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32 Nanoscience & Nanotechnology-Asia, 2015, 5, 32-43

Synthesis of Magnetic Nanoparticles and Nanosheets for Oil Spill

Removal
Osama Saber1,2,*, Nermen H. Mohamed2 and Abdullah Aljaafari1
1
Faculty of Science, King Faisal University, Al-Hassa 31982, P.O. Box 400, Saudi
Arabia; 2Egyptian Petroleum Research Institute, Nasr City, P.O. Box 11727, Cairo,
Egypt

Abstract: Oil spills, particularly from crude oil, cause not only environmental and
ecological problems but also high economic loss because of the importance of crude oil in
modern industrial society. In this work, a facile and economic method based on magnetic
nanoparticles iron oxides was used for the removal of crude oil from water. Various
nanostructures and morphologies of iron oxide were successfully prepared by different
techniques. Magnetite spinel structure Fe3O4 was prepared by micro-emulsion method. Infra-red spectrum and
thermal analyses indicated that the iron oxide particles of Fe3O4 were surrounded and functionalized by
organic species. Scanning and transmission electron microscopes images showed that the magnetite structure
of iron oxide possesses spherical shape and is in the nano scale 13 nm. Using solvent thermal technique,
nano-sheets of hematite structure α -Fe2O3 were prepared with a particle size of 100 nm. The magnetic
properties revealed that the nanoparticles having magnetite structure possess super paramagnetic behavior and
exhibit relatively high saturation magnetization. The experimental results of oil spills concluded that the
nanoparticles of magnetite structure were effective for oil spill removal where 95wt.% of crude oil was
removed from the water surface. The mechanism of oil spill removal may be explained though the fact that
the small nano size, low density, hydrophobic character and high surface area of Fe3O4 facilitate the
penetration process of nanoparticles inside the oil. Finally, the contents of oil spill were simultaneously
aggregated and easily removed by an external magnetic field.
Keywords: Hematite nanosheets, magnetic materials, magnetic measurements, magnetite nanoparticles,
oil spills removal.

1. INTRODUCTION
Oil spill accidents are one of the main reasons
for the huge environmental problems in the world
in addition to the big economic loss. Unfortunately,
thousands of tons of oil is leaked in the ocean, for
example, in 2002, Prestige oil tanker lost 77,000
tons of crude oil in Ocean [1]. Recently, in 2010,
the largest accidental oil spill in the history
was occurred in the deepwater of Gulf of Mexico
for the Britain petroleum company. Crude oil
continued for flowing for three months in the
deepwater releasing five million barrels of crude
oil. In the beginning of 2011, the researchers
reported that oil did not seem to be degrading. It
*Address correspondence to this author at the Faculty of Science,
King Faisal University, Al-Hassa 31982, P.O. Box 400, Saudi
Arabia; Tel: 00966-013-5899440; Fax: 00966-3-5886437;
E-mail: osmohamed@kfu.edu.sa
means that the spill of crude oil not only strictly
poisons the environment, but also causes a severe
danger to the aquatic life. In addition, it causes a
great loss of million tons of energy resources. In
this trend, many researchers [2] have directed their
researches to the oil recovery in the locations of
the oil spill accidents, to avoid the dispersion of
pollutants which result in more problems.
Conventional methods for oil spill removal
depend on four main categories; mechanical
techniques using booms and skimmers, chemical
treatment by dispersants, in-situ burning, and
Bioremediation. During these methods, different
types of materials have been used for oil spill
removal such as solidifiers and absorbents [1-6].
The main disadvantages of these methods are due
to the secondary pollution of environment
produced from the used materials and the low
efficiency of adsorption particularly for the thin

2210-6820/15 $58.00+.00 © 2015 Bentham Science Publishers

Synthesis of Magnetic Nanoparticles and Nanosheets for Oil Spill
layers of oil in addition to the high cost and long
time of the process. Consequently, it is important
and required to introduce facile methods to recover
the crude oil from the water.
Magnetic nanostructured materials with the
large sorption capacity and high efficient recycle
operation have attracted a significant attention for
environmental remediation in addition to their
applications in the fields of medicine and industry
because of their excellent magnetic properties.
Magnetic carbonaceous nanoparticles were
used by Iryanti, et al. [7] for high removal of lead
from water. In the same way, Pyrzynska and
Bystrzejewski [8] reported that carbon nanotubes
with magnetic nanoparticles removed Cobalt and
Copper ions from water with high efficiency.
Furthermore, magnetic composites of multiwall
carbon nanotubes with iron oxide were used as
adsorbents for the removal of nickel and strontium
[9]. The majority of studies of magnetic
nanomaterials in the field of environment focus on
their large sorption capacity. Recently, Zahn et al.
reported a method to separate oil from water by
magnetic fluid [10]. Chen et al. studied the
removal of oil from water by using magnetic
polymer nanocomposites [11, 12]. Ding et al.
investigated the removal of oil leakage by
magnetic graphite [13].
To solve oil spill problems, an innovative
method is used in this study. It depends mainly on
the magnetic properties of iron oxide nanomaterials
besides the morphology and the nano size of the
magnetic particles. In addition, organic species are
used to induce hydrophobic character for iron
oxide particles. The low nano size of the particles
leads to their easy penetration inside the oil spill.
Therefore, the magnetic behavior will be induced
for the oil spill. After that, the contents of oil spill
are aggregated and attracted by an external
magnetic field. In this way, two different types of
iron oxide with different nano size were prepared
and characterized by different techniques. Magnetic
properties and parameters (saturation magnetization,
remanent magnetization, coercivity and remanence)
were measured by Vibrating Sample Magnetometer.
In addition, surface characteristics for nanomaterials
were determined and analyzed by nitrogen
adsorption-desorption at low temperature. Finally,
the efficiency of the prepared magnetic
nanomaterials for oil spill removal was determined
by weight percentage.
Nanoscience & Nanotechnology-Asia, 2015, Vol. 5, No. 1 33
2. EXPERIMENTAL
2.1. Materials
Iron (III) chloride, iron ammonium sulfate,
ammonium hydroxide (28%), oleic acid, iron
acetate, methanol and ethanol were supplied by
Sigma-Aldrich Company. Commercial iron oxide
Fe3O4 in the micro scale was purchased from
Aldrich Company.
2.2. Preparation of Iron Oxide using Micro-
emulsion
Iron oxide was prepared through combination
between di- and tri-valent iron salts. Initially, 0.09
mol of iron tri-chloride and 0.05 mol of iron
ammonium sulfate were dissolved in 500 mL of
de-ionized water through bubbling of argon gas.
An appropriate amount of ammonia was mixed
with the aqueous solution to become alkaline. The
process was carried out at high temperature
(90 °C). 20 mL of oleic acid was added to the
solution under vigorous stirring for 4h. The brown
product was washed and filtrated several times
using di-ionized water and ethanol. The product
was dehydrated in vacuum for 5 h at 70 oC. Finally,
the prepared material was thermally treated at
200 °C for 3 h. The sample was coded as FO-1.
2.3. Preparation of Iron Oxide using Solvent
Thermal Technique
Solvent thermal method which depends on
thermal process under critical temperature and
pressure was used to prepare iron oxide. An
appropriate amount of iron acetate was reacted
with an excess amount of methanol by vigorous
stirring for long time. After completing the reaction,
400 mL of ethanol was added to the mixture.
Then, it was placed in a pressurized vessel. The
decomposition and drying processes for the
contents of the mixture were carried out under
supercritical conditions (temperature 250 °C and
pressure 70 bar). The temperature of the mixture
inside the autoclave was slowly increased to be
higher than the critical temperature. The pressure
followed the rise of temperature and reached a
value higher than the critical pressure. At this
moment, the pressure released slowly from
autoclave with fluxing with nitrogen gas to prevent
further oxidation for the product and to avoid
liquid condensation within the pores of the
powder. During the reduction of pressure, the
autoclave was cooled down to room temperature.
34 Nanoscience & Nanotechnology-Asia, 2015, Vol. 5, No. 1
Finally, the powder was easily collected and coded
as FO-2.
2.4. Physical Measurements
Powder X-ray diffraction (XRD) allowed us to
determine structural and crystal-study of the
prepared materials through Rigaku RINT 2200.
Energy-dispersive X-ray spectroscopy (EDX) was
used to explore the composition of the prepared
materials through electron probe micro analyzer
JED 2300. The main functional groups in the
prepared materials were detected using Fourier
Transform Infrared Spectroscopy (FT-IR) of
Perkin Elmer Spectrum 400. Differential thermal
analysis was performed by Seiko SSC 5200
apparatus with heating of 10 °C/min in flow of
inert gas. Thermal gravimetric analysis of powder
samples (TGA) was performed in TA
thermogravimetric analyzer (series Q500) under
N2 atmosphere. Differential scanning calorimetry
(DSC) analysis was achieved using TA series Q
600 under inert gas with a heating of 10 °C/min.
Scanning electron microscopy (SEM) was
achieved with a JEOL model JSM-6330F.
Transmission Electron Microscopy (TEM) was
carried out on JEM 2100F with acceleration
voltage 200 kV.
2.5. Surface Characterization
The surface properties of the powder were
determined by full adsorption-desorption of
nitrogen gas at low temperature (-196 °C). These
adsorption-desorption isotherms were obtained by
Quanta-chrome Nova sorption system. From
adsorption isotherm, specific surface area, average
pore radius and pore volume were calculated by
using the Brunauer, Emmett and Teller (BET)
equation. In addition, the surface area and porosity
were detected by applying the t-method. The
analysis of desorption data was proposed by:
Barrett, Joyner and Halenda (BJH-method).
2.6. Magnetic Measurements
The most familiar method for determining
magnetic properties of powder is Vibrating
Sample Magnetometer (VSM). VSM was used to
describe the magnetization curves. Also, the
magnetic parameters (saturation magnetization,
remanent magnetization, coercivity and
remanence) were determined from the shape of
magnetization curves and the hysteresis loops.
Saber et al.
2.7. Oil Spill Experiments
Crude oil (Egyptian crude) was collected from
the western desert near EL-Wahat region and
provided by Khalda Company. The physical and
chemical properties of the crude oil are recorded in
Table 1. Oil spill tests were investigated in the
batch tank. Magnetic materials (500 mg) were
placed in 500 mL of oily wastewater. The oil
concentration was 10%. The oil spill mixture was
then shaken for 30 min at room temperature. Oil
spill removal efficiency was calculated by the
application of extractive-gravimetric method
according to the following equation:
R = Cf - Ci / W × 100
where R is the oil spill removal efficiency (%), Cf
is the weight of magnetic material after removal
process (g), Ci is the initial weight of magnetic
material (g) and W is the weight of the added
crude oil (g).
Table 1. Physico-Chemical characteristics of the studied
crude oil sample.
Test Crude Oil
Density at 60 °C 0.75
Density at 15 °C 0.79
Specific Gravity at 15 °C 0.82
API 40.45
Kinematic Viscosity at 60 °C 1.39
Sulfur content, ppm 1927
Pour Point -3
3. RESULTS AND DISCUSSION
3.1. X-ray Diffraction
X-ray diffraction pattern of the iron oxide
(FO-1) which prepared and thermally treated at
200 °C is shown in Fig. (1). Weak and broad peaks
were observed in the X-ray diagram of FO-1
demonstrating the presence of highly disordered
structure of iron oxides because of organic species
that surrounded and functionalized iron oxides
nanoparticles as mentioned later in thermal
analysis and infra-red analysis. These peaks were
matched with JCPDS No. 19-0629 indicating
magnetite spinel structure.
Synthesis of Magnetic Nanoparticles and Nanosheets for Oil Spill
Fig. (1). X-ray diffraction patterns of iron oxides FO-1 thermal treatment at 200 °C with different times.
3.68
Fig. (2). X-ray diffraction patterns of iron oxides FO-2.
There is no evidence for hematite or maghemite
phases in the diagram. Also, the weak and
broad peaks point to formation of nano sizes of
particles agreeing with the results of Scherer’s
equation.
In case of iron oxide (FO-2), it was prepared
using solvent thermal method. X-ray diffraction
pattern of FO-2 showed that the structure of FO-2
is similar to hematite Fe2O3 where, sharp peaks
that observed at d-values of 0.368 nm (012), 0.269
nm (104), 0.251 nm (110), 0.220 nm (113) and
0.180 nm (024) indicate single phase of α -Fe2O3
and match with the JCPDS file 33-0664 as shown
in Fig. (2).
3.2. Thermal Analyses
Fig. (3) shows the TGA–DTA analysis of the
precursor of FO-1. The TGA curve represents four
steps of thermal decomposition. The first step
Nanoscience & Nanotechnology-Asia, 2015, Vol. 5, No. 1 35
2.69
2.51
1.80
2.20
exhibited notable weight loss and was confirmed
with endothermic effect at 70 °C. This effect
corresponded to the dehydration reaction and the
removal of ammonia. The weight loss continued
up to 511 °C agreeing with two endothermic peaks
at 247 °C and 355 °C. This weight loss (15 wt.%)
may be due to the decomposition of organic
species. It suggests that the prepared nanoparticles
FO-1 are surrounded and functionalized by
organic species.
Finally, a small weight loss was observed and
confirmed by a weak exothermic effect at 596 °C.
It may explain the formation of Fe2O3 from the
thermal decomposition of FeOOH during the
process [14].
In case of FO-2, the TG analysis confirmed the
structure of hematite where a negligible weight
loss was observed at 800 °C as shown in Fig. (4).
36 Nanoscience & Nanotechnology-Asia, 2015, Vol. 5, No. 1
Fig. (3). Thermal analyses (TG and DTA) of the precursor
of iron oxide FO-1.
3.3. FT-IR Spectra
The bonding of iron oxides to organic species
was verified by infra-red analysis. Fig. (5) displays
FT-IR spectrum of the precursor of FO-1. It is
known that iron oxide skeleton shows bands in the
range of low frequency (500–1000cm−1). The FT-
IR spectrum appeared clear band at 572.95 cm−1
indicating the Fe-O bonds [15]. Moreover, It
showed a characteristic band of Fe3O4 at 602 cm−1
[16].
The hydroxyl groups usually appear as a broad
band in the range of 3100–3700 cm−1 because of
stretching vibrations of O-H bonds [17]. The
hydroxyl groups stretching vibration appeared as
two weak bands at 3500 and 3336 cm−1, while the
Fig. (5). Infra-red spectrum of the precursor of iron oxide FO-1.
Saber et al.
Fig. (4). Thermal analyses (TG) of the prepared iron oxide
FO-2.
stretching of C-H exhibited strong bands at 2919
and 2850 cm−1 [18].
Furthermore, the peaks that appear at 1576 and
1443 cm−1 confirm the presence of the carboxylic
group (COO-) on the shell of iron oxide particles
[19, 20]. It means that the iron oxide particles were
surrounded and functionalized by organic species.
These results confirmed that the oleic molecules
are bonded to the hydroxyl groups on the shell of
iron oxide forming organic-inorganic nanohybrid
magnetic materials.
On the other side, the FT-IR spectrum for FO-2
confirmed the XRD results and TG analysis where
the two characteristic bands of hematite structure were
observed at 557 and 476 cm-1 [22] as shown in Fig. (6).
Synthesis of Magnetic Nanoparticles and Nanosheets for Oil Spill
Fig. (6). Infra-red spectrum of iron oxide FO-2.
Fig. (7). SEM images of iron oxide FO-1.
3.4. Scanning and Transmission Electron
Microscopes
In order to examine and find out the
morphology and the mean particle size of the
prepared iron oxide, scanning and transmission
electron microscopes (SEM and TEM) have been
used. SEM observations give a general vision on a
large region of the sample permitting one to prove
that there are no large particles in the sample.
SEM images of (FO-1), which thermally treated at
200 °C and coated by a thin layer of platinum are
displayed in Fig. (7). It can be seen that Fe3O4
particles are in the nano scale and have spherical
shape with a diameter less than 25 nm. However,
Nanoscience & Nanotechnology-Asia, 2015, Vol. 5, No. 1 37
aggregations of fine particles were observed as
secondary particles because of their high surface
energies producing from the very small sizes. For
that reason, it is not easy to accurately verify the
size of the nanoparticles by using the SEM images.
TEM images clearly showed that the Fe3O4
particles have spherical shape and mono dispersed
with a diameter of about 11 nm as shown in
Fig. (8). These results were confirmed from the
calculations of surface area analyzer which depend
on the specific surface area of particles [21].
Transmission electron microscopy (TEM) was
used to examine the particle size of FO-2 as shown
38 Nanoscience & Nanotechnology-Asia, 2015, Vol. 5, No. 1
Fig. (8). TEM images of iron oxide FO-1.
Fig. (9). TEM images of iron oxide FO-2.
in Fig. (9). TEM images showed that the particles
look like nano-sheets and are in the range of 100
nm. It means that the structure of α -Fe2O3 can be
described as the stacking of sheets of octahedral
coordinated Fe3+ ions between two closed-packed
layers of oxygen. These sheets are held together by
strong covalent bonds.
3.5. Surface Characteristics
To determine the textural characteristics of the
prepared iron oxide, adsorption-desorption isotherms
of nitrogen were determined at low temperature
(-196 °C). Nitrogen adsorption-desorption isotherm
Saber et al.
of iron oxide Fe3O4 is displayed in Fig. (10a) and
their knowledge including specific surface areas
calculated by BET and BJH methods (SBET and
SBJH), total pore volume and average pore size are
summarized in Table 2.
The adsorption-desorption isotherm showed
that it has type IV of Brunauer and Emmett’s
group and revealed hysteresis loop stopped at
relative pressure P/Po = 0.4. This hysteresis loop is
an indication for the presence of mesoporous
structure. Where, it belongs to the H2 type of the
IUPAC classification which consists of porous
aggregates.
Synthesis of Magnetic Nanoparticles and Nanosheets for Oil Spill Nanoscience & Nanotechnology-Asia, 2015, Vol. 5, No. 1 39

Table 2. Adsorption data derived from adsorption- On the other trend, the nitrogen adsorption–
desorption isotherms for iron oxides prepared desorption isotherm of α-Fe2O3 is displayed in Fig.
by two techniques (11a). It is similar to type I isotherm with no
hysteresis loop. Such isotherm is typical for
Sample Nanoparticles Nanosheets systems that have no micro- or meso-porous
FO--1 FO--2
structures. The obtained Vl-t plots in Fig. (11b)
SBET (m2/g) 105.1 8.9 showed downward deviation confirming macro-
porous structure. The adsorption data for α-Fe2O3
SBJH (m2/g) 119.9 7.9
indicated that the specific surface area, SBET
VpBJH (cc/g) 0.188 0.126 determined by using the BET formula is very low;
RpBJH (nm) 3.1 38.6 SBET = 8.946 m²/g. The surface area, pores size
distribution and their volume were derived by the
BJH method. According to these estimations, the
The obtained Vl-t plots in Fig. (10c) showed main part of the pores for α- Fe2O3 has radius 38.5
upward deviation confirming the mesoporous nm and volume 0.126 cc/g.
texture of Fe3O4. By using the BJH method and
analyzing the desorption part of the isotherm, the 3.6. Magnetic Properties
surface area and pore size distribution in addition The magnetization behavior of the prepared
to their pore volume were calculated as shown in samples of iron oxides (Fe3O4 and α -Fe2O3) was
Table 2. According to these calculations, the investigated by sweeping the external magnetic
majority of the pores were confined in the range of field between -10kOe and +10kOe at 300K.
2 nm and 4 nm (radius), as shown in Fig. (10b). It Magnetization (M) versus magnetic field (H) plot
is clear from Table 2 that the Fe3O4 nanoparticles is shown in Fig. (12). The sample Fe3O4 which has
have a high specific surface area (SBET = 105.1 magnetite structure exhibited S-type curve in the
m2/g and SBJH = 119.9 m2/g). The high surface low magnetic field region and a linear portion
area of nanoparticles can be occupied by at very high magnetic field region as shown in
constructing small particles where the surface to Fig. (12a). Moreover, this curve did not show
volume ratio of each particle is high, or by hysteresis loop. This is a typical behavior of
generating void surface area (mesopores). superparamagnetism.

Fig. (10). Surface properties of iron oxide FO-1: (a) Adsorption–desorption isotherms of nitrogen (b) Pore size distribution and
(c) Vl–t plots of nitrogen adsorption.
40 Nanoscience & Nanotechnology-Asia, 2015, Vol. 5, No. 1
Fig. (11). Surface properties of iron oxide FO-2: (a) Adsorption–desorption isotherms of nitrogen (b) pore size distribution and
(c) Vl-t plots of nitrogen adsorption.
Fig. (12). Magnetization M-H curves of (a) FO-1 and (2) FO-2.
Based on the fact that super paramagnetism
depends largely on size and anisotropy of iron
oxide particles [23], the magnetization values of
the sample Fe3O4 could be explained.
In the case of single domain of magnetite
particles, magnetic surface atoms are difficult to
align with the applied magnetic field and these
surface atoms present a large portion in very small
particles (high surface area of nanometer sized
particles). Also, when particles are small enough,
they are influenced by the thermal fluctuation [24].
Energy of super paramagnetic particles is
comparable with thermal energy, which allows
Saber et al.
spinning of the magnetic vector to be dictated by
the thermal fluctuation, resulting in an incomplete
permanent alignment of all magnetic vectors in the
particles. Yamaura et al. [25] predicted 26 nm as
the critical size below which super paramagnetism
takes place. Therefore, the particles of the sample
Fe3O4 that have average size 13 nm showed super
paramagnetic behavior.
Magnetization curve was measured at room
temperature which renders magnetite particles of
certain dimensions super paramagnetic; thermal
energy overcomes the energy barrier, presented by
the particles anisotropy. Magnetite particles give
Synthesis of Magnetic Nanoparticles and Nanosheets for Oil Spill
Table 3. Magnetic data for iron oxides.
Sample T(K) H(KOe) Hc(Oe)
FO-1 (Fe 3O4) 300 10 25
FO-2 (α-Fe2O 3) 300 10 380
Fig. (13). Effect of magnetic materials on dispersion of oil spills (a) nano-material and (b) micro-material.
relatively high saturation magnetization values
(Ms), with low values of coercivity (Hc) and
remanent magnetization (Mr) as shown in Table 3.
In the case of α-Fe2O3, the magnetization curve
exhibited hysteresis loop indicating ferromagnetic
behavior with low saturation magnetization 1.3
emu/g as shown in Fig. (12b). Moreover, it
showed a remnant magnetization of 0.3 emu/g and
the coercivity was 380 Oe.
3.7. Oil Spill Removal
To study the effect of the nano size of the
magnetic materials on the removal of oil spill, iron
oxides in the micro scale were used for comparison.
Fig. (13b) showed that the iron oxide (Fe3O4) in
the micro scale is not effective for the oil spill
removal although it has strong ferromagnetic
behavior. It means that the magnetic properties are
not the controller factor in the process of the oil
spill removal. In case of using the prepared
magnetic nanoparticles (Fe3O4), the behavior was
different from that of the iron oxide (Fe3O4) in the
micro scale. Where, the contents of the oil were
aggregated and floated above the surface water
after mixing the magnetic nanoparticles with the
oil spill as shown in Fig. (13a). By using a magnet,
it was easy to remove the oil. The percentage of
Nanoscience & Nanotechnology-Asia, 2015, Vol. 5, No. 1 41
Ms (emu/g) Mr (emu/g) Mr / Ms
16.57 2 0.12
1.229 0.3 0.24
the oil removal arrived to 95 wt.% in case of using
the prepared iron oxide nanoparticles (Fe3O4).
These results concluded that the small nano size
of the magnetic particles is the main factor for the
process of oil spill removal. The small nano size of
the particles gives iron oxide the ability to penetrate
inside the oil. Also, the low density of this nano
size can facilitate the process of penetration
through floating the magnetic particles with the oil
at the water surface. In addition, according to the
results of infra-red spectrum, the iron oxide particles
of FO-1 was surrounded and functionalized by
organic species. It means that the iron oxides
particles have hydrophobic character which
accelerated the penetration of magnetic nanoparticles
inside the oil and avoiding water molecules. In the
same time, the superparamagnetic behavior of iron
oxide is more desirable than the ferromagnetic
behavior for the process of oil spill removal. Also,
the high surface area in addition to the porous
structure of the magnetite nanoparticles had a
positive role in oil spill removal.
In case of using iron oxide α -Fe2O3, the
hematite structure failed to remove the oil spill
from water. It may be due to the large nano size
and the ferromagnetic behavior of hematite
42 Nanoscience & Nanotechnology-Asia, 2015, Vol. 5, No. 1
structure. Also, it did not have the advantages of
the prepared Fe3O4 nanoparticles such as high
surface area and porous structure. In addition, the
absence of hydrophobic character of the hematite
structure did not help the sheets of Fe2O3 to
penetrate inside the oil.
3.8. Mechanism of Oil Spill Removal using
Magnetic Nanoparticles
The mechanism of oil spill removal may be
explained though the fact that the small nano size
and low density of Fe3O4 facilitate the process of
penetration through floating of the nanoparticles
with the oil at the water surface. In addition, the
iron oxide particles which surrounded and
functionalized by organic species accelerated the
penetration of magnetic nanoparticles inside the
oil because of hydrophobic character. After that,
the high surface area and the porous structure of
the magnetite nanoparticles increased the adsorption
of oil inside the nano structures. Finally, the
superparamagnetic behavior of the magnetite
nanoparticles generated magnetic behavior for the
oil spill. According to the magnetic behavior of the
oil spill, the contents of the oil were simultaneously
aggregated and easily removed by an external
magnetic field.
4. CONCLUSION
The present study has a dual aim for producing
magnetic nanomaterials with various phases and
morphologies and developing new technique for
oil spill removal. Iron oxide nanoparticles with
magnetite structure were successfully prepared and
characterized by X-ray diffraction, thermal
analyses and infra-red spectrum. SEM images
showed that the fine particles of magnetite
structures have spherical shape of Fe3O4. In the
same trend, TEM images confirmed that they have
small nano size and their diameter are of 11 nm. In
another way, Iron oxides nanosheets with hematite
structure were prepared by the solvent thermal
method. Different characterization techniques
confirmed that the hematite structure α -Fe2O3
looks like sheets with an average diameter of 100
nm. Surface properties of both magnetite and
hematite structures were measured by nitrogen
adsorption-desorption isotherm. The results
indicated that the aggregation of magnetite
nanoparticles created porous structure producing
high surface area. Magnetic measurements showed
high saturation magnetization (Ms), with low
Saber et al.
remanent magnetization (Mr) and Coercivity (Hc) for
magnetite nanoparticles. Also, the magnetization
curve of magnetite nanoparticles revealed super
paramagnetic behavior. In the other side, hematite
nanosheets showed ferromagnetic behavior with
low saturation magnetization.
The effect of the prepared magnetic
nanomaterials iron oxides on the oil spill removal
was measured and compared with the effect of the
commercial magnetic iron oxides in the micro
scale. The experimental results showed that the
percentage of the oil removal arrived to 95 wt.% in
case of using the prepared iron oxide nanoparticles
(Fe3O4). While, both the commercial iron oxide
and the hematite structure failed to remove the oil
spill from water. Moreover, it concluded that the
mechanism of oil spill removal depended on four
stages. Firstly, the small nano size and the low
density of the particles facilitated the process of
the penetration of the iron oxide through floating
its nanoparticles with oil at the water surface.
Secondly, the iron oxide particles which surrounded
and functionalized by organic species accelerated
the penetration of the magnetic nanoparticles
inside the oil because of hydrophobic character.
Thirdly, the high surface area and the porous
structure of the magnetite nanoparticles increased
the adsorption of the oil inside the nano structures.
Finally, the superparamagnetic behavior of the
magnetite nanoparticles generated magnetic
behavior for the oil spill which pushes the contents
of the oil to aggregate. Using external magnetic
field, the oil spill was easily removed.
CONFLICT OF INTEREST
The authors confirm that this article content has
no conflict of interest.
ACKNOWLEDGEMENTS
This work was financially supported through
advanced and strategic technologies grants program
for the national plan for science, technology and
innovation (09-NAN723-06) by KACST, Kingdom
of Saudi Arabia.
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Received: April 01, 2015 Revised: April 30, 2015 Accepted: May 01, 2015
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