Separation and Purification Technology 221 (2019) 303–310

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Remodeling of raw cotton fiber into flexible, squeezing-resistant T

macroporous cellulose aerogel with high oil retention capability for oil/
water separation
⁎
Jintao Wanga,b, , Shuyu Liua
a
College of Materials Science and Engineering, North Minzu University, Yinchuan 750021, PR China
b
State Key Laboratory of Powder Materials and Advanced Ceramics, Yinchuan 750021, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Cellulose-based aerogels reveal great potential as sorbents for oil sorption due to their biodegradability and the
Raw cotton fiber renewability of raw material. Nevertheless, the widely reported aerogels are synthesized by using nanocellulose
Aerogel separated from natural fiber and cellulose derivative, and the relatively high cost limits their application in oil
Sorption capability cleanup. Herein, we report a simple and low-cost route to prepare superhydrophobic cellulose aerogel by using
Oil-retention ability
raw cotton fiber as starting material. The as-prepared aerogel can absorb various oils and organic solvents and
Mechanical durability
the sorption capacities can reach up to 19.8–41.5 times the weight of initial aerogel. The aerogels also reveal fast
sorption rate, good oil-retention ability, and excellent recyclability. Especially, the superior hydrophobiciy en-
dows the fabricated aerogel with high selectivity for oil sorption from water. Besides, the aerogels possess good
chemical durability and can resist corrosive solutions and various oils. After the abrasion of 80 cycles, the
resultant aerogel still can maintain its original hydrophobicity. Due to easy availability of cotton fiber, good oil
sorption performance, and cost-effective preparation process, the raw cotton fiber-derived aerogel can be re-
garded as promising alternative for organic synthetic materials to oil spill cleanup and oily wastewater pur-
ification.

1. Introduction
Frequent occurrence of oil spill accidents and oily wastewater dis-
charge has brought to seriously negative impacts on the aquatic eco-
systems [1]. Therefore, it is necessary to develop a highly efficient and
economical sorbent for the separation and collection of oil from water.
Up to date, the oil sorbents having been reported include natural fibers
[2–4], inorganic minerals [5], carbon aerogels [6], organic synthetic
foams [7–9], and electrospun fibers [10], etc. Organic synthetic foams
and electrospun fibers are difficult to decompose after being aban-
doned, which can cause secondary pollution. Both inorganic mineral
and natural fiber suffer from poor oil sorption efficiency because of the
co-adsorption of water along with the oil. Besides, the practical appli-
cation of two kinds of materials is also restricted by their poor oil-re-
tention capability. Being an ultra-light and highly porous material,
aerogel is regarded as one of the most desirable oil sorbents. They de-
monstrate high oil sorption capacity and floatability as well as fast oil
sorption rate in previous studies.
Aerogels with a highly interconnected three-dimensional (3D)
network, characterized by high porosity, low density, and light weight,
have aroused wide concern in the field of oil spill cleanup. Different
types of aerogels based on graphene [11], polymers [12], cellulose
nanofibrils [13], carbon nanotubes [14], and silica nanoparticles [15]
have been recently reported for oil sorption. Among these fabricated
aerogels, cellulose-based aerogels have attracted much attention as oil
sorbent as they are abundantly available, biodegradable, renewable,
and environment-friendly. Besides, cellulose aerogels exhibit high
structural flexibility and good mechanical stability. So far, a variety of
cellulose-based aerogels, such as carbon aerogels from cellulose-based
waste newspaper [16], nanocrystalline cellulose aerogels from raw
cotton and cotton stalk [17], bacterial cellulose aerogels [18], hy-
drazone-carboxyl ligand-linked cellulose nanocrystal aerogel [19], and
underwater superoleophobic cellulose nanofibre aerogel [20], have
been successfully synthesized in different routes. They demonstrate
highly efficient sorption for oils and organic solvents. Although the
encouraging results have been obtained previously, several challenges
in fabricating cellulose-based aerogel still must be addressed before
they can really compete with the oil sorbents based on organic synthetic

⁎
Corresponding author at: College of Materials Science and Engineering, North Minzu University, Yinchuan 750021, PR China.
E-mail address: wjt1986120@163.com (J. Wang).

https://doi.org/10.1016/j.seppur.2019.03.097
Received 6 December 2018; Received in revised form 22 March 2019; Accepted 30 March 2019
Available online 01 April 2019
1383-5866/ © 2019 Elsevier B.V. All rights reserved.
J. Wang and S. Liu Separation and Purification Technology 221 (2019) 303–310

materials. For most of cellulose aerogels, the fabrication process re-

quires the use of expensive critical point drying method. Furthermore,
these cellulose-based aerogels are generally fabricated through the as-
sembly of cellulose nanofibrils or nanocrystalline cellulose and the
preparation of nanocellulose is very complicated and tedious, which
restricts their large-scale production and application as oil sorbents.
Therefore, considerable efforts should be dedicated to exploring simple
and economical approach to fabricate cellulose aerogels in order to
achieve their wide-spread application in oil spill cleanup.
In this work, we report a simple approach for the synthesis of su-
perhydrophobic cellulose aerogel via one-step dissolution and re-
generation of raw cotton fiber followed by modifying the surface of
aerogel with methyltrimethoxysilane (MTMS) using chemical vapor
deposition process. The obtained cellulose aerogel exhibits excellent
interconnected 3D network structure, which is directly constructed via
a simple self-assembling in solvents rather than the traditional ap-
proach of performing nanocellulose separation and the subsequent self-
assembling. The technique reported here greatly simplifies the pre-
paration process of cellulose aerogels and reduces their preparation
cost. In addition, the as-fabricated aerogels possess highly hydrophobic-
oleophilic property and can selectively absorb a variety of oils or or-
ganic solvents from water. More importantly, the obtained aerogel has
outstanding corrosion resistance, mechanical abrasion resistance, and
recyclability. To the best of our knowledge, no studies have been car-
ried out on fabricating cellulose aerogels for oil sorption application via
using raw cotton fiber directly.

2. Experimental

2.1. Materials

Cotton fiber was purchased from market, Yinchuan, China. NaOH

(analytical grade), urea (analytical grade), thiourea (analytical grade),
kerosene (analytical grade) were supplied by Sinopharm Chemical
Reagents Co., Ltd., China. Methyltrimethoxysilane (MTMS, chemically
pure) was received from Nanjin Chengong Organosilicon Co., Ltd,
China. Ethanol (analytical grade), methanol (analytical grade), N, N-
dimethylformamide (DMF, analytical grade), tetrahydrofuran (THF,
analytical grade), n-hexane (analytical grade), toluene (analytical
grade), and chloroform (analytical grade) were obtained from Ninxia
Shi-Jie Chemical Reagent Co. Ltd., China. Gasoline and diesel were
purchased from the local station, Yinchuan, China.
2.2. Preparation process of superhydrophobic cellulose aerogels
Before use, raw cotton fiber was rinsed with distilled water and
dried at 80 °C. The clean raw cotton fiber (1.5–3.5 wt%) was dispersed
into a precooled (−15 °C) sodium hydroxide solution (14 wt%) and
vigorously stirred for 3 min at 800 rpm [21,22]. Then, the precooled
(−15 °C) solution containing urea (8 wt%) and thiourea (4.5 wt%) was
added the dispersion and agitated for 3 min at 800 rpm. The obtained
cellulose solution was placed in an oven at 50 °C for more than 2 h to
allow gelation. After finishing the gelation, the resultant cellulose gel
was immersed into 6 wt% HCl solution and coagulate for 2 h. After the
coagulation, the gel was rinsed by distilled water until neutral. Freeze-
drying was performed for the cellulose gels for 2 days at −50 °C after
prefreezing the sample at −15 °C for 8 h. The obtained cellulose aerogel
and a small open glass vial with MTMS were placed in a big glass vessel.
Then the glass vessel was sealed and heated in an oven at 70 °C for 3 h
for the hydrophobic modification. The schematic illustration of the
superhydrophobic cellulose aerogel is also displayed in Fig. 1a.
2.3. Measurements of oil sorption capacity
A variety of oils and organic solvents were used to evaluate the
sorption capacity of cellulose aerogels. The dried sample was placed in
Fig. 1. (a) Schematic representation of fabricating superhydrophobic cellulose
aerogels; (b) photographs of superhydrophobic cellulose aerogels with different
fiber concentration; (c) photographs of superhydrophobic cellulose aerogels
(density: 0.041 g/cm3) obtained under different scale of preparation; (d) flex-
ibility of the cellulose aerogel (8 cm * 1.2 cm) containing 3.5 wt% of raw cotton
fiber.
contact with given oil or solvent for 3 min at room temperature. Then,
the sample was taken out from the oil or solvent, drained for 5 s to
allow the surface residual oil to drip away. The oil sorption capacity of
the sample was determined by weighing the samples before and after
the sorption, and calculated by the following formula:
Q = (mt − mi)/mi
where Q is the oil sorption capacity of the sorbents calculated as grams
of oil per gram of sample, mt is the weight of the wet samples after the
oil sorption (g), mi is the weight of dried sorbents before the sorption
(g).
2.4. Characterizations
Fourier transform infrared (FTIR) spectra were recorded on a
Nicolet NEXUS FTIR spectrometer. The XRD patterns of the samples
were carried out on an X’ Pert PRO diffractometer equipped with a Cu K
radiation source (40 kV, 40 mA). The appearance of samples was ob-
served via SEM (JSM–5600LV, JEOL). Before the observation, all
samples were fixed on aluminum studs and coated with gold. Water
contact angle measurements were performed using a Krüss DSA 100
(Krüss Company, Ltd., Germany) apparatus at ambient temperature,
and the volumes of probing liquids in the measurements were ap-
proximately 5 μL.

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3. Results and discussion

3.1. Fabrication and characterization of cellulose aerogels

In the case of the fabrication of this cellulose aerogel for oil sorp-
tion, the concentration of raw cotton fiber is a key parameter of af-
fecting the oil sorption capacity. As presented in Fig. 1b, the developed
cellulose aerogels with different fiber concentration (1.5–3.5 wt%) have
the dimension of 8 cm (diameter) * 2.3 cm (thickness) and same shape
of their reaction vessel, and no visible volume shrinkage or structure
cracking is observed. The density of the cellulose aerogel fabricated at
the fiber concentration of 1.5%, 2.0%, 2.5%, 3.0%, and 3.5% is 0.025,
0.035, 0.041, 0.051, and 0.062 g/cm3, respectively. Obviously, the
density of the obtained aerogels increases slowly with increasing the
fiber concentration. Despite this, the as-fabricated cellulose aerogels via
dissolving and regenerating raw cotton fiber still possess low density,
which are comparable to that of carbon aerogel from poplars catkins
(0.043 g/cm3) [6] and the aerogel fabricated from nanocellulose
(0.023 g/cm3) [13]. In addition, the four pieces of aerogels with dif- Fig. 3. XRD curves of raw cotton fiber and superhydrophobic cellulose aerogel
ferent sizes (diameter: 8 cm; thickness: 5, 3.5, 2.3, 1.2 cm) are fabri- with different fiber concentration.
cated via expanding the scale of preparation (Fig. 1c). It can be seen
that the aerogels with different thickness do not present obvious vo-
aerogels, the absorption peaks of the aerogels modified by MTMS at
lume shrinkages, and the shape of the resulting aerogel can keep nearly
2985 and 1007 cm−1, which is corresponds to stretching vibration of
the same as that of the cellulose gel. It is therefore reasonable to infer
eCH3 and stretching vibration of CeO, respectively, display a slight
that the large-scale production of such cellulose aerogel with arbitrary
increase in peak intensity (Fig. 2b). This finding implies that the MTMS
shape and little volume shrinkage can be easily achieved. The hydrogen
was anchored onto the skeleton surface of the cellulose aerogels. The X-
bonding between the regenerated self-assembled cellulose fibers plays a
ray diffraction spectra of raw cotton fiber and as-synthesized five cel-
key role in the formation of the cellulose aerogels [23], which ensures
lulose aerogels with different fiber concentration ranging from 1.5 wt%
the superior flexibility and robustness of the resultant aerogels. As can
to 3.5 wt% are displayed in Fig. 3. It can be observed that the major
be seen in Fig. 1d, the as-fabricated cellulose aerogel (diameter: 8 cm;
diffraction peaks of raw cotton fiber appear in the position of 2θ close to
thickness: 1.2 cm) is easily bent without destroying its shape, sug-
14.7° (1 0 1), 16.7° (1 0 Ī ) and 22.5° (0 0 2), which are ascribed to the
gesting the excellent flexibility. This developed fabrication approach of
typical peaks of cellulose I [24]. In the case of the five cellulose aero-
cellulose aerogels based on raw cotton fiber, rather than commonly
gels, the typical diffraction peaks of cellulose II can be found in the
used methods based on nanocellulose, provides a facile, inexpensive,
position of 2θ at 12.1° (1 0 1), 20.1° (1 0 Ī ), and 21.8° (0 0 2). The result
and efficient route for the large-scale production of cellulose aerogels.
indicates the crystal structure of the cellulose in raw cotton fiber is
FTIR spectra of raw cotton fiber and the as-prepared unmodified
destroyed completely and rearranged in the dissolving-regenerating
cellulose aerogels with different fiber concentration are illustrated in
process, resulting in the structural transformation from cellulose I to
Fig. 2a. It can be seen that all the samples present the absorption bands
cellulose II.
at 3440, 2985, 1439, 1173, and 1007 cm−1, which are assigned to OeH
Scanning electron microscope (SEM) was used to observe the ap-
stretching vibration, CeH stretching vibration in eCH2e, CeH bending
pearance of the raw cotton fiber and the superhydrophobic aerogels
vibration in eCH2e, CeOeH stretching vibration in glycosidic bond,
fabricated at different fiber concentration. The SEM appearances of the
and CeO stretching vibration, respectively [2]. Obviously, the ab-
samples at two magnifications are shown in Fig. 4. As illustrated in
sorption peaks of raw fiber and the aerogels are almost identical except
Fig. 4a and a1, raw cotton fiber presents smooth surface with a dia-
for the difference of peak intensity. This indicates that no derivative
meter of about 12 μm. In contrast to the raw fiber, the regenerated fi-
reactions occur in the dissolution of raw cotton fiber in the alkali
bers at the different concentration exhibit distorted fiber morphology
system. Compared with the spectrum of the unmodified cellulose
and rough fiber surface, and dissociated cellulose microfibril can be

Fig. 2. FTIR spectra of (a) raw cotton fiber, unmodified cellulose aerogel with different fiber concentration, and (b) superhydrophobic cellulose aerogel with different
fiber concentration.

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J. Wang and S. Liu
Fig. 4. SEM images of (a,a1) raw cotton fiber and superhydrophobic cellulose aerogel with the fiber concentration of (b,b1) 1.5 wt%, (c,c1) 2.0 wt%, (d,d1) 2.5 wt%,
(e,e1) 3.0 wt%, and (f,f1) 3.5 wt%.
clearly observed on the fiber surface (Fig. 4b–f). The low-magnification
SEM images of the as-fabricated cellulose aerogels demonstrate the
weave macroporous three-dimensional network structure consisting of
a network of interconnected uniform cellulose fibers, as displayed in
Fig. 4b1–f1. With the increase of fiber concentration from 1.5 wt% to
3.5 wt%, the obtained cellulose aerogels show more compacted net-
work. The macropores of the five cellulose aerogels are possibly caused
by undamaged long fiber.
3.2. Wetting behavior of cellulose aerogels
The wettability of the as-prepared cellulose aerogels was studied via
contact angle measurement. As displayed in Fig. 5a, the unmodified
cellulose aerogel (2.0 wt%) shows high hydrophilicity with a water
contact angle of nearly 0°. After the modification with MTMS, the water
droplets (dyed with methylene blue) dropped onto the aerogel surface
are close to spherical in shape and the water contact angle is measured
to be 154°, implying the superhydrophobicity of the modified aerogel
(Fig. 5b). The wettability of blue-colored water droplets on the mod-
ified aerogel which is cut is also investigated and illustrated in Fig. 5c.
The finding indicates that not only the surface of the aerogel, but the
inside is extremely superhydrophobic. When the oil droplets (kerosene)
dyed with oil red O are dropped onto the superhydrophobic aerogel
surface, they are absorbed quickly and no oil contact angle is observed,
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Separation and Purification Technology 221 (2019) 303–310
suggesting its superoleophilicity (Fig. 5d). Furthermore, the as-pre-
pared modified cellulose aerogel can keep floating onto water surface
without any immersion even after 7 days (Fig. 5e), and it has no weight
increase after being removed from water surface. In contrast, the un-
modified aerogel sinks into the water completely within 5 s in absence
of any external force (Fig. 5f). The water absorption rate of unmodified
aerogel can reach 4560%. Once the superhydrophobic cellulose aerogel
is put into the oil dyed with oil red O, it would immediately sink into
the bottom (Fig. 5g). After being taken up, the oil-saturated aerogel can
keep integrated shape rather than the collapse of 3D network structure.
In addition, the effect of raw cotton fiber concentration on the water
contact angle was also studied. The result indicates that all the cellulose
aerogels have the water contact angles of greater than 148° and the
aerogel with the fiber concentration of 2.0% can achieve the highest
hydrophobicity (Fig. 5h). As a result, it can be concluded the high
hydrophobicity of the obtained aerogels is attributed to the synergistic
action of hierarchical structures and surface chemical composition. The
wettability findings also indicate the as-prepared aerogel may be ap-
plied to the selective sorption of oil from water.
3.3. Oil sorption capability of cellulose aerogels
The oil sorption capacity of the as-fabricated cellulose aerogels with
raw cotton fiber concentration ranging from 1.5 wt% to 3.5 wt% was
J. Wang and S. Liu Separation and Purification Technology 221 (2019) 303–310

superhydrophobic aerogel with different fiber concentration towards

chloroform, kerosene, and diesel. Obviously, the sorption rate for
chloroform and kerosene is very fast and the sorption saturation can be
achieved within 1 s. In the case of high-viscosity diesel, it needs to take
about 8 s to reach sorption saturation due to the slow diffusion of diesel
into the aerogel pores. For all the three oils, the oil sorption rate does
not present obvious variation with the increase of fiber concentration,
which is mostly because the macropore at all the fiber concentrations is
beneficial to the rapid diffusion of the oil in the three-dimensional
network structure [7]. Besides the sorption rate, the oil-retention ability
is also another parameter of evaluating oil sorbent. To investigate the
oil-retention ability, the beakers with different weights of water are
pressed on the kerosene-loaded aerogels. As displayed in Fig. 6d, no oil
leak phenomenon is observed with the weight of beaker increasing from
33.6 g to 150 g, which is ascribed to the good porous structure and fi-
brous framework of the aerogel. When the weight of the beak increases
to 180 g, only trace amount of oil flows from the oil-loaded aerogel.
Despite this, the oil-retention ability of superhydrophobic aerogels is
enough to satisfy the requirements of actual applications.

3.4. Sorption selectivity and recyclability of superhydrophobic aerogels

In this study, the oil/water separation performance of super-

hydrophobic cellulose aerogel was investigated. As displayed in Fig. 7a,
when a piece of superhydrophobic aerogel (1.5 wt%) is put into contact
with a layer of kerosene (dyed with oil red O) on water, it can float on
the water surface and absorb the oil selectively, resulting in fast de-
crease and disappearance of the water region polluted by the oil. After
the oil-loaded aerogel is removed from water, the water surface be-
Fig. 5. Water droplets on the (a) the unmodified aerogel, (b) MTMS modified
comes clear and transparent, implying an effective route for oil spill
cellulose aerogel, and (c) dissected modified aerogel; (d) kerosene droplets dyed
cleanup. To further confirm the oil/water selectivity of the super-
with oil red O on the surface of the MTMS modified aerogel; photograph of (e)
the modified aerogel and (f) unmodified aerogel after being placed in water; (g) hydrophobic aerogel, chloroform is also chosen as tested oil to form oil/
photograph of the modified aerogel after being placed in kerosene and (h) re- water mixture. As shown in Fig. 7b, when the superhydrophobic
moved from the kerosene; (h) the effect of raw cotton fiber concentration on the aerogel (1.5 wt%) is rendered to contact the chloroform (dyed with oil
hydrophobicity of the MTMS modified aerogel. red O) underwater, the chloroform layer is instantaneously absorbed by
the aerogel and the water is strongly repelled. The outstanding se-
lectivity of the as-prepared aerogel is supposed to benefit from the well-
investigated. As shown in Fig. 6a, the sorption capacity of the modified
developed porous structure and its highly hydrophobic/oleophilic
aerogels for chloroform and kerosene decreases quickly with the in-
property. The recyclability of oil sorbents is also critical for their
crease of cotton fiber concentration. This can be explained by the fact
practical application in oil spill cleanup. In this study, the absorbed oil
that high fiber concentration will decrease the porosity of the resultant
is recovered by vacuum suction filtration of the oil-loaded aerogel [4],
aerogels, offering less space for oil uptake. Meanwhile, the fiber in the
and the recyclability of the superhydrophobic cellulose aerogels is
higher solid content aerogel are more constrained, causing a lower
evaluated after repeating the sorption-desorption process for 16 cycles.
swelling capacity. Furthermore, the sorption capacities of the super-
It should be noted that the vacuum suction filtration can avoid effec-
hydrophobic aerogel for a series of oils and organic solvents were stu-
tively the deformation of cellulose aerogel, which is beneficial to retain
died. As shown in Fig. 6b, the aerogels with the cotton fiber con-
its high sorption capacity. As illustrated in Fig. 7c, the sorption beha-
centration of 1.5 wt% show sorption capacities ranging from 19.8 to
vior is analogous for different types of oils, and no obvious decrease of
41.5 times their weight for a variety of oils and organic solvents in
saturated sorption capacity is found in the whole recycling process,
terms of the viscosity and density of absorbed liquids [7,25]. The water
suggesting good stability of the aerogel skeleton. More importantly,
contact angle and oil sorption capacity of the as-prepared cellulose
more than 90.6% of the absorbed oil can be easily harvested in this
aerogel in this study and other recently reported cellulose aerogel are
way. After being used for 18 cycles, the water contact angle of the
also compared and shown in Table 1, and the results are encouraging.
aerogels shows slight decrease (Fig. 7d), demonstrating that the aerogel
The oil sorption capacity of the obtained aerogel in this study is com-
possesses stable hydrophobicity.
parable to many reported cellulose aerogels by complicated and high-
cost approaches. Although the oil sorption capacities of hierarchical
3.5. Durability of superhydrophobic aerogels
nanocellulose aerogel foam [29] and bacterial cellulose aerogel [18]
are much larger than the as-fabricated cellulose aerogels, the super-
The resistance of the as-prepared cellulose aerogels towards various
hydrophobic aerogel based on raw cotton fiber is much easier to pre-
corrosive solutions was studied. Fig. 8a reveals the digital images of
pare for oily wastewater treatment due to relatively low cost and
acidic (1 M HCl), alkaline (1 M NaOH), salty (1 M NaCl), and hot water
simple, green preparation process. It would be specially mentioned that
droplets on the aerogel surface. It can be observed that all the three
the fabrication route of this cotton fiber-based aerogel is entirely dif-
corrosive droplets and hot water present spherical shape. After the
ferent from the cellulose aerogels having been widely reported. Most of
aerogels are immersed in various corrosive solutions with different pH
cellulose aerogels are synthesized by using cellulose derivative, purified
values and salty (1 M NaCl) solutions for 24 h, they still possess high
cotton linter, or nanocellulose separated from cotton fiber as starting
hydrophobicity with the water contact angle of over 146.5° (Fig. 8b).
materials, the obtainment of cellulose aerogel by one-step remodeling
Such special durability towards corrosive solutions derives from the
of raw cotton fiber is very rare. Fig. 6c reveals the sorption rate of the
existence of air cushion between the aerogel surface and the corrosive

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Fig. 6. (a) Oil sorption capacity of superhydrophobic cellulose aerogels with different raw cotton fiber concentration; (b) oil and organic solvent sorption capacities
of the superhydrophobic aerogel with fiber concentration of 1.5 wt%; (c) the sorption kinetics of superhydrophobic aerogels with different fiber concentration for the
three types of oils; (d) the retention performance of the superhydrophobic aerogel with different weights.

Table 1
Comparison of the as-prepared aerogel and other recently reported cellulose-based aerogels.
Definition Starting materials Water contact Types of oil Sorption capacity Reference
angle (g/g)

Cellulose nanofibril aerogel Cellulose nanofibrils, n-butyl acrylate, styrene, ethylene 149° Toluene 30 [13]
Chloroform 46.6
Cellulose aerogel Paper waste cellulose fibers 145° Crude oil ∼18.5 [26]
Nanocellulose sponge Nanocellulose 160° N-hexane 33 [27]
Toluene 38
Cotton-cellulose aerogels Cellulose fibers from paper waste, cotton strands, < 142.8° N-hexane 40 [28]
polyamide-epichlorohydrin
Hierarchical nanocellulose aerogel Nanocellulose and sodium dodecylsulfate < 90° Cyclohexane 206.8 [29]
foam Vacuum pump oil 145
Bacterial cellulose aerogel Bacterial cellulose 146.5° N-hexane ∼85 [18]
Toluene ∼110
Gasoline ∼100
Macroporous cellulose aerogel Raw cotton fiber 154° N-hexane 19.8 This work
Toluene 25.7
Choroform 41.5

solutions in the immersion process, which acts as an effective obstacle
to prevent the corrosion of the solutions to aerogel architecture. In
addition, no obvious decrease in the water contact angle is observed
after the fabricated aerogels are immersed into different oils (n-hexane,
toluene, chloroform, kerosene, gasoline, and diesel) for 1 h (Fig. 8c).
Hence, these results mean that the as-fabricated cellulose aerogels have
a certain resistance to corrosive solutions and oils, which is crucial for
the oily wastewater treatment under harsh environments.
The mechanical durability of the as-prepared aerogel was also tested
through abrasion with a piece of sandpaper [30]. The 200 mesh sand-
paper acts as abrasion surface, and the mechanical stability of super-
hydrophobic cellulose aerogel is evaluated after abrasion for different
times using the sandpaper. Obviously, no any change in the water
contact angles of the aerogel can be observed in the abrasion tests of 80
cycles (Fig. 8d), and near-spherical water droplets still can stand on the
aerogel surface steadily (Fig. 8e). This indicates that the resultant
aerogel still maintains stable and high hydrophobicity after the initial
aerogel surface is subjected to serious destruction. This phenomenon

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J. Wang and S. Liu Separation and Purification Technology 221 (2019) 303–310

Fig. 7. Removal of (a) red-colored kerosene

on water surface and (b) red-colored
chloroform underwater using super-
hydrophobic cellulose aerogel; (c) recycl-
ability of the superhydrophobic aerogel: O3-
O18=oil sorption cycle condition, D3-
D15 = oil desorption cycle condition; (d)
water contact angles of superhydrophobic
aerogel after being recycled for different
cycles. (For interpretation of the references
to colour in this figure legend, the reader is
referred to the web version of this article.)

Fig. 8. (a) Photograghs of 1 M HCl, 1 M NaOH, 1 M NaCl solutions and hot water on the superhydrophobic aerogel; water contact angles of the resultant aerogels after
being immersed into various (b) corrosive solutions for 24 h and (c) oils for 1 h; (d) change in water contact angles of the superhydrophobic aerogel with scraping
cycles; (e) the photographs of water droplets on the aerogel surface after being scraped for 20, 40, 60, and 80 cycles; (f) the regeneration of new superhydrophobic
porous structure.

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J. Wang and S. Liu
can be attributed to the fact that the as-fabricated cellulose aerogel
possesses irregular micro/nano-porous network structure and its ske-
leton surfaces are completely covered by the chemicals with low surface
energy. A new hierarchical surface with fresh hydrophobic chemicals
will be exposed once the outer cellulose material is scraped (Fig. 8f),
leading to the hydrophobicity of the aerogel after the abrasion. It is also
demonstrated from this study that the obtained cellulose aerogel can
sustain numerous abrasions and remain its superhydrophobicity in ac-
tual application.
4. Conclusions
A light-weight macroporous cellulose aerogel was successfully fab-
ricated via a simple and inexpensive dissolution-regeneration route
using broadly available and cheap raw cotton fiber as starting material.
After being modified with MTMS, the aerogel reveals strong water re-
pellency with water contact angle higher than 154°. The obtained
aerogels can absorb various oils and organic solvents up to 19.8–41.5
times its own weight. Compared with those cellulose aerogels reported
in literature [13,27,29], our cotton fiber-derived aerogel has lower cost
and is easier to realize large-scale production and application as oil-
absorbing materials. Moreover, the as-fabricated aerogels exhibit quick
sorption rate, good oil-retention ability, oil/water selectivity, and re-
cyclability. More importantly, the aerogels demonstrate eminent su-
perhydrophobic stability under harsh environments (acidic, alkaline,
salty solutions and oils), and can resist numerous mechanical abrasions
without obvious loss of superhydrophobicity. Therefore, in view of the
superior sorption performance, environment friendliness of feedstock,
and simple preparation process, the superhydrophobic cellulose aerogel
based on direct dissolution-regeneration of raw cotton fiber is a pro-
mising candidate for selective cleanup and recovery of spilled oil from
water.
Acknowledgments
This research was supported by the key scientific research project in
2019 at North Minzu University (No. 2019KJ11), the National Natural
Science Foundation of China (No. 21767001), the Key Laboratory
Project of 'Powder Materials and Advanced Ceramics' Cofounded by
Ninxia Province and State Ethnic Affairs Commission (No. 1801), and
the Third Batch of Ningxia Youth Talents Supporting Program
(TJGC2018019).
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