A study on growth formation of nano-sized

magnetite Fe3O4 via co-precipitation method

Y. S. Lim, C. W. Lai, S. B. A. Hamid*, N. Muhd Julkapli, W. A. Yehya, M. Z. Karim,
M. F. Tai and K. S. Lau
A simple and cost-effective chemical co-precipitation of aqueous ferrous and ferric salts was used
to synthesis controlled size of magnetite iron oxide nanoparticles. The titration reactions between
the aqueous Fe2+/Fe3+ salt solutions were controlled by an autotitrator unit with continuous
addition of 1 M sodium hydroxide under different heating temperatures from 30 up to 80°C in
oxidising atmosphere. Then, further investigation on the degree of crystallinity of magnetite iron
oxide nanoparticles was conducted by altering the concentration of Fe2+/Fe3+ ions in the ratio
of 1:1, 1:1·25, 1:1·5 and 1:2. The resultant magnetite iron oxide nanoparticles were
characterised by using X-ray diffraction, field emission scanning electron microscopy and
Fourier transform infrared spectroscopy. The ratio of Fe2+/Fe3+ salt solutions and heating
temperatures played a crucial role in controlling the morphology, crystallinity and particle sizes
of magnetite magnetite iron oxide.
Keywords: Co-precipitation, Magnetite, Iron oxide, Titration, Crystallinity

Introduction elimination9 and magnetic resonance imaging.14 Thus, a

The recent advance in the development of Fe3O4 nano-
particle has gained significant interest because of its dis-
tinguished properties and many potential technological
applications. Among different phases of Fe3O4, the
magnetite phase has exhibited interesting properties of
superparamagnetism, large surface area, low toxicity
and bio-compatibility. These special characteristics have
been intensively studied. To date, magnetite Fe3O4 nano-
particle has been widely explored in different areas, such
as magnetic storage area,1,2 ferrofluids3,4 and biomedi-
cine.5–9 Likewise, synthesis of homogenous Fe3O4 nano-
particles (size variation < 5%) with high crystallinity
and surface area is a crucial task. The desired dimension
and crystallinity of Fe3O4 will strongly affect their proper-
ties in those applications.10
The most favourable synthetic route for Fe3O4 nano-
particles is conducting co-precipitation technique
because of easier and higher yields compared to other
techniques.11,12 To date, there is still often a large
variation in size and shape of the magnetite
Fe3O4 nanoparticles produced.9,13 However, the for-
mation of nano-sized magnetite Fe3O4 particle remains
a challenge in developing a promising candidate in the
biological system, including in vivo drug delivery,14 bio-
Nanotechnology & Catalysis Research Centre (NANOCAT), 3rd Floor,
Block A, Institute of Postgraduate Studies (IPS), University of Malaya,
50603 Kuala Lumpur, Malaysia
*Corresponding author, email sharifahbee@um.edu.my
controlled synthesis procedure for the production of
nano-sized magnetite Fe3O4 particle must be investigated
and optimised in getting the right dimensions. Herein, the
formation mechanism of homogeneous Fe3O4 nanoparti-
cles with a high degree of crystallinity was reported.
Materials and methodology
In this part of the experiment, different reactions for the
formation of Fe3O4 particles were conducted by adjusting
the reaction temperature and Fe2+/Fe3+ ratio. The
reagents were used for the synthesis including iron (II)
sulphate heptahydrate (FeSO4·7H2O, 99·5%, Merck),
iron (III) nitrate nonahydrate [Fe(NO3)3·7H2O, 98%,
Sigma Aldrich] and sodium hydroxide (NaOH, pellet,
Sigma Aldrich). In the typical synthesis, 0·005 mol of
FeSO4 and Fe(NO3)3 were mixed and dissolved in
100 mL deionised water for 5 minutes using a magnetic
stirrer. Reaction temperature of co-precipitation process
ranged from 30°C to 80°C. Further investigation on the
degree of crystallinity of magnetite Fe3O4 nanoparticles
was studied by changing the ratio of salt mixture from
1:1 to 1:2. Subsequently, excess 0·5 M NaOH solution
was titrated into the aqueous salt mixture under vigorous
stirring, gradually generating black precipitate. The
titrant was delivered at a fixed rate of 5 mL min−1 until
the pH reached 12 and reaction stopped. Finally, the
resultant black precipitates were washed several times
and dried at 50°C for 24 hours for further characteris-
ation. Fourier transform infrared spectroscopy (FT-IR,
Perkin Elmer-1600 Series) in the range of 400–2000 was

© W. S. Maney & Son Ltd 2014

DOI 10.1179/1432891714Z.0000000001028 Materials Research Innovations 2014 VOL 18 SUPPL 6 S6-457
Lim et al. A study on growth formation of nano-sized magnetite Fe 3 O 4
carried out to identify infrared (IR) absorption spectrum
of our samples to identify the presence of iron oxide spec-
trum (Fe–O bond) with minimum residue compound in
the final samples. Powder X-ray diffraction (XRD) data
of the samples are collected on (Philips PW 1729) with
powder diffractometer with CuKα radiation sources of
40 kV in the 2θ range of 20–70°. The surface morphology
and size of final products were characterised using the
scanning electron microscope (SEM) (Zeiss SUPRA
35VP).
The formation mechanism of Fe3O4 nanoparticle was
proposed by the study of the titration curve of pH
change versus volume. The first derivative of the titration
curve was calculated and plotted, with pH change during
titration process.
Results and discussion
Solutions of Fe2+ and Fe3+ titrated with different ratio
and reaction temperatures are presented in Fig. 1.
Figure 1a and b shows the group of titration curves
with different Fe2+/Fe3+ ratio and reaction temperatures,
while Fig. 1c shows an example of individual titration
curve with calculated first derivative. Figure 1d shows
the respective field emission scanning electron
microscopy surface morphology of Fe3O4 particles syn-
thesised with the ratio of 1:1 at 45°C. The plotted titration
1 Titration curves of Fe2+/Fe3+ salts solution by different parameters: a temperature and b ratio. c The example of individual
titration curve with calculated first derivative and d SEM image of sample ratio of 1:1, reacted at 45°C. Both equivalent points
at different stages can be identified from the individual curve
S6-458 Materials Research Innovations 2014 VOL 18 SUPPL
curves show that the reaction between Fe precursors
and NaOH is taking place in two different stages. First
derivative of the respective titration curves indicates that
there are two equivalence points at which the pH
changes rapidly with base titration until the end-point is
reached.
The occurrence of two equivalent points can be
explained by the reaction of two different salts [FeSO4
and Fe(NO3)3] with different solubility at different con-
ditions ( pH value). Fe salt solution that contained diva-
lent (2+) and trivalent (3+) cations was initially acidic
in nature. Generally, titration with 5 mL min−1 NaOH
base solution triggered two important reactions. The
first reaction occurred at pH 2–4 while the second reac-
tion occurred at pH 8–9. A reddish brown precipitate
was observed during the first reaction, suggesting that
Fe may be oxidised to ferric hydroxide [Fe(OH)3] inter-
mediate compound.15 However, the resultant brown pre-
cipitation turned into black colour precipitation when
pH of the solution reached the second equivalent point
( pH = 9), implying the formation of Fe3O4 nanoparticles
by co-precipitation of Fe2+ and Fe3+ ions. The reaction
stopped at pH 12 to ensure that the precursors were
fully reacted.
Precipitation of divalent and trivalent Fe salts occurred
in alkaline medium forming black precipitate (Fe2O3
nanoparticle). The overall chemical reaction to synthesise
6

2 Fourier transform Infrared spectroscopy spectra of
magnetite in different processing conditions, a change of
Fe2+/Fe3+ratio and b change of reaction temperature
Fe3O4 nanoparticles could be written as follows16:
Fe2+ + 2Fe3+ + 8OH−  Fe3 O4 (black precipitate)
+ 4H2 O
(1)
The trivalent Fe3+ in nitrate solution was hydrolysed and
reacted to form the trivalent [Fe(OH)3] intermediate com-
pound in between pH 2 and 4. According to the previous
study, the reaction to form dark brown colour of trivalent
Fe(OH)3 was proposed in the following chemical reac-
tion15:
Fe3+ + 3OH−  Fe(OH)3 (dark brown) (2)
Then, the divalent Fe2+ in FeSO4 solution was reacted
with base to form the reddish brown precipitate of diva-
lent ferrous hydroxide [Fe(OH)2] between pH 7 and 9,
as presented in equation (3)15
Fe2+ + 2OH−  Fe(OH)2 (reddish brown) (3)
In this case, Fe(OH)2 and Fe(OH)3 salts were likely to be
formed under a continuous titration reaction condition.
From the titration curves, both salts reacted with each
Lim et al. A study on growth formation of nano-sized magnetite Fe 3 O 4
other around pH 9 to form Fe3O4 nanoparticles. The
chemical reaction was presented in equation (4)
Fe(OH)2 + 2Fe(OH)3  Fe3 O4 + 4H2 O (4)
By controlling the Fe2+ and Fe3+ concentration ratio and
temperature, the size and shape of Fe3O4 particles can be
tailored.12 Representative SEM image of the synthesised
samples is shown in Fig. 1d. The SEM image depicted
that the surface morphology of the synthesised Fe3O4
nanoparticles was roughly spheroidal. The Fe3O4 nano-
particles were mainly agglomerated because of the van
deer Waal’s forces between particles.11 It could be
observed that the mean size of about ±70 nm was
obtained for the sample synthesised at a ratio of 1:1 at
45°C.
In this case, IR spectroscopy was useful to detect the
occurrence of magnetite because interaction between
divalent and trivalent cations with electromagnetic radi-
ation takes place in the specific spectra. Figure 2 shows
that the existence of Fe–O stretching peak at 570 cm−1
manifests that the particles were consistent with magnetite
spectrum (570–580 cm−1). The other peak at 800 and
900 cm−1 suggests the existence of iron oxyhydroxide
(goethite) in the final products. Therefore, it could be jus-
tified that Fe(OH)2, Fe(OH)3 and FeOOH co-existed
during synthesis of magnetite Fe3O4 nanoparticles
because of the hydrolysation of ferric and ferrous reac-
tants. Meanwhile, OH− bending could be identified by
detection of a small peak at 1630 cm−1, indicating the
existence of β-FeO(OH)16 as well. The occurrence of the
OH− spectrum was believed to come from the oxidising
atmosphere during the experimental works. When the
reaction temperature increased to 80°C, stronger peak at
800 and 900 cm−1 corresponded to Fe(OH)2 and
Fe(OH)3 could be observed. This shows that at high
temperature, intermediate compound of ferrous and
ferric hydroxide was not fully reacted. Overall, the vari-
ation of Fe2+/Fe3+ concentration showed insignificant
changes in FTIR spectrum.
Phase identification of the Fe3O4 nanoparticles was
done by XRD measurement. As shown in Fig. 3, the
reflection peak position and intensities relatively
matched the Fe3O4 magnetite phase with JCPDS card
no. 01-089-0691. These samples had a theoretical face-
centred cubic spinel structure with diffraction peaks cor-
responding to (2 2 0), (3 1 1), (4 0 0), (5 1 1) and (4 4 0)
planes at around 2θ ≈ 30, 35, 43, 57 and 63°. It could
be noted that further increasing the reaction temperature
and Fe2+/Fe3+ ratio resulted in poor crystallinity.
Besides, the intensity of magnetite peak (3 1 1) was
getting weakened and broadened as the reaction tempera-
ture and the concentration iron ions increased. These
results suggested that Fe3O4 samples were in nano-size
or poor crystallised structure in oxidising atmosphere.
Conclusion
Nanoparticles were synthesised by the co-precipitation
method in oxidising atmosphere by controlling the reac-
tion temperature and Fe2+/Fe3+ ratio. The mean size of
the nanoparticles was about ±70 nm. Magnetite iron
oxide was obtained by Fourier transform infrared spec-
troscopy analysis and X-ray diffraction diffraction
pattern. It was observed that the increase of reaction
Materials Research Innovations 2014 VOL 18 SUPPL 6 S6-459
Lim et al. A study on growth formation of nano-sized magnetite Fe 3 O 4
3 Croatia, X-ray diffraction patterns of the samples synthesised with a varied temperature and b varied Fe2+/Fe3+ ratio
temperature and Fe2+/Fe3+ ratio would result in the
decrease in crystallinity of iron oxide particles. The
sample synthesised with a ratio of 1:1 at 45°C shows
the best crystallinity among all samples. It can be con-
cluded that co-precipitation of magnetite iron oxide nano-
particles using ferric nitrate and ferrous sulphate should
be conducted at mild temperature with a low Fe2+/
Fe3+ ratio in order to obtain high crystallinity
nanoparticles.
Acknowledgements
The authors would like to thank University of Malaya for
funding this research work under National
Nanotechnology Directorate (NND-53-02-03-1090),
and High Impact Research (F0032) and
IPPPPostgraduates Research Grant (PG060-2013B).
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