Journal of Molecular Structure 1075 (2014) 534541

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Journal of Molecular Structure

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

Chromium and copper substituted lanthanum nano-ferrites: Their

synthesis, characterization and application studies
Sheenu Jauhar, Sonal Singhal
Department of Chemistry, Panjab University, Chandigarh 160 014, India

g r a p h i c a l a b s t r a c t

3+

2+

 LaMxFe1xO4 (M = Cr , Cu ;

x = 0.00.5) prepared by solgel

auto-combustion method.
 Ferrites had same symmetry as
LaFeO3.
 Ferrites employed for catalytic
decomposition of hydrogen peroxide
solution.
2+
 Cu substituted ferrites exhibit much
higher catalytic activity than pure
ferrites.
3+
 Cr ions have little effect on catalytic
activity of lanthanum ferrites.

Concentration vs time graph for decomposition of hydrogen peroxide catalysed by LaCuxFe1xO3 annealed
at 400 C.
0.18
0.16
0.14

Conc. of H2O2, C (mol L-1)

h i g h l i g h t s

0.12
0.1
0.08
0.06
0.04

x=0.1
x=0.2
x=0.3
x=0.4
x=0.5

0.02
0
0

10

20

30

40

50

60

70

80

Time (mins)

a r t i c l e

i n f o

Article history:
Received 24 April 2014
Received in revised form 16 June 2014
Accepted 9 July 2014
Available online 17 July 2014
Keywords:
Magnetic materials
Nanostructures
Solgel growth
Electron microscopy (TEM)
Magnetometer
Electrical characterization

a b s t r a c t
Nano-crystalline lanthanum ferrites substituted by chromium and copper having formula LaMxFe1xO3
(M = Cr, Cu; 0.0 6 x 6 0.5) were synthesized using solgel auto-combustion method. The formation of
ferrite particles was conrmed using Fourier Transform Infra-Red (FT-IR) spectra and powder X-ray
Diffraction (XRD) techniques. The entire ferrite compositions were found to be pure phased with same
symmetry as LaFeO3. The average crystallite size was calculated to be 60 nm. The ferrite compositions
were observed to behave as semi-conductors, as their resistivity decreased with increasing temperature.
These ferrite compositions were employed as catalysts in the decomposition of hydrogen peroxide
solution (0.17 M). Pure LaFeO3 was found to have a very low catalytic activity towards the decomposition
of hydrogen peroxide solution, while presence of copper in the lanthanum ferrite lattice was found to signicantly enhance its catalytic activity. The rate constant in case of reactions catalysed by LaCu0.5Fe0.5O3
was nearly 25 times larger than that obtained from reactions catalysed by pure LaFeO3. However,
chromium substitution was not found to inuence the catalytic activity of lanthanum ferrites as
chromium substituted lanthanum ferrites exhibited very low catalytic activity. This was explained on
the basis of relative stability of oxidation states of the substituent ions and the presence of defects in
the crystal lattice.
2014 Elsevier B.V. All rights reserved.

Corresponding author. Tel.: +91 172 2534421 (O), +91 09872118810 (mobile);
fax: +91 172 2545074.
E-mail addresses: sheenu.sarwal@gmail.com (S. Jauhar), sonal1174@gmail.com
(S. Singhal).
http://dx.doi.org/10.1016/j.molstruc.2014.07.022
0022-2860/ 2014 Elsevier B.V. All rights reserved.

Introduction
Lanthanum ortho-ferrite or lanthanum ferrite, with formula of
LaFeO3, is a distorted perovskite-type ferrite. Its structural formula

S. Jauhar, S. Singhal / Journal of Molecular Structure 1075 (2014) 534541

is based upon the perovskite oxides, ABO3. The ionic radius of A ion is
larger than 1.0 , while the size of the B-ion is of the order 0.60.8
[1]. It crystallizes in an orthorhombic unit cell, with Pbnm space
group. Each Fe3+ is surrounded by six anti-parallel Fe3+ ions [2].
In recent years, lanthanum ferrite has attracted immense
interest by virtue of its wide applications in the elds of electronic
and magnetic materials. In addition, it has good catalytic and
gas sensing properties. Lanthanum ferrite is also reported to be
used as an electrode in solid oxide fuel cells [3]. It is also
found to be visible-light photocatalytically active due to its unique
opto-electronic properties and its narrow band gap [4]. In particular, the catalytic and photocatalytic properties of LaFeO3 have been
extensively investigated. The catalytic properties of LaFeO3 are
strongly dependent on grain size, method of preparation and
presence of a substituent ion in the lattice.
Many attempts have been made to enhance the catalytic performance of LaFeO3 by substituting lanthanum or iron ions with other
metal ions. For instance, Furfori et al. [5] synthesized strontium
substituted lanthanum ferrites by solution combustion synthesis
method and studied the catalytic activity of these ferrites in the
reduction of NO by hydrogen gas. The authors reported a signicant
increase in the catalytic activity in substituted lanthanum ferrites as
compared to pure lanthanum ferrite. Similar substitution of LaFeO3
with strontium was carried out by Ivanov et al. [6], who studied the
catalytic activity of strontium substituted lanthanum ferrites in high
temperature N2O decomposition, methane combustion and ammonia
oxidation reactions. The authors reported an enhanced catalytic
activity in case of LaSrFeO3 (surface)La0.4Sr0.6FeO3 composites.
Pecchi et al. [7] synthesized calcium substituted lanthanum ferrites
of the formula La1xCaxFeO3 (x = 0.0, 0.1, 0.2, 0.3, 0.4) and tested these
ferrites in the catalytic combustion of methane. The authors reported
highest catalytic activity in case of La0.4Ca0.6FeO3. Although, extensive
work has been carried out in order to study the catalytic activity of
lanthanum ferrites and related materials, there is still a large pool of
knowledge which remains unexplored in this area.
In the present study, novel heterogeneous catalysts have been
synthesized by substituting Cr3+ and Cu2+ ions in place of Fe3+ ions
in LaFeO3. Further, these catalysts have been employed in the catalytic decomposition of hydrogen peroxide solution. To the best of
the knowledge of authors, the decomposition of hydrogen peroxide
using chromium and copper substituted lanthanum ferrites has not
been previously reported in literature. The reason for selecting the
decomposition of hydrogen peroxide solution as a probe reaction
for testing the catalytic activity of substituted lanthanum ferrites
is the fact that the decomposition of hydrogen peroxide solution
forms underlying reaction for many other processes. For instance,
the decomposition of various dyes in the presence of hydrogen peroxide solution and various catalysts is an active area of research.
Thus, the decomposition of hydrogen peroxide solution can be
employed in various such reactions which might prove benecial
in various industrial and research applications.

Experimental
The method of preparation plays a crucial role in determining
the properties of lanthanum ferrites and related compounds. Various preparation techniques have been employed to synthesize
LaFeO3 and related materials, including solid-state reactions at
high temperature, wet chemical methods like hydrothermal synthesis, solution combustion synthesis, co-precipitation, thermal
decomposition of bimetallic compounds and sonochemical method
[8,9]. These methods have several problems like poor homogeneity, no control over the particle size, high porosity of samples,
development of secondary phases, and lower surface area. The
solgel auto-combustion method is a relatively good method as

535

it involves a simple technique and low processing temperature. It

gives a good control over stoichiometry and leads to production
of ultrane particles with homogeneous distribution.
In the present work, solgel auto-combustion method was used
to synthesize ferrite compositions having formula LaCrxFe1xO3 and
LaCuxFe1xO3 (x = 0.0, 0.1, 0.2, 0.3, 0.4 and 0.5). In this method, the
precursor nitrates [La(NO3)3.6H2O (CDH Chemicals), Fe(NO3)3.9H2O
(Thermo Fischer-Scientic India Pvt. Ltd.), Cu(NO3)2.3H2O (s.d. nechem limited), Cr(NO3)3.9H2O (Qualigens ne chemicals)] were
weighed in desired stoichiometric proportion and dissolved in minimum amount of distilled water. Citric acid (taken in the ratio
metal: citric acid as 1:1) was dissolved separately in minimum
amount of distilled water. The individual solutions were mixed
together and the pH of resultant solution was adjusted to 7 by
adding dilute ammonia solution. The solution was then kept on a
hot plate magnetic stirrer for 23 h, which resulted in the formation
of gel. On continued heating, the gel self-ignited in an autocombustion manner to yield ferrite powders, which were annealed
in a furnace (in air) at temperatures of 400 C, 600 C, 800 C and
1000 C for 2 h to yield ferrite powders.
The elemental analysis of the entire ferrite compositions was
carried out using an electron probe micro analyzer (EPMA) (JEOL8000 M). The elemental analytical data for all the elements in the
entire as obtained samples by EPMA were consistent within 2%.
The entire ferrite samples were characterized using the Fourier
Transform-Infra Red (FT-IR) spectroscopy. The FT-IR spectra were
recorded on a Perkin Elmer RX-1 FT-IR spectrophotometer in the
range 4000400 cm1. Hitachi (H-7500) Transmission Electron
Microscope (TEM), operated at 120 kV was used to record the
micrographs of the samples. The ferrite samples were rst ultrasonically agitated in absolute ethanol for 2 h. Thereafter, a drop
of this microemulsion was placed on carbon copper TEM grids
and dried it in air at room temperature, after which the TEM
images were recorded. Powder X-Ray Diffraction (XRD) patterns
were recorded using a Panalyticals0 XPert Pro spectrophotometer
with Cu Ka radiation (k = 1.5404
A). Si powder sample was used
as an instrument standard and the instrumental broadening,
calcu0
lated from the (1 1 1) peak was found to be 0.7
A. Their electrical
properties were studied using a two probe method. For this purpose, the ferrite sample was molded into a thin pellet. A silver
paint was applied on both the surfaces of the pellet to ensure good
electrical contact. The pellet was held between two electrodes of
specially designed sample holder. The measurements were
recorded in the steps of 10 K in the temperature range of
323423 K (40150 C). The error in measurement of resistivity
was approximately 3%. Further, their catalytic activity was tested
in the decomposition of hydrogen peroxide solution.
The hydrogen peroxide decomposition measurements were performed by diluting 2 mL H2O2 solution (30% w/v) (Thermo FischerScientic India Pvt. Ltd) to make the resultant volume up to 100 mL,
by adding distilled water. Calculated amounts of ferrite catalyst
(10 mol%, 20 mol%, 30 mol% and 40 mol%) were added to the
diluted hydrogen peroxide solution. Then, 5 mL of the hydrogen
peroxide solution was withdrawn at regular time intervals. It was
quickly ltered through a syringe lter to completely remove the
catalyst particles, and was titrated with standardized potassium
permanganate solution (0.03 M), to determine the concentration
of hydrogen peroxide left in solution after regular time intervals.

Results and discussion

Fourier Transform Infra-Red (FT-IR) characterization
The FT-IR spectra of perovskites are expected to exhibit
two bands 550 cm1 and 400 cm1 corresponding to FeO

S. Jauhar, S. Singhal / Journal of Molecular Structure 1075 (2014) 534541

asymmetrical stretching vibrations and FeOFe deformation

vibration respectively. The band due to FeO asymmetric
stretching appears at 555 cm1 in LaFeO3, which is characteristic
of octahedral FeO6 groups in the perovskite compounds. The
FT-IR spectra of the entire ferrite compositions annealed at various
temperatures were recorded. Figs. 1ad shows the FT-IR spectra of
the entire ferrite compositions annealed at various temperatures. It
is worth mentioning that temperature did not have a signicant
effect on the position of the FT-IR frequencies. The entire ferrite
compositions exhibited a peak in the range of 550580 cm1,
corresponding to FeO asymmetrical stretching conrming the
formation of ferrites [10,11]. The positions of FT-IR stretching
vibrations did not change signicantly with change in ferrite
compositions.

120

100

% Transmittance

536

x=0.1
x=0.2
x=0.3

80

60

40

20

0
400

450

500

550

600

650

700

750

800

Wavenumber (cm-1)
Fig. 1b. Typical FT-IR spectra of LaCuxFe1xO3 annealed at 400 C for 2 h.

Transmission Electron Microscope (TEM) characterization

100
90

(b)
(a)
(c)

80

% Transmittance

Lanthanum nano-ferrites have a large surface to volume ratio,

due to their large surface area. This results in a high agglomeration
of the ferrite particles. Therefore, in order to record the Transmission Electron Microscope (TEM) images, ferrite compositions were
rst ultrasonically agitated. The TEM images of the ferrite compositions annealed at all the temperatures were recorded. The TEM
images for LaFeO3 annealed at 400 C, 600 C, 800 C and 1000 C
for 2 h are shown in Fig. 2a. Similar behaviour was observed in case
of entire ferrite compositions. Therefore, the typical TEM
micrographs of substituted ferrites annealed at 400 C and
1000 C are shown in Figs. 2bc. From TEM images, it was
concluded that the particles had a nearly spherical morphology
and the particle size increased with increase in annealing
temperature. However, the particles were agglomerated, due to
the interfacial surface tension [12].

70
60
50
40
30
20
10
400

500

600

800

700

Wavenumber (cm-1)
Fig. 1c. Typical FT-IR spectra of LaCr0.1Fe0.9O3 annealed at (a) 600 C; (b) 800 C and
(c) 1000 C for 2 h.

The phase evolutions of the synthesized ferrites were studied

using the powder XRD technique. The powder XRD patterns of
the entire ferrite compositions annealed at various temperatures
were recorded and the typical patterns obtained are shown in
Figs. 3a, b. From the gure, it was observed that the peaks became
slightly narrower and sharper on increasing the annealing
temperature, as shown in the FWHM values in the gure given in
inset. This was attributed to the reason that as the annealing
temperature was increased, the crystallite size increased. Due to
the increase in crystallite size, the peaks became narrower and
sharper.

100
90

(b)
(c)
(a)

80

% Transmittance

Powder X-Ray Diffraction (XRD) studies

70
60
50
40
30
20
10

100

0
400

90

% Transmittance

450

500

550

600

650

700

750

800

Wavenumber (cm-1)

80
70

Fig. 1d. Typical FT-IR spectra of LaCu0.3Fe0.7O3 annealed at (a) 600 C; (b) 800 C
and (c) 1000 C for 2 h.

60
50
40

x=0.0
x=0.5
x=0.3
x=0.1
x=0.2

30
20
10
0
400

500

600

700

800

Wavenumber (cm-1 )
Fig. 1a. Typical FT-IR spectra of LaCrxFe1xO3 annealed at 400 C.

900

The powder XRD patterns of the entire ferrite compositions

annealed at 1000 C are given in Figs. 4a, b. The entire ferrite
compositions were pure phased with no detectable secondary
phases. The samples had same symmetry as LaFeO3 (JCPDS card
No. 00-015-0148) with Pbnm space group. The entire XRD patterns
showed shifting towards smaller angles, reecting shrinkage in the
lattice with increasing concentration of substituent ions. The structural parameters were analyzed using the Le-Beil renement
method (built in TOPAS V2.1 of BRUKER AXS), within an accuracy

537

S. Jauhar, S. Singhal / Journal of Molecular Structure 1075 (2014) 534541

(a)

(c)

100 nm

100 nm

(b)

(d)

100 nm

100 nm

Fig. 2a. Typical TEM Images of LaFeO3 annealed at (a) 400 C; (b) 600 C; (c) 800 C and (d) 1000 C for 2 h.

(a)

100 nm

(b)

100 nm

Fig. 2b. Typical TEM Images of LaCr0.1Fe0.9O3 annealed at (a) 400 C and (b) 1000 C.

of 0.002 and their values for the ferrite compositions annealed at

1000 C for 2 h are listed in Table 1. It can be seen from Table 1 that
the unit cell volume decreased with increase in the concentration
of the Cr3+ and Cu2+ ions. The decrease in the unit cell volume with
increasing Cr3+ concentration is in accordance with Vegards law,
while the decrease in the unit cell volume on increasing the Cu2+
concentration may be attributed to the fact that on substituting trivalent iron ions by divalent copper ions, then electrical neutrality
is maintained either by a higher oxidation state of iron or decrease

in oxygen content, leading to development of oxygen vacancies

[13]. Both the developments could be a factor in higher volume
reduction. The decreasing trend in the lattice parameter is consistent with the results reported by other research groups [14,15].
The average crystallite size was calculated from the line broadening of most intense peak (1 2 1) using the classical Scherrer relationship [16], Dh k l = 0.9k/Bcos h, where Dh k l is the crystallite size, B
is the half maximum line width, k is wavelength of the radiation
used and h is the angle of diffraction. The average crystallite size

538

S. Jauhar, S. Singhal / Journal of Molecular Structure 1075 (2014) 534541

(a)

(b)

100 nm

100 nm

(d)

(204)

(143)

(331)

(242)

(240)
(141)
(311)

(202)
(230)

(220)

(210)

(112)

(101)
(111)

(204)

(143)

(331)

(242)

(240)
(141)
(311)

(202)
(230)

(220)

(210)

(112)

33

Intensity (arbitrary unit)

(121)

FWHM
0.206
0.214
0.212
0.221
31.9 32

(101)
(111)

Intensity (arbitrary unit)

(121)

Fig. 2c. Typical TEM Images of LaCu0.5Fe0.5O3 annealed at (a) 400 C and (b) 1000 C.

(f)
(e)
(d)
(c)
(b)
(a)

(c)
(b)
(a)
21

30

40

50

60

70

21

30

40

50

60

70

80

Angle (2 )

80

Angle (2 )

(d)
(c)
(b)
(a)

30

40

50

60

70

(204)

(143)

(242)

(331)

(240)

(141)
(311)

(202)
(230)

(112)
(220)

(210)

(101)
21

(111)

Intensity (arbitrary unit)

(204)

(143)

(242)

(141)
(311)

(230)

(220)

(111)

(240)

(202)

(121)
(101)

Intensity (arbitrary unit)

Fig. 4a. Powder XRD patterns of LaCrxFe1xO3 (a) x = 0.0; (b) x = 0.1; (c) x = 0.2; (d)
x = 0.3; (e) x = 0.4 and (f) x = 0.5 annealed at 1000 C for 2 h.

(121)

Fig. 3a. Powder XRD patterns of LaCr0.2Fe0.8O3 annealed at (a) 400 C, (b) 600 C, (c)
800 C and (d) 1000 C for 2 h. (Inset: 1 2 1 peak with Full Width at Half Maxima
(FWHM) values).

(f)
(d)
(c)
(b)
(a)

80

Angle (2 )
21

30

40

50

60

70

80

Angle (2 )

Fig. 4b. Powder XRD patterns of LaCuxFe1xO3 (a) x = 0.0; (b) x = 0.1; (c) x = 0.2; (d)
x = 0.3; (e) x = 0.4 and (f) x = 0.5 annealed at 1000 C for 2 h.

Fig. 3b. Powder XRD patterns of LaCu0.3Fe0.7O3 annealed at (a) 400 C, (b) 600 C, (c)
800 C and (d) 1000 C for 2 h.

Electrical properties
increased with increase in annealing temperature. However, there
was no signicant change in the values of average crystallite size
with changing composition. The average crystallite size was found
to be 60 nm (within an error of 2 nm), for the ferrite compositions annealed at 1000 C for 2 h, and its values are listed in Table 1.

The d.c. electrical resistivity (q) values of the ferrite

compositions were measured using two probe method. The variation of d.c. electrical resistivity with temperature (T), for chromium
and copper substituted lanthanum ferrites, annealed at 400 C,

539

S. Jauhar, S. Singhal / Journal of Molecular Structure 1075 (2014) 534541

Table 1
Lattice parameters, a (), b () and c (); Volume of unit cell, V ()3; and Crystallite size, D (nm) and rst order rate constant, k (min1) of chromium and copper substituted
lanthanum ferrites annealed at 1000 C for 2 h.
Ferrite

a ()

b ()

c ()

V (3)

D (nm)

LaFeO3

5.556

5.565

7.862

243.1

54

LaCrxFe1xO3

0.1
0.2
0.3
0.4
0.5

5.549
5.535
5.533
5.534
5.532

5.547
5.556
5.543
5.541
5.542

7.849
7.832
7.843
7.845
7.839

241.6
240.8
240.5
240.5
240.3

61
57
55
56
55

LaCuxFe1xO3

0.1
0.2
0.3
0.4
0.5

5.543
5.545
5.539
5.533
5.541

5.547
5.535
5.542
5.541
5.517

7.842
7.851
7.838
7.835
7.833

241.1
240.1
240.6
240.2
239.4

53
59
61
62
60

(a)

(ohm- m)

3.5

log

600 C, 800 C and 1000 C, was recorded. The typical log q vs 1000/
T graphs for ferrite compositions annealed at different annealing
temperatures are shown in Figs. 5a, b. It was observed that for
the entire ferrite compositions annealed at various temperatures,
the d. c. resistivity decreased with increase in temperature, reecting the semi-conductor behaviour of ferrite compositions.
In order to understand the behaviour of d. c. resistivity as a
function of temperature, typical log q vs 1000/T graphs for entire
ferrite compositions annealed at 400 C are shown in Figs. 6a, b.
In both the cases, the d.c. resistivity decreased with increase in
the concentration of substituent ion.
Interestingly, the d.c. resistivity was found to be lower for copper substituted lanthanum ferrites as compared to chromium
substituted cobalt ferrites. This may be attributed to the reason
that Cu2+ introduces the anisotropy in the system and creates a
lot of oxygen vacancies, leading to an increase in conductivity or
decrease in resistivity. Bhat et al. [2] reported similar results in
case of zinc substituted lanthanum ferrites.

(b)
(c)
(d)

2.5

1.5

1
2.3

2.4

2.5

2.6

2.7

2.8

2.9

3.1

3.2

1000/T (K-1)
Fig. 5b. Variation of log q with 1000/T for LaCu0.2Fe0.8O3 annealed at (a) 400 C, (b)
600 C, (c) 800 C and (d) 1000 C for 2 h.

Catalytic properties

6.5

x=0.5

Mn H2 O2 ! Mn1 HO HO

x=0.4
x=0.3
x=0.2
x=0.1

5.5

(ohm- m)

5
4.5

log

The decomposition of hydrogen peroxide solution in the presence of a metal ion is believed to occur by an advanced oxidation
process. In this process, hydroxyl radicals (HO) are generated by
the reaction of a metal ion and hydrogen peroxide. The HO radicals
react with hydrogen peroxide to generate HOO radicals, which
further lead to formation of O2. The reaction has been proposed
to occur by the following mechanism [17]:

3.5

3
2.5
2
2.2

5.5

2.4

2.6

2.8

3.2

1000/T (K-1)
(a)
(b)
(c)
(d)

log

(ohm- m)

4.5

Fig. 6a. Variation of log q with 1000/T for LaCrxFe1xO3 annealed at 400 C.

H2 O2 HO ! H2 O HOO

4
3.5

Mn1 HOO ! Mn H O2
3
2.5
2
2.3

2.4

2.5

2.6

2.7

2.8

2.9

3.1

3.2

1000/T (K-1)
Fig. 5a. Variation of log q with 1000/T for LaCr0.1Fe0.9O3 annealed at (a) 400 C, (b)
600 C, (c) 800 C and (d) 1000 C for 2 h.

In the present investigation, lanthanum ferrites substituted with

chromium and copper were employed as catalysts in the decomposition of hydrogen peroxide. It is well known that the catalytic
activity of a catalyst depends on its surface area. Smaller is the
particle size, larger is the surface area and better is the catalytic
activity. Therefore, the ferrite compositions annealed at 400 C were
chosen for this study. This is because of the reason that at lower

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S. Jauhar, S. Singhal / Journal of Molecular Structure 1075 (2014) 534541

0.18

4.5

0.16

x=0.5
x=0.4
x=0.3
x=0.2
x=0.1

3.5

0.14

Conc. of H2O2, C (mol L-1)

log

(ohm- m)

2.5

0.12
0.1
0.08
0.06
0.04

x=0.1
x=0.2
x=0.3
x=0.4
x=0.5

0.02

1.5
2.2

2.4

2.6

2.8

3.2

1000/T (K -1)

10

20

30

40

50

60

70

80

Time (min)

0.09

x=0.5

0.08

x=0.3

0.07
0.06

Log C0/C

annealing temperatures, particle size is small, leading to a larger

surface area.
Further, the concentration of ferrite catalyst was varied from
10 mol% to 40 mol%, in order to determine the optimum concentration of ferrite catalyst. Optimum rate of reaction was obtained
when the catalyst concentration was taken as 20 mol%. Therefore,
the catalyst concentration was xed at 20 mol%. The decomposition of the hydrogen peroxide solution catalysed by the entire
ferrite compositions annealed at 400 C, at 20 mol% concentration
is given in Figs. 7 and 8. All the graphs were corrected for self
decomposition of hydrogen peroxide. From Fig. 7, it can be seen
that the pure LaFeO3 exhibited a very low catalytic activity and
the catalytic activity of chromium substituted lanthanum ferrites
was nearly similar as that of pure LaFeO3. This suggested that the
presence of chromium into the lanthanum ferrite lattice did not
bring a signicant change in its catalytic activity. However, from
Fig. 8, it was observed that the presence of Cu2+ ions into the lanthanum ferrite lattice tremendously enhanced its catalytic activity.
Moreover, as the Cu2+ concentration increased, the catalytic
activity of the ferrites increased. This behaviour can be explained
on the basis of the fact that when Cr3+ ions replace Fe3+ ions in
the lanthanum ferrite lattice, then they do not introduce a large
number of defects in the crystal lattice. Moreover, Cr3+ ions exist
in stable oxidation state. Therefore, these exhibit little catalytic
activity. On the other hand, when divalent Cu2+ ions replace Fe3+
ions of the lattice, then defects are introduced into the crystal
lattice, in order to maintain the electrical neutrality. The presence
of defects (like oxygen vacancies) enhances the adsorption onto

Fig. 8. Concentration vs time graph for decomposition of hydrogen peroxide

catalysed by LaCuxFe1xO3 annealed at 400 C.

x=0.1

0.05
0.04
0.03
0.02
0.01
0
0

10

20

30

40

50

60

Time (min)
Fig. 9. Hydrogen peroxide decomposition in the presence of LaCrxFe1xO3.

x=0.5
1.8
1.6
1.4

Log C0/C

Fig. 6b. Variation of log q with 1000/T for LaCuxFe1xO3 annealed at 400 C.

x=0.4

1.2

x=0.3

x=0.2
x=0.1

0.8

Conc. of H2O2, C (mol L-1)

0.6
0.175

0.4

0.17

0.2

0.165

0
0

20

40

60

80

Time (min)

0.16

Fig. 10. Hydrogen peroxide decomposition in the presence of LaCuxFe1xO3.

0.155
0.15

x=0.1

0.145

x=0.0
x=0.3

0.14

x=0.5

0.135
0.13
0

10

20

30

40

50

60

70

80

Time (min)
Fig. 7. Concentration vs time graph for decomposition of hydrogen peroxide
catalysed by LaCrxFe1xO3 annealed at 400 C.

the surface of catalyst, thereby increasing the catalytic activity.

Moreover, copper ions can conveniently exist in more than
one oxidation states. Consequently, there may be an active participation of copper ions in the decomposition of hydrogen peroxide.
Due to this, the catalytic activity of copper substituted lanthanum
ferrites was more than that of pure lanthanum ferrite. With
increasing copper substitution, more defects are introduced into
the crystal lattice, thereby, increasing the catalytic activity. Similar
results were obtained from the study of d.c. resistivity. The d.c.

S. Jauhar, S. Singhal / Journal of Molecular Structure 1075 (2014) 534541

Table 2
First order rate constant, k (min1) of chromium and copper substituted lanthanum
ferrites annealed at 400 C for 2 h.
Ferrite

k (min1)

LaFeO3

0.0

0.0023

LaCrxFe1xO3

0.1
0.2
0.3
0.4
0.5

0.0021
0.0024
0.0034
0.0036
0.0039

0.1
0.2
0.3
0.4
0.5

0.0267
0.0278
0.0380
0.0437
0.0608

LaCuxFe1xO3

resistivity of chromium lanthanum ferrites was higher than that of

copper lanthanum ferrites, which may be attributed to the presence of defects in copper lanthanum ferrites, which enhance the
conductivity of copper lanthanum ferrites.
From the above gures, it was also concluded that the reaction
followed rst order kinetics. The rst order rate constants of
decomposition reaction of hydrogen peroxide solution in the presence of substituted lanthanum ferrite catalysts were calculated
from the slope of log C0/C vs time graphs, where C0 is the initial
concentration of hydrogen peroxide and C is its concentration at
any given time, t (Figs. 9 and 10). The values of rst order rate
constants for the entire ferrite compositions annealed at 400 C
for 2 h at 20 mol% concentration are given in Table 2. Further,
the recyclability of catalysts was also investigated which revealed
that catalysts could be reused for three times without any loss of
catalytic activity.
Conclusions
Chromium and copper substituted lanthanum nano-ferrites
were synthesized using solgel method and were characterized
using FT-IR spectroscopy, TEM microscopy and powder XRD techniques. The entire ferrite compositions were pure phased and had
the same symmetry as LaFeO3. The ferrite compositions were
employed as catalysts in decomposition of hydrogen peroxide
solution. It was observed that pure LaFeO3 exhibited little catalytic
activity in the decomposition of hydrogen peroxide solution. The
substitution of iron ions by chromium ions did not increase the

541

catalytic activity. However, the substitution of iron ions by copper

ions enhanced the catalytic activity of the lanthanum ferrites to a
great extent. This was attributed to the reason that when trivalent
iron ions are replaced by trivalent copper ions, defects are developed on the surface of the ferrite. Due to this, the adsorption capacity of the catalyst increases, thereby increasing its catalytic activity.
Declaration
The article is original, has been written by the stated authors
who are all aware of its content and approve its submission, has
not been published previously, it is not under consideration for
publication elsewhere, no conict of interest exists, or if such
conict exists, the exact nature of the conict must be declared
and if accepted, the article will not be published elsewhere in the
same form, in any language, without the written consent of the
publisher.
Acknowledgement
The authors express their deep gratitude to DST (SERB) for providing grant under major research project and University Grants
Commission (UGC) for providing fellowship to S. Jauhar.
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