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com Current Opinion in

ScienceDirect Electrochemistry

Editorial overview: Fundamental and theoretical

electrochemistry (2022) as a tool for developing
electrochemical science and technology
Rama Kant and M. V. Sangaranarayanan
Current Opinion in Electrochemistry
2022, 36:101162
This review comes from a themed issue on
Fundamental & Theoretical Electrochemistry
(2022)
Edited by Rama Kant and M.V. Sangara
narayanan
https://doi.org/10.1016/j.coelec.2022.101162
2451-9103/© 2022 Elsevier B.V. All rights
reserved.

Electrochemical systems present an extraordinarily complex interfacial

Rama Kant
Department of Chemistry, University of
Delhi, Delhi, 110007, India
*
Corresponding author: Kant, Rama.
e-mail: rkant@chemistry.du.ac.in
environment and diverse reaction schemes. Interfacial complexities
originate from the stability and dimensionality of the surface, morphology,
roughness, porosity, and heterogeneity of the electrodes. These
complexities govern rate constants of electrocatalytic and non-catalytic
electron transfer reactions as well as the structure and dynamics of
electrical double layer. Electrochemical experiments provide intricate
dependence on the electrode materials, solvent, electrolyte, electroactive
molecules, pH, etc., thereby posing challenges for the contemporary
computational and theoretical methods.

The articles in this section of Current Opinion in Electrochemistry

Rama Kant is currently a senior professor at
the Department of Chemistry, University of
Delhi, India. His current research interest is in
the area of “Theoretical and Fundamental
Electrochemistry,” which includes the devel-
opment of mathematical theories and experi-
ments for Complex Electrochemical Systems.
His prominent contributions are the derivation
of (more than 200) fundamental equations for
the electrochemistry of disordered electrodes,
viz., nano-micro-structured, atomic stepped,
and nano-scale curved metals for electrode
kinetics, electric double layer, and transient
techniques. He is an elected Fellow of Indian
National Science Academy and Indian Acad-
emy of Sciences. He is a recipient of many
international fellowships.
highlight the scope and diversity of theoretical approaches in providing
new insights into various electrochemical systems. Our emphasis has
been to point out how computational, analytical, and numerical ap-
proaches can yield new directions in materials science and technology,
obviating the need for “trial-and-error” experiments. Hence, the theo-
retical methodologies pertaining to lithium-ion batteries, super-
capacitors, water splitting, and biosensors find a prominent place. It is
hoped that the articles will provide new impetus into various contem-
porary issues in bioelectrochemistry and energy storage devices. The
authors have highlighted the challenges and directions of future research
in their areas of expertise, and the reviews will be of immense value to
both specialists and prospective entrants to electrochemistry. It should
be emphasized that modern electrochemistry has become truly inter-
disciplinary and requires contributions from a diverse range of specialists,
viz., Mathematicians, Physicists, Biologists, Medicinal Chemists, and
Engineers. Hence, this is the most appropriate time to take stock of
contemporary research activities spanning electrochemical mate-
rials science.

The articles may broadly be classified as systems governed by.

www.sciencedirect.com Current Opinion in Electrochemistry 2022, 36:101162

2 Fundamental & Theoretical Electrochemistry (2022)
M. V. Sangaranarayanan
Department of Chemistry, Indian Institute of
Technology-Madras, Chennai, 600036,
Tamil Nadu, India
e-mail: sangara@iitm.ac.in
M V Sangaranarayanan obtained his Ph.D.
from the Indian Institute of Science, Banga-
lore, under the guidance of Prof S K Rangar-
ajan and subsequently was an Alexander von
Humboldt Fellow with Prof Wolfgang
Schmickler. He has received Prof C N R Rao
National Prize for research in chemical sci-
ences from the Chemical Research Society of
India. He has served as the President of the
Society for the Advancement of Electro-
chemical Science and Technology, India. He
has published nearly 140 papers in
international journals and co-authored four
textbooks. His research contributions pertains
to non-equilibrium thermodynamics formalism
for chemically modified electrodes, statistical
mechanical modeling of electrical double
layer, interfacial electron transfer, conducting
polymers-based supercapacitors and bio-
sensors. He is a Professor Emeritus at the
Department of Chemistry, Indian Institute of
Technology-Madras, Chennai.
Current Opinion in Electrochemistry 2022, 36:101162
 Electron transfer and its coupling with proton transfer;
 Potential distribution in the electrical double layer and electrocatalysis;
 Dimensional stability, morphology, and nanoscale resolution of electrode surfaces;
 Transport phenomena at electrochemical interfaces;
 Design and fabrication of electrochemical energy devices.
In view of the overlap among the above, several papers can be classified
into more than one of the above sections.
It was customary during the past few decades to analyze the influence of
electrical double layer on electrode kinetic processes using the classical
Frumkin correction for the potential distribution. However, with the
advent of sophisticated computational and analytical techniques, it has
now become feasible to make rapid strides as regards the effect of double
layer on diverse charge transfer processes. In this context, the modeling of
proton-coupled electron transfer (PCET) at electrode surfaces plays a
significant role on account of its implications in various processes. The
effect of electrode surface, morphology, and interfacial interactions
governing the efficiency and performance of these industrial processes
need to be quantified using density functional theories. Sakaushi et al
have presented an authoritative review that lucidly highlights the cur-
rent trends and future perspectives, with emphasis on covalent and non-
covalent interactions, hydrophobicity, crystal structure, etc. The essen-
tial criteria for next-generation dimensionally stable electrodes (DSE)
toward large-scale green hydrogen production by water electrolysis have
been pointed out. The effect of interfacial organization of solvent dipoles
and adsorbates on oxygen reduction reaction has also been critically
analyzed by Sakaushi et al.
It is well known that the future of energy conversion and storage devices
revolves around batteries, fuel cells, and supercapacitors. On account of
the large gravimetric energy densities, lithium-ion batteries are primary
candidates; however, the safety considerations are the main limitations
from the perspective of the common man. Among various alternatives,
solid-state batteries are promising due to the inherent safety associated
with them. In view of the availability of different types of solid electrolytes
for this purpose, a large number of permutations can be envisaged, thereby
leading to “trial-and-error” approaches. In order to obviate this limitation,
Franco et al formulate microstructure-resolved continuum models. They
have clearly brought out the need for continuum models if our objective is
to obtain a comprehensive understanding of the degradation mechanism
and overpotential losses. The coarse-grained molecular dynamics simula-
tion in three dimensions carried out by Franco et al has the ability to design
and optimize the batteries, incorporating most of the “control variables.”
Among several issues pertaining to lithium batteries, the hazards associ-
ated with the use of liquid electrolytes have been of major concern. Apart
from the short-circuiting bottleneck caused by the formation of dendrites,
it is also essential to enhance the transport number of lithium as well as
the C-rate of batteries. Thus, the use of solid electrolytes is of paramount
importance in all-solid-state lithium batteries. In particular, Sodium Super
Ionic Conductor (NASICON)-type solid electrolytes possess the great
promise. The uniqueness of NASICON-type electrolytes consists of their
large specific conductance and ease of synthesis. However, as pointed out
by Paolella et al, the occurrence of several side reactions at different in-
terfaces in conjunction with large impedances constitutes major chal-
lenges. Several strategies such as (i) use of modified electrodes; (ii) new
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 Fundamental and theoretical electrochemistry Kant and Sangaranarayanan
synthetic strategies; and (iii) hybrid NASICON-
polymer composites are recommended by Paolella et al
for futuristic technologies.
Ever since the discovery of organic conductive polymers
by Hideki Shirakawa, Alan Heeger, and Alan MacDiar-
mid in 1970, these have gained immense applicability in
diverse analytical and industrial applications. The elec-
trode surfaces coated with conducting polymers are now
customarily employed as biosensors, supercapacitors,
energy storage devices, and healthcare appliances.
Katarı´na Gmucova´ has provided an overview of recent
applications of conductive polymer composites upon
modification using metal nanoparticles and two-
dimensional materials, such as graphenes, MXenes,
and metal-oxide frameworks. Among several applica-
tions pertaining to environmental chemistry described
by Gmucova´, the electrochemical detection of serotonin
in foods using a nanocomposite of metaleorganic
framework (MOF) supported by polypyrrole nanowires
deserves mention.
Melander et al highlight the issues involved in quanti-
fying electron transfer rate constants using computa-
tional and theoretical methods by carefully unraveling
their dependence on the nanostructured electrode ma-
terials, solvent, nature of electrolytes, electroactive
molecules, and pH of the medium. The promising
computational models using DFT and (semi)analytical
models based on Hamiltonians and non-Hamiltonian
approaches to comprehend the reaction mechanism
have been pointed out by Melander et al.
Rajan et al have emphasized fundamental issues
pertaining to electrochemical processes in novel two-
dimensional (2D) electrode materials, and these are
essential for fine-tuning diffusional mass transport as
well as interfacial double-layer potentials. The emer-
gence of the 2D material allows (i) modulating mass
transport through adjusting the interstitial gaps, work
functions, and potential of zero charge and (ii)
enhancing electron transfer kinetics through topology
and twist angle of sheets. The usefulness of such
microscopic, molecular modeling in the design of elec-
trochemical reactors, batteries, and supercapacitors has
been highlighted by Rajan et al.
On account of the presence of the space charge layers,
the equilibrium and dynamic aspects of semiconductor/
electrolyte interfaces pose challenges entirely different
from those at metal/electrolyte interfaces. The time-
dependent relaxation equations for minority carriers
need to be solved simultaneously for obtaining the
currentepotential response even under “ideal” condi-
tions. The article by Raj Ganesh Pala provides a critical
and timely survey pertaining to hitherto-overlooked as-
pects of semiconductor characteristics for the design of
diverse photoelectrochemical devices. The hierarchical
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3
manner in which various components are assembled has
been lucidly given with the help of flowcharts and il-
lustrations. An overview of the factors governing the
operational performance of photoanodes and photo-
cathodes has also been discussed by Raj Ganesh Pala.
Electron transfer processes involving metalloproteins
constitute one of the most challenging problems in
science, on account of the diverse Gibbs free energy
landscapes, solvent reorganization energies, and speci-
ficity of proteins when immobilized on electrodes. The
paper by Ulstrup et al describes emerging challenges in
long-range electron transfer in metalloproteins. The
conformational triggering in voltammetry and single-
molecule conductivity of two-center redox metal-
loproteins have been pointed out. In particular, the ab
initio quantum chemical studies of CuNIR/OH2 and
CuNIR/NO2-for 740-atom fragments of the type I and
type II Cu-centers reported in this paper provide new
insights. These rigorous voltammetric and computa-
tional studies on distance-dependent electron transfer
processes will be crucial in biosensors, biofuel cells,
photosynthesis, and enzyme catalysis, as pointed out by
Ulstrup et al.
The classical electrical double-layer problem is now
witnessing a renaissance on account of the sophisticat-
ion in experimental protocols and instrumentation. The
modern-day emphasis in this context is on ionic prop-
erties of electrolytes, polarity of solvents, as well as
electrode roughness, dimensionality, morphology, sur-
face curvature, etc. Aslyamov highlights the influence of
electrolytes in increasing the charge accumulation on
account of areal gains. The variation in the surface
coverage of ions has been shown to arise from local
curvature. The inadequacy of existing electrical double
layer has also been emphasized by Aslyamov.
There exist several control variables and optimization
strategies to fabricate lithium-ion batteries. One of the
most valuable tools in all electrochemical studies is the
electrochemical impedance spectroscopy (EIS), on ac-
count of its ability to provide information on mass
transfer, charge transfer, double-layer capacitance, sur-
face heterogeneity, and solution resistance. EIS has the
advantage of mapping various phenomena of differing
time constants in a unified manner. Subramanian et al
have reviewed the present status of the simulation
protocols pertaining to lithium-ion battery models. The
computational efficiency of various simulation tech-
niques has been compared. The importance of carrying
out the frequency response analysis for integrating with
the battery management systems has been emphasized
by Subramanian et al.
In conclusion, all the review articles in this section
briefly illustrate the contemporary progress and future
directions for a few typical topics of fundamental and
Current Opinion in Electrochemistry 2022, 36:101162
4 Fundamental & Theoretical Electrochemistry (2022)
theoretical electrochemistry. However, a single section
is not adequate for extensive coverage of all the exciting
developments and recent progress. The missing topics
will be covered in future issues of the “Current Opinion
in Electrochemistry.”
We hope that these representative papers will attract the
attention of the researchers in electrochemistry as well as
other related research fields. We would like to thank all
the authors for their cooperation and willingness to
contribute to this special issue of “Current Opinion in
Current Opinion in Electrochemistry 2022, 36:101162
Fundamental and Theoretical Electrochemistry,” in
spite of their busy schedule. The reviewers have carried
out the arduous task of providing valuable suggestions for
the improvement of the manuscripts, and their effort is
sincerely appreciated. We express our gratitute to the
Editor-in-Chief of Current Opinion in Electrochemistry,
Professor Richard G. Compton, and Professor Hasuck
Kim, for providing us with this opportunity. It is a plea-
sure to thank the Editorial Manager Dr. Patricia Hudson
for her perseverance, patience, and encouragement, ever
since the beginning of this task.
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