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Journal of the Taiwan Institute of Chemical Engineers

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Application of magnetic adsorbents based on iron oxide nanoparticles

for oil spill remediation: A review
Kaili Qiao a, Weijun Tian a,b,∗, Jie Bai a,b, Liang Wang a, Jing Zhao a, Zhaoyang Du a,
Xiaoxi Gong a
a
College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100, China
b
Key Laboratory of Marine Environment and Ecology, Ministry of Education, Qingdao 266100, China

a r t i c l e i n f o a b s t r a c t

Article history: Oil pollution has posed a great threat to marine ecosystems and human health. In recent years, many
Received 15 October 2018 studies have focused on the functionalization of magnetic iron oxide nanoparticles to obtain efficient ad-
Revised 8 January 2019
sorbents for oil removal from water. This review focuses on recent studies on magnetic materials based
Accepted 23 January 2019
on iron oxide nanoparticles and their applications as oil sorbents. The main techniques used to obtain
Available online xxx
iron oxide nanoparticles are also discussed. The aim of this literature review is to obtain a better under-
Keywords: standing of the materials that could be used to obtain efficient oil adsorbents with magnetic iron oxide
Magnetic adsorbents nanoparticles and suitable synthesis strategies by encapsulating iron oxides with organic or inorganic
Functionalization coatings or embedding them in a matrix/support. Another purpose is to identify the desirable character-
Iron oxidation nanoparticle istics of magnetic materials required for high oil removal efficiency.
Oil removal © 2019 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction a challenge to develop effective remediation solutions to separate

Currently, oil pollution is considered a major environmental
concern. It is estimated that the spilled oil volume reaches four
billion tons per year globally [1]. Oil spill examples such as the
Exxon Valdez oil spill in 1989 [2], Prestige in 2002 (Spain), the
storage tank explosion in Dalian, China, in 2010 and the Deepwater
Horizon oil spill in the Gulf of Mexico in 2010 [3] seriously dam-
aged marine ecosystems [4]. Except for large-scale events, many
smaller crude oil spills also threaten the aquatic environment as
they occur more frequently. In the United States, approximately fif-
teen oil spill accidents occur daily in navigable waters, and hun-
dreds of oil spills have occurred in Nigeria [5,6]. Oil spills could
cause large-scale pollution in a very short time, and it has been
reported that after spillage, the oil could spread quickly and form
oil films on the water surface [7]. According to Aguilera [8], when
an oil spill occurs, seaside flora and some fauna, such as birds and
bivalve mollusks, are affected, and human health could be affected
by oil-contaminated food via the food chain because many of the
oils are persistent contaminants and could be carcinogenic [9]. Cur-
rently, common oil removal techniques can be classified into phys-
ical, chemical and biochemical methods. The main advantages and
limitations of each technique are summarized in Table 1. It is still
∗
Corresponding author at: College of Environmental Science and Engineering,
Ocean University of China, Qingdao 266100, China.
E-mail address: weijunas@ouc.edu.cn (W. Tian).
the spilled oils from the water without releasing residues into the
environment [6].
Recently, the utilization of magnetic materials based on iron
oxide nanoparticles as oil sorbents has attracted increasing atten-
tion after the first attempts made by Turbeville [18]. Iron oxide
nanoparticles are widely studied due to their high adsorption ca-
pacity of oil, magnetic property and biocompatibility [19]. How-
ever, the unavoidable problems of naked iron oxide nanoparticles,
such as agglomeration and oxidization by air due to their high
chemical activity, would cause a loss of magnetism and limit their
application [20]. It is thus necessary to develop strategies to pro-
tect naked ferromagnetic nanoparticles against degradation. Form-
ing protecting shells on the surface of nanoparticles is considered
a good way to stabilize and functionalize nanoparticles [21]. Over
recent years, strategies including grafting organic species, coat-
ing with organic or inorganic layers [22] have been established
to transform iron oxide nanoparticles into advanced materials that
are able to possess high oil adsorption capacity, fast recovery and
promising reusability.
In the following section, we will review the functionalization
methods of iron oxide nanoparticles and their applications as oil
adsorbents. The main techniques performed to synthesize iron ox-
ide nanoparticles are concluded. The key characteristics that lead
to a high oil adsorption capacity are identified. Then, the function-
alized iron oxide nanoparticles and related materials, as well as the
removal results of oils obtained, are presented.

https://doi.org/10.1016/j.jtice.2019.01.029
1876-1070/© 2019 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: K. Qiao, W. Tian and J. Bai et al., Application of magnetic adsorbents based on iron oxide nanoparticles for oil
spill remediation: A review, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2019.01.029
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Table 1
The summary of the techniques for removal of the spilled oils in water.

Methodology Techniques Conditions of application Advantages Limitations References

Physical Booms and Large-scale and thick slick of Treat emulsified oils and oils of Ineffective in rough weather [10,11]
method skimmers freshly spilled oil. variable viscosities (6–20,0 0 0 and sea conditions.
mPa s) efficiently.
No adverse environmental Time consuming and expensive
effects. in a large scale.
Large amount of personnel and
equipment.
Adsorption Floating slicks of oil, the final High removal rate. Difficult to be recovered. [12]
stages of the clean-up in
relatively calm water.
Difficult to be degraded.
Chemical In-situ burning Freshly spilled oil in vast water. Remove large quantities of oil Affected by sea weather [13,14]
method rapidly. Effective in ice or conditions.
cold water.
Minimum oil thickness of
2–3 mm.
Large quantities of smoke and
toxic compounds.
Dispersants Fresh oil slicks with Eliminate large volumes of oil Effective for oils with viscosity [14,15]
low-medium viscosity. rapidly and effectively. < 20 0 0 cSt.
Not effective in calm water. Harmful to aquatic creatures.
Biological Biodegradation Thin slick of oil. Efficient, cheap and Limited to nutrient substance, [16,17]
method environment-friendly. pH and temperature.
Ineffective in spill with large
coherent mass.

2. Preparation of iron oxide nanoparticles 2.3. Hydrothermal synthesis

In the past few decades, considerable efforts have been made to
develop synthesis methods for iron oxide nanoparticles. The com-
monly used methods include coprecipitation, thermal decomposi-
tion, hydrothermal synthesis and microemulsion. As follows, dis-
cussions about these synthesis techniques are presented.
2.1. Coprecipitation
Coprecipitation is a conventional method to prepare iron oxides
that involves the chemical reaction between Fe3+ and Fe2+ salt in a
highly basic solution in the absence of oxygen. To obtain function-
alized iron oxide nanoparticles, the technique could be improved
by adding functional materials or surface active agents in the reac-
tion media to reduce the aggregation and oxidation of naked iron
oxide nanoparticles. The size, shape, structure and magnetic prop-
erties of iron oxide nanoparticles could be affected by the con-
ditions of preparation, such as the type of Fe3+ or Fe2+ salt, the
Fe3+ /Fe2+ ratio, the pH value, the reaction temperature and the
ionic strength of the media [22]. One disadvantage of the method
is that during both the synthesis and purification process, the pH
value has to remain high, which adversely affects the formation of
uniform and monodispersed nanoparticles.
2.2. Thermal decomposition
Thermal decomposition is also a common way to prepare high-
quality monodispersed magnetic iron oxide nanoparticles. The raw
materials used frequently are organometallic compounds primar-
ily including Fe(cup)3 (cup = N-nitrosophenylhydroxylamine) [23],
Fe(acac)3 (acac = acetylacetonate) [24], or Fe(CO)5 [25] in an or-
ganic solution phase containing stabilizing surfactants under rel-
atively high temperatures of 20 0–30 0 °C.
The obtained iron oxide particles obtained via the thermal de-
composition method have a narrow size distribution and are highly
monodispersed while only dissolvable in nonpolar solvents.
Hydrothermal synthesis involves chemical reactions in aque-
ous solutions under hydrothermal conditions, namely, a high tem-
perature aqueous solution (130–250 °C) and high vapor pressure
(0.3–4 MPa). Bhavani et al. [26] successfully prepared iron oxide
nanopowders through a hydrothermal process. The iron-based pre-
cursors could influence the size and shape of the magnetic prod-
ucts, and an appropriate hydrothermal temperature could cause an
increase in the saturation magnetization. Attallah et al. [27] also
investigated whether parameters such as the reaction temperature,
reactant concentration and reaction time in the hydrothermal pro-
cess could influence the structural and magnetic properties of iron
oxide nanoparticles.
2.4. Microemulsion
A microemulsion is a transparent and thermodynamically
stable isotropic synthesis medium of two immiscible liquids
(water and oil) in the presence of surfactants. In water-in-oil
microemulsions, the aqueous phase is dispersed as nanodroplets
surrounded by surfactant molecules in a continuous oil phase
[28]. These nanodroplets provide restricted reaction media to
control the shape and size distribution of particles prepared by
precipitating iron salts. Vidal-Vidal et al. [29] applied a one-pot
microemulsion method to produce coated nanoparticles. The
results showed that the nanoparticles were spherical and coated
with an oleylamine monolayer. Moreover, they had a narrow size
distribution of 3.5 ± 0.6 nm and had high saturation magnetization
values. Chin and Yaacob [30] compared the characterizations of
iron oxide nanoparticles prepared by a water/oil microemulsion
and Massart’s procedure. The results showed that the nanopar-
ticles synthesized via a microemulsion had a smaller size and
higher saturation magnetization.
3. Desired properties of the magnetic sorbents for oil spill
remediation
Ideal oil sorbents should possess favorable properties, includ-
ing high oil adsorption capacity, suitable reusability and absence

Please cite this article as: K. Qiao, W. Tian and J. Bai et al., Application of magnetic adsorbents based on iron oxide nanoparticles for oil
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Fig. 1. (a) Images of (a and b) a water and oil droplet placed on naked Fe3 O4 ; (c and e) a water droplet placed on polymer coated-Fe3 O4 nanocomposites; (d and f) an oil
droplet placed on polymer coated-Fe3 O4 nanocomposites (reprinted with permission from Ref. [32]). 1(b) The removal process of oil from the water surface by magnetic
materials under an external magnetic field (a and d) (reprinted with permission from Ref. [33]).

of secondary pollution to the environment [12,31]. Ideal oil sor-
bents should have the merits of easy preparation, low cost and
environmental friendliness [6]. We present the desired properties
that define magnetic sorbents based on iron oxide nanoparticles
as suitable oil sorbents.
3.1. Hydrophobicity and oleophilicity
Hydrophobicity and oleophilicity represent the ability of the
material to adsorb oil and repel water. Wettability refers to the
ability or tendency of a liquid to spread on a solid surface and
is related to the selectivity of iron oxide to water and oil. When
present on solid surfaces, liquid drops can show different shapes
because of wettability. The wettability of solids could be repre-
sented by the contact angle, which is defined as the angle at which
a liquid interface meets the solid surface. A higher water contact
angle is an indication of a more hydrophobic surface. The sur-
face of the material is hydrophilic/oleophilic when the water/oil
contact angle is less than 90°, and hydrophobic/oleophobic when
the contact angle is greater than 90° [6]. Fig. 1a shows the water
contact angle and the oil contact angle of naked iron oxide and
polymer-coated iron oxide. By appropriately modifying the mag-
netic nanoparticles, it is possible to simultaneously obtain high hy-
drophobicity and oleophilicity with increasing water contact angle
from 0° to greater than 150°.
3.2. Unsinkable property
After oil is spilled, the oil would float and spread on the surface
of the water for a period of time. According to the characteristics of
oil, oil adsorbents should possess unsinkable properties to contact
the oil fully and obtain the greatest removal efficiency. Addition-
ally, oil sorbents with a low density are easier to collect after ad-
sorption. Functionalized iron oxide nanoparticles could meet these
demands and could float on the surface of water when they are
added in oil and water mixtures. Fig. 1b shows the processes of
adsorption and recovery of the floatable magnetic material. It was
observed that the oil (red color) could float on water and form an
oil film. After addition of the polymer-modified Fe3 O4 nanocom-
posites, the black-modified Fe3 O4 could also float on water. This
result might be related to the low density and highly hydrophobic
coatings, which can overcome the weight of the magnetic mate-
rial and repel water to enable the material to float on the water
surface [7,34].
3.3. Ferromagnetism and reusability
The recovery and reuse of absorbents have always been of con-
cern to researchers. If the adsorbents could not be collected after
adsorption, the cost might be higher, and the probability of sec-
ondary pollution might increase. An impressive advantage of mag-
netic materials is that they can be easily recycled with an exter-
nal magnetic field (Fig. 1b). Due to the ferromagnetic properties
of Fe3 O4 nanoparticles, the magnetic materials could not only be
manipulated to move to the oil-polluted region but could also be
collected easily and quickly after adsorption by an external mag-
netic field [34]. The saturation magnetization of magnetic materials
based on iron oxide nanoparticles is 15–92 emu/g. Compared with
naked Fe3 O4 nanoparticles, even though the saturation magnetiza-
tion decreased after modification, the magnetic oil-absorbed ma-
terials could still be collected in 1-2 s with a magnetic bar [7,35].
In this way, the recovery operation becomes easier with simple re-
covery equipment, and the cost of recovery also decreases.
Another desirable property is that the functionalization of mag-
netic iron oxide nanoparticles could be reused after easy treat-
ment. The methods of regeneration of magnetic particles are sim-
ple, mainly including ultrasonic washing in ethanol or hexane for
several minutes [7]. The magnetic materials could be applied suc-
cessively without notable changes in contact angle and oil adsorp-
tion capacity. According to recent studies, magnetic oil adsorbents
can be reused several to 10 0 0 times [36].
4. Magnetic oil sorbents based on iron oxide nanoparticles
As mentioned above, naked iron oxide nanoparticles are eas-
ily oxidized in air and tend to accumulate together. To apply iron

Please cite this article as: K. Qiao, W. Tian and J. Bai et al., Application of magnetic adsorbents based on iron oxide nanoparticles for oil
spill remediation: A review, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2019.01.029
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Fig. 2. The fabrication of sodium oleate-modified Fe3 O4 nanoparticles (reprinted
with permission from Ref. [33].
oxide nanoparticles more widely, the protection and functionaliza-
tion procedures performed during or after the synthesis processes
are important. Except for encapsulating the iron oxide nanopar-
ticles with organic compounds and inorganic compound coatings,
embedding the iron oxide nanoparticles in polymer composites or
combining the iron oxide nanoparticles with activated carbon by
physical and chemical methods are also effective techniques to pre-
pare magnetic oil sorbents. In the following section, the synthesis
of effective magnetic oil sorbents based on iron oxide nanoparti-
cles will be discussed.
4.1. Combining iron oxides with organic compounds
Magnetic sorbents combining organic compounds and iron ox-
ide nanoparticles possess the basic magnetic characteristics of
magnetic nanoparticles and suitable biocompatibility characteris-
tics of organic materials. The functional groups of the organic ma-
terials could offer active sites for iron oxide nanoparticles, which
makes the functionalization process possible and broadens their
application as sorbents for pollutants [37–39]. In addition, the us-
age of organic materials could passivate the iron oxide nanopar-
ticles during or after synthesis to avoid agglomeration. Surfactants
and polymers are often chemically anchored or physically adsorbed
on iron oxide nanoparticles to synthesize single or double organic
compound layer-coated Fe3 O4 nanoparticles [40].
4.1.1. Oleic acid
One of the main methods for the functionalization of iron ox-
ide nanoparticles is the coating of small surfactants on the surface.
Oleic acid is an excellent surfactant and is widely used to modify
ferrite nanoparticles by chemical precipitation. The -COOH groups
of oleic acid have a high affinity with the Fe atoms of iron ox-
ide, in addition to the outward facing hydrophobic tails of oleic
acid and generation of nonpolar shells [41]. The obtained oil-solute
magnetic iron oxide nanoparticles have a strong affinity for oil and
can be used to adsorb oil on the surface of water. The modified
nanoparticles can be obtained by a two-step method that con-
sists of a synthesis of iron oxide consisting of adding an alka-
line solution into a mixture of di- and/or tri-valent iron salts and
a modification process of adding oleic acid [42]. Oleic molecule-
Fe3 O4 hybrid nanomaterials were prepared via the microemul-
sion method and used to treat crude oil. The removal percentage
reached 95 wt.%. The saturation magnetization of the products was
16.57 emu/g. Zhu et al. [33] also used sodium oleate to modify iron
oxide nanoparticles, and the obtained nanoparticles demonstrated
suitable properties for oil removal (Fig. 2). After modification, the
saturation magnetization of the modified iron oxide nanoparticles
was 49.40 emu/g, and the water contact angle was 155°, which
demonstrated that the magnetic nanoparticles could adsorb oil and
repel water.
4.1.2. Macromolecules
Macromolecules are natural materials that have several advan-
tages, including nontoxicity, biocompatibility and biodegradability.
Please cite this article as: K. Qiao, W. Tian and J. Bai et al., Application of magnetic adsorbents based on iron oxide nanoparticles for oil
spill remediation: A review, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2019.01.029
[m5G;February 7, 2019;7:28]
The common macromolecules used for stabilization of magnetic
nanoparticles include starch [43], alginic acid [44] and chitosan
[45–47], and the formed composites could be used for differ-
ent adsorption purposes. Among them, chitosan had already
been applied to modified iron oxide nanoparticles to synthesize
oil adsorbents. Chitosan-coated iron oxide nanoparticles pro-
duced by grafting chitosan onto Fe3 O4 coated with silica and
3-aminopropyltriethoxysilane (APTES) could separate 90% of the
oil from a diesel-in-water emulsion (Fig. 3) [48]. Additionally, the
oil-water separation ability of chitosan-coated iron oxide nanopar-
ticles was less affected by the pH. After treatment, the magnetic
chitosan-coated adsorbent could be reused 8 times and could
maintain excellent separation efficiency [49]. Li et al. [50] pre-
pared magnetic composite resin by suspension copolymerization.
Fe3 O4 nanoparticles were synthesized and modified by oleic acid
and then cross-linked with composite resin. The obtained mag-
netic composite resin with a diameter from 50 to 20 0 0 μm had
a high oil adsorption ability and could collect almost all of the
spilled oil. After adsorption, the magnetic composite resin could
be expediently recovered by magnetic separation techniques.
4.1.3. Biomolecules
Protein wastes from the leather industry were recycled to pre-
pare superparamagnetic collagen/iron oxide nanoparticles for oil
removal [51]. The Fe3 O4 nanoparticles were first modified with
citric acid organic hulls and thereafter interacted with collagen
fibers. The interaction between the citric acid coated on the Fe3 O4
nanoparticles and side chain amino functional groups of colla-
gen molecules is depicted in Fig. 4. This nanocomposite could
selectively adsorb oil from water and could be manipulated by
a magnetic field. The studies demonstrated that the maximum
oil adsorption capacity for used motor oil could reach 2 g/g. An
oil-absorbed magnetic collagen-SPION nanobiocomposite could be
converted into a bifunctional graphitic nanocarbon material or bi-
functional carbon material via heat treatment and could be used
for other applications, providing a sustainable cycle for waste recy-
cling and environmental cleanup.
4.1.4. Polymer
Recently, polymers have gradually become important and at-
tractive coating materials and have received increasing attention.
Polymer-coated iron oxide nanoparticles remain sterically stable
even in complex environments and pose little hazard [52]. Poly-
mers have excellent properties, such as a large surface area, low
skeleton density and high chemical stability [32]. Polymer modi-
fication involves the covalent connection between the rich func-
tional groups of polymers (such as carboxylic acids, phosphates
and sulfates) and the iron oxide nanoparticles via substitution or
ligand exchange reactions. The first step is to synthesize iron oxide
nanoparticles with oxygen bonds. Then, the synthesized nanopar-
ticles and the polymers are connected by a chemical grafting
method or atom transfer radical polymerization [48,53].
To obtain more hydroxyl groups and improve the stability of
the particles during the synthesis stage, the SiO2 outer layer of
iron oxide nanoparticles is usually coated functional modification.
Following this approach, polymer-coated nanoparticles could be
synthesized by a two-step procedure. First, magnetic Fe3 O4 was
prepared, and then, the silanization of Fe3 O4 was performed by
adding sodium dodecyl benzene sulfonate (SDBS) or sodium do-
decyl sulfonate (SDS) followed by grafting of the polymer. The
most impressive results following the aforementioned approach
were obtained by Yu et al. [34] and Chen et al. [32]. They ob-
tained Fe3 O4 @PS nanoparticles that could adsorb oils 3 times their
weight. In addition, the saturation magnetization reached 34.62
and 61.25 emu/g, and the water contact angles were 141.2 and
153°, respectively. Another example involves the polymer-coated
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Fig. 3. Synthetic scheme of the CS-grafted Fe3 O4 (reprinted with permission from Ref. [48]).

Fig. 4. The synthesis of collagen-SPION nanobiocomposites (reprinted with permission from Ref. [51]).

MIONs with double layers prepared by Gu et al. [54]. After the

synthesis of Fe3 O4 @P(St/DVB) nanoparticles, methyl methacrylate
(MMA) was added, and the Fe3 O4 @P(St/DVB) nanoparticles were
coated with a P(MMA/St/DVB) layer through secondary polymer-
ization. The water contact angle of the nanoparticles was 141.2°,
and the nanoparticles could maintain their highly hydrophobic
property in aqueous solutions with different pH values (pH 1–13).
After 10 cycles, the nanoparticles still had a high water contact an-
gle of 140.4° and a high oil absorption capacity of 3.22 g/g.
Another functionalization approach to obtain polymer-coated
iron oxide nanoparticles is through a one-step method by heating
a mixture of the capping molecule and the iron precursor under
alkaline conditions. The simple and cost-effective technique pro-
vided a simple and powerful tool to remove oil from water. The Fig. 5. The synthesis processes of SAS magnetite nanomaterials (reprinted with per-
approach was employed by Palchoudhury and Lead [52] through mission from Ref. [56]).
coprecipitation and by Mirshahghassemi and Lead [55] through a
hydrothermal technique to obtain Fe3 O4 @PVP nanoparticles. De-
spite the difference in the synthesis methods, in both cases, the of modified Fe3 O4 will decrease if the organic shell around Fe3 O4
oil removal under optimum conditions could reach approximately is too thick. Therefore, it is important to develop other methods
100%. An impressive example is that Abdullah et al. [56] obtained for modifying magnetic nanoparticles.
sulfonated asphaltene (SAS) by extracting asphaltenes from heavy
crude oil via sulfonation and applying the SAS as a coating agent 4.2. Combining iron oxide with inorganic materials
to create hydrophobic Fe3 O4 nanoparticles. SAS-Fe3 O4 was synthe-
sized by the coprecipitation method in the presence of FeCl3 ·6H2 O, It is clear that the process of inorganic compound coating can
Na2 SO3 and SAS (Fig. 5). The obtained nanomaterials could adsorb greatly increase the stability of naked iron oxide nanoparticles and
crude oil up to 22.5 g/g with a removal rate of 90%. extend their application scope. Although different types of inor-
In general, the modified iron oxide nanoparticles with organic ganic materials have been employed to modify iron oxide nanopar-
compounds were easily leached by acidic solutions [57], leading ticles, such as silica [58,59] and metal oxide [60–61], attempts to
to a loss of their magnetization. The organic compound-coated functionalize iron oxide nanoparticles as oil sorbents are still in-
iron oxide nanoparticles have another disadvantage: the intrinsic adequate. Nonetheless, as will be shown in the next paragraphs,
stability of the coating is relatively low at higher temperatures nanomaterials coated with inorganic materials are also appropriate
[20]. Another drawback is that the saturation magnetization value materials for oil removal.

Please cite this article as: K. Qiao, W. Tian and J. Bai et al., Application of magnetic adsorbents based on iron oxide nanoparticles for oil
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4.2.1. Carbon
Recently, carbon-coated magnetic nanoparticles have received
considerable attention because magnetite-carbon nanoparticles
have many advantages, such as high chemical and thermal sta-
bility and biocompatibility [20]. Banerjee et al. [62] synthesized
a carbon-Fe3 O4 nanocomposite by pyrolysis of an iron-containing
metal organic framework (MOF) and tested the oil adsorption ca-
pacity of the material. The water contact angle of the nanoparticles
was 143°, indicating a near superhydrophobic character and the
particles could adsorb an amount of oil of more than 40 times its
own weight. Zhu et al. [7] obtained core-shell Fe2 O3 @C nanopar-
ticles by thermal decomposition of the precursor material. The
specific surface area of Fe2 O3 @C was 94.04 m2 /g, and the water
contact angle was approximately 162.9°. These magnetic nanopar-
ticles were unsinkable, hydrophobic and superoleophilic and could
adsorb up to 3.8 times their own weight. After absorbance, the
magnetic nanoparticles could be quickly and easily collected and
regenerated. The magnetic nanoparticles still maintained a large
water contact angle, which was greater than 150° after six cycles.

4.2.2. Silica
Silica is one of the most common inorganic compounds for
preparing functionalized iron oxide nanoparticles [22]. A silica
shell could not only protect the iron oxide cores from oxidation by
air and agglomeration generation but also provide stability to the
iron oxide cores in solution. Yu et al. [63] fabricated Fe3 O4 @SiO2
submicrometer materials via a simple template approach at room
temperature. Tetraethyl orthosilicate (TEOS) was used as the sil-
icon source, and hexadecyl trimethylammonium bromide (CTAB)
was used as the template. The water contact angle of the magnetic
nanoparticles was 148.8°, and the specific surface area reached Fig. 6. (a) The preparation of magnetic sponges (AIBN: azodiisobutyronitrile)
306.45 m2 /g. The magnetic nanoparticles had a significant absorp- (reprinted with permission from Ref. [77]); 6(b) The synthesis of magnetic P(St-
tion capacity for several types of oils, including lubricating oil, DVB) foams (reprinted with permission from Ref. [78]).

salad oil, edible oil and diesel oil. The magnetic nanoparticles could
adsorb oils up to 11.51 times their own weight. In addition, the
magnetic nanoparticles could be reused for 20 cycles with high oil
removal efficiencies and without significant changes in the water
contact angle.
The process of coating iron oxide with inorganic materials
is much less developed; therefore, understanding the formation
mechanisms and effective synthetic methods to obtain stable, dis-
persible magnetic nanoparticles is needed.
4.3. Inserting iron oxides into fibers or membranes
Electrospinning is a method to fabricate micrometer or
nanometer fibers through nonmechanical fiber drawing under a
strong electric field. An electrostatic force was used to accelerate
polymer droplets at the Taylor cone vertex of a capillary. When the
electric field force was sufficiently large, polymer droplets could
overcome the surface tension and form a jet stream. During the
injection process, after the evaporation or curing of solvent, the
stream finally fell on the receiving device to form a nonwoven fab-
ric mat [64,65]. At present, a variety of magnetic nanofibers, such
as Fe3 O4 /PVA nanofibers [66], C/Fe3 O4 composite nanofibers [67],
magnetic PAN/Fe3 O4 nanocomposite fibers [68] and Fe3 O4 /PVP
nanofiber films [69], have been prepared by electrospinning tech-
niques. Song [35] designed a magnetic fibrous sorbent with a
high oil adsorption capacity using the electrospinning method. The
synthesized PS/Fe3 O4 fibrous sorbent was homogeneous, and the
Fe3 O4 nanoparticles were well dispersed in the fibers. The pore
diameter of the fibrous sorbent (7.63 μm) was smaller than that
of pristine PS (8.34 μm), which might be attributed to the Fe3 O4 -
induced magnetic attraction. The magnetic PS/Fe3 O4 had a high
lipophilicity and could selectively adsorb oil from water. The mag-
netic PS/Fe3 O4 exhibited a rapid oil adsorption process that lasted
only 1–2 s. The magnetic fibrous sorbent could be collected quickly
by an external magnetic field as the saturation magnetization was
14 emu/g.
4.4. Magnetic porous materials
A widely employed approach to synthesize efficient magnetic
oil sorbents is to attach iron nanoparticles to the pore walls and
struts of certain porous material by different techniques. Three-
dimensional porous materials in the form of aerogels, sponges and
foams are considered oil sorbents due to their low density, high
porosity and specific surface area [70]. Fe3 O4 nanoparticles should
be modified with a SiO2 shell in advance to make them com-
patible with the organosilanes and to obtain a uniform magnetic
porous material, otherwise phase separation is inevitable [71]. The
magnetic particles increased the roughness, hydrophobicity and
oleophilicity of the porous material.
A simple method to synthesize magnetic porous material is
to transfer iron oxide nanoparticles to porous materials by dip-
coating and adsorption [13,72]. This method could improve the
hydrophobicity and oil adsorption efficiency of the porous mate-
rial. However, there might be a loss of iron oxide particles during
the processes of oil adsorption and magnetic collection because
the particles are weakly bound, which impairs the reusability of
the oil adsorbent and threatens environmental safety [73,74]. An
example of this approach is the work of Calcagnile et al. [75],
where the PTFE-PU foams obtained by triboelectric charging were
placed onto a glass substrate coated with toluene-based Fe3 O4 .
The Fe3 O4 solution was transferred throughout the entire thick-
ness of the reticulated network of foam pores by capillary action.
The magnetic PU foam with superhydrophobic and superoleophilic

Please cite this article as: K. Qiao, W. Tian and J. Bai et al., Application of magnetic adsorbents based on iron oxide nanoparticles for oil
spill remediation: A review, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2019.01.029
JID: JTICE
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K. Qiao, W. Tian and J. Bai et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx 7

Table 2
The summary of the properties of different magnetic sorbents for oil removal.

Magnetic Functional material Synthesis Method Saturation Water Contact Application Sorption Reference
sorbents Magnetization Angle Capacity/Removal
(emu/g)

Fe3 O4 @OA Oleic acid Microemulsion 16.57 N/A Crude oil 95 wt.% [42]
Fe3 O4 @SO Sodium oleate Co-precipitation 49.40 155° Engine oil N/A [33]
QC-coated Fe3 O4 Quaternized chitosan Modified stober 30.5 N/A Emulsified oil 90% [48]
method and
“grafting to”
reaction
Magnetic Gelatin glue Suspension N/A N/A Kerosene 100% [50]
composite resin co-polymerization
Magnetic Collagen Heat treatment N/A N/A Motor oil 2 g/g [51]
collagen-SPION
Fe3 O4 @PS Styrene (St) and Emulsion 34.62/61.25 141.2°/153° Diesel oil/ 3 times of its own [32,34]
sodium dodecyl polymerization Lubricating oil weight
sulfonate (SDS)
Fe3 O4 @P(St/DVB) Methyl methacrylate Hydrothermal N/A 141.2° Diesel oil 3.63 times of their [54]
@P(MMA/St/DVB) method weight
Fe3 O4 @PVP Polyvinyl pyrrolidone Modified polyol/ N/A N/A Crude oil/ MC252 Near 100% [52,55]
Hydrothermal oil
method
Fe3 O4 @SAS Sulfonated asphaltene Co-precipitation 75–92 N/A Crude oil 90% [56]
Fe2 O3 @C Iron containing metal Pyrolysis 26–49 143° Oil/hydrocarbon 40 times of its own [62]
composite system organic framework weight
Polysiloxane- Terephthalic acid and Thermal N/A 162.9° Lubricating oil 3.8 times of their [7]
coated polysiloxane decomposition own weight
Fe2 O3 @C
Fe3 O4 @SiO2 Tetraethyl Template approach 58.3 148.8° Lubricating oil, 11.51 times of their [63]
orthosilicate salad oil, edible own weight
oil, diesel oil
PS/Fe3 O4 fibrous Polystyrene Electrospinning 14 N/A Edible oil near 100% [35]
sorbent
Magnetic foams PTFE-PU foams Adsorption N/A 160° Mineral oil 13 times of its own [75]
weight
Magnetic Cellulose aerogel In-situ incorporation N/A N/A Paraffin oil 28 times of its own [76]
cellulose aerogel weight
Magnetic sponge Sponge Polymerization N/A 140.1° engine oil, crude oil 9.9–20.3 g/g [77]
induced
macrophase
separation
Magnetic P(St-DVB) foams High internal phase N/A 150° Diesel oil 24.5–57.6 times of [78]
P(St-DVB) foams emulsions its own weight
Fe3 O4 –CNT Carbon nanotube Chemical vapor N/A 140° Diesel oil and 99% [36]
sponges sponges deposition gasoline
Magnetic carbon Coconut/ Palm Co-precipitation 15 N/A Premium oil and 9.33 g/g and 80% [82,83]
shell-based carbon used oil/ Palm oil

properties could float on the surface of water and adsorb oil up
to more than 13 times its weight. However, the maximum amount
of iron oxide nanoparticles that could be reclaimed was 80% of
the initial quantity due to the loss of magnetic particles upon
interaction with oil. A type of cellulose aerogel with hydrophobic,
magnetic and highly porous properties was prepared and applied
to selectively adsorb oil from the water surface [76]. The obtained
magnetic aerogel could reach an oil adsorption capacity up to
approximately 28 times its own weight within 10 min. An external
magnetic field was sufficient to remove and recover the magnetic
material from the water surface. The magnetic aerogel could be
reused by washing with ethanol.
Another method is to crosslink or graft iron oxide nanoparti-
cles onto porous materials, which decreases the leaching of Fe3 O4
from the porous material. An impressive example is that of Wu
et al. [77] involving the insertion of modified Fe3 O4 nanoparti-
cles into a sponge by polymerization-induced macrophase sepa-
ration (Fig. 6a). This approach provided magnetic sponges with
a high hydrophobicity (water contact angles of 140.1°) and oil
adsorption capacity from 9.9 to 20.3 g/g. In addition, the ad-
sorption processes were fast and lasted only 10 min at which
point adsorption saturation was reached. Zhang et al. [78] devel-
oped another one-step method (high internal phase emulsions)
to prepare magnetic P(St-DVB) foams (Fig. 6b). The magnetic
P(St-DVB) foams showed a very high degree of hydrophobicity and
oleophilicity (water contact angle >150° and oil contact angle ap-
proximately equal to 0), and they could adsorb oil up to 57.6 times
their own weight. In addition, the magnetic P(St-DVB) foams ex-
hibited superior reusability and could be reused 20 times without
a notable decline in the adsorption capacity.
A remarkable performance was obtained by Li et al. [79] in
preparing a magnetic carbon fiber aerogel through one-step py-
rolysis of Fe(NO3 )3 -coated cotton in an argon atmosphere. The
magnetic carbon fiber aerogel could adsorb oil selectively and
rapidly due to its superhydrophobicity and superoleophilicity. After
adsorption, the magnetic carbon fiber aerogel could be controlled
by a magnetic bar for retrieval. The aerogel exhibited a good
reuse performance and still maintained a high oil absorption
capacity after ten times of use. According to Gui et al. [36],
Fe3 O4 –CNT sponges with a high affinity for diesel oil and gaso-
line could be fabricated using ferrocene and dichlorobenzene as
precursors by chemical vapor deposition. The oil adsorption ca-
pacity reached 56 g/g with a removal efficiency of 99%. Remark-
ably, the magnetic sponges could be reused for 10 0 0 cycles with-
out great changes in the structure, contact angle and sorption
capacity.

Please cite this article as: K. Qiao, W. Tian and J. Bai et al., Application of magnetic adsorbents based on iron oxide nanoparticles for oil
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JID: JTICE
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8 K. Qiao, W. Tian and J. Bai et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx
4.5. Combining iron oxide with activated carbon
Activated carbon is an impressive adsorbent with which to ad-
dress environmental problems because it has a high specific sur-
face area and a rich pore structure. The synthesis and application
of magnetic activated carbon have received considerable attention
in recent years because the materials combine the magnetism of
magnetite and the high adsorption capacity of activated carbon
[80,81].
According to Raj and Joy [82], activated carbon was first pre-
pared by pyrolyzing coconut shells. Then, activated carbon/Fe3 O4
composites were obtained by in situ coprecipitation. An ammonia
solution was added to the solution containing Fe3+ , Fe2+ and acti-
vated carbon, and the mixture was heated to facilitate the binding
of iron oxide nanoparticles to surface functionalities of the acti-
vated carbon. The activated carbon had a higher adsorption capac-
ity of premium oil (9.33 g/g) than that of used oil (5.54 g/g). After
modification by iron oxide nanoparticles, the adsorption capacity
of premium oil and used oil increased to 12.93 g/g and 7.65 g/g,
respectively. After adsorption, the magnetic activated carbon could
be recovered by heat treatment and an external magnetic field. The
premium and used oil adsorption capacity decreased to 4.26 g/g
and 4.89 g/g, respectively. After the first cycle, the adsorption val-
ues remained almost constant from the second to the sixth cy-
cle. Palm shell-based carbon was also used to prepare magnetic
sorbents for oil removal [83]. First, palm shell-based carbon was
prepared by carbonization (combined with activation). Then, car-
bon/iron oxide composites were synthesized via a coprecipitation
technique by heating a mixture of carbon, Fe3+ and Fe2+ in an al-
kaline environment. The removal efficiency of oil could reach 80%.
The magnetic activated carbon could be collected after adsorption
by a magnetic process due to its magnetic properties.
The magnetic iron oxide nanoparticles could roughen the sur-
face of activated carbon and increase the specific area of carbon.
Additionally, the functionalization of carbon by magnetic nanopar-
ticles could increase the oil adsorption efficiency and reusability.
However, the main synthesis method of magnetic activated carbon
is coprecipitation, which may result in agglomeration and oxida-
tion during the adsorption process, such as iron oxide nanoparticle
binding on the surface of carbon. It is important to develop syn-
thesis techniques to obtain stable magnetic activated carbon.
Table 2 illustrates the properties of magnetic sorbents and their
oil removal efficiencies. The water contact angles of these mag-
netic materials were usually greater than those of naked iron oxide
nanoparticles. The synthesis method and functionalization mate-
rial influence the saturation magnetization. Generally, a thick shell
could lead to a decrease in the saturation magnetization. Moreover,
magnetic porous materials and magnetic carbon may have a lower
level of saturation magnetization because the synthesis processes
require the adsorption or immobilization of magnetic nanoparticles
on/into the support materials, which may result in a lower content
of iron oxide nanoparticles.
The functionalization materials also have a great effect on the
oil removal efficiency. Hydrophobic/lipophilic materials are consid-
ered ideal functionalization materials because they have a strong
affinity for oil. The magnetic nanoparticle adsorbents obtained by
encapsulating iron oxide nanoparticles with organic compounds
usually presented a high oil removal efficiency (near 100%). There
are two main reasons, one was that the organic compound pos-
sessed hydrophobicity/lipophilicity, and the other was that the
nanoparticles contained a network of nanoscale structures and a
large surface area, which could lead to a high adsorption capacity
for some contaminants [84]. The magnetic porous materials also
had a high oil adsorption capacity of 23.3 g/g (or nearly 100%). The
ideal characteristics of porous materials for oil sorption are high
porosity, large surface area, and low density. Another benefit of
Please cite this article as: K. Qiao, W. Tian and J. Bai et al., Application of magnetic adsorbents based on iron oxide nanoparticles for oil
spill remediation: A review, Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2019.01.029
[m5G;February 7, 2019;7:28]
porous materials for oil spill treatment is the recovery of oil [85].
Several recovery methods could be applied, including mechani-
cal squeezing, extraction, and distillation [86–88]. Magnetic porous
materials could combine the advantages of porous materials and
the magnetic properties of magnetic iron oxide nanoparticles.
5. Conclusions and perspectives
The review shows that magnetic oil sorbents have several ad-
vantages. One impressive property is magnetism, which allows a
quick and efficient retrieval; another key parameter for efficient oil
adsorption is the degree of hydrophobicity, which permits the sor-
bent to adsorb oil and repel water; the third necessary trait of an
efficient magnetic sorbent is a low density, which allows full con-
tact with the oil film, resulting in a considerable removal efficiency
of oil and allowing efficient retrieval by an external magnetic
field. Magnetic nanomaterials could be obtained by encapsulat-
ing iron oxide nanoparticles with organic or inorganic compounds.
Furthermore, magnetic porous sorbents and magnetic activated
carbon are also desirable oil sorbents.
Although there are various strategies to obtain functionalized
iron oxide nanoparticles, it is still a challenge to synthesize high-
quality and stable magnetic oil sorbents. In the future, develop-
ment of high performance adsorbents is required. Sorbents with
a high adsorption capacity, high reusability, low cost, and toxin-
free performance are attracting attention. Meanwhile, the increas-
ing population rate has increased the rate of food consumption,
resulting in massive amounts of biowaste globally. For this rea-
son, an inventive way of producing magnetic sorbents using easily
biodegradable biomass to produce low-coast sorbents with higher
oil sorption capacity has been developed.
In the near future, the preparation of magnetic oil sorbents
with a high stability and availability and realization of large-
scale or industrial applications will be greatly investigated. To
accomplish the application under real case conditions, researchers
have to resolve several practical questions, such as the amount of
magnetic materials to add and how wave action might complicate
the recovery of swelled-up particles. Research on the strength
of the external magnetic field used to retrieve the magnetic
material after adsorption should also be conducted. To realize
industrial commercialization, the synthesis method of magnetized
nanoparticles should be simple and cost-effective. Furthermore,
the synthesis method should not introduce harmful chemicals
and should enable recovery and recycling use. Recyclability is an
important parameter for industrial commercialization. The adhe-
sion between magnetic nanoparticles and supporting materials is
largely affected by the synthesis method of magnetic materials.
Certain magnetic materials were produced by inserting Fe3 O4
nanoparticles into fibers and membranes or by crosslinking or
grafting in sponges and foams. After the regeneration treatment,
these magnetic adsorbents could be recycled several times without
a clear decline in the adsorption capacity, and no great changes
were observed in the structures or contact angles. However, certain
magnetic materials were synthesized by procedures where mag-
netic nanoparticles were transferred to porous materials through
simple dip-coating or triboelectric charging or being attached
to the surface of biochar by coprecipitation. After several cycles
of oil-water separation, the magnetic materials still maintained
suitable oil adsorption capacities. However, the drawbacks of these
materials are mainly connected to the partial release of weakly
bound particles into the environment during the oil absorption
process. The latter will compromise the reusability of the sorbent
and result in diverse environmental safety issues. In the future,
researchers should consider the regeneration efficiency and cyclic
stability when synthesizing magnetic oil adsorbents.
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K. Qiao, W. Tian and J. Bai et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx
However, future work should also focus on research on the
toxicity and degradability of naked or functionalized iron oxide
nanoparticles. If any nanoparticles were left behind, they would
float in oceans indefinitely, possibly agglomerating with existing
pollutants such as plastic garbage; therefore, it may be better
to produce particles made of degradable polymers. In the future,
polymers made of natural products, such as sugar, that will dis-
solve into harmless components if left in the environment should
be concentrated on. From environmental and economic points of
view, the optimal solution of an oil spill might be a combination
of several different methods. In the case of oil spills, the treatment
method could include oil adsorption and oil biodegradation. Mag-
netic adsorbents with a high oil adsorption capacity could be used
as supports to carry microorganisms such as bacteria and fungi to
treat oil pollution.
Acknowledgments
The authors gratefully acknowledge support from the Natural
Science Foundation of China (No. 51579228) and the Natural Sci-
ence Foundation of Shandong Province, China (No. ZR2014EEM016).
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