Indian Journal of Engineering & Materials Sciences

Vol.16, August 2009, pp. 288-290

Preparation and characterization of nickel doped, A and B Site LaCoO3 perovskite

Chandrakant Singh & Meeta Rakesh*
G N Khalsa College, Matunga, Mumbai 400 019, India

Received 16 May 2008; accepted 4 March 2009

This paper presents an approach to the preparation of LaCoO3 perovskite and nickel doped LaCoO3 in A and B site both,
to see the effect of nickel doping in both the site catalyst synthesized by co-precipitation method. The novelty of the
experiment is nickel doped in A-site of LaCoO3 perovskite to see effect of nickel doping into their physical properties (i.e.
crystalline phase and microstructure). Samples have been characterized by X-ray diffraction (XRD), scanning electron
microscope (SEM), Branauer–Emmett-Teller (BET) nitrogen adsorption technique.

Keywords: Perovskite; LaCoO3, La1-x Ni xCoO3 , LaCo1-y NiyO3; Co-precipitation method

Perovskite type materials have been specifically the mixed metal nitrate solution excess of
investigated in details for their possible application in ammoniumhydroxide (NH4OH) was added so that
heterogeneous catalysis1-5. Perovskite is one of the metal oxy-hydroxide precipitate formed. Precipitate
most fascinating groups of catalytic materials having was washed with distilled water to pH-7, vacuum
densely packed cubic lattice of general formulae filtered and dried in oven for overnight at 110°C dried
ABO3. A ion can be rare earth, alkaline earth, alkali precipitate was grinded and kept for calcinations in
and other large ions such as Pb2+, Bi3+ that fits into muffle furnace at 800°C for 8 h. X-ray diffraction were
dodecahedral site of the framework the B ion can be obtained on a XPERT-PRO diffractometer, using
3d, 4d, and 5d transition metals, which occupy the CuKα radiation in the 2θ range from 5° to 80° in steps
octahedral site. Perovskite compound can also tolerate of 0.017° with a counting time 5.06 s. Morphology and
significant partial substitution and non-stoichiometry,
while still maintaining perovskite structure studies
have been carried out where doping is done to distort
the framework of perovskite to increase the activity of
catalyst6. The novelty of the experiment is, nickel is
doped in A site of LaCoO3 to obtain distorted cubic
structure. In this paper, preparations and
characterizations of the new materials La1-x Ni xCoO3
(X = 0.1, 0.2, 0.3) have been described and their
structural features and physical properties as
compared to the superconducting system
LaCo1-y NiyO3 (Y= 0.1, 0.2, 0.3) have been discussed.

Experimental Procedure
The LaCoO3, La1-x Ni xCoO3 (X = 0.1, 0.2, 0.3),
and LaCo1-y NiyO3 (Y= 0.1, 0.2, 0.3) were prepared by
the co-precipitation method. For this concentrated
solution of lanthanum, nickel and cobalt nitrates were
prepared. The concentrations were selected in order to
obtain La:Ni:Co atomic ratio of (1-X):X:1 and 1:
(1-Y):Y, where X and Y is the substitution degree to
—————— Fig. 1— X-ray diffraction profiles of LaCoO3, La1-x Ni xCoO3
*For correspondence (E-mail: meetarakesh@gmail.com) (X = 0.1, 0.2, 0.3), and LaCo1-y NiyO3 (Y= 0.1, 0.2, 0.3)
 SINGH & RAKESH: LaCoO3 PEROVSKITE 289

Fig. 2— SEM photograph of : (a) LaCoO3; (b) LaCo0.9Ni0.1O3; (c) LaCo0.8Ni0.2O3; (d) LaCo0.7Ni0.3O3; (e) La0.9Ni0.1CoO3;
(f) La0.8Ni0.2CoO3; and (g) La0.7Ni0.3CoO3
size of the crystallites were determined from scanning
electron microscopy (SEM), images taken with a Joel
JSM-6380 microscope. BET were determined using
nitrogen adsorption/desorption isotherm at 130°C
over catalyst sample.
Result and Discussion
Figure 1 shows the XRD pattern of the sample
LaCoO3, LaCo1-y NiyO3 (Y= 0.1, 0.2, 0.3), and La1-x
Ni xCoO3 (X = 0.1, 0.2, 0.3). X-ray diffraction pattern
of LaCoO3, LaCo0.9 Ni 0.1O3, LaCo0.8Ni0.2O3 and
LaCo0.7Ni 0.3O3 gave perovskite cubic phase (P), when
nickel substituted in A-site, i.e., La1-xNixCoO3
(Y= 0.1, 0.2, 0.3) some impurities of La2O3(*) and
La(OH)3 (●) with some weak unidentified peaks (+)
formed other than perovskite phase. These
observations indicate a distortion of perovskite
crystalline structure. It further proves that as the
290 INDIAN J. ENG. MATER. SCI., AUGUST 2009
Table 1— BET surface area result of the prepared sample
Sample code Chemical composition Surface area (m2/g)
(a) LaCoO3 6.22
(b) LaCo0.9Ni0.1O3 7.12
(c) LaCo0.8Ni0.2O3 8.44
(d) LaCo0.7Ni0.3O3 12.65
(e) La0.9Ni0.1CoO3 7.04
(f) La0.8Ni0.2CoO3 14.95
(g) La0.7Ni0.3CoO3 18.13
nickel atomic ratio increases at A-site, distortion in
the perovskite structure also increases.
Figure 2a shows SEM of LaCoO3, indicating
bigger grain size. When Co site is substituted by
Ni, the SEM indicates that grain sizes have become
more finer as evident from Figs 2b-2d. However, the
substitution at A site, i.e., La with minimum of 0.1
and 0.2 does not yield fine grain size as seen in Figs
2e and 2f. The most fine, highly dispersed phase can
be seen in Fig. 2g with A site (La) substitution of 0.3
by Ni. These results provide useful insight into the
grain size structure and morphology.
The calculated surface areas are given in Table 1.
Specific surface area of the catalyst nitrogen
adsorption/disorption isotherms have been measured
at 130°C samples. LaCoO3 has specific surface area
of about 6.22 m2/g. As the nickel atomic ratio
increases in LaCoO3 either A or B site, the specific
surface area increases. However, due to B site
substitution, increase in surface area is lower than A
site substitution as can be seen through the result in
figures. For example, La0.7Ni0.3CoO3 has a specific
surface area of 18.13 m2/g compared to
LaCo0.7Ni0.3O3 with an area of 12.65 m2/g. The doping
leads to distortion in catalyst structure, thus providing
enhanced catalytic activities. Increased surface area is
also linked with higher catalytic output with more
reaction sites.
Conclusions
The structural characterization and some physical
properties of perovskite catalyst series LaCoO3,
LaCo1-y NiyO3 (Y= 0.1, 0.2, 0.3), and La1-x Ni xCoO3
(X = 0.1, 0.2, 0.3) prepared by co-precipitation
method were carried out. The XRD patterns
concluded that maximum distortion of the perovskite
crystalline structure occurred when nickel is doped in
A-site. It increases as atomic ratio of nickel increases
in LaCoO3.
The SEM image shows the mean particle size was
in the nanoscale range between 10 nm to 40 nm. It
was also found that as nickel atomic ratio increases at
A site, it also increases the fineness and uniformity of
particle size which can have high catalytic activity.
Specific surface area increases as substitution
degree of nickel in LaCoO3 increases, maximum
surface area was found in La0.7Ni0.3CoO3, i.e., 18.13
(m2/g) where substitution is highest at 0.3 with A site
doping corresponding similar doping at B site gives
lower surface area.
Acknowledgements
The author would like to thank Dr. Rakesh Kumar,
Scientist and Head, NEERI Mumbai zonal laboratory
for helpful discussion and providing experimental
support.
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