ORR by Sabarinathan

international journal of hydrogen energy xxx (xxxx) xxx
Available online at www.sciencedirect.com
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A quick guide to the assessment of key

electrochemical performance indicators for the
oxygen reduction reaction: A comprehensive
review
Narayanamoorthy Bhuvanendran a,d, Sabarinathan Ravichandran a,b,

Qian Xu a, Thandavarayan Maiyalagan c, Huaneng Su a,*
a
Institute for Energy Research, Jiangsu University, 301 Xuefu Road, Zhenjiang, 212013, China
b
School of Material Science and Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang, 212013, China
c
Department of Chemistry, SRM Institute of Science and Technology, Kattankulathur, 603203, Tamilnadu, India
d
Department of Chemistry, Saveetha School of Engineering, Saveetha Institute of Medical and Technical Sciences
(Saveetha University), Chennai, 602105, Tamilnadu, India.
highlights graphical abstract
This review provides crucial in-

sights and information on electro-
chemistry of ORR.
Overview on electrochemical
techniques, measurements and
calculation procedures.
The desired experimental approach
for evaluating ORR electrocatalyst
efficiency.
A beginner's guide to perform
cathodic ORR for fuel cell
applications.
article info abstract
Article history: Oxygen reduction reaction (ORR) is a vital electrochemical reaction for energy conversion
Received 7 August 2021 that has fascinated the interest of materials researchers to promote active and cost-
Received in revised form effective electrocatalysts with improved reaction kinetics. Numerous, researches have
23 October 2021 been undertaken to achieve the desired characteristic cathode materials to revolutionize
Accepted 7 December 2021 energy conversion devices including fuel cells and metal-air batteries (where ORR occurs).
Available online xxx More importantly, the evaluation of electrocatalyst efficiency for ORR using typical elec-
trochemical experiments, data collection, and analysis must be performed systematically
Keywords: and uniformly. This review provides a systematic guide to assess the electrochemical ef-
Oxygen reduction reaction ficiency because it includes standard and widely recognized experimental protocols for
Kinetic parameters each electrochemical technique, as well as easy-to-follow lab procedures and a detailed
* Corresponding author.
E-mail address: suhuaneng@ujs.edu.cn (H. Su).
https://doi.org/10.1016/j.ijhydene.2021.12.072
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article as: Bhuvanendran N et al., A quick guide to the assessment of key electrochemical performance indicators for the
oxygen reduction reaction: A comprehensive review, International Journal of Hydrogen Energy, https://doi.org/10.1016/
j.ijhydene.2021.12.072
2 international journal of hydrogen energy xxx (xxxx) xxx
RRDE analysis of essential kinetic ORR parameters with a theoretical framework. The major
Electrochemical techniques function of each electrode in cyclic voltammetry, hydrodynamic linear scan voltammetry
Experimental methods with rotating disc electrodes, and electrochemical impedance spectroscopy for ORR were
Lab practices demonstrated, as well as the construction of a three-electrode electrochemical cell. By
following standard protocols and experimental procedures, an aspiring electrochemist
would be capable to enforce fundamental and advanced electrochemical techniques much
efficiently in their understanding of ORR kinetics evaluation.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Electrochemical characterization techniques for ORR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Cyclic voltammetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Linear scan voltammetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Electrochemical impedance spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Supporting electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Working electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Reference electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Potential conversion to RHE (both acid and alkaline electrolyte) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Counter electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Method of measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Catalyst ink preparation and coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
CV measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
LSV measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Accelerated durability test (ADT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
EIS studies (conductivity measurements) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Solid-state measurements (two probe conductivity cell) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Solution-phase measurement (three-electrode electrochemical cell) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Standardization of experimental procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Key electrochemical parameters for ORR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Electrochemically active surface area (ECSA) from cyclic voltammograms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
ECSA from hydrogen desorption/adsorption peak area of noble metal catalysts in acidic medium . . . . . . . . . . . . 00
ECSA from metal-oxide reduction peak of noble metal catalysts in alkaline medium . . . . . . . . . . . . . . . . . . . . . . . . 00
ECSA from the double-layer capacitance of non-noble metal catalysts in both acidic and alkaline medium . . . . 00
ECSA from CO stripping of noble metal catalysts in both acidic and alkaline medium . . . . . . . . . . . . . . . . . . . . . . . 00
Percentage of catalyst (Pt) utilization and roughness factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Polarization curves (LSV) for ORR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Onset potential, half-wave potential, and limiting current density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Kinetic current density of ORR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Mass activity and specific activity of ORR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Tafel slope (b), exchange current density (J0), and electron transfer co-efficient (a) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Number of electron transfer (from K-L plot) and apparent rate constant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Percentage of H2O2 formation and number of electron transfer (from RRDE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Calibration of collection efficiency (N) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
ORR rate constants (k1, k2 & k3) from the Damjanovic mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Activation energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Turnover frequency (TOF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Conductivity from EIS studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
international journal of hydrogen energy xxx (xxxx) xxx 3
List of abbreviations including units and nomenclature QHads Hydrogen adsorption region (mC/cm2)
Qref Charge associated with reference metal (mC/cm2)
AFC Alkaline fuel cells
Qo Charge of oxide-reduction peak (mC/cm2)
ORR Oxygen reduction reaction
QCO Charge acquired of CO desorption (stripping) (mC/
PEMFC Polymer electrolyte membrane fuel cells
cm2)
DMFC Direct methanol fuel cells
m Mass of the metal catalyst (mg/cm2)
O2 Oxygen
Cdl Electrochemical double-layer capacitance (F/cm2)
H2O Water
ja Anodic current density (mA/cm2)
H2O2 Hydrogen peroxide
jc Cathodic current density (mA/cm2)
OH Hydroxyl ion
Dj Difference between the current value of ja and jc
HO 2 Peroxide ion
n Scan rate (V/s)
WE Working electrode
Cs Specific capacitance (F/cm2)
RE Reference electrode
Eonset Onset potential (V)
CE Counter electrode
E1/2 Half-wave potential (V)
RDE Rotating disc electrode
JL Limiting current density (mA/cm2)
RRDE Rotating ring disc electrode
Jk Kinetic current density (mA/cm2)
CV Cyclic voltammetr
Jp Current density acquired at a particular potential
LSV Linear scan voltammetry
(mA/cm2)
EIS Electrochemical impedance spectroscopy
MA Mass activity (mA/mg)
ECSA Electrochemical active surface area (m2/g)
SA Specific activity (mA/cm2)
HClO4 Perchloric acid
b Tafel slope (mV/dec)
H2SO4 Sulfuric acid
J0 Exchange current density (A/cm2)
KOH Potassium hydroxide
a Electron transfer co-efficient
NaOH Sodium hydroxide
R Gas constant (J/Kmol)
u Electrode rotation rate (rpm) or Angular velocity
F Faraday constant (C/mol)
(rad/s)
T Temperature (ºC)
GC Glassy carbon
h Overpotential (V)
ID Disc current (mA)
E Applied potential (V)
IR Ring current (mA)
n Number of electron transfer
SSCE Silver-silver chloride electrode
K-L Koutecky-Levich
SCE Saturated calomel electrode
k Apparent rate constant (cm/s)
MMO Mercury-mercury oxide electrode
CO2 Concentration of oxygen (mol/cm3)
MSE Mercury-mercurous sulfate electrode
DO2 Diffusion coefficient of oxygen (cm2/s)
SSSE Silver-silver sulfate electrode
n Kinematic viscosity (cm2/s)
RHE Reversible hydrogen electrode
N Collection efficiency of RRDE
SHE Standard hydrogen electrode
Ea Activation energy (kJ/mol)
NHE Normal hydrogen electrode
ICP Inductively coupled plasma analysis
ERHE Potential versus RHE (V)
TOF Turnover frequency (s1)
EM Measured potential (V)
A Electrode surface area (cm2)
E0(Ref) Standard potential of the secondary reference
Ns Number of active sites on the catalyst surface
electrodes (V)
(mole)
ADT Accelerated durability test
sP Proton conductivity (S/cm)
PC Potential cycling
L Thickness of the film (mm)
RSA Real surface area (cm2)
R Resistance (ohm)
GA Geometrical surface area (cm2)
Rt Charge transfer resistance (ohm)
CSA Chemical surface area (m2/g A)
RU Electrode resistance (ohm)
Rf Roughness factor
Zd Warburg impedance (ohm/s)
QHdes Hydrogen desorption region (mC/cm2)
the complex multi-step reaction mechanism with the forma-

Introduction tion of highly reactive oxygen intermediates [5e8]. Oxygen
reduction reaction (ORR) is one of the key electrochemical
Oxygen electrochemistry is fundamental and very important reaction takes place at the cathode, which significantly in-
for green energy conversion technologies like fuel cells, fluences the overall energy conversion efficiency of the fuel
rechargeable batteries, and water electrolyzers [1e4]. The cells. Electrocatalysts and their surface sciences are important
electrochemical behavior of oxygen has got significant factors in the promotion of ORR kinetics [9e11]. The complex
importance as an oxidant in fuel cell reactions, which involves
reaction mechanism and sluggish kinetics of ORR demand an upon adsorption and only breaks later during electron trans-
efficient electrocatalyst. In general, the ORR taking place at the fer. It involves molecular O2 adsorption and direct proton/
cathode side of the polymer electrolyte membrane fuel cells electron transfer, leading to the formation of (HO2*) H2O2, and
(PEMFC) and direct methanol fuel cells (DMFC) in acidic elec- H2O2 could be further reduced to H2O as a final product. In
trolytes [12e14]. both mechanisms, a reaction step that involves the redox
In both acidic and alkaline medium, the ORR occurs mainly system is the oxidation of the water molecule over the Pt
by two different reaction pathways of (i) direct four-electron electrode surface [36,38e41].
transfer, i.e., oxygen (O2) to water (H2O) or hydroxyl (OH) In this review, we focused on a comprehensive analysis of
formation and (ii) serial two-electron transfer from O2 to electrochemical oxygen reduction measurements and their
hydrogen peroxide (H2O2) or peroxide (HO 2 ), which further significant information and guidance of techniques with key
reduced by another set of electrons (two-electrons) transfer to laboratory practices for young researchers to better under-
produce an H2O molecule (Fig. 1) [1,2,5,13e16]. The mecha- stand. The primary significance of this is to provide detailed
nism of ORR has several elementary steps with adsorption/ clarifications on critical kinetic parameters of ORR to evaluate
desorption process and electron/proton transfer as follows: (i) the efficacy of electrocatalysts. This includes the fundamental
adsorption of the oxygen on the active catalyst sites; (ii) theoretical concept of ORR kinetics as well as its reaction
electron transfer from the hydrogen oxidation at the anode to mechanism in both acidic and alkaline media. Besides that,
the oxygen molecule at the cathode; (iii) breaking of oxygen the method of vital electrochemical measurements, electrode
bond (dissociation of oxygen bond) or weakening from the maintenance, potential conversion, the effect of hydrody-
surface of the catalyst; and (iv) removal of intermediates namic using rotating disc electrodes, and two types of
associate with hydrogen ion and forming a final product of impedance spectroscopy measurements for ORR are all rep-
water molecule [17e20]. resented. We believed that this collective information may
In an acid medium, the multistep reaction mechanism of provide a better understanding to enhance our experimental
ORR involves four proton and four-electron transfers to pro- and interpretation skills, which would be more beneficial to
duce H2O from O2 with various intermediates formation those working on oxygen electrocatalysis for energy conver-
including O*, HO* HOO* and (where O*, HO* and HOO* are sion applications.
oxygen, hydroxyl, and peroxide adsorbed over the active
catalyst sites) [1,7,8,20e23]. Hence, the ORR mechanism on the
catalyst surface was theoretically proposed by two distinct Electrochemical characterization techniques for
mechanisms are ‘dissociative mechanism’ and the ‘associative ORR
mechanism’ at a low and high current density region, respec-
tively [8,24e28]. The electrochemical measurements are performed using a
The simple dissociative and associative mechanism ORR three-electrode electrochemical cell, preferably a double jac-
on a Pt (111) surface was proposed as given below keted electrochemical cell, which is coupled with a cryostat/
[17,26,29e36]. thermostat circulating water bath to maintain the specified
reaction temperature. The electrochemical cell was provided
Here, the ‘*’ symbolizes an active Pt site. The adsorbed with three major electrodes for the working electrode (WE),
oxygen molecule on a Pt surface breaks the OeO bond and reference electrode (RE), and counter electrode (CE), the gas
forms adsorbed atomic O, which gets two electrons in two purging inlet was directly immersed into the electrolyte so-
consecutive steps to form water. Subsequently, there is no lution and the outlet tube was connected to maintain the flow
adsorbed O2 on the Pt surface, which cannot form H2O2. This of gas [36,42e44]. Fig. 2a shows the graphical illustration that
dissociative mechanism could be conceived as a detailed class represents the double jacketed three-electrode electro-
of the direct 4-electron transfer pathway [24,27,37]. The chemical cell setup. All three electrodes were linked with the
associative mechanism in which O2 does not dissociate before electrochemical workstation (Potentiostat/Galvanostat) and
being hydrogenated and OeO bond integrity is conserved the working electrode could be controlled by a rotator with a
Fig. 1 e Scheme of the ORR mechanism in both acid and alkaline electrolyte solution.
fixed rotation rate (rpm) for hydrodynamic conditions [44,45]. electrochemical active surface area (ECSA), reduction peak
The working electrode could be a modified electrode with a potential, and current to estimate the performance for ORR.
catalyst layer through a drop-cast method and dried properly
before using for measurement. The electrochemical reactions
take place at the catalyst surface from the working electrode,
which is involved with the current flows between WE and CE Quick cuts: 1 Potential window
by applying a potential to the WE in relation to the standard For voltammetry studies, either CV or LSV the potential
potential of CE. This phenomenon was clearly shown in the window can be fixed based on the pH of the electrolyte
circuit diagram (Fig. 2b) of the three-electrode electrochemical and nature of catalyst materials.
cell [36,46].
To conduct the ORR studies, the WE preferably was using a
disc electrode, either a rotating disc electrode (RDE) or a
rotating ring disc electrode (RRDE), made of glassy carbon (disc Linear scan voltammetry
electrode) and the catalyst materials, which was cast over the
disc surface area for further studies [44,47]. Moreover, vol- Linear scan voltammetry (LSV) is a distinctive voltammetry
tammetry is the most prominent electroanalytical technique technique to examine the redox (oxidation/reduction)
used to probe the kinetics of electrochemical reactions in behavior of an electroactive species thru applying the po-
evaluating the current as a function of potential. The kinetics tential for an anodic (reverse, i.e., upper limit to lower limit)
of ORR can be probed through the electron transfer mecha- and the cathodic (forward, i.e., lower limit to upper limit)
nism by employing the cyclic voltammetry (CV) and linear sweep respectively [57,58]. Unlike the CV profile, the LSV
scan voltammetry (LSV) techniques in stationary and hydro- recorded in a single direction of potential sweep either
dynamic approaches respectively [43,48]. In addition to that, forward or reverse. By performing LSV under hydrodynamic
the conductivity of the catalyst and its influence on ORR has conditions, the rate of electron transfer between the elec-
been studied through the electrochemical impedance spec- trode and electrolyte interface can be understood and used
troscopy (EIS) technique (either in solid or liquid phase) using to assess the kinetics and mass transfer effects [47,59]. In
a frequency response analyzer [43,49,50]. which, the LSV profiles recorded using RDE and RRDE elec-
trodes to determine the kinetics ORR at various electrode
Cyclic voltammetry rotation rates and a fixed scan rate. In general, the LSV
profiles are predominantly used to estimate the specific
Cyclic voltammetry is the extensively applied electroanalyt- electrochemical reactions such as reduction and oxidation
ical technique for estimating the electrochemical reaction and depending on the three major influencing factors of, (i) the
its kinetics. In general, the CV studies furnish the information electron transfer rate; (ii) the reactivity of electroactive
about redox behavior of the electroactive materials, the ki- species; and (iii) the potential scan rate [60]. Herein, the
netics of heterogeneous electron transfer reactions, coupled kinetics of ORR could be determined based on the typical
chemical and electrochemical reactions, and the adsorption parameters such as limiting current density, kinetic current
process, etc., [51,52]. During the CV measurement, the po- density, mass, and specific activities that can be estimated
tential of a static working electrode (in an unstirred solution) from the respective LSV profiles. The mass-transfer effect
could be linearly applied at a constant rate of potential scan- over the electrode surface can be elucidated using the hy-
ning. The current resulting from the electron transfer at an drodynamic LSV profiles at various electrode rotation speed
active reaction site with respect to applied potential is used to through the Koutecky-Levich equation [7,59]. Furthermore,
construct the current-potential plot, and it is a cyclic vol- based on the LSV profiles recorded under specific condi-
tammogram [52]. From the CV profiles for the catalysts in tions, the actual electrocatalytic performance could be pre-
acidic or alkaline electrolyte solutions, the adsorption/ cisely investigated.
desorption of oxygen species on an active catalyst surface can
be determined based on the appearance of typical peaks at the
lower potential region [53,54]. As like that, the oxidation/
Quick cuts: 2 Direction of potential sweeping
reduction of oxygen species can be observed from the
respective peaks at high potential regions during forward and Forward sweep (low to high potential)
backward potential scanning [55,56]. The CV profile provides Backward sweep (high to low potential)
the basic information of the electrocatalysts such as
Fig. 2 e Infographics of a double-jacketed three-electrode electrochemical cell configuration with all three electrodes (a) and
a three-electrode loop circuit diagram (b).
Electrochemical impedance spectroscopy electrochemical reactions [72]. An acidic electrolyte solution is

usually 0.1 M perchloric acid (HClO4) or 0.5 M sulfuric acid
EIS is an electroanalytical technique for analyzing the (H2SO4), whereas an alkaline electrolyte solution is usually
electron-transfer mechanism that takes place at the 0.1 M KOH or 0.1 M NaOH [65,73].
electrode-electrolyte interface in an electrochemical reaction In general, the pH of the supporting electrolyte solution has a
[61,62]. EIS is a promising method for understanding the significant influence on the ORR kinetics and the electro-
chemical transformations of electrochemical reactions by catalytic activity of the catalyst materials, depending on the
acquiring the mechanistic and kinetic properties of electrode potential window, selectivity, and binding energy of their
materials for energy conversion and storage applications adsorbate. The neutral pH of the electrolyte solution is better
[62,63]. EIS is widely used to investigate the intrinsic proper- suitable for the microbial fuel cell (MFC), and the cathodic ORR
ties of catalyst materials that affect conductivity and fuel cell follows a similar reaction mechanism to that of the PEMFC and
efficiency limitations. According to the EIS theory, the elec- AFC, but with slower reaction kinetics [74,75]. Furthermore, the
trochemical properties of catalyst materials are influenced by electrolyte frequently used in MFC for cathodic ORR is phos-
several factors related to their electrochemical reactions [64]. phate buffer solution (PBS), and thus the ORR kinetic parame-
The electrochemical behavior of catalysts using the EIS ters measured to evaluate catalyst performance and
method is characterized by three fundamental factors: (i) experimental procedures were the same as we provided in this
ohmic resistance (ion or electron transfer), (ii) double-layer review for ORR which occurs in either acidic or alkaline me-
capacitance (kinetic effect), and (iii) charge transfer resis- dium. The ORR is common to all three types of electrolytes so-
tance or polarization resistance (mass transfer effect) [65]. lutions, whether acid, alkaline, or neutral, but the performance
Furthermore, the diffusion properties of electroactive species of electrocatalysts followed by the ORR kinetics is significantly
as a result of reactant/product species adsorption on the pH dependent. As a result, the provided experimental tech-
electrode surface (referred to as Warburg impedance) [61e64]. niques and kinetic parameter evaluation can be appropriately
Based on the nature of the materials and the required infor- used to measure the electrocatalytic activity for ORR in MFC,
mation for an appropriate evaluation, two different methods leading to a significant correlation between the fuel cell types.
can be adopted for the measurement of conductivity using EIS
analysis: (i) three-electrode cell (solution phase) and (ii) two-
electrode cell (solid phase) measurements [66e69]. Electrodes
Supporting electrolyte As mentioned earlier, the three-electrode cell setup is dedi-

cated to half-cell fuel cell studies, especially ORR measure-
During the electrochemical measurement of both CV and LSV ments to evaluate electrocatalyst efficiency. Among the three
studies, the reaction can be carried out in a solution phase, in different kinds of electrodes, the working electrodes are
which the aqueous acidic or alkaline solutions are being used preferably a disc kind of electrode that is mounted in a Teflon-
as a supporting electrolyte under inert or oxygen saturated like material with appropriate connections to conduct vol-
conditions [70,71]. As a practice, whether in an acidic or tammetry studies under both static and hydrodynamic con-
alkaline solution, the pH value, diffusion coefficient, and ki- ditions [47,76,77]. Before conducting the experiments, all three
nematic viscosity of the supporting electrolyte were consid- electrodes must be cleaned, calibrated, and maintained ac-
ered and taken into account to estimate the kinetics of the cording to the manufacturer's instructions [45,78].
Working electrodes (c) Mercury e mercury oxide electrode (Hg/HgO, MMO)

(d) Mercury e mercurous sulfate electrode (Hg/Hg2SO4,
One of the most widely known hydrodynamic electrodes is the MSE)
rotating disc electrode [47,77,78]. The RDE is mainly employed (e) Silver-silver sulfate electrode (Ag/Ag2SO4, SSSE)
as the working electrode and it is made up of noble metals
(platinum, gold, etc.) and some of the conducting carbon To ensure universality and ease of comparison with other
materials (graphite, pyrolytic carbon, and glassy carbon (GC), reports, all potentials were reported against hydrogen elec-
etc.) [79]. Using a rotor setup, the disc is rotated at such a fixed, trodes, either reversible hydrogen electrode (RHE), normal
known frequency of its central axis, and the current through hydrogen electrode (NHE), or standard hydrogen electrode
the disc is quantified continuously as a function of potential (SHE) [90,92]. SSCE and SCE are among the most common and
applied and rotation speed ‘u’ [47,77,80]. promising electrodes due to their ease of construction and
The movement of solution away from the disc caused by maintenance, as well as the fact that they have a stable po-
rotating the electrode might result in formation of a vacuum tential and could be used in both acidic and alkaline media [90].
at the disc center, causing more electroactive ions (analyte) to
be attracted from the bulk solution towards the electrode
surface (Fig. 3a) [81]. The rotation of the disc produces a Quick cuts: 3 Maintenance of REs
‘pump’ effect, with solution being drawn from the bulk and
For SSCE and SCE, an inner solution must be refilled
travelling continuously toward the surface of the disc elec-
weekly once (for regular usage) to avoid potential drift.
trode, over the disc, and back into the bulk solution. This
In alkaline medium, SCE could be used instead of SSCE
‘pumping action’ helps the reproducibility of electrode re-
to avoid OH diffusion to RE.
actions by the flow of analyte as the flux from the bulk to the
electrode surface [79]. The Levich equation is named after the
Russian electrochemist Veniamin Levich, who first stated the
relationship between RDE currents and analyte concentration
Potential conversion to RHE (both acid and alkaline
with the effect of rotation rate [82,83].
electrolyte)
The central disc of a rotating ring-disc electrode is sur-
rounded by a concentric ring electrode in a modified shape of
In general, the pH of the electrolyte should be used when
RDE. An insulator, such as Teflon or epoxy resin, is used to fill
converting potential values against RHE [90,93]. The standard
the gap between the ring and the disc (gap size: 320 mm, PINE
potential of the secondary reference electrode varies relying
Research Instrumentation, USA). Since it can calculate rate
on the type and concentration of the filling solution, and the
constants faster than any other method, such type of elec-
Equation (1) can be used to convert potential against RHE with
trode is a powerful analytical tool for steady-state measure-
different secondary reference electrodes such as SSCE, SCE,
ments [84e86]. The RRDE produces two types of currents: disc
MMO, and others [90].
current (ID) and ring current (IR). Disc current (ID) refers to how
much analyte is produced (via Faraday's laws), while ring ERHE ¼ EM þ E0ðRef Þ þ ð0:059 pHÞ (1)
current (IR) refers to how much analyte is brought back to
starting material (Fig. 3b) [77,80]. where, ERHE - potential versus RHE; EM - measured potential
and E0(Ref) - the standard potential of the secondary reference
Reference electrodes electrodes. The pH of the electrolyte solution should also be
measured and used properly.
The REs are the most critical part of a three-electrode elec-
trochemical cell and are used in voltammetry techniques such Counter electrodes
as CV, LSV, and EIS. The choice of REs for an electrochemical
measurement is identified by the electrode potential range Counter electrodes, also known as auxiliary electrodes, play a
and pH of the electrolyte solution [87,88]. The two most critical role in completing the electrical circuit of a three-
common types of REs are primary electrodes (generally electrode electrochemical cell [84]. The main function of the
hydrogen electrodes) and secondary electrodes (probably all CE is to respond to the counteraction of the reaction at the WE.
other electrodes except hydrogen electrodes). According to As the WE undergoes a reduction reaction, the CE enacts an
Caton, an ideal RE should have the following characteristics oxidation reaction, and the current starts to flow [48]. The
[89,90]: (i) stable potential, (ii) non-polarizable, (iii) reversible geometrical surface area of the CE must be larger than the
after measurement (back to standard potential after external surface area of the WE to confirm that the kinetics of the re-
potential applied), (iv) obey the Nernst equation, and (v) the action arising at the counter electrode does not impede those
inner solid portion of the secondary electrodes must be involved at the working electrode [48,84]. The CE must allow
sparingly soluble with the electrolyte solution [91,92]. Some the current to flow without creating a chemical change in the
common secondary electrodes used for electrochemical solution being examined in all electrochemical methods, as
studies are [89,90], this would change the outcome of the experiment or mea-
surement. Platinum wire or mesh counter electrodes are
(a) Silver-silver chloride electrode (Ag/AgCl, SSCE) resistant to oxidation, solvents, and acids. Because of its
(b) Saturated calomel electrode (Hg/Hg2Cl2, SCE) inertness, platinum is an ideal material for a counter electrode
electrochemical cell are configured at a fixed distance and

immersed in an electrolyte solution with a reasonable level
distance from the bottom of the cell, where they are con-
nected to a potentiostat controlled by the instrument's soft-
ware [44,96].
Catalyst ink preparation and coating
The catalyst ink was then prepared by dispersing a certain

amount of catalyst powder in a mixture of water/alcohol sol-
vents and Nafion alcoholic solution. In this case, the water-to-
alcohol ratio (typically isopropyl alcohol or ethanol) was set at
3:1, with a few microliters of 5% Nafion added to the mixture.
This mixture was ultrasonicated for 20e30 min in an ice-cold
Fig. 3 e Graphical representation of (a) rotating disc bath to ensure homogeneity, and a specific amount of catalyst
electrode (RDE) and (b) rotating ring-disc electrode (RRDE). ink was drop casted on the mirror finished GC (working elec-
trode) surface. This catalyst layer on the GC can be dried in
two ways: (i) under ambient conditions with an IR lamp for
[94]. The pH of the electrolyte and the nature of electro- quick solvent evaporation; and (ii) RDE-GC was mounted on an
chemical reactions have influenced the choice of CE in some inverted rotator set up with a rotating speed of 700 rpm for
cases, while carbon-based materials such as graphite rods 15 min [78,97]. The final conformation is to obtain a uniform
have been used in others [94,95]. distribution of catalyst ink on the GC surface, as well as proper
drying without any spillage on Teflon or peel off from the
electrode surface.
Quick cuts: 4 Will the use of Pt as a counter electrode

CV measurement
influence ORR activity?
Pt (CE) oxidation in concentrated acidic electrolyte The CV curves of the given electrocatalysts were recorded
solutions during electrochemical reactions at higher under an inert atmosphere (either N2 or Ar saturated) in an
potential ranges has a significant impact on working aqueous electrolyte (either acid or alkaline medium) solution
electrode (catalyst) performance, particularly for non- at a fixed scan rate (probably 0.05 V/s or 0.1 V/s) using a three-
noble metal catalysts. electrode electrochemical cell [97,98]. In both acidic and
At the same time, Pt (CE) electrochemical dissolution alkaline mediums, the potential window could be chosen be-
may be less intense in concentrated alkaline electro- tween 0.025 and 1.4 V vs. RHE [14,21,77]. In practice, the po-
lyte solutions than in acidic medium. tential window could be set based on the RE being used, such
The use of Pt as a counter electrode for ORR in acidic as SSCE or SCE, and the standard electrode potential sub-
media is still debatable; alternate CE usage is currently tracted from the above range [14,48]. Before capturing the
most suggested. actual CV profile, the catalyst surface should be pre-
conditioned through continuous potential cycling (PC) for
the entire range of the potential window at a fixed scan rate
until a standard pattern is obtained [48].
Method of measurements LSV measurement
In the first step, the working electrode (GC-RDE, or GC-disc/Pt- The ORR polarization curves (LSV) were measured in an O2-
ring-RRDE) should be polished with alumina slurry of different saturated electrolyte solution at a lower scan rate of 0.01 or
particle sizes (between 5 and 0.05 mm) added to a microfiber 0.005 V/s in hydrodynamic conditions with an electrode
polishing cloth and washed several times with ultrapure rotation rate of 400e2400 rpm using a rotator setup [45,97]. To
water [45,78]. The electrode was then placed on the specially achieve well-defined, repeatable results during LSV studies
mounted screwed gauge for catalyst coating, which had a under hydrodynamic conditions, the electrolyte solution flow
mirror-finished surface. A reasonable amount of electro- must be laminar, not turbulent. Hence, the electrode rotation
catalyst is drop-casted over the WE, i.e. the complete speed must be less than 3000 rpm, with 400e2400 rpm being
geometrical disc (GC) area. After it has been properly dried, the an acceptable speed for testing [99,100]. In addition to that, a
catalyst-coated WE can be used for electrochemical mea- double jacketed electrochemical cell can be used to maintain
surements [78,96]. In this case, the nature of the electrolyte the reaction temperature during the measurements, which
(pH) and electrocatalyst content should be taken into account was regulated by a circulating water bath connected to a
when choosing both RE and CE. All three electrodes in an thermostat.
Solution-phase measurement (three-electrode electrochemical

Quick cuts: 5 Electrode rotation rate (RPM) cell)
The solution flow within the cell appears to become A three-electrode electrochemical setup with a high surface
Laminar (up to 4000 rpm). area counter electrode to reduce capacitive losses, a catalyst-
According to Levich equation, the limiting current is coated RDE as the working electrode, and a secondary refer-
proportional to the square root of rate of electrode ence electrode were used to record the impedance spectra
rotation. under potentiostatic mode [111]. In this cell configuration,
The electrode rotation rate between 400 and 2400 rpm which is similar to CV and LSV measurements, the electrolyte
becomes optimal to prevent turbulence in the elec- solution should be saturated with high pure oxygen gas. By
trolyte solution, which allows ionic mobility to be sweeping the frequency from 100 kHz to 0.1 Hz at 10 points per
unidirectional (laminar). decade, the impedance spectra were measured with an AC
amplitude either in 0.005 V or 0.01 V [61,107]. In this case, all
measurements were conducted in a single sine mode. The
Accelerated durability test (ADT) impedance spectra were fitted to the suitable components to
complete the circuit diagram with negligible error percentage
Durability is a significant criterion for evaluating the electro- using the software tool associated with the electrochemical
catalysts' long-term efficiency of ORR in low-temperature fuel workstation [112].
cells. The accelerated durability test (ADT) can be performed
using the CV technique to assess the electrocatalyst dura- Standardization of experimental procedure
bility, and the performance can be monitored using ORR-LSV
profiles recorded at regular intervals during potential cycling In relation to the standardized procedure for electrochemical
[97]. The PC was conducted at a fixed scan rate of either 0.05 or experiments, normalization of obtained parameters, back-
0.1 V/s between 0.6 and 1.2 V vs. RHE. Both the CV and LSV ground correction to eliminate the influence of non-catalyst
studies were performed in an O2-saturated electrolyte solu- materials and non-faradaic current, and, most importantly,
tion, including the LSV profile was measured at 1600 rpm and calibration of instruments and other electrochemical devices
a scan rate of 0.01 V/s [101e104]. such as electrodes could be used to assess performance and
compare to other catalysts. The statistical approach can also
EIS studies (conductivity measurements) be used to assess and evaluate the electrocatalytic perfor-
mance of electrode materials at three different levels. They
The conductivity of electrocatalysts (either in the form of free- are, (i) the standard deviation between recurrent cycles in-
standing catalyst layers (membrane) or as catalyst ink coated side an experiment; (ii) the standard deviation between
over the WE) can be measured using the EIS technique by repeat experiments from the same lab and researcher; and
observing at the Nyquist plot [50,66]. To perform EIS mea- (iii) the standard deviation out of a collection of experiments
surements, we can use two different experimental cell setups: from at least three-four different labs under the same con-
(i) a two-probe cell (solid-state measurement) [105,106] and (ii) ditions [113,114].
a conventional three-electrode electrochemical cell (solution- Furthermore, errors and other disruptions during the
phase measurement) [61,63,107]. half-cell reactions may have a considerable impact on the
measurement, causing an overestimation or underestima-
Solid-state measurements (two probe conductivity cell) tion of the catalytic performance. In general, there are two
To measure the through-plane solid-state conductivity, a two- types of errors that might occur during any kind of labora-
probe conductivity cell made up of a Perspex cell with copper tory measurement: (i) manual errors and (ii) instrumental
rod electrode (specified circular disc surface area) placed errors. The usual sources of engineering errors during
perpendicular to the copper plate electrode by spring tension electrochemical measurements include sampling, chemical
(Fig. 4) [108]. For solid-state conductivity measurements, a free- analyses, impurities in reagent chemicals, corrosion, un-
standing catalyst film of polymer nanocomposite membranes compensated voltages, signal bias and noise, supporting
with known thickness can be sandwiched between the elec- thermophysical and thermochemical statistics, and mea-
trodes, which has been pre-hydrated by soaking in ultrapure surements of temperature, voltage, amperage, electrical
water for 24 h prior to the experiment [108]. The surface water charge, pressure, and mass [115]. These errors must be
should be wiped out carefully without crushing before placing taken into account when reporting the results of electro-
the pre-hydrated catalyst film at the electrode. When dealing chemical measurements, which are estimated with a stan-
with solid powder materials, a thin pellet can be made using a dard deviation and marked as “±“. Furthermore, the
pellet machine and tested similarly [109]. In general, through- estimation of catalytic activity from electrochemical results
plane conductivity experiments are used to study the ionic can be nullified by either normalization or background
(proton) conductivity of catalyst layers. An electrochemical subtraction of the influence of other components. Addi-
workstation equipped with a Frequency Response Analyzer was tionally, instrumental errors must be avoided through
used to perform a solid-state conductivity test in potentiostatic proper maintenance and the elimination of electrical dis-
mode with a perturbation potential of 0.01 V over the frequency turbances through the use of a faraday cage-like setup
range from 0.1 to 100 kHz using the EIS technique [110]. during electrochemical cell studies.
QHdes from 0.0 to 0.3 V (Fig. 5) and taking that Qref ¼ 210 mC/cm2
Quick cuts: 6 Standard protocols for experimental of commonly used for polycrystalline Pt electrodes [98,121].
procedure. The ECSA of Pt and Pt-based catalysts can be calculated
Before beginning the tests, calibrate the electro- based on the following relations (2) & (3) [93,122],
chemical equipment, weighing balance, electrodes,
QHdes þ QHads
and other supporting devices according to the manu- QH ¼ (2)
2
facturer's instructions.
Follow the protocol for operating the instrument. QH
Maintain the same standard conditions throughout ECSA ¼ (3)
Qref m
the measurement.
Before performing the measurement, clean the glass- where QH is the charge acquired during for H-desorption/
ware and electrodes well. adsorption (in mC/cm2), m is the metal loading (in mg/cm2) over
For synthesis and electrochemical tests, use high pu- the GC electrode, and Qref is the charge associated with the
rity chemicals, solvents, and gases. monolayer hydrogen adsorption on active Pt surface (210 mC/
Make use of the high purity Millipore water with the cm2) [93,98,123].
desired conductivity.
Conduct trail-and-error experiments to validate the ECSA from metal-oxide reduction peak of noble metal catalysts
true performance of the electrode materials and obtain in alkaline medium
concordance results for final calculations. In the case of noble metals such as Pd, Au, and Ag-based
catalysts, the oxide reduction peak can be used to estimate
the ESCA of the electrocatalyst materials [124,125]. Unlike Pt,
the ESCA of these noble-metal-based electrocatalysts could
Key electrochemical parameters for ORR not be determined using the hydrogen desorption peaks from
CV due to the lack of adsorption of hydrogen on the Ag/Au
Electrochemically active surface area (ECSA) from cyclic surface [124]. Therefore, the ECSA is calculated from the
voltammograms charge associated to oxide reduction formed by the adsorption
of an oxygen monolayer on Ag [125] (Fig. 6), and a similar
The surface of the solid electrodes are not smooth and its real behavior was obtained for Au [124] surface. For Ag electro-
surface area (RSA) in one of the crucial parameter, which is catalysts, the ECSA was determined based on the following
much higher than the geometrical surface area (GA) of the Equation (4) [124,125],
electrodes [116,117]. The RSA values are varied for different
QO
electrocatalytic materials and the ratio of RSA and GA is ECSA ¼ (4)
Qref m
termed as the roughness factor (Rf) [118].
where Qo is the charge of oxide-reduction peak from the
ECSA from hydrogen desorption/adsorption peak area of noble backward scan (in mC/cm2), m is mass of the metal catalyst (in
metal catalysts in acidic medium mg/cm2) on working electrode, and Qref is the charge acquired
Fig. 5 shows the typical cyclic voltammogram of poly- by the adsorption of oxygen monolayer on Ag surface (420 mC/
crystalline Pt in the ‘butterfly’ pattern recorded in sulfuric acid cm2) [125], Au surface (386 mC/cm2) [124] and Pd surface
medium [98,119,120]. Well-defined hydrogen desorption (405 mC/cm2) [125,126].
(dashed area, QHdes) and adsorption (QHads) peaks were
noticed in the potential range between 0.0 and 0.3 V during the ECSA from the double-layer capacitance of non-noble metal
forward and reverse scan. The electrochemical surface areas catalysts in both acidic and alkaline medium
(ECSA) were estimated by quantifying the charge related to the For non-noble metal-based electrocatalysts, the ECSA can be
effectively calculated from the electrochemical double-layer
capacitance (Cdl) evaluated at the non-Faradaic potential re-
gion of the respective CVs at different scan rates (Fig. 7)
[127,128]. The Cdl of the catalyst materials can be considered
as a prominent quantitative indicator to estimate the acces-
sible surface area for electrochemical reactions. It can be
determined from the plot of the difference of anodic-cathodic
current density values versus the range of various scan rates
(likely 5, 10, 20, 40, 60, 80, 100, and 120 V/s), where the slope
value can be obtained from the linear trend of the plot [128].
The Cdl was determined by adapting the following Equations
(5) and (6) using the slope value of the plot Dj vs. n [129e131].
Dj ¼ ja jc (5)
dðDjÞ
Fig. 4 e Pictorial view of two probe (through-plane) solid- Cdl ¼ (6)
2 dy
state conductivity cell (home-made design).
where, ja and jc are the anodic and cathodic current density could elucidate the significance of the catalyst surface struc-
(mA/cm2) values and Dj is the difference between the current ture and its electronic properties [138e140].
value of ja and jc, n is the scan rate (V/s). Hence, the ECSA of the
catalysts can be quantified using the following Equation (7) Percentage of catalyst (Pt) utilization and roughness factor
[131,132],
The efficacy of the electrocatalyst can be calculated by esti-
Cdl mating the number of exposed Pt atoms among the catalyst
ECSA ¼ (7)
Cs material dispersed on the GC electrode readily accessible for
where, Cs is the specific capacitance of the electrode with a surface electrochemical reactions [141e143]. The percentage
flat surface, which is found between 20 and 60 mF/cm2, of catalyst utilization is related to the catalyst surface phe-
therefore, we can take a modest value of 40 mF/cm2 to calculate nomenon that can be determined using the ECSA and the
the ECSA of the non-noble metal based catalysts chemical surface area (CSA) from the crystallite size of the
[129,131,133,134]. active catalysts measured by XRD analysis. The CSA can be
determined by the following Equation (9) [144e146]:
ECSA from CO stripping of noble metal catalysts in both acidic
6 104
and alkaline medium CSA ¼ (9)
r d
In order to estimate the ECSA of the electrocatalysts, the
electrochemical oxidation of pre-adsorbed CO, also termed as where r is the density of the Pt catalyst (21.4 g/cm2) [146,147]
CO stripping measurement through CV studies was consid- and d is the average crystallite size calculated from the XRD
ered as the most reliable approach than Hupd method [135]. patterns (A).
The CO stripping measurement can be carried out by sweep- The measurement of Pt utilization percentage can be
ing the potential from 0.0 to 1.2 V in 0.1 M acidic electrolyte estimated from the ratio between ECSA and CSA as follows
solution, which prior purged with CO gas for 10 min and fol- (10) [145,148],
lowed by N2 gas for 30 min to expel the excess of CO from the
ECSA
electrolyte at a fixed potential (0.1 V vs RHE), as shown in Fig. 8 Pt utilization % ¼ 100 (10)
CSA
[136]. More importantly, the fresh surface of the catalyst
Hence, the Pt utilization percentage could be considered as
should be cleaned by few potential cycles under the N2 at-
one of the contributing factors for the larger ECSA of the
mosphere then the CO stripping procedure could be done.
catalyst, which plays a significant role to improve kinetics of
The ECSA was evaluated according to the following Equa-
the electrochemical reactions (ORR) [149,150]. In addition to
tion (8) [137,138],
this, the determination of the roughness factor (Rf) of the
QCO catalysts is more significant to describe the efficiency of the
ECSA ¼ (8)
Qref m electrocatalysts for ORR. The Rf can be estimated by the given
Equation (11) [151e153],
where QCO is the charge acquired of CO desorption (stripping)
(mC) from active sites of the catalyst, m is the catalyst loading !
.
on working electrode (GC), and Qref is the standard reference QH Q
ref
value of CO stripping, the monolayer adsorption of CO on Pt Rf ¼ (11)
Apparent surface area
surface given as 420 mC/cm2 [138]. In addition to that, the ratio
of ECSAs obtained from Hupd and CO stripping measurements where QH and Qref are the charges associated with H-desorp-
tion/adsorption and the adsorption of monolayer hydrogen on
Fig. 5 e CV of a polycrystalline Pt electrode in N2-saturated Fig. 6 e CV of Ag electrode in N2-saturated 0.1 M KOH at

0.5 M H2SO4 at a scan rate of 0.05 V/s and 25 C. 0.1 V/s and 25 C.
active catalyst sites respectively. The apparent surface area is

a geometrical surface area of the working electrode (cm2). = = =
IL ¼ 0:62 nFCO2 D 3 y16 u
2 12
(12)
Polarization curves (LSV) for ORR
The LSV curves are significantly providing the electrokinetic Quick cuts: 7 Key potential values
information of ORR, which is fundamental to understand the
Onset potential (Eonset ) e a starting point of ORR
electrochemical behavior of the catalysts under certain condi-
current.
tions [97]. The surface modification of fresh and mirror-finished
Half-wave potential (E12 ) e an indicator to probe the
=
GC-RDE working electrode with a thin catalyst layer was used
catalysts efficiency by the difference on overpotential
to catalyze the ORR. For an individual electrocatalyst, the ob-
(E12 ¼ JL 2).
=
=
tained polarization curve can be dissevered into three distinct
Overpotential (ƞ) e the difference between theoretical
regions comprising both kinetic and mass transfer effects
(std. electrode potential or equilibrium potential of
[154,155]. From Fig. 9, the kinetic-controlled region can be
oxygen) and experimental (onset potential) values.
observed above 0.95 V (high potential), where the rate of ORR is
relatively sluggish and the current density could be much
lesser. Whereas, the ORR current density begins increasing at a
particular potential with up to 0.55 V is marked as a mixed ki- The limiting current, IL (mA), is normalized by the elec-
netic and diffusion-controlled region [59,60]. In this region, the trode's geometrical surface area to obtain the limiting cur-
rate of the reaction accelerates as the potential decreases with rent density (JL) value [161,162]. The value of JL for a 4-
the significant increase of the ORR current density. Finally, the electron transfer of ORR should be a constant value at
plateau region of the curve at below 0.6 V (low potential) attri- 1600 rpm over the working electrode with dia. 5 mm for a
butes the diffusion-controlled region, in which the ORR current given concentration of electrolyte solution, such as
density can be precisely determined by the diffusion rate of 5.277 mA/cm2 for 0.5 M H2SO4, 6.332 mA/cm2 for 0.1 M HClO4,
reactants to the electrode rotation speed [59,60]. and 5.968 mA/cm2 for 0.1 M KOH [158]. Furthermore, many
aspects, like catalyst selectivity, the catalyst active surface
Onset potential, half-wave potential, and limiting current area, viscosity, and oxygen diffusion of the electrolyte solu-
density tion, can influence the deviation within theoretical and
experimental values [158,163].
The characteristic feature of the ORR kinetics can be deter-
mined from the crucial parameters are of the onset potential Kinetic current density of ORR
(Eonset, V vs. RHE) and half-wave potential (E1/2, V vs. RHE),
measured directly from polarization (LSV) curves [154]. The The ORR disc current density in the potential between 0.7 and
potential for the current to deviate from the baseline is known 0.95 V vs. RHE is relatively independent of the electrode
as the onset potential. Furthermore, the definition of onset rotation rate, indicating that current densities in this specific
potential is still up for discussion, since it differs from one potential region are purely controlled by the kinetics of oxy-
report to another [97,156]. The onset potential can be deter- gen reduction and thus referred to as kinetic current density
mined experimentally in a variety of ways. The intersection of (Jk) [60,164]. Moreover, the Jk value can be calculated using the
the tangents between the baseline and the increasing current Equation (13) below, which is a mass-transfer corrected cur-
in the ORR-LSV curve is a suggested practice [154]. The onset rent density of ORR [45,60,164e166].
potential has also been suggested as a value equal to 5% of the
ðJL JP Þ
diffusion-limited current density derived from the polariza- Jk ¼ (13)
ðJL JP Þ
tion curve [60,157]. On the other hand, a potential with an ORR
current density of less than 0.1 mA/cm2 has been suggested where, Jp is the current density acquired at a particular po-
[155]. For cross-laboratory comparison, an analogous criterion tential and JL is the highest diffusion-limiting current density
is strongly recommended. The half-wave potential is likely obtained from the diffusion plateau region.
another important parameter that can be calculated directly
from the LSV curve's midpoint, that is the potential corre- Mass activity and specific activity of ORR
sponds to half of the limiting current density. As the onset and
half-wave potential values are more positive, the catalyst Based on the mass-transfer corrected current density (i.e.,
becomes more active [59,154,158]. The steady-state limiting kinetic current density, Jk) value, the mass activity (MA, mA/
current density (JL, mA/cm2), which can be determined from mg) and specific activity (SA, mA/cm2) are determined and
the diffusion-limiting region of the ORR-LSV curve, which used to assess the catalyst efficiency for ORR. The MA and SA
means the highest current value in the ORR and significantly values were calculated using the following Equations (14) and
impacted by experimental conditions [159]. The Levich equa- (15) respectively [59,124,167,168],
tion (12), for direct four-electron transfer of ORR can be used to
Jk
determine the theoretical value of JL, which is significantly Mass activity ¼ (14)
Catalyst loading
different from the experimentally determined values found in
various literature [158e160].
Fig. 7 e (a) CVs for the PeFe2O3/Ce-Pi at scan rates of 5, 10, 30, 50, 70, and 90 120 mV/s. (b) The linear relationship between
the capacitive current at 1.20 V vs. different scan rates for the as-prepared catalysts. Reproduced with permission [127].
Copyright 2019, Elsevier.
Fig. 8 e (a) CO stripping CV with simulation (COSS-CV) of the Pt/C catalyst in 0.1 M HClO4 at 0.02 V/s. The COSS-CV is
performed after holding the potential at 0.1 V for 40 min in N2 purged electrolyte. (b) Close-up of the CO stripping region of
the CVs from (a). Reproduced with permission [136]. Copyright 2014, Journal of The Electrochemical Society.
Mass activity
Specific activity ¼ (15)
ECSA
where, the catalyst loading refers to the mass of catalyst
coated on the WE's surface, and ECSA is derived from CV
studies of the individual catalysts under particular conditions
[169]. Furthermore, the mass and active surface area
normalized kinetic current density was considered to be the
most significant kinetic parameters, describing the intrinsic
properties of the catalysts and allowing us to compare them to
the state-of-the-art in Pt/C and other benchmark catalysts for
ORR published in the literature [168e171].
Quick cuts: 8 Why low scan rate for ORR-LSVs?

With a lower scan rate, the electrochemical process of
ORR in LSV is similar to steady-state. On the other hand,
it is sensitive to surface hydroxyl group blockage and
substantial contaminants, which may impede catalytic Fig. 9 e Typical ORR polarization curve for Pt/C catalyst in
efficiency and lead to the assertion of reaction orders 0.1 M HClO4 at 1600 rpm with a scan rate of 0.01 V/s.
below unity. Reproduced with permission [60]. Copyright 2020, Cell
Press.
Tafel slope (b), exchange current density (J0), and electron The above equation, which was correlated with mass-
transfer co-efficient (a) transfer corrected current-potential, can be simplified
further as follows, where d(lnJc)/dE is the Tafel plot's slope. It
The electrocatalytic reactions are comprised of several can be written as (Eq. (19)) [188].
elementary steps, which have a different forward and back-
RT
ward reaction rate depending on the applied potential, ac- a¼ b (19)
F
cording to the Butler-Volmer equation [172,173]. The
logarithmic current-potential relationship was eventually According to the published literature, the electron transfer
revealed mathematically by Tafel. Tafel analysis is a tool for coefficient, exchange current density, and reaction order for
evaluating electrocatalytic efficiency and elucidating the re- ORR were used as semi-empirical values to assess the elec-
action mechanism involving the surface adsorption of reac- trocatalysts' performance [172,173,181,194,195].
tive species (oxygen and its intermediates) on electrocatalyst
active sites [173e175]. In addition, the Tafel Equation (16) Number of electron transfer (from K-L plot) and apparent
provides information associated with the rate-determining rate constant
step of the ORR mechanism [173,176e179].
RDEs and RRDEs are effective techniques for studying the ki-
h ¼ a þ b logðJkÞ h ¼ Eeq Eonset (16) netics of multistep charge transfer reactions as well as
chemical-charge transfer reactions in accordance [77,87,96].
2:303 RT The combination of the Levich equation and Butler-Volmer
b¼ logJ0 (17)
aF equation proposed the relation to evaluating the number of
where h is the overpotential, a and b are the intercept and electron transfers involved (n) during the ORR under hydrody-
Tafel slope (Eq. (17)) respectively, a is the electron transfer namic conditions using RDE/RRDE [60,65,158,192]. The ORR-LSV
coefficient, R is the gas constant, F is the Faraday constant, T is profiles of the electrocatalyst (Pt/C) were recorded at electrode
the temperature and Jk and J0 are kinetic and exchange current rotation rates between 400 and 2400 rpm with respective K-L
density respectively. plots at different potentials (Fig. 12a and b) [107,196]. The
In general, Tafel plots (Fig. 10) can be constructed between diffusion-limiting current densities (mass-transfer controlled)
the logarithm of mass-transfer corrected current density (log Jk) showed a significant increasing trend with respect to electrode
and applied potential (E), which is used to ascertain the kinetic rotation rate shortly after 0.8 V vs. RHE [166,197e199].
mechanism of ORR, exchange current density (J0), and the Based on the current values over the electrode rotation
electron-transfer coefficient (a) [176,180e183]. The Tafel plot rate, the Koutecky-Levich (K-L) Eqs. (20) and (21) be used to
shows two linear regions for polycrystalline Pt and Pt-based calculate the ‘n’ value by plotting the inverse of the limiting
catalysts, with slopes of about 60 mV/dec at low overpotential current density (1/JL) against the square root of rotation rate
and nearly 120 mV/dec at high overpotential [174,180,181, (u1/2), which is termed as the K-L plot [60,164,199,200].
184,185]. The coverage of adsorbed oxygen species can be
1 1 1
defined in respect of high surface coverage of adsorbed oxygen ¼ þ (20)
J Jk JL
intermediates at low overpotential (Temkin isotherm) and low
surface coverage of oxygen intermediates at higher over- 1 1 1
potential (Langmuir isotherm) regions [175,186e190]. The de- ¼ þ (21)
J nFkCO2 Bu1=2
viation in the Tafel slope value is frequently interpreted as an
indication of a change of reaction mechanism due to variation where ‘J’ is the sum of the observed current density (mA/cm2),
in reaction conditions, such as intermediate coverage and Jk and JL are the kinetic and diffusion-limiting current den-
surface morphology caused by the electrical potential [181,191]. sities (mA/cm2) respectively. Then, the ‘n’ is the number of
Using the Tafel plot, the extrapolation of the current- electrons transferred during the reaction, F is the Faraday
potential curve up to the thermodynamic potential of ORR constant (C/mol), k is the apparent rate constant (cm/s), CO2 is
(1.229 V vs. RHE) allowing to measure the exchange current the concentration of oxygen (mol/cm3), ‘u’ is the rotation rate
density of the catalysts for ORR. Fig. 11 exemplifies a clear of the electrode (rpm) [164,201].
method for measuring the exchange current density directly By rearranging the above K-L equation, the kinetic rate
from the Tafel plot for both ORR benchmark electrocatalysts constant (k) (Eq. (22)) and the number of electrons transferred
and standard Pt/C [192]. Generally, an ORR electrocatalyst (n) per oxygen molecule can be calculated from the corre-
material with a high J0 and low b is most favored, indicating sponding K-L slope value (B) (Eqs. (23) and (24))
that it would have improved kinetics. Furthermore, the elec- [164,199,201e206],
tron transfer coefficient is a magnitude that ranges between Jk
0 and 1, expressing the influence of the electrode potential on Jk ¼ nFkCO2 /k ¼ (22)
nFCO2
the energy of the transition state; for ORR, the value is typi-
cally about 0.5 [181]. The following expression was suggested
23
=
by an IUPAC technical report to estimate the cathodic electron 16
=
B
B ¼ 0:62 nF DO2 y CO2 /n ¼ (23)
transfer coefficient (Eq. (18)), which can be used for ORR [193].
23
=
= 16
0:62 F DO2 y CO2
RT dðlnJc Þ
a¼ (18)
F dE
Percentage of H2O2 formation and number of electron

transfer (from RRDE)
During the ORR, the formation of intermediate species is

playing a critical role which determining the kinetics and
proposing the mechanism subject to the number of electrons
involved and the pH of the electrolyte solution [77,214,215].
Thus, the number of intermediates impacts the overall elec-
trode efficiency and reflecting in a fuel cell performance
[80,216]. A rotating ring disc electrode (RRDE), which is the
most sensitive and direct tool for measuring intermediate
formation, was used to quantify the percentage of hydrogen
Fig. 10 e Tafel plots for anodic and cathodic regions of the
peroxide (H2O2) in acidic and peroxide (HO2-) in an alkaline
current-overpotential curve. Reproduced with permission
medium [80,107,166,217]. Fig. 13 shows ORR-LSV profiles of
[183]. Copyright 2001, Wiley-VCH Verlag GmbH & Co. KGaA.
disc and ring current densities and the respective ‘n’ and the %
of H2O2 formation at various potential [145]. Using RRDE, the
polarization curves have recorded the current from the disc

electrode surface where the oxygen gets reduced and then the
23
=
16
=
B
B ¼ 0:2 nF DO2 y CO2 /n ¼ (24) reduced oxygen species oxidized at the ring electrode surface,
23
= 16
=
where namely ring (IR) and disc (ID) currents respectively and
0:2 F DO2 y CO2 plotted as a function of the disc potential [17,196,218]. The
where, the above parameters, such as Faraday's constant (F), RRDE-LSV measurement was performed by maintaining the
bulk oxygen concentration (CO2), oxygen diffusion coefficient ring potential at 1.2 V vs. RHE, where the peroxide oxidation
(DO2), and kinematic viscosity (n) for various electrolyte solu- could be diffusion-limited and such high potential was suffi-
tions at a given concentration, were summarized as stated in cient to facilitate complete the oxidation of any intermediates
the literature (Table 1) [107,124,125,133,145,164,166,207e213]. (H2O2), while reaching at the ring surface by the centrifugal
The ‘n' value can be measured using the K-L slope value by flow of the electrode rotation [17,166,196,217].
introducing the electrode rotation rate in either Eq. (23) or Eq. Based on the ring and disc current values, the formation of
(24), when ‘u’ is the angular velocity in radians per second (rad intermediate species (H2O2 or HO2-) and the number of elec-
s1) or when ‘u’ is in revolutions per minute (rpm) respec- trons transferred during ORR with the effect of diffusion
tively. The following mathematical expression (25) can be control can be determined using the Equations (26) and (27) as
used to convert angular velocity to revolutions per minute and given below [17,166,219]:
vice versa [79].
ð2JR =NÞ
H2 O2 ð%Þ ¼ 100 (26)
ðJD þ JR =NÞ
rad s1 ¼ rpm 0.10472 (or) rpm ¼ rad s1 / 0.10472 (25)
where JD is the disc current density, JR is the ring current
density, and N is the RRDE collection efficiency.
The number of electrons transferred during the ORR (n)
value was calculated from the disk current (JD) and ring cur-
rent (JR) densities by the following equation [17,204,219].
JD
n¼4 (27)
ðJD þ JR =NÞ
where, N is the collection efficiency of the RRDE, which is

the fraction of product between the disc and the ring
electrodes.
Quick cuts: 9 RRDE - Pt ring vs. Au ring

Although the oxidation of ORR intermediate (H2O2) in
acidic medium is not a mass-transfer-limited operation.
Hence, the widely used RRDE method with a Pt ring is not
Fig. 11 e The exchange current was measured for both ORR suitable for alkaline medium. An adequately balanced
benchmark electrocatalysts and state-of-the-art Pt/C Au ring, on the other hand, is ideal for (HO
2 ) collection
catalysts. Reproduced with permission [192]. Copyright and provides accurate n values.
2021, Elsevier.
Fig. 12 e (a) ORR-LSV profiles of Pt/C catalysts observed at 0.01 V/s in 0.1 M KOH solution with different rotation rates and (b)
corresponding K-L plots at various potentials. Reproduced with permission [107]. Copyright 2020, John Wiley & Sons Ltd.
Calibration of collection efficiency (N) between 400 and 2400 rpm at 0.01 V/s. The ‘N’ value can be
estimated by using the following Equation (28) [199,204,217]:
In RRDE, the disc electrode will act as a generator, and the ring
JR
electrode performed as a collector to the species generated at N¼ (28)
JD
the disc. In this, the rate of formation of intermediate species
could be an influencing factor determined by the current where the disk current (JD) and ring current (JR) densities and
produced at the ring (collector) electrode [220]. The estimation the calculated ‘N’ value should be matched well with the
of collection efficiency (N), which is the fraction of a stable manufacturer data [217].
oxygen species produced over the disc that could be collected
on the ring for a given geometrical surface area of the disc and ORR rate constants (k1, k2 & k3) from the Damjanovic
ring electrodes, is critical in determining RRDE efficacy. The mechanism
current recorded on the ring was influenced by the electrode
rotation rate and the kinetics of the electrochemical reaction Damjanovic proposed the following general mechanism for
at the disc, can be used to estimate the ‘N’ value [215,217,220]. oxygen reduction: a direct four-electron transfer reaction that
The oxygen transported to the disc surface is transformed to produces water, and/or a two-electron transfer reaction that
intermediate (peroxide) at a rate determined by the applied produces hydrogen peroxide (H2O2), which is an intermediate.
potential and mass transfer limitations in ORR. When the This intermediate could be reduced further by another two-
formed intermediate at the disc is moved to the ring, where it electron transfer, producing water as a final product
is oxidized back to oxygen [215,220]. [221e223]. The actual reaction path is invariable between
Using the standard ferrocyanide/ferricyanide redox couple these two mechanisms, and H2O2 intermediate formation is
([Fe(CN)6]3-/[Fe(CN)6]4-) with supporting electrolyte is generally detected in the majority of cases. If the amount of interme-
used to calculate collection efficiency, where the redox reac- diate formation is small, the reaction is close to the theoretical
tion of the Fe3þ/Fe4þ couple is a simple, one-electron, and value of four-electron transfer. The reaction pathways are
reversible reaction [204]. When calibrating the collection effi- depicted as [23,166,218,224e226]:
ciency, the N2 saturated supporting electrolyte (1 M KNO3 or
0.1 M KOH) with 10 mM K3[Fe(CN)6] solution was used to
recording the polarization curves using RRDE under hydro-
dynamic conditions [17,217]. The potential window was
ranged 0.4e1.5 V vs. RHE and at the ring electrode potential of
1.55 V vs. RHE. The electrode rotation speed was maintained
Table 1 e The following is a list of some of the most relevant K-L equation values, as compiled from published literature.
Parameters Electrolyte solution
0.5 M H2SO4 0.1 M HClO4 0.1 M KOH 0.1 M NaOH
Faraday constant (F) (C/mol) 96 485 96 485 96 485 96 485
Concentration of oxygen (CO2) 1.10 106 1.20 103 1.26 106 1.38 106
(mol/cm3)
Diffusion coefficient of oxygen (DO2) 1.40 105 1.90 105 1.98 105 1.90 105
(cm2/s)
Kinematic viscosity (n) 0.01 0.01 0.01 0.01
(cm2/s)
Fig. 13 e RRDE-polarization (a) disc and (b) ring curves for PteIr/MWCNT and Pt/MWCNT catalysts recorded in N2 purged
0.1 M HClO4 electrolyte at 0.1 V/s; trend graph of (c) percentage of H2O2 and (d) number of electrons transferred during ORR as
a function of applied potential. Reproduced with permission [145]. Copyright 2020, Elsevier.
1600 rpm at 0.01 V/s [166,230]. From the ORR current density
To estimate the each kinetic rate constants of k1, k2, and k3
values at a fixed potential, the Arrhenius plot was constructed
based on the experimental results of the given Equation (29)
between log jo vs. 1/T, and its slope value used to calculate the
[166,201,227e229].
Ea by the following equation (30) [184,201,232,234].
j1 N 1 2Z1 S2 Z2 NS1
k1 ¼ S2 Z1 ; k2 ¼ ; k3 ¼ (29) v logj0
j1 N þ 1 j1 N þ 1 j1 N þ 1 Ea ¼ 2:3R (30)
vð1=TÞ
where, Z1 ¼ 0:2D2=3
O2 n
1=6
and Z2 ¼ 0:2D2=3
H2 O2 n
1=6
& DH2O2 ¼ 6.8 £
where j0 is the exchange current density (mA/cm2), R is the gas
6 2 1
10 cm s ; J1 and S1 are the intercepts and slopes of the plot constant (8.3145 J/Kmol) and T is the temperature in ºC [231].
ID/IR versus w1/2, respectively. S2 is the slope of the plot ID/(ID -
I) vs w1/2. Higher values of k1 and k3 designate that the ORR Turnover frequency (TOF)
mechanism follows a direct 4-electron transfer as resulting
from the K-L plot [166,224,227,230]. Turnover frequency (TOF) is one of the key parameters to
assess the intrinsic properties of the electrocatalysts for ORR.
Activation energy TOF can be defined as the number of oxygen molecules reduced
per unit active catalyst sites per unit time [231,235e238]. The
The Arrhenius law of activation energy can be used to assess higher magnitude of TOF values representing the improved
the effect of reaction temperature on ORR kinetics [231,232]. kinetics of ORR on active catalyst sites and can be determined
An empirical relationship between the apparent rate constant from the ORR current density at specific potential and the
and the reaction temperature provides the classical approach number of active sites of the catalyst involved in the reaction
for estimating the activation energy (Ea) of the reaction. The Ea obtained from the inductively coupled plasma (ICP) analysis or
values about the kinetics of the reaction, which could provide voltammetry techniques [154]. The TOF value can be calculated
valuable insights about the intrinsic properties of the reaction using the following relation (31) [235,239],
mechanism [231,233]. For ORR, LSV profiles were recorded at
various temperatures (25 C to 65 C) using a double-jacket ðJ AÞ
TOF ¼ (31)
electrochemical cell connected to a precise temperature con- ðn F mÞ
trol thermostat, and the electrode rotation rate was about
Fig. 14 e Nyquist plot and its equivalent circuit, showing the effect of diffusive impedance. Reproduced with permission
[243]. Copyright 2015, Brazilian Scientific Journals.
where, J is the ORR current density (mA/cm2), A is the elec- and reaction interface. The Nyquist plot, also known as the
trode surface area (cm2), n is the number of electrons trans- Argand depiction or the Cole-Cole plot, represents a complex
ferred during ORR (n ¼ 4), F is the Faraday constant (96 485 C/ plane with number of points, each signifying the direction and
mol) and m is the number of moles of active metals on the magnitude of the impedance vector of a frequency [243].
electrode surface (mole) [154,231]. Fig. 14 depicts a typical EIS (Nyquist plot) diagram with an
On the other hand, the TOF can be calculated using the ORR electrical circuit fit, which has complex Cartesian coordinates
kinetic current density using the following Equation (32) [238], for the real (resistive part) and imaginary (capacitive or
impedance part) impedance axes [63,243]. The Nyquist plot
Jk
TOF ¼ (32) was constructed on a Cartesian plane over a wide frequency
ðn e Ns Þ
range between 100 KHz and 10 mHz (normally 10 KHz to
where, Jk is the ORR kinetic current density (mA/cm2), n is the 0.1 mHz) provides classical configuration based on the influ-
number of electrons transferred during ORR (n ¼ 4), e is the ential electrochemical mechanism. In the Nyquist plot, the
charge of an electron (1.6 1019 C), Ns is the number of active polarization resistance (electrode resistance, RU) can be
sites on the catalyst surface (mole) [231,237]. determined by extrapolating the left side of the curve to the
real impedance (x-axis), whereas the charge transfer resis-
Conductivity from EIS studies tance (Rct) is the diameter of the semicircle to which the right
The EIS measurement was performed using a two-electrode

through-plane conductivity cell, and semi-circle curves were
obtained in a plot between real and imaginary impedance
known as the Nyquist plot [240e242]. In a Nyquist plot, those
semi-circles should be fitted to a mathematical model that
represents a type of electrical circuit termed the equivalent
circuit. This circuit is typically made up of resistors, capaci-
tors, and impedance components [61,63,66]. Using specific
fitting software, the value of the Resistance can be assessed
from the best fitting of the equivalent circuit [68]. The proton
conductivity (sP) of the free-standing catalyst films was
calculated by the following Equation (33) by the actual ohmic
resistance acquired from the respective Nyquist plots at a
higher frequency region [106,108].
L
sP ¼ (33)
A R
where, sP-conductivity of the sample, (S/cm); L-thickness of
the film, (mm); A-surface area of the electrode, (cm2); and R-
ohmic resistance, (ohm).
The EIS is usually interpreted using the correlation be- Fig. 15 e Schematic of typical Nyquist plots with various
tween the impedance data and the equivalent circuit point of impedance for electrical double layer capacitor
describing the physical processes occurring in the system electrodes or devices. Reproduced with permission [246].
during the electrochemical reaction at the electrode surface Copyright 2018, American Chemical Society.
side has been extrapolated. This equivalent circuit repre- references

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international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

A quick guide to the assessment of key

Narayanamoorthy Bhuvanendran a,d, Sabarinathan Ravichandran a,b,

highlights graphical abstract

This review provides crucial in-

article info abstract

the complex multi-step reaction mechanism with the forma-

Electrochemical impedance spectroscopy electrochemical reactions [72]. An acidic electrolyte solution is

Supporting electrolyte As mentioned earlier, the three-electrode cell setup is dedi-

Working electrodes (c) Mercury e mercury oxide electrode (Hg/HgO, MMO)

electrochemical cell are configured at a fixed distance and

Catalyst ink preparation and coating

The catalyst ink was then prepared by dispersing a certain

Quick cuts: 4 Will the use of Pt as a counter electrode

Method of measurements LSV measurement

Solution-phase measurement (three-electrode electrochemical

Fig. 5 e CV of a polycrystalline Pt electrode in N2-saturated Fig. 6 e CV of Ag electrode in N2-saturated 0.1 M KOH at

active catalyst sites respectively. The apparent surface area is

Polarization curves (LSV) for ORR

Quick cuts: 8 Why low scan rate for ORR-LSVs?

Percentage of H2O2 formation and number of electron

During the ORR, the formation of intermediate species is

where, N is the collection efficiency of the RRDE, which is

Quick cuts: 9 RRDE - Pt ring vs. Au ring

The EIS measurement was performed using a two-electrode

side has been extrapolated. This equivalent circuit repre- references

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