Journal of Colloid and Interface Science 387 (2012) 213–220

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Journal of Colloid and Interface Science

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Kinetics and mechanism of electrochemical oxygen reduction using

Platinum/clay/Nafion catalyst layer for polymer electrolyte membrane fuel cells
B. Narayanamoorthy a, K.K.R. Datta b,1, S. Balaji a,⇑
a
Department of Chemistry, Faculty of Science, Sri Chandrasekharendra Saraswathi Viswa Mahavidyalaya (SCSVMV University), Enathur, Kanchipuram 631 561, India
b
Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Bangalore 560 064, India

a r t i c l e i n f o a b s t r a c t

Article history: This work demonstrates the use of amino functionalized Mg-phyllosilicate clay/Nafion nanocomposite
Received 27 April 2012 film embedded with Pt nanoparticles (Pt/AC/N) for catalyzing oxygen reduction reaction (ORR) in sulphu-
Accepted 1 August 2012 ric acid medium. Pt/AC/N nanocomposite films were surface characterized using transmission electron
Available online 15 August 2012
microscope. Cyclic and linear scan voltammetry studies were carried out under hydrodynamic conditions
taking rotating-ring disc electrode (RRDE) as the working electrode. The effects of clay content, Pt mass
Keywords: loading, electrode rotation rate, and temperature on the ORR kinetics were studied. The Tafel slopes were
Aminoclay
found to vary between 118 and 126 mV dec1 indicating a good ORR kinetics. The exchange current den-
Pt/aminoclay
Nafion
sity values calculated after mass transfer correction ranged from 5.8  107 to 2.4  106 A cm2. From
ORR the RRDE disc currents, Koutecky–Levich plots were constructed and the ORR mechanism was found
RRDE to follow a four electron path with minimum H2O2 formation of 1.6%. The effect of temperature on
LSV ORR kinetics was found at 25, 40, and 50 °C. The energy of activation calculated to be 7.68 kJ mol1
and comparable to the standard Pt/C catalyzed ORR systems.
Ó 2012 Elsevier Inc. All rights reserved.

1. Introduction
Fuel cells are expected to reduce the dependence on carbon
fuels not far away from now and provide great promise as future
energy sources as they convert chemical energy to electrical en-
ergy with a significantly greater efficiency than in standard com-
bustion processes [1–3]. Among fuel cells, polymer electrolyte
membrane fuel cells (PEMFCs) are highly attractive due to the
ambient temperature working conditions and portability [4,5].
But to achieve the commercial viability, technical advances are still
progressing to decrease the cost while improving the efficiency of
the cathode catalysts where the sluggish oxygen reduction reac-
tion (ORR) takes place. The ORR is a complex multistep reaction
involving the exchange of four electrons [6] to form water.
Fuel cell researchers believe that optimizing the existing cata-
lyst layers (CLs) with respect to composition and structure, devel-
oping novel fabrication technologies, and introducing innovative
approaches may help to improve ORR kinetics. Actually, the CL pro-
vides a three phase boundary where the reactant gas, protons, and
electrons undergo reaction [7]. The properties and composition of
the CL determine the electrochemical reaction rate and power
output of the system. Therefore, an optimal CL design is required
⇑ Corresponding author. Fax: +91 44 27264285.
E-mail address: prof.balaji13@gmail.com (S. Balaji).
1
Present address: Regional Centre of Advanced Technologies and Materials, Faculty
of Science, Department of Physical Chemistry, Palacky University, 771 46 Olomouc,
Czech Republic.
to improve the catalyst utilization and reduce cost. The important
processes occurring in a catalyst layer include interfacial ORR at
the electrochemically active sites, proton transport in the electro-
lyte phase, electron conduction in the electronic phase (i.e., Pt/C),
and oxygen diffusion through the gas phase [8]. Therefore, highly
functionalized thin CL is required to be developed possessing many
desirable characteristics for improving ORR performance [9].
The crucial part of the fuel cell system is the membrane-electrode
assembly (MEA), which consists of a proton exchange membrane
(Nafion) with a layer of catalyst coated on both sides and a porous
gas diffusion layer (GDL) in contact with each side of CL [10,11].
MEAs are usually fabricated by airbrushing the catalyst layer ink
onto a Nafion 117 membrane. The normal choice for catalyst support
is carbon black (CB). Despite its widespread use, CB is known to un-
dergo electrochemical oxidation to surface oxides and eventually to
CO2 at the cathode of a fuel cell, and also exposed to highly acidic and
humid environments in presence of high potential and temperature
(ca. 80 °C), which drastically reduces Pt surface activity, and many
studies have reported the agglomeration and loss of precious metal
content due to carbon corrosion [12,13]. In the literature, there are
few reports available that used Pt embedded over naturally occur-
ring clay/Nafion as the CL for ORR [14]. Zhang et al. have adopted
chemical vapor deposition method for fabricating platinum nano-
particles (Pt/NPs) over Cloisite 20A clay, which indeed requires a
good experimental set up and also time consuming [15].
We report the synthesis of amino functionalized clay (herein
after aminoclay (AC)) from its precursor materials and fabrication

0021-9797/$ - see front matter Ó 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2012.08.002
214 B. Narayanamoorthy et al. / Journal of Colloid and Interface Science 387 (2012) 213–220
of Pt NP embedded nanocomposite films with AC/Nafion (AC/N)
through in situ chemical reduction. The prepared Pt/AC/N catalyst
layers were surface characterized using high-resolution transmis-
sion electron microscope (HRTEM). The electrocatalytic properties
toward ORR were qualitatively evaluated using cyclic voltammetry
(CV) and linear scan voltammetry (LSV) in static and hydrody-
namic modes with rotating-ring disc electrodes (RRDEs). The ef-
fects of varying AC content, Pt mass loading, and temperature on
ORR kinetics were found, and the mechanistic pathway was eluci-
dated and presented.
2. Experimental section
2.1. Chemicals and materials
3-Aminopropyltriethoxysilane (Aldrich) and MgCl26H2O were
used as the precursor materials for the AC synthesis. Chloroplatinic
acid hexahydrate (Aldrich) was used as the platinum precursor
solution. Sodium borohydride (Fluka) was used as a reducing agent.
NafionÒ perfluorinated ionomer resin solution (5 wt%, Aldrich)
(equivalent weight 1100) dissolved in aliphatic alcohol was used
as the polymer matrix. Absolute ethanol (sd fine) and N,N0 -dimeth-
ylformamide (DMF) (Rankem) were used as co-solvents to recast
the Nafion membrane. Vulcan XC-72 carbon (Cabot) was used as
the carbon support. High pure AR nitrogen and oxygen gases were
procured from Praxair (India). Sulphuric acid (Rankem) was used as
the electrolyte medium. All the materials were used as received.
Millipore water (18 MX cm) was used for all preparations.
2.2. Preparation of Pt/AC/N nanocomposite films
The AC and Pt NP supported on AC (Pt/AC) were prepared by the
method reported in the literature [16]. Pt/AC/N nanocomposite
films were prepared by the solvent casting procedure as follows.
A desired amount of Pt/AC from previous stage was mechanically
mixed into de-ionized water. Then, a mixture of commercial
5 wt% Nafion solution, DMF, and ethanol with a volume ratio of
2:1:1 was added to the aqueous mixture of Pt/AC and the whole
mixture was sonicated using an ultrasonication bath at room tem-
perature for 10 min. This mixture was then stirred at 95 °C until a
gel-like suspension was obtained. The Pt/AC loading inside the
nanocomposite film was varied from 2 wt% to 10 wt% giving a Pt
mass loading of 18.2–209.2 lg cm2 on the electrode. For compar-
ison of ORR activities, Pt NP embedded Vulcan carbon/Nafion (Pt/
VC/N) films were prepared following the same procedure as above.
Current density (jd = ID/A) is calculated by taking the RRDE disc sur-
face area (0.2471 cm2).
2.3. Surface and particle size characterization technique
TEM was used to obtain high resolution images of the CL in order
to investigate the microstructure and dispersion of AC sheets and Pt
NP. For TEM analysis, the sample was re-dispersed in absolute eth-
anol by sonication before drop casting on a carbon-coated copper
grid. TEM measurement was recorded on a JEOL JEM-3010 electron
microscope with an applied acceleration voltage of 300 kV.
2.4. Electrochemical characterization
The electrochemical measurements were conducted to investi-
gate the catalytic activity of the Pt/AC/N nanocomposite films for
ORR in acidic medium. RRDE measurements were performed in
0.5 M H2SO4 solution in a three electrode double walled home-
made cell thermostated at the required temperature by water cir-
culation (Equibath). A platinum sheet was used as the counter
electrode and a thin gap RRDE taken as the working electrode
(Pine), while the reference electrode used was Ag/AgCl in 3 M
KNO3 with double junction frit (Pine). The glassy carbon disc of
the RRDE working electrode was loaded with an aliquot of 15 lL
of the prepared colloidal catalyst ink and allowed to dry in N2
atmosphere. For convenience, all potentials are reported relative
to the reversible hydrogen electrode (RHE) by adding +210 mV.
The working electrode was polished to a mirror finish using
0.05 lm alumina slurry (Buehler) prior to each catalyst coating.
The static and hydrodynamic voltammetry experiments were con-
ducted with a computer interfaced bi-potentiostat (Autolab
PGSTAT-128N) controlled by Nova software in conjunction with a
rotator (Pine) fitted with GC-disc/Pt-ring RRDE electrode. Voltam-
metric studies were carried out after nitrogen or oxygen purging
for 15 min before start of the experiment and forming a blanket
during the experiment to prevent the access of atmospheric gases.
Prior to each voltammetry, the potential cycling was carried out in
the potential window 0.0–1.2 V vs RHE, to ensure an identical ini-
tial surface state in all experiments. Blank CV experiments were
conducted in N2 purged 0.5 M H2SO4 to characterize the active lay-
ers in terms of electrochemically active surface area (ECSA) due to
the exposed Pt NP present in the catalyst layer based on the hydro-
gen desorption charge transfer. Thereafter, RRDE experiments were
continued with the same catalyst coated electrode for observing
ORR activity. The steady state and hydrodynamic LSV readings un-
der oxygen saturated conditions obtained through cathodic sweep
(reverse scan) of the disc electrode at 10 mV s1 from 1.2 V to 0.0 V
(vs RHE) were used to construct the polarization curves and to
compare the half cell electrochemical activity. For measuring the
ring currents during the voltammetry at the disc, the ring potential
was maintained at 1.2 V vs RHE, where the oxidation of peroxide is
diffusion limited and such potential is sufficiently high to enable
the complete oxidation of any H2O2 reaching the ring by centrifu-
gal flow due to the rotation. The ring (IR) and disc (ID) currents were
measured simultaneously and plotted as a function of the disc po-
tential. The collection efficiency (N = IR/ID), corresponding to the
percentage of H2O2 formed on the disc and detected at the ring,
was checked using experimental values of IR and ID. Using ferri/fer-
ro cyanide redox couple in 1 M KNO3, the collection efficiency was
found to be 0.37. This calculated value agrees well with the manu-
facturer data [17]. For Electrochemical Impedance Spectroscopy
(EIS) measurements, frequency response analyzer (FRA) equipped
Autolab PGSTAT128N was used to measure the conductivity of
Pt/AC/N catalyst films in potentiostatic mode at 10 mV in the fre-
quency range 0.1–100 kHz. A homemade two-probe conductivity
cell (Perspex) designed with two Cu plates to measure the
through-plane conductivity was used. Pt/AC/N nanocomposite film
was placed between the two Cu discs. Measurements were carried
out at 25 ± 1 °C. A known thickness of the catalyst film was cut into
circular pieces (4 mm dia.). Before measurements, the films were
immersed in de-ionized water for 24 h and the surface water was
wiped out gently without squeezing. The true ohmic resistance
was measured by taking the real impedance at the point that the
imaginary impedance was equal to zero.
3. Results and discussion
3.1. Schematic diagram
Fig. 1 shows the schematic representation of the Pt embedded
AC/N CL along with optical images of 6 wt% AC/N, 35.4 lg cm2
Pt/AC/N, and 70.4 lg cm2 Pt/AC/N nanocomposite films.
3.2. Surface characterization
The morphology and distribution of the Pt NP embedded in AC/
N nanocomposite film are shown in Fig. 2. From the HRTEM image,
 B. Narayanamoorthy et al. / Journal of Colloid and Interface Science 387 (2012) 213–220 215

Fig. 1. Schematic diagram of Pt/AC/N catalyst layer with optical images of (a) 6 wt% AC/N, (b) 35.4 lg cm2 Pt/6 wt%AC/N, and (c) 70.4 lg cm2 Pt/6 wt%AC/N catalyst films.

we observe Pt NP of the size less than 5 nm which is uniformly dis-
persed on AC/N matrix (Fig. 2a) without agglomeration. Further-
more, on closer examination of nanocomposite film by HRTEM,
we observe the lattice fringes corresponding to the crystalline Pt
(Fig. 2b).
3.3. Electrochemical characterization
3.3.1. Cyclic voltammetry
CV response of Pt/AC/N nanocomposite film coated over the
working electrode toward the electrochemical reduction of oxygen
was analyzed in the potential range between 0.1 and +1.4 V vs
RHE at 25 °C. Fig. 3 shows the CVs of Pt/AC/N nanocomposite films
in terms of current density (based on geometrical surface area of
the working electrode) in nitrogen purged 0.5 M H2SO4 at the scan
rate of 50 mV s1 at 25 °C. The CV of the Pt/VC/N film is also in-
cluded for comparison (dotted lines). Before each experimental
run, potential cycling was carried out in the window 0.0 and
+1.2 V vs RHE for 10 times to get a stable CV pattern. CVs were
reproducible in the consecutive scans and remained stable con-
firming that during the experiment, there was no dissolution of
the components from the CL. Though the CV resemble the pattern
of polycrystalline Pt [18], it lacks the well defined multiple peaks
due to hydrogen adsorption in the cathodic sweep and it is desorp-
tion in the reverse sweep like the characteristic CV on Pt electrodes
in H2SO4 solutions [19], which exhibit two peaks in the anodic
branch from 0.0 V to +0.2 V vs RHE and these peaks are attributed
to adsorption on different crystallographic planes on the surface of
Pt, which are appropriately oriented to cause adsorption of hydro-
gen. In this study, both the CVs (AC and VC) are almost similar with
a single hydrogen adsorption and desorption region, indicating the
presence of Pt NP in the CL. The platinum oxide region formed at
+1.15 V and its complete reduction around +0.6 V indicate the un-
ique features of active surface Pt. But, the O2 reduction current for
VC/N supported Pt is less than that of AC/N supported Pt NP. The
obtained current density value is comparable to some of the stan-
dard Pt/C systems reported on Pt [20,21].
The ECSA of Pt was then obtained from N2–CV curve (Fig. 3) by
integrating the H-desorption region (in the positive going potential
from 0.1 V to +0.2 V), subtracting the double-layer charging cur-
rent, and dividing the resulting coulombic charge by 210 lC cm2
Pt [22,23]. This calculation though originated from polycrystalline
Pt still widely used in ORR studies for comparison purposes. In Ta-
ble 1, the ECSA for different AC loadings and Pt loadings are pro-
vided. It was observed from Table 1 that only at an optimum AC
loading (6 wt%), the ECSA was maximum, whereas for Pt, as the
mass loading increases, the ECSA decreases. This might be due to
the unavailability of Pt surface area, distributed over Nafion islands
rather than on AC and becomes inaccessible, for hydrogen
adsorption.

Fig. 2. High-resolution transmission electron microscope (HRTEM) images of 35.4 lg cm2 Pt/6 wt% AC/N catalyst layer, (a) 5 nm scale and (b) 2 nm scale.
216 B. Narayanamoorthy et al. / Journal of Colloid and Interface Science 387 (2012) 213–220

seen from Fig. 4 that at 0.2 V, the observed current densities were
found to be 3.15 and 4.2 mA cm2, respectively, for VC/N and AC/N
supports. The high ORR current of AC compared to VC shows the
ability of AC to bind Pt NP and less Pt surface contamination due
to CO adsorption formed from carbon corrosion [24]. It is evident
that the oxygen reduction is diffusion-controlled at potentials be-
low +0.4 V and is under mixed diffusion–kinetic control in the po-
tential region between +0.4 and +0.65 V. Oxygen reduction activity
of the catalysts is calculated taking the limiting currents. It should
be noted that the sloppy increase in peak current from +0.65 to
+0.4 V indicates the potential dependent ORR current as reported
elsewhere [25,26].
The onset potential for Pt/AC/N is 40 mV positively shifted than
Pt/VC/N, indicating an early initiation of ORR kinetics over AC sup-
port. From LSV, three defined regions are observed. (i) Kinetically
controlled charge-transfer region from 0.75 V to 0.65 V where the
current density was not affected by the rate of mass transfer and
it is independent of the rotation rate; (ii) sloppy mixed kinetic
and diffusion controlled region from 0.65 V to 0.4 V, where the cur-
rent is partially controlled by mass transport and partially con-
Fig. 3. CVs of 6 wt% AC and VC supported Pt NP over Nafion matrix in N2 saturated trolled by the kinetics of electron transfer; and (iii) diffusion/
0.5 M H2SO4. mass transfer controlled region also called limiting current region
below 0.4 V, which increase linearly with w1/2.

Table 1 3.4. Effect of clay loading

Electrochemical active surface areas (ECSAs) of Pt/AC/N catalyst film for different AC
and Pt mass loadings calculated from hydrogen desorption regions of cyclic
voltammograms at 25 °C. To find the optimum AC content in the nanocomposite films, the
a b 2
mass of AC was varied keeping the same Nafion content and an
Catalyst layer AC loading (wt%) Pt mass loading (lg cm )
composition
arbitrarily fixed Pt mass loading (70.4 lg cm2). The observed
2 4 6 8 10 18.2 35.4 70.4 209.2 ORR currents of LSV at 2000 rpm with the sweep rate of 10 mV s1
ECSA (m2 g1) 3.8 4.3 5.1 1.8 1.4 33.6 11.3 5.1 1.9 at 25 °C are shown in Fig. 5a. We can see a high current density of
A
70.4 lg cm 2
of Pt.
3.5 mA cm2 for 6 wt% AC, whereas for 2 wt%, 4 wt%, 8 wt% and
b
6 wt% AC. 10 wt% AC loading, the obtained current densities were lesser than
that of 6 wt% AC support. Therefore, for further studies, 6 wt% was
taken as the optimum level of AC support for obtaining good ORR
current. In the reported literature, the observed trend in ORR activ-
ity, for different Nafion loadings was correlated with ionic conduc-
tivity of the solid catalyst films [27,28].
To strengthen the observed trend in ORR activity for different
clay loadings, the solid state conductance of composite films was
measured by ‘‘Electrochemical Impedance Spectroscopy’’ employ-
ing ‘‘two probe’’ method (through plane conductivity). It was ob-
served that (Fig. 5b) the composite film with 6 wt% AC
composition indeed possessed a high conductivity among all the
other clay compositions. This dependence of AC support content
on ORR activity might be due to the better exfoliation at 6 wt%
AC that provides an optimum three-phase zone of the electrocata-
lyst layer for ORR.

3.5. Effect of Pt loading

LSV current densities in terms of disc electrode surface area, at

Fig. 4. LSVs of 6 wt% AC and VC supported Pt NP over Nafion in O2 saturated 0.5 M
H2SO4.
3.3.2. Linear scan voltammetry
The ORR of the CL was investigated in O2 saturated 0.5 M H2SO4
using the RRDE. The cathodic sweep was carried out in the poten-
tial range +1.2 V to 0.0 V vs RHE. Fig. 4 presents the LSV of Pt/VC/N
and Pt/AC/N nanocomposites with 2000 rpm recorded at 10 mV s1
scan rate with the Pt loading of 35.4 lg cm2 at 25 °C. It can be
different Pt mass loading conditions from 18.2 to 209.2 lg cm2
over 6 wt% AC/N, obtained with the sweep rate of 10 mV s1 at
25 °C and 2000 rpm are shown in Fig. 6a. It was observed that only
at the optimum Pt mass loading of 35.4 lg cm2, a maximum cur-
rent density was obtained. As the loading increases, the limiting
current density increases initially and then decreases for higher
mass loading. This might be due to the less accessibility of Pt NP
distributed outside AC regions and buried inside the Nafion at
higher loadings. Thus, only at the optimum loading of 35.4 lg cm2
Pt, a maximum current density of 4.2 mA cm2 was realized. Also,
it can be observed that at the optimum loading of 35.4 lg cm2 Pt,
the reduction current in the mixed kinetic and diffusion region of
LSV sharply increases, indicating less diffusion resistance offered
by the CL compared to the higher loading conditions where the
 B. Narayanamoorthy et al. / Journal of Colloid and Interface Science 387 (2012) 213–220
Fig. 5. (a) LSVs of Pt/AC/N catalyst layer for various AC loadings in O2 saturated
0.5 M H2SO4 and (b) Nyquist plots of 70.4 lg cm2 Pt/AC/N catalyst layer for various
AC loadings at 25 °C.
increase in the reduction current of mixed kinetic and diffusion
limited region is less.
The half wave potential observed for different Pt loadings were
in the range 0.41–0.46 V vs RHE and the highest half wave poten-
tial of 0.46 V seen for 35.4 lg cm2 Pt indicating that ORR kinetics
is good under this optimum loading. The Koutecky–Levich equa-
tion (refer Section 3.6) is used to obtain the kinetic parameters of
ORR under different rotation rates. The K–L plots for different Pt
mass loadings are shown in Fig. 6b, together with the theoretically
calculated plot for four electron transfer process. The plots are all
linear having the slope in the range 9.96–14.45 mA cm2 rpm1/2
with least slope for the optimum loading of Pt, which gives the
number of electrons transferred in the reduction process as 3.8
near to the theoretical value of 4. In order to find the stability of
the catalyst layer under the optimized conditions of AC and Pt
loading, a separate study was conducted. It was found that at
35.4 lg cm2 of Pt loading with 6 wt% AC over Nafion, the prepared
CL exhibited good stability, and after 2000 potential cycles, nearly
78% of the initial limiting current was found maintained and re-
ported [29].
217
Fig. 6. (a) LSVs for the Pt/AC/N nanocomposite films with different Pt loadings in O2
saturated 0.5 M H2SO4 and (b) Koutecky–Levich plots for the data presented in (a).
3.6. Kinetics of oxygen reduction
LSV was carried out at different rotation rates and the disc
currents collected in the mixed diffusion and kinetically con-
trolled regions are used for constructing the Koutecky–Levich
(K–L) plots as follows [30,31]. The overall current density (j) data
obtained from different rotation speeds can be separated into
the diffusion (jd) and kinetic (jk) contributions. jk represents the
current in the absence of any mass transport effect and provides
a good indication of the ORR kinetics on the surface of a catalyst.
Since the surface Pt atoms are contributing toward the ORR, the
thickness of the film and the diffusion of reactant in the film can
be neglected [32]. Therefore, the following K–L equation can be
applied.
1 1 1
¼ þ
j jk jd
1 1 1
¼ þ
j jk Bw0:5
218 B. Narayanamoorthy et al. / Journal of Colloid and Interface Science 387 (2012) 213–220
Fig. 7. RRDE disc and ring current density profiles of Pt/AC/N nanocomposite film in
O2 saturated 0.5 M H2SO4 at different rotation rates at 25 °C during linear sweep.
where j is the observed total current density at the limiting region,
w is the rotation speed of the electrode (rpm). K–L plots present the
relationship of j1 vs w1/2 and can be used to analyze the ORR
activity. The term B has the following expression (when ‘‘w’’ is in
terms of rpm),
B ¼ 0:2nF½DO2 2=3 m1=6 C O2
where ‘‘n’’ is the number of electrons transferred in the reaction, F
the Faraday’s constant (96,500 C), [O2] the bulk concentration of
oxygen (1.1  106 mol cm3), DO2 the diffusion coefficient of oxy-
gen in 0.5 M H2SO4 (1.4  105 cm s1), and m the kinematic viscos-
ity of the solution (1  102 cm s1). The term 1/Bw1/2 of the K–L
equation corresponds to the diffusion-limited current density,
which is directly proportional to the square root of the electrode
rotation speed. Ring and disc currents at different rotation rates
ranging from 500 to 2000 rpm, with a constant sweep rate of
10 mV s1 are shown in Fig. 7, for 35.4 lg cm2 Pt over 6 wt% AC/
Nafion at 25 °C. The kinetic current density (jk) values can be ob-
tained from the following relation [33]:
ðjp  jd Þ
jk ¼
ðjp  jd Þ
where jP is the measured current density at corresponding half
wave potential and jd is the disc (diffusion-limited) current density.
Number of electrons transferred (n) was calculated from the slope
of K–L equation.
The corresponding K–L plots at different mixed potential re-
gions are shown in Fig. 8. The slopes of the linear plots give the
Fig. 8. Koutecky–Levich plots at different potentials for Pt/AC/N nanocomposite
film in O2 saturated 0.5 M H2SO4.
number of electrons transferred during the oxygen reduction.
The existence of different intercept values indicates different ki-
netic parameters at different potentials, and the non-zero intercept
shows that the ORR kinetics is not simply controlled by diffusion.
The number of electrons transferred was in the range 3.2–3.8 with
the average of 3.45. Since it is not a perfect four electron transfer
reduction process, the formation of small amount of H2O2 interme-
diate is predictable.
The formation of H2O2 intermediate can be calculated from the
equation using ring and disc currents [31]:
ð2IR =NÞ
H2 O2 ð%Þ ¼  100
ðID þ IR =NÞ
where ID is the faradic current at the disc, IR is the faradic current at
the ring, and N is the RRDE collection efficiency (N = 0.37) [17].
From the disc and ring currents, the percentages of hydrogen perox-
ide were calculated. It was observed that H2O2 formation was less at
2000 rpm and increased at lower rotation rates. Nevertheless, only a
maximum of 1.6% H2O2 was formed signifying predominant four
electron pathway.
From the kinetic current density in mixed kinetic–diffusion con-
trolled region from 0.3 V to 0.6 V vs RHE, Tafel slope values were
calculated (log jk vs E (V)). K–L plots obtained are all linear and
show parallel behavior in the mixed control polarization region,
indicating first-order ORR kinetics with respect to oxygen. jk values
at various temperatures were calculated at 0.46 V vs RHE and were
found to vary from 2.6 to 3.3 mA cm2. From the K–L slope, the
number of electrons transferred in the process was found to be
3.8 for the Pt loading of 35.4 lg cm2, indicating the direct four
electron path of ORR kinetics.
The general mechanism of oxygen reduction proposed by Dam-
janovic shown in the following scheme [31]: direct four electron
transfer reaction leading to the formation of water; and/or two
electron transfer reaction leading to the formation of hydrogen
peroxide intermediate. The intermediate H2O2 again undergoes
reduction forming water. The actual course of the reaction is inev-
itably between these two mechanisms, and H2O2 intermediate for-
mation nevertheless detected in most of the cases. If the quantity
of the intermediate formation is less, then the reaction is near to
the theoretical value of four electron transfer. The reaction path-
ways can be illustrated as follows:
 B. Narayanamoorthy et al. / Journal of Colloid and Interface Science 387 (2012) 213–220 219

constant and the enhancement of the electrocatalytic kinetic

reduction of the adsorbed oxygen. Tafel slopes and kinetic param-
eters are found from the linear portion of the corresponding plots
for each temperature (Table 2). From the plot of Tafel slope as a
function of temperature, the exchange current density (i0) and
the charge transfer coefficient (a) were evaluated. Tafel slope is
varying in the narrow range (116–126 mV dec1) with tempera-
ture, leading to a dependence of a with temperature (0.48–0.51).
Inset of Fig. 9 shows the Arrhenius plot (log j vs 1/T) for the data
of Fig. 9. The apparent activation energy was evaluated from the
linear regression analysis of the slope of Arrhenius plot in the tem-
perature range 25–50 °C and was found to be 7.68 kJ mol1 and
comparable to the standard Pt/C catalyzed ORR systems [35].

4. Conclusion

Amino functionalized clay/Nafion nanocomposite films embed-

ded with Pt NP were prepared with various ratios of AC additive
and Pt NP. The films were surface characterized using TEM. TEM re-
sults revealed that the formation of well exfoliated AC sheets in
Fig. 9. LSVs of Pt/AC/N catalyst layer in O2 saturated 0.5 M H2SO4 at various Nafion matrix. Pt NP of size 2–5 nm predominantly over AC surface
temperatures (inset: Arrhenius plot of log j vs 1000/T).
and some smaller fractions on Nafion were observed. The ECSA
obtained from CV data in nitrogen atmosphere was found to vary
between 1.9 and 33.6 m2 g1 for the Pt mass loadings of 18.2–
209.2 lg cm2. The catalytic activity of the nanocomposite film to-
ward ORR found that for 6 wt% AC/N embedded with 35.4 lg cm2
Pt loading yielded the maximum current density of 4.2 mA cm2.
K–L plots obtained are all parallel, indicating the first order reduc-
tion kinetics with respect to oxygen. Tafel slopes for 35.4 lg cm2
Pt loading at different temperatures was calculated to be from 118
In order to calculate the individual kinetic constants k1, k2, and to 126 mV dec1, indicating a good ORR kinetics. The activation en-
k3 from the experimental values, the following equations were ergy was found to be 7.68 kJ mol1 for catalyst layer containing
used [31,34]. 35.4 lg cm2 Pt. From RRDE ring and disc current measurements,
the percentage of H2O2 formation for various compositions of AC
j1 N  1 2Z 1 S2 Z 2 NS1 additive and Pt NP was estimated to be less than 1.6%, suggesting
k 1 ¼ S2 Z 1 ; k2 ¼ ; k3 ¼
j1 N þ 1 j1 N þ 1 j1 N þ 1 the predominant four electron pathway. The value of ‘‘n’’ was
where Z 1 ¼ 0:2D2=3 and Z 2 ¼ 0:2D2=3 found in the range 2.7–3.8, and for 35.4 lg cm2 Pt loading, it
O2 m H2 O2 m
1=6 1=6
and DH2O2 = 6.8 
6 2 1
10 cm s [31]; J1 and S1 are the intercepts and slopes of the plot was found to be 3.8. It was observed that ORR predominantly takes
ID/IR vs w1/2, respectively. S2 is the slope of the plot ID/(ID  I) vs a four electron path with very low H2O2 production for the Pt load-
w1/2; ID is the disc diffusion limiting current. For the Pt loading ing of 35.4 lg cm2. The kinetic constants for the mechanistic
of 35.4 lg cm2/6 wt% AC/N catalyst film at 25 °C, the values were pathway was calculated and presented.
found to be k1 = 6.92  105 cm s1; k2 = 6.75  108 cm s1; and
k3 = 2.35  105 cm s1. Higher values of k1 and k3 indicate that Acknowledgments
the oxygen reduction mechanism follows near to four electron
pathway as deduced from K–L plot. This work was financially supported by the Board of Research in
Nuclear Sciences (BRNS), Department of Atomic Energy (DAE),
3.7. Effect of temperature Govt. of India, under Basic Sciences program through Sanction
No. 2009/37/29/BRNS. S.B. thanks the JNCASR, Bangalore, for the
The LSV profiles at 25, 40, and 50 °C are shown in Fig. 9. It can be award of visiting scientist fellowship and profoundly thanks the
seen that the kinetics of the electrochemical reaction is in the management of SCSVMV University for having funded and created
increasing trend showing the temperature dependence of the rate the necessary laboratory facilities to carry out this research project.

Table 2
ORR parameters derived from LSVs catalyst films using ‘‘GC disc – Pt ring’’ RRDE electrode at 1600 rpm at various temperatures. (Pt: 35.4 lg cm2; 6 wt% AC).

Temp. jda On set Half wave Half wave current density jkb Tafel slope value ac 106 i0d 103 ke
(°C) (mA cm2) potential (V) potential (V) (mA cm2) (mA cm2) (mV dec1) (A cm2) (cm s1)
25 2.61 0.91 0.46 1.30 2.61 124 0.48 0.58 4.56
40 3.21 0.93 0.48 1.58 3.14 125 0.48 1.15 5.42
50 3.31 0.93 0.50 1.66 3.31 118 0.51 2.42 5.78
a
jd: Disc current density.
b
jk: Kinetic current density at corresponding half wave potentials.
c
a: Charge transfer coefficient.
d
i0: Exchange current density.
e
k: Apparent rate constant.
220 B. Narayanamoorthy et al. / Journal of Colloid and Interface Science 387 (2012) 213–220

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