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The electrocatalysis of oxygen evolution reaction on La1−xCaxFeO3−δ perovskites in alkaline solution
The electrocatalysis of oxygen evolution reaction on La1−xCaxFeO3−δ perovskites in alkaline solution
ScienceDirect
Article history: The electrocatalytic oxygen evolution reaction (OER) on iron based perovskites with
Received 20 May 2017 composition La1xCaxFeO3d (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.
* 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 4683
and it is a practical point of interest [9]. Hence, for several influence the activity for OER. It has been observed that sub-
decades, the production of H2 from water is being researched stitution of bivalent cation such as strontium (Sr2þ) for La3þ in
upon [1,4,10,11]. Electrolytic splitting of water is one of the the La1xSrxCoO3 perovskite series, in addition to increasing
most convenient methods, in which pure H2 can be produced the average oxidation state of Co, has an effect of straight-
along with O2 in high amounts by passing an electric current ening the octahedral cage, aligning atoms along the CoeOeCo
through water [1,12]. However, stable, efficient, and cost- axis resulting in an increase in the activity [30]. This align-
effective electrocatalysts are required to electrolyze water. In ment of CoeOeCo bonds and increase in the oxidation state
water electrolysis, anodic reaction in alkaline media, i.e., ox- of the Co cations enhances the overlap between the occupied
ygen evolution reaction (OER) is represented by 4 O 2p valence bands and unoccupied Co 3d conduction band.
OH / O2[ þ 2H2O þ 4e, while the cathodic reaction is This overlap in addition to increasing the activity also im-
2H2O þ 2e / H2[ þ 2OH. In practice, the efficiency of water proves the conductivity as an added feature [30].
electrolysis is restricted by sluggish and kinetically slow Recently, nontoxic and most abundant transition metal
anodic reaction, OER [13e15]. This slow OER causes a large iron (Fe) based electrocatalysts have been investigated for the
anodic overpotential during the electrolysis. For this reason, OER. It is reported that the tetravalent iron (Fe4þ) ion is the
considerable research has been done to understand the OER OER active site on the iron type oxides [31e33]. Hence, in the
mechanism and minimize the energy loss during electrolysis present study, an effort has been made to enhance the
[12e21]. oxidation state of Fe present at B-site of perovskites from
To over come the energy losses during the electrolysis, an Fe3þ to Fe4þ. This will enhance the overlap between occupied
effort has been made in the past to use electrocatalysts for 2p valence bands and unoccupied 3d conduction bands
enhancing the rate of electrochemical reaction [5,12e15]. The thereby improving the conductivity similar to that for Co as
RuO2 and IrO2 electrocatalysts frequently used, and have mentioned in the previous paragraph [30,34]. Additionally,
shown the best catalytic activity and stability for OER till date the Fe4þ ion in the perovskite will have a high-spin d4
[20]. Other than pure oxides of Ru and Ir, various mixed oxides configuration of t32g e1g [35], i.e., eg-filling is close to unity for B-
such as mixtures of IrO2 and Pt, IrO2 and TiO2, IrO2, and RuO2 site. This ideal close to unity eg filling balances the adsorption
have also been used for the OER [19,21e23]. However, the cost of reactants and desorption of intermediates, which helps in
and limited abundance of these metals have lead to difficulty enhancing the electrochemical activity [14,36]. The formation
in scaling up the electrolytic process. Consequently, for of Fe4þ in perovskites can be achieved by substituting a
several decades now, the attention has been directed towards divalent cations at the A-site. In the present work, Ca2þ has
the usage of earth-abundant elements for efficient and stable been substituted for lanthanum (La3þ) in the A-site leading to
electrocatalysts for the OER. Several works on efficient elec- La1xCaxFeO3 perovskite-type oxides and evaluated for their
trocatalysis by relatively cheap oxides and hydroxides of OER activity in alkaline media. Results indicate that the
transition elements such as Ni, Co, Fe, etc. for OER have been substitution of Ca2þ decreased the OER activity initially and
reported [12,15,18,24e26]. further increase in Ca2þ substitution enhanced the activity of
Perovskite-type oxides with a general formula of ABO3 are OER.
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- Materials and methods
tural stability of perovskites permits partial or complete
substitution of earth-abundant alkaline earth metals in the A- Synthesis of La1xCaxFeO3 perovskites
site and transition metals in the B-site resulting in
A1xA'x B1yB'y O3 [16,27]. This A and B-sites substitution influ- Lanthanum-calcium ferrites i.e., La1xCaxFeO3 (x ¼ 0.0 to 1.0)
ence the physical properties as well as electrocatalytic prop- were synthesized by nitrate combustion method using lan-
erties [17]. Several studies have been carried out on thanum(III) nitrate hexahydrate (La(NO3)3$6H2O), calcium
perovskites for OER to understand the parameters influencing carbonate (CaCO3) dissolved in concentrated HNO3 and
the electrocatalytic activity, with further purpose of iron(III) nitrate nonahydrate (Fe(NO3)3$9H2O) solutions, and
improving the activity of known materials or predicting new glycine (C2H5NO2) as the fuel. The degree of Ca2þ cation sub-
active materials. It has been reported that the OER activity stitution for La3þ cation at the A-site of perovskites (La1x-
increases along the direction from LaFeO3 to SrCoO3 when CaxFeO3) was varied from 0.0 to 1.0. The chemicals were used
both A and B-sites are substituted [16]. This OER activity as received without further purification. Solutions were mixed
enhancement was attributed to the broadening of antibond- and heated at 250 C using a hot plate with continuous stirring
ing (s* bond) between M-O-M in the lattice [16,28] and in- at 250 rpm. Initially, the solution boiled with frothing and
crease in the oxidation state of a transition metal (M) present formation of foam. After foam formation subsided, it ignited
at B-site ion [16]. Further, it was also reported that the OER to burn with a flame yielding a solid product within a minute.
activity of oxygen deficient Ca2Mn2O5 was higher than that of These solids were dried at 80 C for overnight using hot-air
the stoichiometric CaMnO3 [29] highlighting the role of oxy- oven (Nirmala Scientific Industries, India). The powders of
gen vacancies as well. Moreover, this suggests that the pres- these solids were made by grounding the solid product using
ence of intrinsic molecular level porosity on the oxygen- mortar and pestle. Later, these powders were calcined in air at
deficient sites in Ca2Mn2O5 perovskite facilitated the ion 800 C for 3 h using a furnace (Nirmala Scientific Industries,
transport for OER via oxygen vacancies [29]. Other than India). The Fe2O3 electrocatalyst was also synthesized with
oxidation state and oxygen vacancies, the bond angles also 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
I 2 2
3 þ 2S2 O3 4S4 O6 þ 3I
(2)
Fig. 3 e Rietveld refinement plots of the X-ray diffraction profiles of La1¡xCaxFeO3 (x ¼ 0.0 to 1.0) perovskite samples.
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
1x Cax Fe1y Fey O3 , while for later it would be RHE, the first reaction that occurs is the oxidation of Fe to
La1xCaxFeO3d. 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
La1xCaxFeO3d. 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