Materials Science-Poland, 32(1), 2014, pp.

34-38
[Link]
DOI: 10.2478/s13536-013-0153-1

A facile thermal decomposition route to synthesise

CoFe2O4 nanostructures
K. K ALPANADEVI , C.R. S INDUJA , R. M ANIMEKALAI∗

Department of Chemistry, Kongunadu Arts and Science College, Coimbatore, Tamilnadu, India, PIN – 641 029

The synthesis of CoFe2 O4 nanoparticles has been achieved by a simple thermal decomposition method from an inorganic
precursor, cobalt ferrous cinnamate hydrazinate (CoFe2 (cin)3 (N2 H4 )3 ) which was obtained by a novel precipitation method
from the corresponding metal salts, cinnamic acid and hydrazine hydrate. The precursor was characterized by hydrazine and
metal analyses, infrared spectral analysis and thermo gravimetric analysis. Under appropriate annealing, CoFe2 (cin)3 (N2 H4 )3
yielded CoFe2 O4 nanoparticles, which were characterized for their size and structure using X-Ray diffraction (XRD), high
resolution transmission electron microscopic (HRTEM), selected area electron diffraction (SAED) and scanning electron mi-
croscopic (SEM) techniques.
Keywords: CoFe2 O4 nanoparticles; XRD; HRTEM; SAED; SEM
© Wroclaw University of Technology.

1. Introduction method [5], sol-gel method [13], etc., thermal de-

composition of inorganic precursors is found to be
Spinel ferrites of nano scale are the most fas- interesting because of its simplicity, reproducibil-
cinating materials of this era, owing to their broad ity and easy scale-up. This synthetic route does
scope of applications in modern science and tech- not require expensive chemicals. It is a low-energy
nology. They have interesting structural, magnetic reaction and can be carried out in a silica cru-
and electrical properties [1]. Cobalt ferrite has cible in an open atmosphere. The purpose of this
been widely studied due to its excellent chemi- work is to prepare CoFe2 O4 in nanoscale by the
cal stability, mechanical hardness, reasonable satu- thermal decomposition of the inorganic precursor
ration magnetization and high magneto-crystalline CoFe2 (cin)3 (N2 H4 )3 .
anisotropy [2]. These properties make it a promis-
ing candidate for many applications, such as mag-
netic data storage, magnetic drug targeting, biosen-
2. Experimental procedure
sors and magnetic refrigeration [3], ferrofluids 2.1. Preparation of cobalt ferrous cinna-
and high-density information storage [4], spintron- mate hydrazinate CoFe2 (cin)3 (N2 H4 )3
ics [5], biomedicine [6], sensitive electrochemical
sensor [7] and sustainable hydrogen production [8]. The CoFe2 (cin)3 (N2 H4 )3 compound was pre-
Recently, CoFe2 O4 nanoparticles have been proven pared by the addition of an aqueous solution
to be effective magnetic feeders and have found ap- (50 mL) of hydrazine hydrate (1 mL, 0.02 mol) and
plication as nanofluid for enhanced oil recovery [9]. cinnamic acid (1.18 g, 0.0079 mol) to the corre-
sponding aqueous solution (50 mL) of cobalt ni-
Among the diverse methods employed for the trate hexahydrate (0.58 g, 0.0018 mol) and ferrous
synthesis of CoFe2 O4 nanoparticles, such as hy- sulphate heptahydrate (2.22 g, 0.0079 mol). The
drothermal technique [10], co-precipitation [11], brown orange product, which had been formed im-
micro-emulsion method [12], citrate-precursor mediately, was kept aside for an hour for digestion,
then filtered and washed with water, alcohol, fol-
∗ E-mail: manimekalair@[Link] lowed by diethylether and air dried.
 A facile thermal decomposition route to synthesise CoFe2 O4 nanostructures 35

2.2. Preparation of cobalt ferrite nanopar- found to match closely with the calculated val-
ticles ues (13.64), (25.11) and (47.60) for hydrazine,
cobalt and iron, respectively, the chemical for-
Cobalt ferrite nanoparticles were obtained from
mula CoFe2 (cin)3 (N2 H4 )3 has been tentatively as-
the autocatalytic decomposition of the precursor. In
signed to the precursor, cobalt ferrous cinnamate
this method, the dried precursor was transferred to
hydrazinate.
a silica crucible and heated to red hot condition
in an ordinary atmosphere for about 45 minutes.
3.2. FT-IR analysis of the precursor
The precursor started decomposing violently. The
total decomposition of CoFe2 (cin)3 (N2 H4 )3 led to From the IR spectrum of CoFe2 (cin)3 (N2 H4 )3 ,
the formation of CoFe2 O4 , which was quenched to it was observed that the N–N stretching frequency
room temperature, ground well and stored. was identified at 972 cm−1 , which unambiguously
proved the bidentate bridging nature of the hy-
2.3. Characterization of the precursor drazine ligand [15]. The asymmetric and symmet-
The hydrazine content in the precursor was de- ric stretching frequencies of the carboxylate ions
termined by titration using KIO3 as the titrant [14]. were seen at 1639 and 1411 cm−1 , respectively
The percentage of cobalt and iron in the precur- with the ∆υ ( υasymm − υsym) separation of 228 cm−1 ,
sor was estimated by the standard methods given which indicated the monodentate linkage of the
in the Vogel’s textbook [14]. The infrared spec- carboxylate groups. The N–H stretching was ob-
trum of the solid precursor sample was recorded served at 3367 cm−1 . The IR data thus con-
by the KBr disc technique using a Shimadzu spec- firmed the formation of cobalt ferrous cinnamate
trophotometer. The simultaneous TG-DTA experi- hydrazinate.
ment was carried out in Universal V4.5A TA In-
strument, in nitrogen atmosphere at the heating rate
3.3. Thermal analysis of the precursor
of 20 °C per minute using 5 – 10 mg of the sam- As can be observed in Fig. 1, the precursor loses
ple. The temperature range was from an ambient to weight in three particular steps. The first step is the
700 °C. removal of two of the hydrazine molecules between
room temperature and 210 °C with a weight loss of
2.4. Characterization of nanoparticles 9 %. The corresponding peak in DSC is observed
The particle size of the synthesised nanoparti- as an exotherm. The second step is dehydrazina-
cles was determined by high resolution transmis- tion of the remaining hydrazine molecule and one
sion electron microscopy (HRTEM) operating on of the three carboxylate groups, which takes place
Jeol Jem 2100 advanced analytical electron micro- between 210 and 400 °C. The weight loss from
scope. Scanning electron microscopy (SEM) was 400 to 610 °C is attributed to the third step involv-
performed with a HITACHI model S-3000H by fo- ing the decarboxylation of the remaining two car-
cusing on nanoparticles to study the morphology. boxylate moieties in the dehydrazinated precursor,
To check phase formation and purity, XRD pattern which gives CoFe2 O4 as the final residue.
was recorded using an X-Ray diffractometer (X’per
PRO model) with CuKα radiation, at 40 keV in the 3.4. Characterization of CoFe2 O4
2θ range of 10 – 80 degrees. nanoparticles
3.4.1. XRD analysis
3. Results and discussion XRD pattern of CoFe2 O4 nanoparticles is
shown in Fig. 2. Six characteristic peaks can be
3.1. Chemical formula determination of indexed as the cubic structure CoFe O , which
2 4
the precursor is in accordance with the reported data (JCPDS
Based on the observed percentage of hydrazine File No 22-1086). The peaks with 2θ values of
(13.09), cobalt (24.32) and iron (47.17), which are 30.52°, 35.85°, 43.38°, 53.97°, 57.29° and 62.92°
36 K. Kalpanadevi, C.R. Sinduja, R. Manimekalai

Fig. 1. TG-DSC curve of CoFe2 (cin)3 (N2 H4 )3 .

correspond to the crystal planes (220), (311), (400), (a)

(422), (511) and (440) of crystalline CoFe2 O4 , re-
spectively. The average crystallite size, estimated
using Debye-Scherrer formula, D = kλ /(β cosθ ),
where, θ is Bragg diffraction angle, k is Blank’s
constant, λ is the source wavelength (0.154 nm),
and β is the width of the XRD peak at half maxi-
mum height, is found to be around 12 nm. No char-
acteristic peaks for other impurities are detected,
confirming that the product obtained is phase pure.

(b)

Fig. 3. HRTEM image of CoFe2 O4 nanoparticles.

nanoparticles are of polydispersed spherical shape.

The presence of some bigger particles should be at-
tributed to the aggregation or overlapping of some
Fig. 2. XRD pattern of CoFe2 O4 nanoparticles. small particles. The average grain size observed
from the micrograph is about 12 – 13 nm, which
is in agreement with the calculation using Scher-
3.4.2. HRTEM analysis rer’s equation. Fig. 4 shows the selected area elec-
HRTEM micrographs of CoFe2 O4 are shown tron diffraction (SAED) pattern indicating sharp
in Fig. 3, which show the particle size distribu- rings, which reveal the polycrystalline nature of the
tion of CoFe2 O4 nanoparticles. It is evident that the nanoparticles.
 A facile thermal decomposition route to synthesise CoFe2 O4 nanostructures 37

(a)

Fig. 4. SAED pattern of CoFe2 O4 nanoparticles.

3.4.3. SEM analysis

The morphology of CoFe2 O4 was characterized
by scanning electron microscope. The SEM pic-
tures in Figs. 5a and 5b clearly show that the ferrite
powder is mostly formed of nano-sized homoge-
nous grains with the presence of some agglomer-
ated particles. EDX spectrum of CoFe2 O4 nanopar-
ticles is presented in Fig. 6, which furnishes the
chemical compositional analysis of the nanoscale (b)
CoFe2 O4 .
Fig. 5. a) SEM image of CoFe2 O4 nanoparticles
(× 10000); b) SEM image of CoFe2 O4 nanopar-
4. Conclusion ticles (× 20000).
By using a facile thermal decomposition route,
CoFe2 O4 nanoparticles were successfully synthe-
sized and characterized by XRD, HRTEM, SAED
and SEM techniques. The average particle size of
CoFe2 O4 nanoparticles determined from XRD and
HRTEM is about 12 nm. The present method is
simplistic and commercially feasible. It is also ef-
ficient in terms of time and equipment. Hence, this
method is an efficient and economical way to mass
production of ultrafine cobalt ferrite powder.

References
[1] H OU Y.H. et al., J. Phys. D Appl. Phys., 43 (2010)
445003.
[2] Y UE Z HANG , Z HI YANG , D I Y IN , YONG L IU , C HUN -
LONG F EI , J. Magn. Magn. Mater., 322, (2010), 3470. Fig. 6. EDX spectrum of CoFe2 O4 nanoparticles.
38 K. Kalpanadevi, C.R. Sinduja, R. Manimekalai

[3] Z HENFA Z I , Y UPING S UN , X UEBIN Z HU , W ENHAI [9] N OORHANA YAHYA , M UHAMMAD K ASHIF, NADEEM
S ONG, J. Magn. Magn. Mater., 321, (2009), 1251. NASIR , M AJID N IAZ A KHTAR , N OORASIKIN M OHD
[4] L AURENT S., F ORGE D., P ORT M., ROBIC C., E LST Y USOF, J. Nanopart. Res., 17 (2012),115.
V.L., M ULLER R.N., Chem. Rev., 108, (2008), 2064. [10] L I X.H, X U C.L, Nanoscale Res. Lett., 5 (2010), 1039.
[5] R AJATH VARMA P.C., M ANNA R.S., BANERJEE D., [11] G YERGYEK S., M AKOVEC D., J. Nanopart. Res., 12
R AAMA VARMA M., S URESH K.G., N IGAM A.K., J. (2010), 1263.
Alloy. Compd., 453 (2008), 298. [12] S HARIFI I., S HOKROLLAHI H., D OROODMAND M.M.,
[6] K HOO KOKSIONG , N URFARHANA A MARI , S AFI R., J. Magn. Magn. Mater., 324 (2012), 1854.
TANCHUNYUAN , S HAHIDANRADIMAN , [13] G UL I.H., M AQSOOD A., J. Alloy. Compd., 465 (2008),
R EDZUWANYAHAYA , M UHAMAD S AMUDI YASIR, 227.
Sains Malays., 42 (2013), 167. [14] VOGEL I., A Textbook of Quantitative Inorganic Analy-
[7] A NITHA K UMARY V., D IVYA J., M ARY NANCY T.E., sis, 4th Ed., Longman, UK, 1985.
S REEVALSAN K., Int. J. Electrochem. Sc., 8 (2013), [15] B RAIBANTI A., DALLAVALLE F., P ELLINGHELLI
6610. M.A., L EPORATI E., Inorg. Chem., 7 (1968), 1430.
[8] R AJENDRA S. G AIKWAD , S ANG -YOUN C HAE , R A -
JARAM S. M ANE , S UNG -H WAN H AN AND O H -S HIM Received 2013-09-23
J OO, Int. J. Electrochem., 6 (2011), 1. Accepted 2013-12-10