i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 4 6 8 2 e4 6 9 0

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The electrocatalysis of oxygen evolution reaction

on La1¡xCaxFeO3¡d perovskites in alkaline solution

Ravi Sankannavar, A. Sarkar*

Department of Chemical Engineering, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India

article info abstract

Article history: The electrocatalytic oxygen evolution reaction (OER) on iron based perovskites with
Received 20 May 2017 composition La1
xCaxFeO3
d (0.0  x  1.0) in alkaline solution has been investigated. The
Received in revised form perovskite samples were synthesized by combustion method. Energy dispersive spec-
10 August 2017 troscopy and X-ray photoelectron spectroscopy were used to determine the bulk and the
Accepted 14 August 2017 surface composition, respectively. The X-ray diffraction and iodometric titration method
Available online 11 September 2017 were employed to examine the phases and the oxidation state, respectively. It was
observed that incorporation of calcium (Ca2þ) ions in the lattice of LaFeO3 decreases the
Keywords: lattice parameters and the cell volume systematically as evaluated by Rietveld method.
Water electrolysis Furthermore, increase in the degree of Ca2þ substitution from 0.0 to 1.0, increases the
Oxygen evolution reaction average oxidation state of iron from Fe3þ to Fe4þ in addition to creating oxygen vacancies.
Perovskite The evaluation of OER kinetics on a rotating disk electrode setup suggests that incorpo-
Rietveld refinement ration of Ca2þ decreases the activity initially (0.0  x  0.4), but further substitution in-
Oxidation state creases the activity. The maximum activity was observed for x ¼ 1.0. This change in the
OER activity suggests an interplay between the bond lengths and angles, oxygen vacancy
and the average oxidation state of Fe.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

recommended approach [3,4]. Use of H2 gas as a fuel for

Introduction
In the present era, there is a growing demand for energy and
fuel due to increase in the world population. The entire
human population across the world depend mostly on the
energy derived primarily from fossil fuels. However, limited
availability of these fossil fuels and emission of pollution-
causing gasses into the environment has drawn the atten-
tion of researchers towards renewable and non-conventional
sources of energy and fuels [1,2]. To overcome the energy
crisis and minimize the emissions, utilization of hydrogen (H2)
as an energy carrier for mobile and stationery applications is a
generating of heat by combustion, and electricity by the fuel
cell produces only water, which makes it environmental
friendly [5]. However, storage and transportation of H2 gas is
critical to use H2 as a fuel in any future hydrogen-based
economy and research done to address the these issues has
been discussed in the literature [6,7]. Production of H2 from
steam reforming of methane is a dominant method and pro-
duces H2 in large quantity. However, H2 gas produced by this
steam reforming produces greenhouse gases such as carbon
dioxide and carbon monoxide [8].
In this context, production of H2 by splitting water into H2
and oxygen (O2) is one of the cleanest ways available presently

* Corresponding author.
E-mail address: a.sarkar@iitb.ac.in (A. Sarkar).
http://dx.doi.org/10.1016/j.ijhydene.2017.08.092
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 4 6 8 2 e4 6 9 0
and it is a practical point of interest [9]. Hence, for several
decades, the production of H2 from water is being researched
upon [1,4,10,11]. Electrolytic splitting of water is one of the
most convenient methods, in which pure H2 can be produced
along with O2 in high amounts by passing an electric current
through water [1,12]. However, stable, efficient, and cost-
effective electrocatalysts are required to electrolyze water. In
water electrolysis, anodic reaction in alkaline media, i.e., ox-
ygen evolution reaction (OER) is represented by 4
OH
/ O2[ þ 2H2O þ 4e
, while the cathodic reaction is
2H2O þ 2e
/ H2[ þ 2OH
. In practice, the efficiency of water
electrolysis is restricted by sluggish and kinetically slow
anodic reaction, OER [13e15]. This slow OER causes a large
anodic overpotential during the electrolysis. For this reason,
considerable research has been done to understand the OER
mechanism and minimize the energy loss during electrolysis
[12e21].
To over come the energy losses during the electrolysis, an
effort has been made in the past to use electrocatalysts for
enhancing the rate of electrochemical reaction [5,12e15]. The
RuO2 and IrO2 electrocatalysts frequently used, and have
shown the best catalytic activity and stability for OER till date
[20]. Other than pure oxides of Ru and Ir, various mixed oxides
such as mixtures of IrO2 and Pt, IrO2 and TiO2, IrO2, and RuO2
have also been used for the OER [19,21e23]. However, the cost
and limited abundance of these metals have lead to difficulty
in scaling up the electrolytic process. Consequently, for
several decades now, the attention has been directed towards
the usage of earth-abundant elements for efficient and stable
electrocatalysts for the OER. Several works on efficient elec-
trocatalysis by relatively cheap oxides and hydroxides of
transition elements such as Ni, Co, Fe, etc. for OER have been
reported [12,15,18,24e26].
Perovskite-type oxides with a general formula of ABO3 are
considered as potential OER active electrocatalysts due to
their high catalytic activity, and the ability to incorporate
different metal ions retaining the structure [17]. High struc-
tural stability of perovskites permits partial or complete
substitution of earth-abundant alkaline earth metals in the A-
site and transition metals in the B-site resulting in
A1
xA'x B1
yB'y O3 [16,27]. This A and B-sites substitution influ-
ence the physical properties as well as electrocatalytic prop-
erties [17]. Several studies have been carried out on
perovskites for OER to understand the parameters influencing
the electrocatalytic activity, with further purpose of
improving the activity of known materials or predicting new
active materials. It has been reported that the OER activity
increases along the direction from LaFeO3 to SrCoO3 when
both A and B-sites are substituted [16]. This OER activity
enhancement was attributed to the broadening of antibond-
ing (s* bond) between M-O-M in the lattice [16,28] and in-
crease in the oxidation state of a transition metal (M) present
at B-site ion [16]. Further, it was also reported that the OER
activity of oxygen deficient Ca2Mn2O5 was higher than that of
the stoichiometric CaMnO3 [29] highlighting the role of oxy-
gen vacancies as well. Moreover, this suggests that the pres-
ence of intrinsic molecular level porosity on the oxygen-
deficient sites in Ca2Mn2O5 perovskite facilitated the ion
transport for OER via oxygen vacancies [29]. Other than
oxidation state and oxygen vacancies, the bond angles also
4683
influence the activity for OER. It has been observed that sub-
stitution of bivalent cation such as strontium (Sr2þ) for La3þ in
the La1
xSrxCoO3 perovskite series, in addition to increasing
the average oxidation state of Co, has an effect of straight-
ening the octahedral cage, aligning atoms along the CoeOeCo
axis resulting in an increase in the activity [30]. This align-
ment of CoeOeCo bonds and increase in the oxidation state
of the Co cations enhances the overlap between the occupied
O 2p valence bands and unoccupied Co 3d conduction band.
This overlap in addition to increasing the activity also im-
proves the conductivity as an added feature [30].
Recently, nontoxic and most abundant transition metal
iron (Fe) based electrocatalysts have been investigated for the
OER. It is reported that the tetravalent iron (Fe4þ) ion is the
OER active site on the iron type oxides [31e33]. Hence, in the
present study, an effort has been made to enhance the
oxidation state of Fe present at B-site of perovskites from
Fe3þ to Fe4þ. This will enhance the overlap between occupied
2p valence bands and unoccupied 3d conduction bands
thereby improving the conductivity similar to that for Co as
mentioned in the previous paragraph [30,34]. Additionally,
the Fe4þ ion in the perovskite will have a high-spin d4
configuration of t32g e1g [35], i.e., eg-filling is close to unity for B-
site. This ideal close to unity eg filling balances the adsorption
of reactants and desorption of intermediates, which helps in
enhancing the electrochemical activity [14,36]. The formation
of Fe4þ in perovskites can be achieved by substituting a
divalent cations at the A-site. In the present work, Ca2þ has
been substituted for lanthanum (La3þ) in the A-site leading to
La1
xCaxFeO3 perovskite-type oxides and evaluated for their
OER activity in alkaline media. Results indicate that the
substitution of Ca2þ decreased the OER activity initially and
further increase in Ca2þ substitution enhanced the activity of
OER.
Materials and methods
Synthesis of La1
xCaxFeO3 perovskites
Lanthanum-calcium ferrites i.e., La1
xCaxFeO3 (x ¼ 0.0 to 1.0)
were synthesized by nitrate combustion method using lan-
thanum(III) nitrate hexahydrate (La(NO3)3$6H2O), calcium
carbonate (CaCO3) dissolved in concentrated HNO3 and
iron(III) nitrate nonahydrate (Fe(NO3)3$9H2O) solutions, and
glycine (C2H5NO2) as the fuel. The degree of Ca2þ cation sub-
stitution for La3þ cation at the A-site of perovskites (La1
x-
CaxFeO3) was varied from 0.0 to 1.0. The chemicals were used
as received without further purification. Solutions were mixed
and heated at 250  C using a hot plate with continuous stirring
at 250 rpm. Initially, the solution boiled with frothing and
formation of foam. After foam formation subsided, it ignited
to burn with a flame yielding a solid product within a minute.
These solids were dried at 80  C for overnight using hot-air
oven (Nirmala Scientific Industries, India). The powders of
these solids were made by grounding the solid product using
mortar and pestle. Later, these powders were calcined in air at
800  C for 3 h using a furnace (Nirmala Scientific Industries,
India). The Fe2O3 electrocatalyst was also synthesized with
the same procedure.
4684 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 4 6 8 2 e4 6 9 0
Material characterization
The composition of as synthesized perovskite samples were
quantitatively analysed by energy dispersive spectroscopy
(EDS) using a JEOL JSM-7600F e scanning electron microscope.
The near surface compositional analysis of La0.6Ca0.4FeO3
perovskite was carried out in a Kratos AXIS supra analytical X-
ray photoelectron spectroscopy (XPS). Monochromatic (Al Ka)
X-ray source (600 W) with pass energy of 160 eV and resolution
of 2 eV was used for survey scan. The charging effects were
corrected by adjusting the scans to the adventitious C 1s
spectral line (CeC) at binding energy of 284.7 eV. The collected
XPS spectra for La0.6Ca0.4NiO3 were analysed using the ESCApe
software.
The powder X-ray diffraction studies were performed in
an EMPYREAN, PANalytical diffractometer with Cu Ka radia-
tion operating at 30 mA and 40 kV. The scanning rate was
0.017 (2q)/20 s and the scan range was 20e80 in 2q. X'pert
HighScore Plus software (version 2.1.0) was used for the
phase identification by comparing with the International
Centre for Diffraction Data (ICDD). Rietveld refinement was
carried out using the Fullprof Suite program (3.00) [37] for
refinement of the lattice parameters and quantification of
phases.
Electrochemical measurements
Electrochemical measurements were performed on a thin film
electrocatalyst coated glassy carbon electrode (GCE). Briefly,
the electrocatalyst ink of both the perovskite and Fe2O3 sam-
ples was prepared by adding 5 mL of deionized water and 50 mL
of basic nafion to a mixture of 3 mg of electrocatalyst and 2 mg
of Vulcan carbon (XC-72R). The basic nafion was prepared by
diluting 5 wt% nafion dispersion (Sigma Aldrich, U.S.A.) with
deionized water in volume ratio of 1:1 and adjusted the pH to
14 by adding few drops of 5 M NaOH. Weight percentages of
electrocatalysts and carbon were 60 and 40, respectively in the
electrocatalysts ink prepared. This electrocatalyst ink was
sonicated for 30 min and 20 mL of the ink was immediately
drop-casted onto a GCE (5 mm dia., Pine Instruments). Elec-
trocatalyst and nafion loading density onto GCE were 61.16
and 22.27 mg cm
2, respectively. The electrocatalyst drop-
casted GCE electrode was then dried under an infrared lamp
for around 15 min.
Cyclic voltammetry
The electrocatalyst coated GCE was then fitted to a Pine AFM
rotor, and the electrode was immersed into a standard three-
compartment electrochemical cell containing argon, Ar
(99.99%, Mars Gas Company, Mumbai) saturated 0.5 M NaOH
electrolyte. Argon gas was continuously purged throughout
the experiment. Platinum (Pt) mesh and Hg/HgO (0.5 M KOH)
were used as counter and reference electrodes, respectively.
Cyclic voltammetry (CV) experiments were performed in the
potential range of
0.42 to 1.58 V at scan rates of 5 and
50 mV s
1 for Fe2O3 and La1
xCaxFeO3 electrocatalysts,
respectively. The experiments were conducted using the
Gamry (model: Interface 1000, U.S.A) potentiostat.
The potential recorded using a Hg/HgO secondary refer-
ence electrode was converted experimentally to the
reversible hydrogen electrode (RHE), and it is briefly described
as follows. A home-made RHE was prepared by sealing a Pt
wire inside a glass tube at one end, and enough wire was left
outside the tube as a terminal for connection. This glass tube
was filled with 0.5 M NaOH solution and immersed into a
three-compartment electrochemical cell containing 0.5 M
NaOH electrolyte. The electrolyte was continuously purged
with Ar-gas throughout the experiment. Hydrogen gas was
generated inside the glass tube by electrolysis with the RHE
as a working electrode and a Hg/HgO electrode as the refer-
ence electrode by applying a negative potential (
4 V versus
Hg/HgO). The generation of H2 gas inside the tube was
continued till the solution levels of inside and outside the
tube are equal, signifying that the pressure inside the tube
and atmospheric pressure are same. Later, the open-circuit
voltage (OCV) or equilibrium potential of the RHE was
measured and found to be
0.882 V versus Hg/HgO. Hence,
the potential applied using Hg/HgO reference electrode was
converted to this RHE using a relationship, ERHE ¼ EHg/HgO þ 0.882
V v/s RHE. Henceforth, the potential reported in this article are
versus RHE.
Oxygen evolution reaction activity measurement
For the OER activity studies, thin-film rotating disk electrode
(RDE) measurements were carried out in a similar manner as
the cyclic voltammetry experiments described in section
Cyclic voltammetry. Briefly, the thin-film electrocatalysts
coated electrode was fitted to the rotor and immersed in a O2
(99.99%, Mars Gas Company, Mumbai) saturated 0.5 M NaOH
solution (500 mL). Same three-electrode configuration was
used and O2-gas was continuously purged to obtain an equi-
librium value of the potential (Eeq) where all the ionic species
involved in the electrochemical OER are present.
Hence, the OCV of the electrode was measured in the same
setup before the OER measurements. For OER, potential scans
(10 cycles) were performed between a potential of 1.08 and
1.78 V at 10 mV s
1 with a rotational rate of 1600 rpm. Prior to
the measuring of the OCV and OER, the electrocatalyst was
cleaned by cycling the potential of the electrode in Ar-
saturated 0.5 M NaOH solution for five cycles.
Oxidation state measurement by iodometric titration
method
Twenty milligram of electrocatalyst was dissolved in 1 mL of
concentrated HCl (35 wt%) and 10 mL of DI water by boiling it
for 5 min. After cooling it to room temperature, z0.15 g
NaHCO3 was added to the solution to remove any air present
in the conical flask and thereafter it was immediately closed
with a stopper. Fifteen mL of 10% KI solution was added to the
above solution and the generated I
3 (Eq. (1)) was immediately
titrated against 0.015 M sodium thiosulfate solution (Eq. (2))
using starch as an end point indicator which forms an intense
blue colored complex with tri-iodide anion. During titration,
the tri-iodide anion (I
3 ) reacts with the thiosulfate anion
(S2O2

3 ) and turns the blue colored complex to colorless. The
overall reaction of this iodometric titration is presented in Eq.
(3). Titrations were done in triplicate for all samples. This
titration procedure was adopted from Jeffery et al. [38] and
Guggilla and Manthiram [39].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 4 6 8 2 e4 6 9 0 4685

2Fenþ þ 3I
4nFe2þ þ I

3 ; ðn ¼ 3 or 4Þ (1)

I
2
2

3 þ 2S2 O3 4S4 O6 þ 3I


(2)

2Fenþ þ 2S2 O2

3 4nFe
2þ
þ S4 O2

6 ðnet reactionÞ (3)

Results and discussion

Analysis of elemental composition by EDS and XPS

The composition of the perovskite samples were analysed by

EDS and are presented in Table 1. The composition observed
to be in good agreement with the nominal values.
Fig. 1 shows the XPS data for the sample La0.6Ca0.4FeO3. The
data prominently reveals presence of Ca 2p, La 3d, Fe 2p, and O
1s in the spectra. As mentioned earlier, the spectra were cor-
rected using the C 1s peak value of 284.7 eV as a reference. The
binding energies at 851.19 and 834.25 eV are assigned to La 3d3/
2 and La 3d5/2, respectively. The peaks at binding energy values
of 710.41 and 724.03 eV corresponds to the Fe 2p3/2 and Fe 2p1/2,
respectively. The O 1s spectra at 529.94 eV is attributed to the
contribution of LaeO, CaeO, and FeeO in the lattice of the
perovskite considered. Presence of another O 1s peak at
532.03 eV is closely related to the hydroxyl groups resulting
from the adsorbed water molecules. The data suggest pres-
ence of all the metal ions on the surface as well as some
adsorbed water. The binding energies for La, Ca, Fe and O are
in agreement with the literature values published by the NIST
[40]. The atomic ratio of La:Ca:Fe was found to be 0.84:0.56:1
and was slightly higher than the theoretical ratio, which in-
dicates the electrocatalyst surface was enriched in La and Ca.
Analysis of structure by XRD and Rietveld refinement
The XRD patterns of the synthesized electrocatalysts after
heat treatment at 800  C in air are shown in Fig. 2. It was
observed that the XRD reflections for the electrocatalysts with
x  0.6 matched well with those corresponding to the pure
phase of LaFeO3 (ICDD reference card number 01-082-1958)
albeit with progressive shift in 2q. Evidently, all the electro-
catalysts with x  0.6 belong to orthorhombic crystal system of
Pnma (62) space group. Moreover, when x was increased from
0.6 to 0.8, the LaFeO3 phase transformed to Ca2Fe2O5 phase
Fig. 1 e X-ray photoelectron spectroscopy spectra of
La0.6Ca0.4FeO3 perovskite sample.
(ICDD reference card number 01-071-2108) retaining the
orthorhombic crystal system with Pcmn (62) space group.
When x was further increased to 1.0, a secondary phase
(5.54 wt%) of cubic Fe2O3 (ICDD reference card number 01-073-
0603) was observed along with the Ca2Fe2O5 phase.
The shifting of 2q values to a higher position (0.0  x  0.6)
corresponds to a contraction of the lattice structure which
may be due to (a) substitution of smaller Ca2þ ions and/or (b)
creation of smaller Fe4þ ions. It may be mentioned here that
substitution of Ca2þ may not be fully responsible for the
contraction of the lattice. Substitution of Ca2þ may change the
oxidation state of iron which in turn will change the lattice
parameters. Nonetheless, to investigate the influence of Ca2þ
substitution on cell parameters, Rietveld refinement of cell
parameters on all the heat treated electrocatalysts were per-
formed (Fig. 3). The Rietveld refinement results such as cell
parameters, interatomic distances, FeeOeFe angle along the
chains of FeO6 octahedra are presented in Table 2. It was
observed that the values of cell parameters (a and b) decreases
almost linearly with increase in the Ca2þ substitution
(Table 2). For x  0.6, distances between La/Ca and O ions (La/
CaeO) decreased with an increase in the Ca2þ substitution.
Further, this decrease in the La/CaeO distances caused the

Table 1 e : The elemental composition of perovskite

samples La1¡xCaxFeO3 (x ¼ 0.0 to 1.0) analysed by the
energy dispersive X-ray spectroscopy (EDS). The values
represent the average of two spots on the same sample.
x Nominal atomic % Measured atomic % by EDS
2þ
(Ca ) La Ca Fe O La Ca Fe O
0.0 20 0 20 60 21.53 0.00 19.42 59.06
0.2 16 4 20 60 16.85 3.84 20.74 58.57
0.4 12 8 20 60 12.93 8.19 20.18 58.72
0.6 8 12 20 60 9.02 13.36 22.43 55.20 Fig. 2 e X-ray diffraction patterns of synthesized
0.8 4 16 20 60 4.51 17.00 20.04 58.47 La1¡xCaxFeO3 (x ¼ 0.0 to 1.0) electrocatalysts after
1.0 0 20 20 60 0.00 20.70 22.31 57.00
calcination at 800  C.
4686 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 4 6 8 2 e4 6 9 0

Fig. 3 e Rietveld refinement plots of the X-ray diffraction profiles of La1¡xCaxFeO3 (x ¼ 0.0 to 1.0) perovskite samples.

 and V is the cell

Table 2 e Rietveld refinement results of La1¡xCaxFeO3 perovskites. Here a, b and c are lattice parameters (A),
volume (A3).

x in La1
xCaxFeO3 0.0 0.2 0.4 0.6 0.8 1.0

Phase LaFeO3 LaFeO3 LaFeO3 LaFeO3 Ca2Fe2O5 Ca2Fe2O5 Fe2O3
Space group Pnma Pnma Pnma Pnma Pcmn Pcmn R3c
a (
A) 5.5643 5.5217 5.4845 5.4467 5.4442 5.5996 5.0979
b (
A) 7.8542 7.8071 7.7558 7.7231 15.0598 14.797 5.0979
c (
A) 5.5554 5.5297 5.5039 5.4416 5.5276 5.4291 13.9874
V (
A 3) 242.79 238.38 234.12 228.90 453.20 449.84 314.81
La/CaeO ( A) 2.611 2.590 2.556 2.560 2.51802 2.4779 e
FeeO ( A) 2.0010 2.0027 2.0003 1.9513 2.1558 2.0449 2.1457
FeeOeFe ( ) 157.60 153.65 152.55 165.50 156.51 161.49 126.49
c2 (%) 1.81 1.55 1.59 1.76 2.33 1.24
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 4 6 8 2 e4 6 9 0 4687

bending of the FeeOeFe angle to lower angles upto x ¼ 0.4. contraction in lattice structure indicated by the decrease in
While, at x ¼ 0.6 the angle was observed to be 165.50 . As the lattice parameters in all the samples (Table 2). This
mentioned earlier, this bending of angles away from 180 is contraction in the lattice structure can be explained by the
likely to influence the OER activity. oxidation of Fe3þ having an ionic radius of 0.645 A [43] to Fe4þ
which has an ionic radius of 0.585 
A. Further, this formation of
Oxidation state measurement by iodometric titration a smaller Fe4þ ion in the B-site decreases the La/CaeO dis-
method tances as seen from the Rietveld refinement results, though
no specific trend was observed for the FeeO distance (Table 2).
It may be noted that when Ca2þ cations are substituted for
La3þ, the condition of electroneutrality is accomplished either Cyclic voltammetry of perovskites
by (i) formation of the higher oxidation state of transition
metal present in the B-site [41] and/or (ii) creation of oxygen The CVs of Fe2O3 and all perovskites synthesized in the pre-
vacancies, which leads to oxygen deficient perovskites [29]. In sent study are shown in Fig. 4. The prominent reaction for
the present work, the former would imply that Fe3þ oxidizes to Fe2O3 upon cycling the potential in 0.5 M NaOH are also indi-
Fe4þ and this valency change can be expressed as cated in Fig. 4a. As the potential is moved positive to 0.0 V v/s
La3þ 2þ 3þ 4þ
1
x Cax Fe1
y Fey O3 , while for later it would be RHE, the first reaction that occurs is the oxidation of Fe to
La1
xCaxFeO3
d. The oxidation states of iron in the perovskites ferrous hydroxide. A further increase in the potential leads to
synthesized as determined by iodometric titration are pre- formation of ferric oxy-hydroxide. As shown in the cyclic
sented in Table 3. It can be observed that the average oxida- voltammograms, each of these reactions corresponds to a
tion state of the iron (Fe) increases from þ3 oxidation state current wave. Reversing the potential reverses the reactions
with an increase in the degree of Ca2þ substitution. Thus it can and at very low potential large current due to evolution of H2
be concluded that the increase in the average oxidation state gas was observed. On moving the potential positive again, a
of Fe upon Ca2þ substitution in the synthesized perovskites small hump probably indicating oxidation of the evolved H2
enhanced the average oxidation state of transition metal was also observed along with the other reactions. In general,
present in the B-site and confirms the presence of Fe4þ ions. the features match quite well with the reported literature
However, the values of the measured oxidation state of Fe are
always lower than those calculated based on the condition of
net electroneutrality (Table 3). Hence, we suspect that the
electroneutrality is achieved by introduction of oxygen va-
cancies (d) in the perovskites, and these are represented as
La1
xCaxFeO3
d. The results obtained here also show that Ca2þ
substitution not only leads to formation of the OER active sites
containing Fe4þ ion at B-site but also creates oxygen vacancies
that may lead to higher ionic conductivity in the electro-
catalysts synthesized. Similar results have been obtained by
Ciambelli et al. [42] where the presence of Fe4þ and oxygen
vacancies have been observed in the calcium-substituted
lanthanum ferrites.
It may be pertinent here to revisit the results obtained from
the XRD analysis and Rietveld refinement. The ionic radii of
both La3þ (1.03 A) and Ca2þ (1.00 
A) [43] are similar and Ca2þ is
only slightly smaller. Thus, a large change in lattice parameter
is not expected upon Ca2þ substitution. However, as
mentioned earlier substitution of Ca2þ caused significant

Table 3 e The measured average oxidation state of iron

and that calculated by the net electroneutrality, and
oxygen content (3¡d) using iodometric titration. The
values before and after ‘±’ sign represent the average and
standard deviations, respectively of the three readings.
x (Ca2þ) Oxidation state 3
d
Measured Calculated
0.0 þ3.055 ± 0.001 þ3 3.03
0.2 þ3.159 ± 0.003 þ3.2 2.98
0.4 þ3.257 ± 0.003 þ3.4 2.93 Fig. 4 e Cyclic voltammograms (5th cycle) of (a) Fe2O3 at
0.6 þ3.417 ± 0.007 þ3.6 2.91 5 mV s¡1 and (b) La1¡xCaxFeO3¡d (x ¼ 0.0 to 1.0) at
0.8 þ3.58 ± 0.01 þ3.8 2.89 50 mV s¡1 in Ar-saturated 0.5 M NaOH solution showing
1.0 þ3.85 ± 0.02 þ4 2.93 the anodic and cathodic reactions.
4688 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 4 6 8 2 e4 6 9 0

[44,45]. Interestingly, similar features were also observed for

the perovskites with x ¼ 0.8 and 1.0 (Fig. 4b). These have three
anodic and two cathodic peaks similar to the peaks of Fe2O3
(Fig. 4a), but x ¼ 1.0 has higher anodic and cathodic currents
compared to x ¼ 0.8. This shows that the redox reactions
observed in the CVs of perovskites with x ¼ 0.8 and 1.0
correspond to redox reactions occurring on a separate Fe2O3
phase. This corroborates well with the phase identification
and quantification from XRD data where the presence of Fe2O3
(5.54 wt%) for x ¼ 1.0 was revealed. Though no peaks corre-
sponding to Fe2O3 was identified for x ¼ 0.8, the similarity in
the cyclic voltammograms for x ¼ 0.8 and 1.0 suggest presence
of Fe2O3 as separate phase for the x ¼ 0.8 sample also. For
perovskites with x < 0.8; no redox features were identified in
the same potential range and the cyclic voltammograms
prominently showed features corresponding to a double layer
capacitor.
Oxygen evolution reaction activity
Fig. 5 presents the current-voltage data for OER. As shown in
Fig. 5, the OER currents of La1
xCaxFeO3
d decreases when the
value of x increases from 0.0 to 0.4 and then the OER currents
increases as x increases further to 1.0. The highest activity was
observed for x ¼ 1.0 i.e., CaFeO3
d which is at least 1.45 times
higher than other electrocatalysts studied in the present
study. However, as pointed out earlier, the sample had Fe2O3
(z5.54 wt%) as impurity. Oxygen evolution studies on only
Fe2O3 electrocatalysts made by the same procedure suggest
that the influence of Fe2O3 impurity on the activity of CaFeO3
d
is not substantial. The initial decrease in activity may be due
to the bending of the FeeOeFe bond away from 180 , although
the oxidation state increases as La is substituted by Ca. Elec-
trocatalyst with x ¼ 0.4, has both the lowest OER activity and
also the lowest FeeOeFe angle. In contrast beyond x  0.6, the
activity increases possibly due to both the presence of higher
oxidation state of iron at B site, and also straightening of the
FeeOeFe bond. However, it needs to be reiterated that the
phase change for x ¼ 0.8 and 1.0 and presence of a secondary
Fig. 6 e Overpotential, h v/s current density, j plots (empty
symbols) for La1¡xCaxFeO3¡d (x ¼ 0.0 to 1.0) perovskites
used for the oxygen evolution reaction in O2 saturated
0.5 M NaOH solution. The Tafel plots are indicated by the
solid lines with filled symbols.
phase for x ¼ 1.0 prevented a direct correlation of change of
FeeOeFe angle with OER activities in the present study.
The Tafel plots are presented in the Fig. 6 by plotting the
overpotential (h) versus the logarithm of current density (j) for
electrocatalysts used for the OER measurements. The over-
potential was calculated by subtracting the OCV measured at
equilibrium with respect to the RHE from the applied poten-
tial, i.e., h ¼ Eapplied
Eeq. The Tafel parameters such as Tafel
slope (b), transfer coefficient (a), and exchange current density
(j0) are presented in Table 4 and the data show that x ¼ 0.4 has
both the highest Tafel slope (242.1 mV dec
1) as well as the
highest exchange current density in comparison with other
electrocatalysts. Interestingly, it was observed that substitu-
tion of Ca (x  0.4), decreases the exchange current density (j0)
and the logarithm of the exchange current density varied
linearly with Ca substitution. Similar to the exchange current
density, the Tafel slopes (b) also decreases linearly upon
substitution of La by Ca for x  0.4. These results point out to
an curious interplay of Tafel slopes and the exchange current
densities which result in the lowest activity for
La0.6Ca0.4FeO3
d and the highest activity for CaFeO3
d.

Table 4 e Kinetic parameters of OER on La1¡xCaxFeO3¡d

perovskites in 0.5 M NaOH electrolyte. The open circuit
voltage (OCV v/s RHE) of the electrocatalysts was
measured in O2 saturated 0.5 M NaOH solution prior to
the OER measurements. Here b, a, and j0 represent Tafel
slope, transfer coefficient, and exchange current density,
respectively.
x (Ca2þ) OCV (V) R2 b (mV dec
1) a j0 (mA cm
2)
0.0 0.822 0.9986 171.7 0.35 2.34  10
5
0.2 0.864 0.9982 158.1 0.38 7.30  10
6
Fig. 5 e Currents for oxygen evolution reaction for 0.4 0.889 0.9999 242.1 0.25 3.18  10
4
La1¡xCaxFeO3¡d (x ¼ 0.0 to 1.0) perovskite samples at 0.6 0.894 0.9995 194.7 0.31 7.86  10
5
10 mV s¡1 in O2 saturated 0.5 M NaOH solution at 0.8 0.874 0.9989 123.3 0.48 3.88  10
7
1.0 0.872 0.9983 81.9 0.73 1.56  10
10
1600 rpm; inset shows the OER currents at 1.75 V v/s RHE.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 4 6 8 2 e4 6 9 0
Conclusion
Calcium-substituted lanthanum ferrites (La1
xCaxFeO3
d)
perovskite-type oxides were synthesized by solution com-
bustion method. Rietveld refinement of XRD patterns show
that the substitution of bivalent Ca2þ for trivalent La3þ in
the A-site causes contraction in the lattice structure. On the
other hand, titration results indicate that substitution of
Ca2þ oxidizes the B-site transition metal ion Fe3þ to Fe4þ ion
and introduced oxygen vacancies on the perovskites. Both
the XRD and the cyclic voltammetry data were used to
identify Fe2O3 impurity present for x ¼ 0.8 and 1.0 samples,
which exhibited redox reactions comparable to the redox
reactions on Fe2O3 alone. The substitution of Ca2þ ions in
the perovskites initially decreased the activity for OER upto
x  0.4, while further substitution improved the activity for
OER, and it was found to be 2.5 times higher for x ¼ 1.0 than
that for x ¼ 0.0. Hence, the present study suggests that
suitable substitution of inexpensive earth-abundant metals
in perovskites (ABO3) type structure will help in designing
efficient electrocatalysts for OER for alkaline water elec-
trolysis. This use of perovskite type electrocatalysts pre-
pared using transition metals and earth-abundant metals
may help in the replacing electrocatalysts containing noble
and expensive elements with limited sources for alkaline
water electrolysis.
Acknowledgments
This work was presented at the Eleventh International Sym-
posium on Advances in Electrochemical Science and Tech-
nology (ISAEST-11) held during 8e10 December 2016 at Hotel
Kohinoor Asiana, Chennai, India. We greatly acknowledge the
Department of Science and Technology, India with the Ram-
anujan Fellowship for financial support. Authors also thank
the Department of Metallurgical Engineering and Materials
Science (MEMS), Central Surface Analytical Facility (ESCA),
and Sophisticated Analytical Instrument Facility (SAIF) of IIT
Bombay for performing XRD, XPS, and EDS analysis,
respectively.
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