Materials Letters 115 (2014) 241–243

Contents lists available at ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Fabrication of hydrophobic and magnetic cellulose aerogel with high

oil absorption capacity
Suk Fun Chin n, Ain Nadirah Binti Romainor, Suh Cem Pang
Department of Chemistry, Faculty of Resource Science and Technology, Universiti Malaysia Sarawak, 94300 Kota Samarahan, Sarawak, Malaysia

art ic l e i nf o a b s t r a c t

Article history: Hydrophobic, magnetic and highly porous cellulose aerogel was prepared by a simple method for fast
Received 25 July 2013 and selective absorption of oil from water surface. The aerogel was able to absorb oil up to about 28 times
Accepted 17 October 2013 of its own weight within 10 min and could be easily removed and recovered from the water surface by an
Available online 24 October 2013
external magnet. It could be either reused after washing with ethanol, or incinerated with the absorbed
Keywords: oil. The potential application of cellulose aerogel as an oil absorbent was demonstrated by its ease of
Magnetic preparation, low cost of precursor materials, magnetically retrievability, as well as high oil absorption
Biomaterials capacity and efficiency.
Cellulose aerogel & 2013 Elsevier B.V. All rights reserved.
Porous materials
Oil absorption

1. Introduction
Frequent occurrences of oil spillage on water bodies have caused
numerous negative impacts on the aquatic environment [1]. Therefore,
there is a pressing need to develop a fast, efficient and economical
absorbent for cleaning up oil spills from the water surface. Existing oil
absorbents use activated carbons [2], sawdusts [3] and aerogels [4].
Both activated carbon and sawdust suffer from poor oil absorption
efficiency due to the co-adsorption of water along with the oil. Being
an ultra-light and highly porous material, aerogel has been demon-
strated to be a very efficient oil absorbent. Aerogels are usually
prepared by drying wet gels via methods such as critical point drying
or freeze drying in order to remove liquid without collapsing the
porous structure network [5]. Silica aerogels have been widely used as
oil absorbents. However, silica aerogels are very fragile and brittle [6].
Recently, carbon nanotube aerogels have been shown to have an oil
absorption capacity of 80–180 times of its original weight [7].
However, carbon nanotubes are relatively more costly and are thus
unsuitable for large scale oil spill cleanup.
Cellulose-based aerogels show promising potential as oil absor-
bents as they are renewable, available abundantly, low in cost and
exhibits high oil absorption capacity. Besides, cellulose aerogels
exhibit high structural flexibility and good mechanical proper-
ties [8]. Nanocellulose aerogels were treated with octyltrichlorosi-
lane using vapor phase deposition to obtain hydrophobic surfaces
for the separation of oil from oil/water mixture [9]. In another study,
nanocellulose aerogels were functionalized with a layer of titanium
n
Corresponding author. Tel.: þ 60 82582999.
E-mail addresses: sfchin@frst.unimas.my, sukfunchin@gmail.com (S.F. Chin).
dioxide (TiO2) using atomic layer deposition for oil removal [10].
These deposition methods are complicated and required the use of
sophisticated equipment. Another challenge of using oil absorbents
is their removal from water surfaces after an oil clean up.
In this work, we have reported a facile method for the
preparation of hydrophobic and magnetic cellulose aerogel by
in-situ incorporation of magnetic Fe3O4 nanoparticles into the
cellulose aerogels and followed by coating the surfaces of aerogels
with a thin layer of TiO2 using the sol–gel process. These magnetic
cellulose aerogels could be recovered from water easily by apply-
ing an external magnetic field.
2. Experimental
Materials: All chemicals were of reagent grade and used without
further purification. Commercial cellulose powder was obtained
from Whatman. Ultra-pure water (18.2 MΩ cm) was obtained from
a water purifying system (Model: ELGA, Ultra Genetic) and used
throughout the experiment.
Sample Preparation—Preparation of magnetite nanoparticles
(Fe3O4): Magnetic Fe3O4 nanoparticles were prepared by the
co-precipitation method as reported in our previous studies [11].
Preparation of cellulose aerogel: 1% w/v of cellulose solution was
prepared by dissolving cellulose fibers in sodium hydroxide:thiourea:
urea (NTU) aqueous solvent system (8:6.5:8 w/v%) to form a homo-
geneous cellulose solution. Cellulose gel was regenerated by solvent
exchange with ethanol. Cellulose aerogel was then obtained by (CO2)
supercritical point drying of the cellulose gel.
Preparation of magnetic cellulose aerogel: 50 mg of Fe3O4 nano-
particles were dispersed homogenously in 10 mL of cellulose

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.10.061
242 S.F. Chin et al. / Materials Letters 115 (2014) 241–243
solution by ultrasonication. All of the Fe3O4 nanoparticles were
incorporated in-situ into the cellulose gel as the gel was being
regenerated during solvent exchange with ethanol. Magnetic
cellulose aerogel was obtained by CO2 supercritical point drying
of the cellulose gel.
Surface functionalization of magnetic cellulose aerogel: The sur-
face of magnetic cellulose aerogel was coated with titanium
dioxide (TiO2) by the sol–gel method [12]. A measured amount
of titanium tetraisopropoxide (TTIP) was added into magnetic
cellulose aerogel, and the mixture was stirred for 24 h at room
temperature to allow complete hydrolysis and condensation of
TTIP. TiO2 coated magnetic cellulose aerogel was isolated by an
external magnet, and then washed three times with ethanol to
remove excess of TTIP and free TiO2.
Sample Characterization: Samples were characterized using
both TEM (JEOL JSM-6710F) and SEM (JEOL JEM-1230).
Oil absorption experiments: The oil absorption capacity of
samples was determined based on the method as reported in
the literature [13]. Briefly, a measured amount of paraffin oil was
mixed with water to form an oil/water mixture. A weighted
amount of cellulose aerogel or magnetic cellulose aerogel was
dispersed in the oil/water mixture. The oil absorption process was
repeated at various predetermined time intervals. The oil absorp-
tion capacity was calculated based on Eq (1). Magnetic cellulose/
TiO2 aerogel was recovered and reused in separate oil absorption
experiments.
Oil absorption capacity ¼ ðW Wo Þ=ðWo Þðg=gÞ
where W is weight of magnetic cellulose/TiO2 aerogel after oil
absorption and Wo is the weight of magnetic cellulose/ TiO2
aerogel before oil absorption.
3. Results and discussion
The mean particle sizes of Fe3O4 nanoparticles used in this study
ranged somewhere between 7–10 nm, as determined from the TEM
Fig. 1. (a) TEM image of Fe3O4 nanoparticles used in this study; SEM images of (b) magnetic cellulose aerogel used (c) magnetic cellulose/TiO2 aerogel; (d) TEM image of
magnetic cellulose aerogel/TiO2 aerogel and (e) EDX spectra of magnetic cellulose aerogel/TiO2 aerogel.
micrograph (Fig. 1(a)). Fig. 1(b) shows the SEM micrograph of
magnetic cellulose aerogel comprised networks of nanofibers and
was highly porous in nature. The surfaces of nanofibers networks
were observed to be thicker and rougher after being coated with
TiO2 (Fig. 1(c)). The TEM micrograph (Fig. 1(d)) shows that Fe3O4
nanoparticles were embedded within the cellulose fibers. These
Fe3O4 nanoparticles were physically embedded or encapsulated
within the cellulose fibers during the formation of cellulose aerogel.
The TiO2 coating and cellulose were barely discernible due to the
low contrast between them. The energy dispersive X-ray (EDX)
spectrum (Fig. 1(e)) shows the presence of carbon (C), titanium (Ti)
and iron (Fe) elements in the sample, thereby confirming the
presence Fe3O4 nanoparticles and the formation of TiO2 on the
surfaces of cellulose aerogel nanofibers.
The oil absorption capacity of the magnetic cellulose/TiO2
aerogel was evaluated by dispersing the aerogel in an oil/water
mixture. Magnetic cellulose/TiO2 aerogel was observed to float
on the oil layer due to their hydrophobicity and oleophilicity
(Fig. 2(a)) attributing to the hydrophobic TiO2 coating on the
cellulose aerogel. The aerogel was observed to absorb oil rapidly
and could be easily removed by using a magnet after the absorp-
tion studies as shown in Fig. 2(b). Fig. 2(c) shows that most of the
oil on the water surface had been absorbed by the aerogel.
The oil absorption capacity of the samples as a function of time
was shown in Fig. 3. It is noteworthy that the magnetic cellulose/
TiO2 aerogel could absorb oil up to about 28 times its original
weight within 10 min as shown in Fig. 3(a). After the absorption
ð1Þ
process, the magnetic cellulose/TiO2 aerogel was regenerated by
immersing in ethanol to remove the absorbed oils and could be
reused for another absorption study. No deterioration in the oil
absorption capacity of reused aerogel was observed (Fig. 3(b)).
Furthermore, the dry weight of reused aerogel remained the same
as before and they still floated on the oil/water mixture indicating
that their hydrophobicity was intact. In contrast, unmodified
cellulose aerogel only absorbed oil up to about 5 times of its
original weight due to the hydrophilic nature of its surfaces (Fig. 3
(c)). A control experiment was conducted by immersing the
 S.F. Chin et al. / Materials Letters 115 (2014) 241–243
Fig. 2. Photograph of (a) magnetic cellulose/TiO2 aerogel in oil/water mixture; (b) magnetic cellulose/TiO2 aerogel can be removed by a magnet and (c) the oil layer on water
surface was removed.
Fig. 3. Oil absorption capacity of the (a) magnetic cellulose/TiO2 aerogel, (b) reused
magnetic cellulose/TiO2 aerogel and (c) cellulose aerogel as a function of time.
magnetic cellulose/TiO2 aerogel in water only. The weight of the
magnetic cellulose/TiO2 aerogel had remained constant after
30 min (result was not shown) indicating that no water was being
absorbed. This observation further confirmed that the surfaces of
the magnetic cellulose/TiO2 aerogel was hydrophobic in nature
and only absorbed oil selectively.
4. Conclusion
In conclusion, we have developed a simple method for the
preparation of highly porous and magnetic hydrophobic cellulose/
TiO2 aerogel by CO2 supercritical point drying of magnetic cellulose
243
gel and followed by surface coating with TiO2. This magnetic
cellulose/TiO2 aerogel could absorb oil selectively up to about 28
times of its original weight, and could be removed easily from water
surface by using an external magnet. The potential utility of this
magnetic cellulose/TiO2 aerogel as an efficient and economical oil
absorbent for oil removal from water surface is therefore envisaged.
Acknowledgment
The authors gratefully acknowledged the financial support pro-
vided for this work by the COMSTECH/IFS (Committee on Scientific
and Technological Coorperation/International Foundation of Science)
under the grant agreement No F/5207–1.
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