∼0.4 to ∼0.8. The
′
0
corresponding k 0 values linearly decreased to yield kOS = 0.60 cm s–1 at 𝜃 = 0 and
𝛾 = 1.29 from the slope. The concentration dependence of k 0 is anomalous and
apparently inconsistent with the Marcus theory, but is accountable by considering
the self-inhibitory mechanism. It should be noted that self-inhibitory effects on
heterogeneous ET have also been known as autoinhibition in classical polarography
[134], but is rarely discussed in modern electrochemistry. More recently, Bard and
coworkers employed SECM to suggest a self-inhibitor effect at a Pt UME tip, where
both FcCH2 OH and FcCH2 OH+ were adsorbed from a mixture of water and dimethyl
sulfoxide (DMSO) to yield low k 0 values of ∼0.28 cm s−1 [135].
We also employed SECM-based CV with micrometer gaps [136] to discover the
importance of surface adsorption and self-inhibitory ET in the multistep electrode-
position of a multielement material, magnetite, Fe3 O4 . This mechanistic study is
significant, because magnetite [137] is a multifunctional compound that is attractive
for magnetic memory devices [138–140], electrocatalysis [141–143], and lithium-ion
batteries [144]. Specifically, we found that the well-established electrodeposition of
magnetite from an alkaline solution of Fe(III)–triethanolamine (TEA) [145] can be
preceded by the reductive generation and following adsorption of Fe(II)–TEA on the
Au substrate surface. Importantly, the adsorbed Fe(II) intermediate was unresolvable
from co-deposited Fe3 O4 in situ by other electrochemical techniques and was readily
oxidized in air and undetectable by ex-situ spectroscopy and microscopy [145]. The
adsorbed intermediate was identified through the quantitative analysis of complicated,
but highly informative SECM-based CVs. In the SG/TC mode, the substrate potential
was scanned to the negative direction, where Fe(II)–TEA was reductively generated
from Fe(II)–TEA, adsorbed on the substrate, and converted to magnetite to lower a tip
current based on the oxidation of Fe(II)–TEA (the bottom panel of Figure 1.10). The tip
current was lowered further during the reverse scan owing to the further deposition
of magnetite and was not recovered even at positive potentials, where Fe(II)–TEA
was produced by the electrodissolution of magnetite, but was immediately oxidized
to Fe(III)–TEA. By contrast, the tip current based on the reduction of Fe(III)–TEA
in the feedback mode was largely enhanced by the electrodissolution of magnetite
during the reverse scan to yield a transient peak response in addition to a sigmoidal
quasi-steady-state response (the top panel of Figure 1.10). It should be noted that
SECM-based CV with micrometer-gaps tend to yield larger transient responses
based on surface adsorption and desorption in comparison with SECM-based NV as
Figure 1.10 Experimental (solid lines) and 30

simulated (circles) SECM-based CVs in Feedback Mode
feedback (top) and SG/TC (bottom) modes
with a 25 μm-diameter Au tip over a 20
2 mm-diameter Au substrate in a 5 M NaOH
Tip Current (nA)

solution containing 5 mM Fe(III)–TEA. Tip
potentials, −1.12 and −0.75 V vs Ag/AgCl 10 experiment (forward)
for the respective operation modes. experiment (reverse)
Potential sweep rate, 0.025 V s−1 . Switching simulation
potential, −1.26 V vs Ag/AgCl. Source: 0
SG/TC Mode
Reprinted with permission from Bhat et al.
[136]. Copyright 2017 American Chemical
Society. –10
0.025 V/s in 5 M NaOH
–1.4 –1.2 –1.0 –0.8 –0.6 –0.4

Substrate Potential (V vs Ag/AgCl)
demonstrated for adsorption-coupled outer-sphere oxidation of FcTMA+ on HOPG

[110] and electrosorption of hydrogen on Pt electrodes [146, 147].
Advantageously, eight parameters for the three-step deposition of magnetite were
determined precisely by the finite element analysis of the amperometric tip current
free from the background response, thereby eliminating the need for background sub-
traction. A large Γi,s value of 5.4 × 10−9 mol cm−2 indicates that the multiple layers of
Fe(II)–TEA and, subsequently, magnetite were deposited. Moreover, the adsorption of
Fe(II)–TEA was strong, not only because of strong interactions between Fe(II)–TEA and
the substrate with log𝛽 i (l mol−1 ) = 5.2, but also because of strong attractive interactions
among adsorbates with gi′ = + 3.3, which was attributed to the adsorption and conver-
sion of Fe(II)–TEA to an oxide or a hydroxide. In contrast to conductive magnetite,
insulating oxide and hydroxide self-inhibited outer-sphere ET of the Fe(III/II)–TEA
couple, which was considered in the finite element analysis to improve a fit between
experimental and simulated voltammograms.
1.7 Coupling Between Outer- and Inner-Sphere ET

Here we consider a model based on simultaneous outer- and inner-sphere ET
(Figure 1.1) when both forms of a redox couple are similarly adsorbed on the electrode
surface to yield ΓO,s 𝛽 O = ΓR,s 𝛽 R = Γs 𝛽 and, subsequently, EIS
0′ 0′ ′
= EOS = E0 in Eq.
(1.10), thereby coupling both pathways thermodynamically. Moreover, steady-state
[21, 40, 41] and transient [21, 23, 42] voltammetry were considered theoretically
to conclude that outer- and inner-sphere pathways are indistinguishable kinetically
when adsorption equilibrium is maintained. This conclusion implies a paradox that
the resultant voltammetric wave resembles that of only outer-sphere ET coupled
with mass transport even when inner-sphere ET is exclusive [22], thereby missing
signatures of adsorption phenomena, which we call the Laviron–Amatore paradox.
Alternatively, only adsorption waves based on inner-sphere ET may be obtainable to
miss information about outer-sphere ET owing to the paradox [42] when desorption
kinetics is much slower than the time scale of electrochemical measurements. Here,
we justify the Laviron–Amatore paradox by considering the kinetic convolution of
outer- and inner-sphere ET as reported in our recent work [148]. When ET is mediated
through both pathways, the overall ET rate, v, is given by
v = vOS + vIS (1.16)
where vOS and vIS are rates of outer- and inner-sphere ET, respectively. The extended
Amatore model of self-inhibitory outer-sphere ET yields [130, 148]
vOS = (1 − 𝜃O − 𝜃R )[kOS
red ox
CO (0, t) − kOS CR (0, t)] (1.17)
with
[ ]
𝛼OS F(E − EOS
′
0
red 0
)
kOS = kOS exp − (1.18)
RT
[ ]
(1 − 𝛼OS )F(E − EOS
′
0
ox 0
)
kOS = kOS exp (1.19)
RT
Moreover, vIS is given by [21]
red ox
vIS = kIS ΓO − kIS ΓR (1.20)
with
[ ]
𝛼IS F(E − EIS
′
0
red 0
)
kIS = kIS exp − (1.21)
RT
[ ]
(1 − 𝛼IS )F(E − EIS
′
0
ox 0
)
kIS = kIS exp (1.22)
RT
When 𝛼 OS = 𝛼 IS = 𝛼 (∼0.5) and 𝛽 O = 𝛽 R = 𝛽 (and, accordingly, ΓO,s = ΓR,s = Γs ), a com-
bination of Eqs. (1.16)–(1.22) yields
{ [ ′ ] [ ′ ]}
0 𝛼F(E − E0 ) (1 − 𝛼)F(E − E0 )
v=k cO (0, t) exp − − cR (0, t) exp (1.23)
RT RT
with
0
kOS + 𝛽Γs kIS
0
k0 = (1.24)
1 + 𝛽c0
where c0 is the total bulk concentration of the redox couple and C O (0, t) + C R (0, t) = c0
is assumed owing to similar adsorptivities of oxidized and reduced forms in contrast
to earlier examples where the reduced (or oxidized) form was adsorbed more strongly
(Figure 1.8b). Overall, Eqs. (1.23) and (1.24) support the Laviron–Amatore paradox that
outer- and inner-sphere ET is unresolvable when adsorption equilibrium is maintained
for both forms of a redox couple with similar adsorptivities. Equation (1.23) shows that
0
v is equivalent to vOS when k 0 is replaced with kOS , thereby predicting voltammetric
0
responses without a feature of inner-sphere ET. Moreover, Eq. (1.24) ensures that kOS
0 0
and kIS are not separately determinable from an experimentally measurable k value.
Recently, we proposed [73] that coupling between outer- and inner-sphere ET may be
a reason why high k 0 values of the Ru(NH3 )6 3+/2+ couple determined by various nano-
0
electrochemical methods (Table 1.3) exceed the highest possible kOS value of 2.2 cm s−1
Table 1.3 Standard ET rate constants of Ru(NH3 )6 3+ at carbons and metals.
Electrode k0 (cm s−1 ) Method Note Ref.
— 2.2 — Marcus theory [149]

Pt nanoparticle 36 ± 4 Voltammetry Low-TOC water [150]
Carbon nanoelectrode ≥10 Voltammetry Low-TOC water [91]
eC (KCl protection) ≥6.9 SECM Low-TOC water [73]
eC 1.7 ± 0.2 SECM Low-TOC water [73]
CF 0.9 Voltammetry Low-TOC water [148]
SWCNT 4±2 SECCM Ambient air [106]
SWCNT (metallic) 10 ± 5 SECCM Ambient air [107]
Glassy carbon ≥2.0 AC voltammetry [151]
Pt nanoelectrode 79 ± 44 Voltammetry [97]
Pt nanoelectrode 17.0 ± 0.9 Voltammetry [94]
Au nanoelectrode 13.5 ± 2 Voltammetry [95]
predicted by the Marcus theory for adiabatic outer-sphere ET [149]. For instance, the-
oretical k 0 values based on Eq. (1.24) increase up to 46 cm s−1 for the Ru(NH3 )6 3+/2+
0
couple by using kIS = 5.39 × 106 s−1 and Γs = 1.5 × 10−10 mol cm−2 for the monolayer of
HS(CH2 )3 (pyridine)Ru-(NH3 )5 3+ [152] and 𝛽 = 5.39 × 104 cm3 mol−1 for Ru(NH3 )6 3+
[153] at Au electrodes. More specifically, Eq. (1.24) with c0 = 5 mM yields a slightly
lower k 0 value of 36 cm s−1 , which agrees very well with a k 0 value of 5 mM Ru(NH3 )6 3+
at single Pt nanoparticles [150]. Importantly, the Pt nanoparticles were investigated in
low-TOC water, which also yielded diffusion-limited minimum k 0 values of ≥10 and
≥6.9 cm s−1 at carbon nanoelectrodes and KCl-protected eC electrodes to exceed the
Marcus prediction and also include the predictions based on Eq. (1.24). Low-TOC water
yielded a low and finite k 0 value of 0.90 cm s−1 at carbon-fiber (CF) UMEs, which was
not electrochemically activated and was also exposed to ambient air as well as Ga+
and electron beams for electrode fabrication. In fact, the low k 0 value at CF UMEs
was similar to that of non-protected eC electrodes in low-TOC water [73]. Similarly,
the Marcus prediction of 2.2 cm s−1 was exceeded also at nanoelectrodes made of Pt
[94] and Au [95], where both Ru(NH6 )3 3+ and Ru(NH6 )3 2+ are adsorbed [153, 154]. The
finite k 0 values, however, were limited to ∼15 cm s−1 and lower than predicted by Eq.
(1.24), perhaps because nanoelectrodes were quickly contaminated owing to fast mass
transport of organic impurities in ultrapure water purified only by filtrations [65]. Sim-
ilarly, k 0 values of single SWCNTs were higher than the Marcus prediction, but were
lower than expected from Eq. (1.24), perhaps because these k 0 values were measured
by SECCM of SWCNTs exposed to ambient air [106, 107]. It should be noted that
high k 0 values of 79 ± 44 cm s−1 were overestimated by using recessed Pt nanoelectrodes
[97], which may be attributed to electrostatic damage [84]. AC voltammetry was too
slow to determine a k 0 value of higher than 2 cm s−1 at glassy carbon electrodes [151],
where both Ru(NH6 )3 3+ and Ru(NH6 )3 2+ are adsorbed [155] to mediate both outer- and
inner-sphere ET.
It should be noted that Eq. (1.24) is similar to the equation proposed by Anson [29]
to account for the non-linear concentration dependence of exchange current, i0 , [30] by
assuming both outer- and inner-sphere ET of the Fe3+/2+ couple at the Pt electrode, i.e.
0
i0 = nF[kOS 0
C + kIS Γs x𝛼IS (1 − x)1−𝛼IS ] (1.25)
where C is the equal bulk concentration of Fe3+ and Fe2+ , and x is the fraction of
adsorbed Fe3+ . Equation (1.25) is not identical to Eq. (1.24), because Anson did not
consider a specific adsorption isotherm or the self-inhibition of outer-sphere ET by
adsorbates. Interesting, Brown and Anson employed the Marcus theory to estimate
[37]
0
kIS = 6 × 108 kOS
0
(1.26)
0 0 −1 −1
where kOS and have units of s and cm s , respectively, both outer- and
kIS
inner-sphere ET are adiabatic and have the identical reorganization energy, and a
pre-exponential factor of inner-sphere ET is given by kT/h. Laviron proposed a larger
coefficient for kIS0
= 2 × 109 kOS
0
[40, 42] from the expression derived by Mohilner using
the Marcus theory [156]. Equation (1.24) for the Ru(NH3 )6 3+/2+ couple [73] employed
0
a kIS value of 5.39 × 106 s−1 for the monolayer of HS(CH2 )3 (pyridine)Ru-(NH3 )5 3+
0
[152], which was much smaller than a kIS value of 1.3 × 109 s−1 expected from Eq.
0 −1 0
(1.26) with kOS = 2.2 cm s . The kIS values are very different, potentially because the
0
kIS value of HS(CH2 )3 (pyridine)Ru-(NH3 )5 3+ self-assembled on the Au electrode was
lowered by electron tunneling through the spacer between the ruthenium redox center
0
and the electrode surface [152] to represent nonadiabatic ET. Moreover, kIS may be
3+/2+
overestimated for the Ru(NH3 )6 couple by Eq. (1.26), because the pre-exponential
factor was determined for inner-sphere ET of 9,10-phenanthrolinequinone and
because adiabatic mechanisms and identical reorganization energies were assumed
for outer- and inner-sphere ET [37]. Attempts have been made to theoretically assess
pre-exponential factor [157] and reorganization energy [158]. The latter predicted that
the reorganization energy of p-dicyanobenzene was lower at the IHP than at the OHP
to accelerate inner-sphere ET by a factor of ∼10. The lower reorganization energy of an
adsorbed redox species has been suggested, e.g. by Gerisher [159] and McCreery [160].
Outer- and inner-sphere ET can be coupled also through a heterogeneous
self-exchange reaction (Eq. (1.5)), which is unimportant when equilibrium adsorption
is maintained for both oxidized and reduced forms of a redox couple [23, 112]
(Figure 1.11a) or when both outer- and inner-sphere ET are reversible [112]
(Figure 1.11b). We obtained this conclusion generally by using electrochemical
potentials without specific expressions for heterogeneous ET or surface adsorption
[112], which was somehow misrepresented in a recent article [89]. The electrochemical
electrode electrode Figure 1.11 Heterogeneous self-exchange

ET at conductor with (a) equilibrium
R O R O adsorption steps or (b) reversible ET steps.
Red arrows indicate the forward reaction of
R O R O Eq. (1.5). Source: Reprinted with permission
from Amemiya [112]. Copyright 2017
R O R O American Chemical Society.
conductor conductor
(a) (b)
potential of species i, 𝜇i , is defined for both adsorbed and non-adsorbed forms of a

redox couple without the need of an adsorption isotherm. The rate of a self-exchange
reaction is zero when both of adsorption steps are at equilibrium (i.e. 𝜇O = 𝜇Oads
and 𝜇R = 𝜇Rads [161]) or when both of ET steps are reversible (i.e. 𝜇O + 𝜇e = 𝜇R
and 𝜇Oads + 𝜇e = 𝜇Rads [162], where 𝜇e is the electrochemical potential of electron),
because the net electrochemical potentials are identical for reactants and products of a
self-exchange reaction as given by
𝜇 Oads + 𝜇R = 𝜇Rads + 𝜇O (1.27)
Accordingly, it is a misconception that a self-exchange reaction is important in the
model of ET kinetics based on equilibrium adsorption [55]. By contrast, adsorption
isotherms, e.g. Langmuir isotherms for competitive adsorption (Eqs. (1.6) and (1.7)),
can be used to calculate the equilibrium constant of self-exchange reaction, K ex , to yield
[112]
[ ]
0′ 0′
nF(EIS − EOS ) ΓR,s 𝛽R
Kex = exp = (1.28)
RT ΓO,s 𝛽O
This equation reconfirms that the equilibrium of the self-exchange reaction is
determined by the equilibrium of heterogeneous ET and surface adsorption and is
independent of electrode potential. Moreover, Eq. (1.28) gives K ex = 1 when outer and
inner-sphere ET occurs simultaneously with ΓO,s 𝛽 O = ΓR,s 𝛽 R = Γs 𝛽 and, subsequently,
0′ 0′ ′
EIS = EOS = E0 in Eq. (1.5). In this case, forward and reverse rate constants, kfex and kbex ,
respectively, of the self-exchange reaction are identical, because of Kex = kfex ∕kbex .
A self-exchange reaction can be kinetically controlled and distinguished from
other steps only when at least one of adsorption steps and one of ET steps is kinet-
ically controlled [112]. Importantly, Anson indicated that a self-exchange reaction
is a second-order reaction and can be kinetically distinguished from outer- and
inner-sphere ET [29]. Quantitatively, the corresponding rate of self-exchange reaction,
vex , is given by
vex = kfex ΓO CR (0, t) − kbex ΓR CO (0, t) (1.29)
where ΓO and ΓR also vary with C O (0, t) and C R (0, t), respectively, to follow the
second-order kinetics. The self-exchange reaction does not directly contribute to a
current response in contrast to outer- and inner-sphere ET. The self-exchange reaction,
however, is still relevant, because it affects concentrations of a redox couple on and near
the electrode surface. DuVall and McCreery proposed that dopamine (DA) oxidation
to dopamine-o-quinone (DOQ) can be medicated through not only an inner-sphere
pathway, but also a self-exchange pathway [163] (Figure 1.12).
1.8 Resolving Outer- and Inner-Sphere ET

Attempts were made to resolve outer- and inner-sphere ET of a redox couple, and,
0 0
subsequently, determine kOS and kIS values separately. For instance, Laviron employed
0
fast-scan CV [42] to determine kIS values from surface waves [164] for small aromatic
molecules adsorbed on mercury electrodes in the aqueous media [165–168]. In these
0
studies, kOS values were not determinable, because both outer- and inner-sphere ET
DAsoln Figure 1.12 Schematic models for

DAads
adsorption-dependent oxidation of DA to DOQ
DAads DAsoln through (a) inner-sphere and (b) self-exchange
DAads DAads pathways with apparent standard rate
o
o
kapp DOQads constants, kapp . Source: Reprinted with
o
kapp permission from DuVall and McCreery [163].
DAads Copyright 2000 American Chemical Society.
DOQads
DAads
DOQsoln
DOQads
DOQsoln DAads
(a) (b)
were driven simultaneously owing to similar adsorptivities of oxidized and reduced

0′ 0′
forms [42], i.e. EIS ≈ EOS , and were unresolvable at slow scan rates. Accordingly,
0
kOS values were measured without surface adsorption in the non-aqueous media
0
and used in Eq. (1.26) to yield kIS values that were similar to those measured in the
aqueous media. More recently, Amatore and coworkers employed fast-scan CV to
resolve outer- and inner-sphere pathways for the reduction of benzyl chloride at silver
0 0
electrodes [22]. In this study, kOS and kIS values were separately determinable, because
the corresponding voltammetric waves were observed at separate potentials (∼0.6 V)
when the scan rate was fast enough. We are unaware of any report where outer- and
inner-sphere ET that occur at similar potentials were resolved, which is possible in
principle when adsorption equilibrium is not maintained.
Recently, we investigated DA oxidation by fast-scan NV based on double-CF UMEs
with a nanometer-wide gap [148] (Figure 1.13), which may serve as a powerful approach
to resolve outer- and inner-sphere ET. Double-CF UMEs were originally developed to
improve the time resolution of NV by employing fast scan rates of up to 100 V s−1 ,
which is ∼1000 times faster than reported with any nanogap-based electrochemical
cell (i.e. ≤0.1 V s−1 [33]). We simulated fast scan NV at double-cylinder UMEs with a
nanometer-wide gap as a model of two CFs sealed in a glass capillary [169]. Simulated
NVs fitted well with experimental NVs based on voltammetric responses to Ru(NH3 )6 3+
at a CF generator electrode and amperometric responses to Ru(NH3 )6 2+ at a CF collec-
tor electrode at up to 100 V s−1 to determine consistent gap widths of ∼0.18 μm and a
k 0 value of 0.9 cm s−1 (Table 1.3). Advantageously, a transient background response of
amperometric collector electrode was suppressed ∼100 times in comparison with that
30 μm 4 μm
(a) (b)
Figure 1.13 Scanning electron microscopy of (a) a double-CF UME sealed in a glass capillary and (b) a
nanogap between CFs. Source: Reprinted with permission from Pathirathna et al. [148]. Copyright
2018 American Chemical Society.
of the voltammetric generator electrode, thereby eliminating the need for background
subtraction for quantitative data analysis.
Double-CF UMEs voltammetrically oxidize DA at a generator electrode to pro-
duce DOQ, which is amperometrically detected at a collector electrode separated
by a ∼180 nm-wide gap. In principle, DA oxidation can be mediated both outer-
and inner-sphere pathways to produce both adsorbed and non-adsorbed forms of
DOQ. These pathways were unresolvable at slow scan rates (0.1 V s−1 in the top
panel of Figure 1.14a), where diffusional voltammograms with a sigmoidal shape can be
attributed to an outer- or inner-sphere pathway, or both [170], i.e. the Laviron–Amatore
paradox. An inner-sphere pathway was manifested at faster scan rates (100 V s−1 in the
top panel of Figure 1.14b) to yield surface waves at the generator electrode without
a diffusional character. Accordingly, voltammetry at the single generator electrode
cannot assess whether DA oxidation can be mediated through an outer-sphere pathway.
By contrast, corrector responses were sigmoidal without an adsorption feature at all
scan rates (the bottom panels of Figure 1.14a,b). At fast scan rates (e.g. 100 V s−1 ),
forward peaks at 0.45 V were due to capacitive coupling with the generator response
and were not due to DOQ reduction at the collector electrode, because the forward
peaks were observed even when the collector potential was too positive to reduce
DOQ. Qualitatively, the sigmoidal shape of the collector response is attributed to the
reduction of only DOQ that was generated through an outer-sphere pathway at the gen-
erator electrode, because the desorption of DOQ generated through an inner-sphere
pathway at the generator electrode was too slow to yield a transient response at the
collector electrode. More quantitatively, ∼35% of DOQ should be desorbed from
the generator electrode with a desorption rate constant of 22 s–1 [170] during the
20
Collector Current (nA) Generator Current (μA)
1 100 V/s
Collector Current (nA) Generator Current (nA)
0.1 V/s
10
0
0
–1
80
0
40
0
–10
–40
–20 –80
–0.5 0.0 0.5 1.0 –0.5 0.0 0.5 1.0
Generator Potential (V vs Ag/AgCl) Generator Potential (V vs Ag/AgCl)
(a) (b)
Figure 1.14 Generator and collector current responses of double-CF UMEs at (a) 0.1 and (b) 100 V s−1
in Tris buffer containing 0 (black), 50 (blue), and 100 (red and green for first and second cycles,
respectively) μM DA. Collector potential at −0.3 V. Source: Reprinted with permission from Pathirathna
et al. [148]. Copyright 2018 American Chemical Society.
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duty, which I received out of respect for her real excellence of heart,
and thanked her in a manner which made Sir Peter my friend for life.
Daphne said not a word when I took her hand, but handing me a little
parcel ran out of the room. I afterward found it to be a little housewife
made by her own hands.
I went down to the chaise, puzzled at her conduct, but, looking up
for the last time to the windows, I saw her peering from behind a
curtain. I raised the parcel to my lips, and, as she saw it, a smile
broke over her face. My last glimpse of her was like an April day,—
she was all smiles and tears,—and it was destined to remain in my
memory.
Giles Vernon was waiting for me at the corner of the street. We
were to make the journey to Plymouth together.
“Well,” he cried, when we found ourselves rolling along to meet
the coach, “I have had my cake and eaten it.”
“How I envy you!” I said bitterly. “I have not had my cake. Every
shilling of my prize-money is in bank, except about two hundred
pounds.”
“Poor chap!” answered Giles feelingly. “How much more of life
have I seen in London than you! I have seen everything, including
that queen of hearts, Lady Arabella Stormont. She has treated me
cruelly, the jade! But I will bring her to my hand at last, that I swear to
you.”
I longed that he might know of that episode with Overton in Sir
Peter Hawkshaw’s cubby-hole at five o’clock in the morning.
We had a pleasant journey to Plymouth, and were troubled with
few regrets at leaving London. We expected, in the foolishness of
youth, to capture many more such prizes as the Indomptable and
Xantippe. The Belvidera was nearly ready, and in a few weeks we
sailed on our second cruise. I shall not give the particulars of that
cruise. It was such an one as all the officers of his Majesty’s service
were engaged in, during those eventful years. We were constantly at
sea; we kept a tireless lookout for our enemies, and hunted and
pursued them into their own harbors. We never slept for more than
four hours at a time, in all our cruising. We lived on beef and biscuit
for months at a time; sometimes we had scurvy in the ship, and
sometimes we did not. We struggled with mighty gales, that blew us
hundreds and even thousands of miles out of our course; and we
sweltered in calms that tried men’s souls. In all that time, we
watched night and day for the enemy, and, when found, chased him,
and never failed to get alongside when it was possible; and we
fought him with the greatest good-will. We had good and ill fortune
with the ship, but her colors were never lowered. And it was five
years before we set foot in London town again.
Only a year of that time was Giles Vernon with me. He then got
promotion which took him out of the ship. I had the extreme good
fortune to be with Nelson at the Nile. On that great day, as sailing-
master of the Belvidera, I took the frigate around the head of Admiral
Villeneuve’s line,—she was the leading ship,—and placed her where
she was enabled to fire the first raking broadside of the battle. I got a
wound in the forehead which left a scar that remains to this day; but I
also received the personal thanks of my Lord Nelson, which I shall
ever esteem as the greatest honor of my life. I had heard nothing of
Giles for nearly a year, when, among Admiral Villeneuve’s officers, I
found one, a young lieutenant like myself, who told me that Giles had
been captured, while on a boat expedition, and was then in prison at
Dunkerque.
I wrote him a dozen letters at least, by officers who were paroled;
and when the ship was paid off, the following spring, I lost no time in
getting to London, and using what little power I had in trying to have
him exchanged. Sir Peter was in great favor at the Admiralty. As
soon as I reached London, I went immediately to call in Berkeley
Square. My Lady Hawkshaw was at home, and received me in great
state, black feathers and all; and with her sat Daphne Carmichael.
I believe Lady Hawkshaw was really glad to see me; but Daphne,
after speaking to me, remained with her eyes fixed on her
embroidery, I noted, however, that she was a very charming girl, and
her eyes, under her long, dark lashes, were full of fire and
sweetness. But she had not, and never could have, the glorious
beauty of Lady Arabella Stormont. Lady Hawkshaw demanded of me
a particular account of my whole cruise, and everything that had
happened at the battle of the Nile. This I gave, to the best of my
ability. She then invited, or, rather, commanded me to take up my
quarters in Berkeley Square, and told me that I had three thousand
and ten pounds, nineteen shillings and seven-pence to my credit in
bank.
After this, she was called upon to leave the room for a moment,
and I civilly inquired of Daphne how Lady Arabella was.
“She is well,” responded Daphne, rather tartly, I thought; “and as
devoted to Captain Overton as ever. You know Arabella ever liked
him rather more than he liked her.” At which ungenerous speech, I
said one word, “Fie!” and Daphne, coloring to the roots of her hair,
yet attempted to defend herself.
“I only tell you what all the world says, and so say my uncle and
aunt. Arabella could have married a dozen times,—she is all of
twenty-one, you know,—and married very splendidly, but she will not.
Sir Peter rages, and swears that he will marry her off in spite of
herself; but Arabella is her own mistress now, and laughs at Sir
Peter.”
“And does she still play cards?”
Daphne raised her eyes. It seemed to give that otherwise sweet
girl positive pleasure to call over Lady Arabella’s faults.
“Yes,” she said. “Loo, lansquenet—anything by which money can
be lost or won. Three times a week she goes to the Duchess of
Auchester’s, where play is high. We go there to-night; but I do not
play.”
I had not thought there was so much malice in Daphne, until that
conversation.
I left my adieux for Lady Hawkshaw, and repaired to the
Admiralty, where Sir Peter happened to be, that day. I explained that
I should have come to him at once, but for my inordinate wish to see
Lady Hawkshaw; and that I found her looking at least twenty years
younger since we met last. At which Sir Peter beamed on me with
delight, and, I believe, mentally determined to give me a thousand
pounds additional, in his will.
I then stated my real business, which was to get Giles Vernon
exchanged; and Sir Peter, without a moment’s hesitation, agreed to
do all he could for me; and then, as usual, directed me to have my
portmanteau sent to Berkeley Square, as Lady Hawkshaw had done.
Before I left the Admiralty, machinery had been put in motion to
secure Giles Vernon’s exchange. I returned to Berkeley Square, and
again took up my abode there.
VII
One month from the time I arrived in London, I was on my way to
Portsmouth to meet Giles Vernon, who had been brought over with a
batch of exchanged officers from France.
In that month, during which I had lived continuously in Berkeley
Square, things were so little changed, except in one respect, which I
shall mention presently, that I could scarcely persuade myself five
years had passed. Peter and Polly, as Giles disrespectfully called
them, had not grown a day older, and quarreled as vigorously as
ever. Lady Arabella was then her own mistress, although still living
under Sir Peter’s roof; but, as far as I could see, this spoiled child of
nature and fortune had always been her own mistress. I found that
Overton had been away for some years on foreign service, and, after
distinguishing himself greatly, had lately returned suffering from
severe wounds and injuries to his constitution. He was, however, in
London, and able to ride and walk out, and visit his friends; but it was
doubted by many whether, on the expiration of his leave, he would
ever be fit for duty again.
I heard and saw enough to convince me that Lady Arabella had
been wild with grief and despair when she heard of his wounds; and,
although since his return to London he avoided company generally,
she managed to see him occasionally, and spent much of her time
driving in the parks upon the mere chance of seeing him taking his
daily ride or walk. Lady Arabella Stormont had everything in life that
heart could wish, except one. She had chosen to give her wilful and
wayward heart to Philip Overton, and it must be acknowledged that
he was a man well fitted to enchain a woman’s imagination. Overton
had disdained the spontaneous gift of Arabella’s love; but I believe
her haughty and arrogant mind could never be brought to believe
that any man could be really insensible to her beauty, her rank, and
her fortune. Overton could not in any way be considered a great
match for her. His fortune was modest, and his chance of
succeeding to the Vernon estates remote; but, with the desperate
perversity of her nature, him she would have and no other. It always
seemed to me as if Overton were the one thing denied her, but that
she had determined to do battle with fate until she conquered her
soul’s desire.
For myself, she treated me exactly as she had done five years
before,—called me Dicky in her good humors, and a variety of
sneering names in her bad humors,—and, little as it may be
believed, I, Richard Glyn, lieutenant in his Majesty’s sea-service,
with three thousand pounds to my name, would have gone to the
gibbet rather than marry Lady Arabella, with her thirty thousand
pounds.
Perhaps Daphne Carmichael had something to do with it. She
was the same gentle, winning creature at nineteen as at twelve. She
was still Sir Peter’s pet, and Lady Hawkshaw’s comfort; but I had not
been in the house a week before the change I alluded to came
about, and the change was in me concerning Daphne. I began to
find it very hard to keep away from her. She treated me with great
kindness before others, but when we were alone together, she was
capricious. I began to despair of ever finding a woman who could be
kind to a man three times running. And I was very much surprised at
the end of a fortnight to find myself experiencing the identical
symptoms I had felt five years before, with Arabella—only much
aggravated. There was this difference, too. I had admired Arabella
as a star, afar off, and I think I should have been very much
frightened, if, at the time, she had chosen formally to accept my
devotion. Not so with Daphne. I felt I should never be really at ease
until I had the prospect of having her by my side the rest of my life. I
reached this phase at the end of the third week. At the end of the
fourth, I was in a desperate case, but it was then time to go to
Portsmouth to meet Giles, according to my promise, and I felt, when
I parted from Daphne, as if I were starting on a three years’ cruise,
and I was only to be gone a day and a half. She, dear girl, showed
some feeling, too, and I left, bearing with me the pack which every
lover carries,—pains and hopes.
I left London at night, and next morning on reaching Portsmouth,
as I jumped from the coach, I ran into Giles’ arms; he had reached
Portsmouth some hours in advance of the time.
He showed marks of his imprisonment in his appearance, but his
soul had ever been free, and he was the same brave and joyous
spirit I had ever known. Not being minded to waste our time in
Portsmouth, we took coach for London town at noon. As we were
mounting, a countryman standing by held up a wooden cage full of
larks, and asked us to buy, expatiating on their beautiful song.
“I will take them all, my lad,” cried Giles, throwing him a guinea.
The fellow gaped for a moment, and then made off as fast as his
legs could carry him. I wondered what Giles meant to do with the
birds. He held the cage in his hand until we had started and were
well into the country; then, opening the little slide, he took out one
poor, fluttering bird, and, poising on his finger for a moment, the lark
flew upward with a rush of joyous wings.
Each bird he liberated in the same way, all of us on the coach-top
watching him in silence. As the last captive disappeared in the blue
heavens, Giles, crushing the cage in his strong hands, threw it away.
“I have been a prisoner for fourteen months,” he said, “and I shall
never see any harmless living thing again imprisoned without trying
to set it free.”
We reached London that night, and Giles went to his old
lodgings, where his landlady was delighted to see him, as all women
were who knew Giles Vernon. She gave us supper, and then we sat
up all night talking. I had thought from the guinea he had thrown the
vender of larks, that he had money. I found he had none, or next to
none.
“And how I am to live until I get another ship, I am at a loss, my
boy,” he cried, quite cheerfully. “Two courses are open to me—play
and running away with an heiress. Do you know of a charming girl,
Dicky, with something under a hundred thousand pounds, who could
be reconciled to a penniless lieutenant in his Majesty’s navy? And
remember, she must be as beautiful as the dawn besides, and of
good family, and keen of wit—no lunkhead of a woman for me.” To
this, fate impelled me to reply that Lady Arabella Stormont was still
single.
“Faith!” cried Giles, slapping his knee, “she is the girl for me. I
always intended to marry her, if only to spite her.”
I was sorry I had raked up the embers of his passion of five years
before, and attempted to cover my step by saying,—
“She is still infatuated with Overton, whom, however, she sees
rarely, and that only at the houses of others; but he has ever looked
coldly upon her.”
“She’ll not be coldly looked on by me. And let me see; there is
her cousin you used to tell me about,—the Carmichael girl,—
suppose you, Dicky, run away with her; then no two lieutenants in
the service will have more of the rhino than we!”
I declare this was the very first time I had remembered Daphne’s
thirty thousand pounds. She had the same fortune as Lady Arabella.
The reflection damped my spirits dreadfully.
Giles saw it directly, and in a moment he had my secret from me.
He shouted with delight, and immediately began a grotesque
planning for us to run away with the two heiresses. He recalled that
the abduction of an heiress was a capital crime, and drew a fantastic
picture of us two standing in the prisoners’ dock, on trial for our lives,
with Lady Arabella and Daphne swearing our lives away, and then
relenting and marrying us at the gallows’ foot. And this tale, told with
the greatest glee, amid laughter and bumpers of hot brandy and
water, had a singular effect upon me. It sobered me at once, and
suddenly I seemed to see a vision, as Macbeth saw Banquo’s ghost,
passing before my very eyes,—just such a scene as Giles described.
Only I got no farther than the spectacle of Giles a prisoner in the
dock, on trial for his life. My own part seemed misty and confused,
but I saw, instead of the lodging-house parlor, a great hall of justice
dimly lighted with lamps, the judges in their robes on the bench, one
with a black cap on his head, and Giles standing up to receive
sentence. I passed into a kind of nightmare, from which I was
aroused by Giles whacking me on the back and saying in a surprised
voice,—
“What ails you, Dicky boy? You look as if you had seen a ghost.
Rouse up here and open your lantern jaws for a glass of brandy and
rid yourself of that long face.”
I came out of this singular state as quickly as I had gone into it,
and, ashamed to show my weakness to Giles, grew merry, carried
on the joke about the abduction, and shortly felt like myself, a light-
hearted lieutenant of twenty-one. I proposed that we should go to the
play the next night,—or rather that night, for it was now about four in
the morning,—and shortly after we tumbled into bed together and
slept until late the next day.
Giles and I went to Berkeley Square in the afternoon, professing
just to have arrived from Portsmouth. Giles expressed his thanks in
the handsomest manner to Sir Peter for his kindness, and made
himself, as usual, highly agreeable to Lady Hawkshaw. Neither Lady
Arabella nor Daphne was at home, but came in shortly after Giles
had left. Lady Arabella made some slighting remark about Giles, as
she always did whenever opportunity offered. Daphne was very kind
to me, and I gave her to understand privately that I was ready to haul
down my flag at the first summons to surrender.
The family from Berkeley Square were going to the play that
night, and I mentioned that Giles and I would be there together. And
so, just as the playhouse was lighting up, we walked in. After the
curtain was up, and when Mrs. Trenchard was making her great
speech in Percy, I motioned Giles to look toward Lady Hawkshaw’s
box. Her ladyship entered on Sir Peter’s arm; his face was very red,
and he was growling under his breath, to which Lady Hawkshaw
contributed an obligato accompaniment in a sepulchral voice; and
behind them, in all the splendor of her beauty, walked Lady Arabella,
and last, came sweet, sweet Daphne.
The first glimpse Giles caught of Lady Arabella seemed to renew
in an instant the spell she had cast on him five years before. He
seemed almost like a madman. He could do nothing but gaze at her
with eyes that seemed starting out of his head. He grew pale and
then red, and was like a man in a frenzy. It was all I could do to
moderate his voice and his looks in that public place. Luckily, Mrs.
Trenchard being on the stage, all eyes were, for the time, bent on
her.
I hardly knew how we sat the play out. I had to promise Giles a
dozen times that the next day I would take him to Berkeley Square.
When the curtain went down, he fairly leaped his way out of the
playhouse to see Lady Arabella get into the coach.
That was a fair sample of the way he raved for days afterward.
He haunted Berkeley Square, where he was welcomed always by Sir
Peter and Lady Hawkshaw, asked to dine frequently, and every mark
of favor shown him.
Lady Arabella remained cold and indifferent to him. About that
time Overton appeared a little in his old haunts, although much
changed and sobered. Neither wounds nor illness had impaired his
looks and charms, but rather he had become an object of interest
and sympathy from his gallant behavior in the field. Sir Peter, who
had always liked him, began to pester him to come to Berkeley
Square, which he did a few times, because he could not well decline
Sir Peter and Lady Hawkshaw’s pressing and friendly invitations. I
believed, however, that in spite of his forced composure he felt
cruelly abashed before Lady Arabella. She, however, showed an
amazing coolness, and even began to be a little kind to Giles, from
some obscure motive of her own. I believe every act of her life with
regard to men had some reference to her passion for Overton.
She suddenly fell into my arms. Page 145
All this time, though, from the night of the play, Daphne and I had
been secretly happy; for on the very next day, catching her alone, I
told her, in plain and seamanlike language, that I loved her, and
when she showed a disposition to cut and run, I said to her, very
boldly,—
“Since you scorn my love, I have the resource that every one of
my calling has in these days. I shall soon go to sea, and upon the
deck of my ship I can find death, since life is nothing to me without
my Daphne’s love.”
At which, without the least warning, she suddenly fell into my
arms, crying,—
“You’ll break my heart, if you talk in that way!” and I perceived
that she was only manœuvering for position.
I do not know exactly what happened next, except I was in that
heaven, Daphne’s arms, when I looked up and caught the butler and
two footmen grinning at me. But it mattered not.
Next morning Daphne and I met in the drawing-room, as usual,
after breakfast; but what a meeting it was! We had barely time to
scuttle back to our chairs when Sir Peter entered with the
newspaper, and informed me that the Bellona frigate was being fitted
for the West Indies, and he thought he could get me a berth in her, at
which I felt myself grow weak in the knees, so great is the power of
love.
Presently he went out. Then Daphne and I began to speculate
upon Sir Peter’s personal equation in our affairs.
“He will never let me marry you,” she said. “He will say I am too
young.”
This depressed me so that I could say nothing in reply. Daphne
continued, quite in an offhand manner,—
“If we should elope, he would make a great hullabaloo.”
This admirable suggestion at once commended itself to me.
“His hullabaloo could not separate us, if we were married,” I
replied.
“True,” said Daphne; “and after all, he and Lady Hawkshaw as
good as eloped, and she was but eighteen—a year younger than I.”
Thus was I supplied with another argument.
I again swear that I had not a thought of Daphne’s fortune in all
this. I would have taken the dear girl with nothing but the clothes
upon her back.
True to his word, Sir Peter worked like a Trojan to get me a berth
on the Bellona, and, meaning to do Giles the greatest service in the
world, tried likewise for him; and mightily afraid we were that he
would soon succeed.
This brought matters to a crisis with Daphne. I mentioned the
word “elope” to her again, and she made a great outcry, after the
manner of young women, and then began straightway to show me
precisely how it might be done, protesting, meanwhile, that she
would never, no, never, consent. We both agreed, though, that it was
proper we should lay the matter of our marriage before Sir Peter and
Lady Hawkshaw; but I saw that Daphne, who was of a romantic turn,
had her imagination fired by the notion of an elopement.
“A pair of good horses and a light traveling chaise!” she
exclaimed. “If only it were not wrong!”
“No, no! Four horses!” cried I, “and there is nothing wrong in
either a two or a four horse chaise.”
Daphne clapped her hands.
“A trip to Scotland—I have always longed for Scotland. I know a
dozen people who have married in Scotland, and happy marriages,
every one of them. But I forbid you, Richard, to think of an
elopement.”
“We shall set out at midnight; we shall not be missed until
morning, and we shall have at least twelve hours’ start. Then, at
every stage, we shall leave something behind, which will ensure a
broken axle, or a linchpin gone, for our pursuers.”
We were both so charmed with the picture we had conjured up,
that when I said, “Suppose, after all, though, that Sir Peter
consents?” Daphne’s face fell; but presently she smiled, when I said,
—
“If he does consent, why, then, there is no harm in our marrying
any way we like, and he will excuse us for running away. And if he
does not consent, there is no help for it,—we must elope!”
I considered myself a casuist of the first order. I felt obliged to
take the first opportunity of letting Sir Peter know the state of affairs,
and, as usual, I determined to begin through Lady Hawkshaw.
“And,” as Daphne shrewdly remarked, “they will certainly differ,
so we shall at least have one of them on our side.”
I sought Lady Hawkshaw, and found her in her usual place, in the
Chinese room. I began, halting, stammering, and blushing, as if I
were a charity school-boy, instead of a lieutenant in his Majesty’s
service, who had been thanked by Lord Nelson.
“M-m-my lady,” I stuttered, “I have experienced so much k-k-
kindness from you that I have come to you in the greatest
emergency of my life.”
“You want to get married,” promptly replied Lady Hawkshaw.
I was so staggered by having the words taken out of my mouth,
that I could only gape and stare at her. To render my confusion
worse, she added,—
“And you want to marry Daphne.”
“I can not deny it, Madam,” I managed to say.
“Will you ring the bell?” she asked.
I rang the bell like a churchwarden, and the footman came, and
Lady Hawkshaw immediately sent him for Sir Peter.
I think my courage would wholly have given out at that, except for
a glimpse of Daphne, flitting up the stairs. The dear girl wished to
give me heart, so she told me afterward.
Sir Peter appeared, and was greeted by Lady Hawkshaw as
follows:—
“Sir Peter, here is Richard Glyn wanting to marry Daphne. He has
but three thousand pounds; but she might go farther, and fare
worse.”
Sir Peter literally glared at me. He gasped once or twice, then
broke out in a torrent.
“He wants to marry my ward, does he—my ward, with thirty
thousand pounds, in her own right! I wonder, damme, he didn’t
propose to marry Arabella, too. Young gentleman, you are too
modest. Heiresses in England go about hunting for poor lieutenants
to marry. I suppose you think it would be a fine stroke for me to
marry my ward to my nephew! Ha, ha! Ho, ho!”
His laughter was demoniac.
“Sir Peter,” said Lady Hawkshaw severely,—for I remained mute,
—“I am astonished at your violence and unreason. Did you never
hear of an heiress—and a fine, handsome girl, too, with many
accomplishments, and of a great family—marrying a poor lieutenant
without a penny, and without an ancestor?”
“By Jupiter, I never did!” roared Sir Peter.
“Then, Sir Peter,” cried Lady Hawkshaw, rising with awful dignity,
“you forget all about Lieutenant Peter Hawkshaw and the Honorable
Apollonia Jane Howard.”
At this, Sir Peter fairly wilted for a few moments; and I heard
something strangely like a tittering in the next room.
But Sir Peter presently recovered himself in a measure.
“But—but—there are lieutenants and lieutenants, Madam, I was
considered a man likely to rise. And besides, if I remember rightly, I
was not an ill-looking fellow, Madam.”
“Sir Peter, you were no taller then than you are now—five feet
four inches. Your hair was red, and you were far from handsome.
Richard Glyn is as good-looking as you ever were in your life; and he
has already made his mark. Richard Glyn,” turning to me, “you are at
liberty to marry Daphne Carmichael.”
“Richard Glyn,” bawled Sir Peter, “if you dare to think you are
going to marry Daphne Carmichael,—mind, I say, if the thought ever
enters your damned head,—it will be as much as your life is worth! I
am going, this moment, to the First Lord of the Admiralty, to see if I
can’t have you sent to the West Indies, or the Gold Coast, with my
best wishes and endeavors to keep you there for ten years at least.”
“And what will you do with me, dear Uncle Peter?” suddenly
asked a soft voice; and Daphne, who had stolen into the room (she
must have been very near), stood before him, and nestled her pretty
head against his shoulder.
Sir Peter was too astonished, for a moment or two, to speak. The
whole thing had fallen upon him like the shock of an earthquake. But
in a little while he recovered his voice, and all of his voice, too; he
shouted as if he were on the bridge of the Ajax, with a whole gale
blowing, and the enemy in sight.
“Do!” he shrieked. “What shall I do? Bread and water, miss, for
six months! Discipline, miss!” And much more of the same sort.
This roused Lady Hawkshaw to take our part. She shouted back
at Sir Peter; and I, not to be outdone, shouted that Daphne was
mine, and I was hers, as long as life should last; and presently Sir
Peter flung out, in a royal rage, and Lady Hawkshaw flung after him;
and Daphne sank, in tears, on my shoulder, and I kissed her a
hundred times, and comforted her. But I knew Sir Peter was a
determined man, in some respects; and I felt assured he would
shortly carry out his threat to send me to sea, and, once at sea, it
might be years before I should again set foot in England. Scotland,
then, sounded sweetly in our ears. I found, in truth, that when it
came actually to going off, Daphne’s romantic willingness changed
to a natural hesitation at so bold a step. But the near prospect of
going to the Bellona turned the scale in my favor, and I won from her
a sort of oblique consent. And another thing seemed to play directly
into our hands. Sir Peter had business at Scarborough, which might
detain him some time; and, although it was late in the autumn, he
determined to take his family with him. I believe it was by way of
separating Daphne and me that he came to the decision. Lady
Hawkshaw was to go, and his two wards; and they were to remain a
month. This was so obviously showing us the road across the
border, that I told my sweet Daphne, plainly, I should carry her off; at
which she wept more, and protested less, than I had yet seen her.
In the whole affair, I had counted upon the assistance of Giles
Vernon; and on the very night the party left for Scarborough, after a
tearful farewell between Daphne and me, I went to Giles’ lodgings, to
make a clean breast of it.
Giles’ voice called me up stairs; and when I reached his room,
there, spread out on the bed, I saw a beautiful suit of brown and
silver.
“Do you see that?” cried Giles. “That is my wedding suit. For it I
spent fifty of the last hundred pounds I had in the world, and it is to
marry Lady Arabella Stormont that I bought it.”
I thought he was crazy, but I soon perceived there was method in
his madness. He told me seriously enough that he meant to carry off
Lady Arabella Stormont from Scarborough.
“But—but—she does not like you,” I said, hesitating and amazed.
“We shall see about that, my lad,” he said, and then began to tell
me of what he thought a great change in his favor with Arabella. He
put many trifling things which I had not noted in such a light that
under his eloquent persuasion I began to believe Lady Arabella
really might have a secret weakness for him, which pride prevented
her from discovering. He had never failed to win any woman’s regard
yet; and it had always seemed a miracle to me, Richard Glyn, who
had fallen under his spell so many years ago, how anybody could
resist him. He wound up his argument by saying, in his usual
confident manner,—
“Trust me, there is something compelling in the love I feel for
Arabella. Women are all alike, my boy. They want a master. Once
put the bit in their mouths, and they adore you for it. Let me have the
spirit to run away with that adorable creature, and see how quickly
she will come to my call. You will shortly see her clinging to me like
peaches to a southern wall.”
“And her fortune?”
“She is none the worse for that. But I swear to you, Dicky Glyn,
that I would carry her off as the Romans did the Sabine maidens, if
she had not a shilling,”—which I believed to be true; for his was an
infatuation which takes account of nothing.
He then began to tell me of his plans, and in them he showed his
usual shrewdness and boldness. The trip to Scarborough had put
Scotland in his head. He was likely to be sent to sea any day, to be
gone, perhaps, for years; just the arguments I had used to myself
first and to Daphne afterward.
I remembered that scene five years before, with Overton and
Lady Arabella in Sir Peter’s cubby-hole; and the memory of it made
me think with dread of Giles Vernon’s marrying Arabella. But I could
not speak openly; and, after all, she was so strange a creature that
one could scarcely judge her by the standard of other women. And
then the plan I had to confide to him very effectually withdrew the
charges of any battery I might have brought to bear on him.
When he had finished his tale, and I had told mine, Giles was in
an ecstasy. He laughed in his uproarious good humor.
“Oh, you sly dog!” he shouted. “So you are up to the same
game!”
I explained that I had not much to fear. Daphne was undoubtedly
fond of me, and Lady Hawkshaw being on our side, and other
reasons in our favor,—all of which fitted Giles’ case exactly. And at
last I gave up, in sheer despair, and agreed to Giles’ suggestion that
we should together carry off the two damsels of our hearts; and then
and there we made our plans, sitting up until the gray dawn came.
Oh, the madness of it! the wildness of it! But we were two dare-
devil and happy-go-lucky lieutenants, without the prudence of
landsmen. We loved, and we were liable at any moment to be torn
away for many years from the idols of our hearts. Runaway
marriages were common; and only the parents and guardians were
offended in those cases, and forgiveness generally followed. We
were about to commit a great folly; but we thought we were nobly
sustaining the reputation of his Majesty’s sea-officers for our spirit
and gallantry with the fair sex, and looked not to the dreadful
consequences of our desperate adventure.
VIII
Giles Vernon and I agreed that it was necessary we should strike
the blow as soon as possible, while we had the weather-gage, so to
speak, of Sir Peter; and on the day after his traveling chariot took its
way north, a very plain post-chaise followed it, and in it were Giles
Vernon and myself.
Giles was in a state of the wildest happiness conceivable. There
is something appalling in that fervor of mind when the human
creature, forgetting all the vicissitudes of this life, treads on air and
breathes and lives in Heaven. Thus I was made sad by his gladness,
but I dared not show it, lest it be mistaken for a want of spirit in our
enterprise, so I joined with him in his joy and revelry.
We reached Scarborough at four o’clock in the afternoon, and put
up at a small inn on the outskirts of the town, and some little way on
the road to the north. We sallied forth immediately to find out
something about our inamoratas, and Fate—whether it was that
kindly goddess who leads our footsteps toward those we love, or
whether it was the cruel Destiny which delights in torturing men—at
once directed us. We were walking along near the playhouse, which
had been lately opened in the town, when we saw Jeames, Lady
Hawkshaw’s own footman, go inside the playhouse and buy some
tickets of the man at the door. As soon as he was well out of the way
I sneaked in, and, thrusting two shillings into the man’s hand,
inquired if Sir Peter and Lady Hawkshaw and the young ladies would
favor the performance that night. The man grinned and showed me a
slip of paper, on which was written in Lady Hawkshaw’s bold hand,
“Three stalls for Lady Hawkshaw and party.”
This made me hope that Sir Peter would not be present, for I
thought our chances of getting off would materially improve if he
were not on the spot.
The play was to be over at half-past ten, and it may be imagined
that we had plenty to do until then. We engaged four of the best
pairs of nags in the town. We arranged to pay the postboys
according to the time they took us over the border, and we felt in
ourselves the strength of Titans, to overcome whatever resistance
might be offered. Of course we counted on the surprise, and we
determined that the best disposition to make of Lady Hawkshaw was
for Giles Vernon to appear suddenly, when the people were coming
out, place Lady Hawkshaw in her coach, and then make that bold
dash for love and beauty which we had determined upon. Our
postboys, who were not new to the perils of elopements, grinned at
the prospect, and were instructed to remain near Lady Hawkshaw’s
coach and impede it as much as possible, so that it might be the last
to reach the door of the theater.
Our arrangements were complete by eight o’clock, and from that
hour until ten we employed ourselves in disposing of a good supper
at the tavern. We were in a gale of rapture then. It seemed to us both
as if we were in that happy and exultant mood, when the enemy is
within gun-shot and the ship is cleared for action; and we only
awaited the signal for victory. We had some punch, but both Giles
and myself knew enough to be exceedingly careful in attacking it.
“Dicky, my lad,” cried Giles, banging me in the back, “this day is
the anniversary of the day we whipped the Indomptable and the
Xantippe!”—and so it was. “So we shall capture the Indomptable, in
the Lady Arabella, and we will disable the Xantippe,—ha! ha!—in my
Lady Hawkshaw.”
This I thought a very fine joke indeed, and we drank to it.
“Dicky,” began Giles again, wiping his mouth after the punch, “I
never thought I could be constant to any woman, as I have been to
Arabella. By Heaven, the whole sex is so seductive that it was the
last one I saw I loved the best. But since I knew that witch of a girl,
St. Anthony himself could not be more impervious to female charms
than your humble servant,” which was true enough. “And as for
Overton,—that psalm-singing devil,—I defy him. Give me but a
week, and he shall see Arabella hanging upon me so fondly! Let him

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Figure 1.1 The reaction scheme of outer- and

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(b) 2rg (d)

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SG/TC Mode SG/TC Mode

Feedback Mode Feedback Mode

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