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Hydrophobic and flexible cellulose aerogel as an

efficient, green and reusable oil sorbent†
Cite this: RSC Adv., 2015, 5, 82027
Runjun Lin, Ang Li, Tingting Zheng, Lingbin Lu* and Yang Cao

Received 30th July 2015
Accepted 21st September 2015
DOI: 10.1039/c5ra15194e
www.rsc.org/advances
Adsorbent materials as well as hydrophobic modification methods have been at the forefront of research
creating environmentally hazardous waste. Herein, we report a facile, green preparation method for
cellulose aerogels. Cold plasma technology was employed for hydrophobic modification of the aerogel
surface using trimethyl-chlorosilane (TMCS) as the plasma. Notably, the modification procedure was
considerably more rapid (less than 3 min), more efficient and economically viable than traditional
methods. The highly flexible modified cellulose aerogels are hydrophobic (ca. 150
), oleophilic and
ultralight (as low as 0.0196 g cm3). Compared to conventional oil adsorbent materials, these low-cost,
environment-friendly cellulose aerogels exhibit excellent adsorption properties (peanut oil, 34.5 g g1) as
well as remarkable reusability (more than 15 times). Therefore, the preset work would play a significant
role in further advancing the fields of adsorbent materials and hydrophobic modification methods.

necessary. Cellulose aerogels have been investigated for

Introduction
Frequent oil spills and increasing amounts of organic contam-
inants have caused severe damage to our environment and
ecosystem.1 Currently, the most prevailing technologies use
porous or semi-porous materials with high adsorption capac-
ities, and these materials can remove organic contaminants
from water. There are several efficient absorbent materials
currently available, such as twisted carbon ber aerogels (TCF),2
carbon nanotube sponges (CNT),3–5 cellulose nanobril aerogels
(CNF),6,7 cellulose nanocrystal aerogels (CNC),8 ultra-yweight
aerogels (UFAs),9 graphene oxide aerogels (GO)10,11 etc. which
exhibit high oil capacities as well as excellent reusability.
However, the majority of these materials are either carbon
based or nano-sized materials or both. Such materials are not
only too expensive for commercial applications, but the prepa-
ration of these materials also involves complicated and
sophisticated processes. Therefore, developing alternative
materials which are suitable for commercial purposes is
Key Lab of Advanced Materials of Tropical Island Resources, Ministry of Education,
College of Materials and Chemical Engineering, Hainan University, No. 58, Renmin
Avenue, Haikou 570228, Hainan, China. E-mail: lulingbin@126.com
† Electronic supplementary information (ESI) available: Table S1–S3 list the
compressive strength data of 2 wt% cellulose aerogel, adsorption capacity of 3
wt% modied cellulose aerogel, and the atomic composition of cellulose
aerogel before and aer hydrophobic modication, respectively. Fig. S1–S5
illustrate the N2 sorption isotherms of 3 wt% cellulose aerogels, compressive
strain–stress proles, and adsorption capacities versus modication time, the
silylation of cellulose with TMCS, and NMR spectra of cellulose aerogels before
and aer hydrophobic modication, respectively. In addition, supplementary
Video 1 and Video 2 exhibit exibility and hydrophobic and oleophilic
properties of modied cellulose aerogels, respectively. See DOI:
10.1039/c5ra15194e
decades and they have shown great potential to be applied as
heat insulators,12 catalyst carriers, and for contaminant
adsorption;13,14 cellulose-based drug delivery systems have been
extensively studied. Due to its abundance, renewability and
nontoxicity, cellulose aerogels have been an area of focus in
materials research.15,16 Cellulose aerogels have attracted exten-
sive attention, especially, in absorbent materials research.17 The
major driving force behind the intense activity in this area is the
increasingly harsh environment, and the environmentally
friendly, low-cost and reusable properties of cellulose aerogels
make them potential alternative absorbents.
Hydrophobic modication of adsorbents is an essential
process to achieve efficient separation of organic contaminants
from water. Cellulose aerogels contain a large number of
hydroxyl groups. Although these hydroxyl groups cause strong
hydrophilia they provide many chemical sites for hydrophobic
modication at the same time. Hydrophobic modication has
been widely studied and applied in various elds such as anti-
freezing,18–20 gene transfection,21,22 coating,23,24 oil separation,25
etc. Organosiloxanes26,27 or silanes28,29 are the most common
modiers, that exert a signicant hydrophobic effect. However,
there are several disadvantages of the modication process.
First of all, these chemicals are not only expensive, but they are
too unstable to store. Secondly, organosiloxane or silanes are
mostly utilized in sol–gel methods or even vapor deposition
methods.29 These methods not only consume a large quantity of
the modiers but also change the inner structure of the
samples; however, they introduce excellent hydrophobic prop-
erties. In addition, poor efficiency and long modication
periods for these methods make them less favorable for further
application.

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Surface modication using cold plasma technology has been
developed to introduce hydrophobicity onto the surface of
materials. In this regard, cold plasma technology is thought to
be the optimal method, because the depth of plasma-induced
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deposition is only a few nanometers;30 this means that the
inner structure of a sample still remains hydrophilic while its
surface becomes hydrophobic. Although CCl4, CF4, SF6, etc. are
generally deemed as the ideal plasmas,31,32 there are several
associated problems, such as high discharge power, long
modication periods and medium hydrophobic effect, which
need to be solved.
Herein, we report a facile and green method for preparing
light-weight, porous cellulose aerogels. Our objective was to
develop an environment-friendly, economically viable adsor-
bent material that not only possesses high adsorbent capacity
but also exhibits improved reusability compared to traditional
adsorbents, whose oil intake can be up to ca. 15 times their
original dry weight.33 Surface modication of cellulose aerogels
was achieved through a cold plasma method using trimethyl-
chlorosilane (TMCS) as the plasma. The mechanical proper-
ties of the hydrophobic, oleophilic, ultralight cellulose aerogels
were studied. In addition, we attempted to understand the
mechanism involved in the hydrophobic modication.
Experimental section
Materials
Cellulose (cotton linter), provided by Hubei Chemical Fiber Co.,
Ltd, was used without further purication. The a-cellulose
content of the cellulose was more than 95%. Mh was measured
to be 1.01  105 with cadmium ethylenediamine (cadoxen) as
the solvent at 25
C using a viscometer [where, h ¼ 3.85  102
M0.76 (mL g1)34]. Sodium hydroxide (NaOH) and urea
((NH2)2CO) were purchased from Guangzhou Chemical
Reagents Factory and Guangdong Guanghua Chemical Factory
Co., Ltd, respectively. Trimethyl-chlorosilane (TMCS) and
sulfuric acid were purchased from Aladdin Industrial Corpora-
tion and Luoyang Chemical Factory respectively. All chemical
reagents were used without further purication. Deionized
water was used for all experiments unless otherwise mentioned.
Preparation of cellulose aerogels
Cellulose was repeatedly rinsed with distilled water and anhy-
drous ethanol and dried. To obtain an alkaline sol, the dried
cellulose was then added into a precooled (18
C for 20 min)
aqueous solution containing NaOH and urea with constant
stirring; the weight percentages of cellulose, NaOH and urea in
the nal mixture were 1–5%, 7% and 12%, respectively. The
cellulose alkaline sol was ultrasonicated (to eliminate bubbles)
before injected into molds. Next, 17 wt% sulfuric acid solution,
used as coagulator, was dropped into the cellulose alkaline sol
slowly, and nally, cellulose gel was obtained aer 6 h of
undisturbed immersion. Subsequently, the gels were washed
with deionized water repeatedly. For freeze-drying, the washed
samples were rst frozen at 80
C for at least 12 h and then
lyophilized in a precooled lyophilizer for approximately 48 h.
82028 | RSC Adv., 2015, 5, 82027–82033
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Cold plasma hydrophobic modication
Hydrophobic cellulose aerogels were prepared using HD-1A
plasma equipment provided by the Chinese Academy of
Sciences; TMCS was used as the cold plasma. In the plasma
equipment, the plasma excitation uses a glow discharge with a
variable power, which is coupled to a reactor. The incident
power (Pi) and the reected power (Pr) are measured with a
power meter. The impedance is adjusted until the reected
power is very low (Pr < 1 W). Dry cellulose aerogels were placed
in the cold plasma chamber and treated under a glow discharge
system. The discharge system was then started when the
vacuum degree reached a constant value (ca. 200  50 Pa in
these experiments). The hydrophobic aerogels were nally
obtained aer discharging under a specied power (150 W in
these experiments) and time (2–15 min in these experiments).
Characterization
Estimation of density and porosity. Bulk density of cellulose
aerogel (rb) was dened as the ratio of the aerogel’s mass to its
volume. Porosity of cellulose aerogel was calculated using the
following equation: porosity (%) ¼ 1  rb/rs where, rb and rs
represent the bulk density and skeletal density of cellulose
aerogel, respectively. rs-cellulose ¼ 1.528 g cm3.
Liquid adsorption capacity (Cm). To determine liquid
adsorption capacity of the cellulose aerogels, different solvents
were examined including water, diesel, ethanol, gasoline,
peanut oil, and pump oil. A 2 wt% cellulose aerogel was
immersed in a given solvent for 10 min, and the weights of the
aerogels before (Wbefore) and aer (Waer) solvent uptake were
measured. The corresponding adsorption capacity was calcu-
lated using the following equation.
Cm (g g1) ¼ (Wafter  Wbefore)/Wbefore
Each sample was tested more than three times to obtain an
average value.
Evaluation of compressive properties. The cellulose aerogels
were molded in a cuboid (40 mm  40 mm  10 mm) shape.
While evaluating compressive properties in air as the medium,
the cellulose aerogels were dried in an electric oven at 60
C for
6 h prior to the measurements; however, for other media, the
cellulose aerogels were soaked in the corresponding media until
saturated adsorption was reached, prior to the measurements.
Compressive tests were performed with a microcomputer
controlled electronic universal testing machine provided by
Jinan HengXu Testing Machine Technology Co., Ltd. The
sample was placed between the testing plates and compressed
with a speed of 0.3 mm min1 to 90% of its original thickness.
Three replicates were measured for each sample.
Analysis of structure and morphology. The chemical struc-
ture of the cellulose aerogel was investigated and compared
with modied cellulose aerogel using an FTIR spectrometer
(model: TENSOR 27, Bruker) with a resolution of 1 cm1.
Morphology was examined using a scanning electron micro-
scope (SEM) (model: S-4800N, Hitachi, Japan) with an
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acceleration voltage of 10 kV aer 60 s of metallization with Au.
The solid state 13C-NMR spectrum was recorded at room
temperature, using a 4 mm CP-MAS probe on a Bruker Advance
III 400 Hz NMR spectrometer. Approximately 200 mg of dried
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material was cryo-ground to a ne powder and packed in 7 mm
zirconia rotors. The surface chemical composition of the
samples was analyzed using X-ray photoelectron spectroscopy
(XPS, PHI-5300) with an Al Ka radiation source. No degradation
of the specimens during the XPS analyses was detected.
Results and discussion
Characterization of the cellulose aerogels
We prepared light-weight and porous cellulose aerogels using a
facile method. Fig. 1 depicts the density and porosity of the
cellulose aerogels. It is evident from Fig. 1 that with decreasing
cellulose concentration, the sample density could reach as low
as 0.0196 g cm3, while the porosity could be as high as 98.7%.
This is dominantly caused by the increased stacking
compactness of the cellulose bers. At high cellulose concen-
trations, cellulose bers interact and pile with each other
densely, leading to a robust structure. Fig. 2 illustrates repre-
sentative SEM micrographs of the cellulose aerogel samples. A
woven porous three-dimensional network structure can be seen,
and the diameter of the bers is generally equal to ca. 20 mm, a
typical size of cellulose bers dissolved in NaOH/urea solu-
tion.35 No signicant changes were observed aer hydrophobic
modication. Fig. S1† shows the nitrogen sorption isotherms of
the 3 wt% cellulose aerogel. It obviously belongs to Type II
according to IUPAC, which means that the cellulose aerogels
have a non-porous structure and the cellulose chains intertwine
each other, leaving large amounts of space. As reported by Isobe
et al.,36 cellulose dissolves in NaOH/urea solution by forming a
shell surrounded with alkali hydrates, urea hydrates and free
water, which could penetrate into the cellulose, destroying
intra- and inter-molecular hydrogen bonds. In the present
study, we destroyed the complex shell by treating it with sulfuric
acid solution. As is evident from the SEM micrographs (Fig. 2),
Fig. 1 Density and porosity of cellulose aerogels with increasing
cellulose concentration. The two photographs show the sample
placed on a flower petal (left) and Setaria viridis (right), respectively.
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Fig. 2SEM images of the 3 wt% cellulose aerogel before (a) and after
hydrophobic modification (b).
the bers in the shell as well as the spatial conformation are
preserved. The surface of the bers is clean and at, indicating
complete removal of solvent. As a result, the cellulose aerogel
properties, including the adsorption properties and mechanical
properties, were affected.
Adsorption properties and reusability
We examined the liquid adsorption capacity (Cm) of the cellu-
lose aerogels, as exhibited in Fig. 3. It is evident from Fig. 3a
that the adsorption capacity of the cellulose aerogels decreases
rapidly with increasing cellulose concentration. This is due to
the ascending density but decreasing porosity of the cellulose
aerogels with increasing cellulose concentration, providing less
space for solvent uptake. Compared with commercial oil
sorbent sheets, the cellulose aerogels exhibit a higher adsorp-
tion capacity, suggesting that cellulose aerogels can also be
used as efficient contaminant sorbents besides the advantages
mentioned above. Fig. 3b presents the adsorption capacities of
the 2 wt% cellulose aerogel in different solvents and the data
further conrm that cellulose aerogels have great potential to be
used as sorbents of various solvents and oils.
Unlike conventional low-density aerogels that are brittle and
fragile,37 the cellulose aerogels prepared in the current study
exhibit high exibility due to their porous three-dimensional
woven network structure (ESI Video 1†). Table S1† lists the
compressive properties of the 2 wt% cellulose aerogels in
different media. Our data revealed that the cellulose aerogels
can be compressed without disintegration aer being subjected
to a strain of 90%. However, we observed that the samples did
not return to their original features aer relieving the
compressive load. This could be due to a lack of a restoring
Fig. 3 (a) Tap-water and peanut oil adsorption capacities of cellulose
aerogels with increasing cellulose concentration; (b) adsorption
capacities of 2 wt% cellulose aerogel, examined for various solvents.
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force related to the inner structure of the gel, and SEM images
(Fig. 2) reveal a porous and interconnected 3D network struc-
ture of the cellulose aerogel. Compared to the twisted carbon
bers fabricated by Bi et al.,2 the cellulose bers are less twisted.
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Apparently, in addition to the effects of the sample’s inner

characteristics, other factors, such as temperature, anisotropy,
humidity and medium, affect the mechanical properties of the
sample, as revealed in Fig. S2.†
To test the reusability of the aerogels, we immersed an aer-
ogel in an organic solvent (ethanol) and measured the weight
before and aer drying; the experiment was repeated 15 times.
In this experiment, the cellulose aerogel was dried in a vacuum
oven at 50
C aer each adsorption cycle. The results shown in
Fig. 4 suggest that the adsorption capacity of the cellulose aer- Fig. 5 Water contact angle of the 3 wt% cellulose aerogel versus cold
ogel remains more or less constant even aer being used for plasma modification time.
several cycles. The slight increment in adsorption capacity aer
cycle 1 could be due to washing out the residuum of the cellu-
lose aerogel by ethanol. The results above together indicate that Fig. 6b clearly shows that diesel is readily absorbed, while the
cellulose aerogels have a good reusability as the organic MAO droplet still retains its spherical shape. Cold plasma
contaminants can be washed out by ethanol or are soluble in technology is dened as an external modication technology,
ethanol. because the depth of the deposition of the plasma-induced
treatment is only a few nanometers over the surface. However,
Hydrophobic modication even aer slicing the modied aerogel into halves, the section
still retains its hydrophobic character, as shown in Fig. 6c (we
To achieve water/oil separation, cellulose aerogels were modi-
could not measure the water contact angle due to the uneven
ed using cold plasma technology. Fig. 5 presents a plot of
section). It can be collectively attributed to the high chemical
water contact angle versus modication time at a constant
activities of cold plasmas and the porous structures of cellulose
power (150 W). Clearly, the average water contact angle of the
aerogels. Fig. 6d presents an image that clearly captures the
modied cellulose aerogels could reach ca. 150
, which means
separation of CCl4 (dyed with iodine) from water using a
that the modied aerogels are hydrophobic enough to separate
modied cellulose aerogel. Further details are provided in ESI
oil from water. It is worth noting that the modication process
Video 2.† However, compared to unmodied cellulose aerogels,
took less than 3 min. To the best of our knowledge, this is a
we did not nd any signicant change in the oil adsorption
considerably more efficient and rapid method than any repor-
capacity of the modied cellulose aerogels, as listed in Table
ted to date. In addition, the oil adsorption capacity versus
S2.†
modication time is also depicted in Fig. S3,† and no signicant
For further understanding hydrophobic modication
changes were observed.
mechanism, we compared the XPS survey spectra of the
The photographs presented in Fig. 6 show the selective
unmodied cellulose aerogel and modied cellulose aerogel
adsorption properties of the cellulose aerogels. It is evident
(Fig. 7). Before data analysis, the survey spectra were charge
from Fig. 6a that the surface of the unmodied cellulose aerogel
is extremely hydrophilic and oleophilic; the surface readily and
rapidly adsorbs the droplets of methyl orange aqueous (MOA)
and diesel. In contrast, the surface of the modied cellulose
aerogel exhibits ultra-hydrophobic but oleophilic properties.

Fig. 4 Recyclability study of the cellulose aerogels. 15 cycles and 10

cycles of adsorption–evaporation (with vacuum drying) were applied
to recycle unused 3 wt% cellulose aerogel (a) and modified cellulose
aerogel (b) for sorption of ethanol, respectively. The inset picture
shows that the modified cellulose aerogel was still hydrophobic after
being used for 10 cycles.
Fig. 6 (a) Unmodified cellulose aerogel is hydrophilic and oleophobic;
(b) modified cellulose aerogel is oleophilic but hydrophobic; (c) the
inner section of modified cellulose aerogel retains its hydrophobicity.
(d) The separation of CCl4 (dyed with iodine) from water using
modified cellulose aerogel (ESI Video 2†).

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Fig. 7 XPS low-resolution survey spectra of cellulose aerogel before
(a) and after (b) hydrophobic modification.
corrected using the graphite component of the C 1s signal at
284.6 eV. It is evident from Fig. 7 that the unmodied cellulose
aerogels only show O 1s and C 1s peaks near 584 eV and 285 eV,
respectively. However, two additional peaks near 150 eV and 100
eV, corresponding to Si 2s and Si 2p, respectively, are observed
in the spectrum of the modied cellulose aerogel, indicating the
presence of silicon on the surface.38 Fig. 8a depicts the high-
resolution spectrum of the C 1s peak, providing information
on the carbon chemistry. As reported earlier39,40 the carbon
signal can be resolved into four distinct peaks, each reecting
the local chemical environment of the carbon atoms. The four
component peaks are, therefore, categorized as follows: (i) the
C-1 peak corresponds to no oxygen bonds, (ii) the C-2 peak
corresponds to carbons with one oxygen bond (assigned to C–
O– and C–OH), (iii) the C-3 peak corresponds to carbons with
Fig. 8 High-resolution XPS survey spectra of the C 1s peak, O 1s peak and Si 2p peak.
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two oxygen bonds (assigned to –O–C–O–), and (iv) the C-4 peak
corresponds to carbons with three oxygen bonds (carbocylic C).
By comparing the two C 1s spectra, remarkable differences can
be seen, as shown in Fig. 8a and b. The intensity of the C-1 peak,
attributed to aliphatic carbon, increases dramatically, while the
intensities of the other carbon peaks decline. Table S3†
summarizes the atomic compositions based on the relative
peak areas in the high-resolution XPS survey spectra of C 1s of
the investigated samples. We believe that silylation could be
responsible for these changes. As depicted in Fig. S4,† during
the silylation procedure, TMCS reacts with the surface hydroxyl
groups of the cellulose aerogels.38 The high-resolution XPS
spectra of Si 2p also conrm this assumption.41 Compared to
traditional sol–gel or hydrolysis methods, cold plasma tech-
nology can efficiently and rapidly provide more energy for the
activation of trimethyl-silane that is required for silylation,
forming hydrophobic cellulose aerogels.
In addition, slight decreases in binding energies could be
observed aer cold plasma modication in both the C 1s
spectrum and O 1s spectrum. Two factors, including broken
inner hydrogen bonds and increased electron cloud density of
the six-membered rings in cellulose chains, may account for the
chemical shi. As cellulose transforms form hydrophilic to
hydrophobic, trimethyl-silane radicals replaced the hydrogens
of hydroxyl groups and linked to the cellulose chains by C–O–Si
bonds. The solid state 13C-NMR spectra of unmodied and
modied cellulose aerogels also testify our assumption. Fig. S5†
shows that the chemical shis of C-1 and C-4 in the modied
cellulose aerogels do not change compared to the unmodied
cellulose aerogels. However, the C-2, C-3 and C-5 split remark-
ably, and the peak of C-6 shis to higher eld. All of these
ndings together indicate that the numbers of inner hydrogen
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bonds are reduced and the homogenous electron density is
broken. Consequently, the electron density increases, while the
binding energies of O 1s and C 1s decrease.
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Conclusions
We developed a hydrophobic, ultralight, porous and exible
cellulose aerogel with excellent adsorption properties and
reusability in a considerably facile and rapid way. The adsorp-
tion capacity of these cellulose aerogels is not only dramatically
higher than commercial oil adsorbent sheets, but the capacity
remains more or less constant even aer 15 cycles. The average
water contact angle of the cellulose aerogels is ca. 150
. The
hydrophobic modication procedure of these aerogels, based
on cold plasma technology with TMCS as the plasma, took less
than 3 min. Modied cellulose aerogels can successfully sepa-
rate organic contaminants from water. The hydrophobic
modication mechanism, analyzed using several methods,
indicates that TMCS rst activates to form a trimethyl-silane
radical and then reacts with hydroxyls groups forming C–O–
Si(CH3)3 bonds using the high energy provided by the cold
plasma technology. Importantly, here we report a breakthrough
procedure. Our method not only modies the surface chemical
composition but it also alters the inner structure of the aerogels
because of the high activity of the modier. These modied
cellulose aerogels are environment-friendly, green, reusable,
abundant, and highly absorbent materials. Therefore, these
cellulose aerogels can be used for separating organic contami-
nants. Notably, compared to traditional sol–gel, hydrolysis or
immersion methods using organosiloxane as the modier, cold
plasma technology with an organosiloxane as the plasma is an
extremely efficient, rapid, cheap and environment-friendly
procedure.
Conflict of Interest
The authors declare no competing nancial interest.
Acknowledgements
The authors acknowledge nancial support from the Projects of
Science Foundation of Hainan Province (No. 512113) and the
Special Fund for Integrated Industry-University-Research of
Hainan Province (No. Cxy20140039).
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