Article

www.acsnano.org

Carbon Microtube Aerogel Derived from

Kapok Fiber: An Efficient and Recyclable
Sorbent for Oils and Organic Solvents
Pin Song, Jiewu Cui, Jun Di, Daobin Liu, Manzhang Xu, Bijun Tang, Qingsheng Zeng, Jun Xiong,
Changda Wang, Qun He, Lixing Kang, Jiadong Zhou, Ruihuan Duan, Bingbing Chen, Shasha Guo,
Fucai Liu, Jun Shen, and Zheng Liu*
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

Cite This: ACS Nano 2020, 14, 595−602 Read Online

Downloaded via NATL LBRY OF SERBIA on February 21, 2020 at 10:37:38 (UTC).

ACCESS Metrics & More Article Recommendations *

sı Supporting Information

ABSTRACT: A carbon microtube aerogel (CMA) with hydro-

phobicity, strong adsorption capacity, and superb recyclability was
obtained by a feasible approach with economical raw material, such as
kapok fiber. The CMA possesses a great adsorption capacity of 78−
348 times its weight. Attributed to its outstanding thermal stability
and excellent mechanical properties, the CMA can be used for many
cycles of distillation, squeezing, and combustion without degradation,
which suggests a potential practical application in oil−water
separation. In addition, the adsorption capacity still retained 98%
by distillation, 97% by squeezing, and 90% by combustion after 10
cycles. Therefore, the obtained CMA has a broad prospect as an
economical, efficient, and environmentally friendly adsorbent.
KEYWORDS: kapok fiber, carbon microtube aerogel, hydrophobicity, oil−water separation, adsorption capacity, environmental protection

their industrial application.19,22 It has been proven that

I t is well-known that there is an urgent need to develop an

economically viable strategy to solve the problem of
environmental pollution, which is caused by petroleum
derivatives and various toxic and harmful organic solvents.1−4
Although a few methods, such as combustion and adsorption,
were used to tackle this problem, commonly used adsorbents,
including expanded perlite,5 zeolite,6 and activated carbon,7
not only show inefficiency but also may introduce other types
of pollutants.2,5−11
Due to the excellent properties of the three-dimensional
(3D) carbon-based network including low density, good
conductivity, high porosity, and large specific surface area,
many studies and applications have been demonstrated in
catalyst carriers, supercapacitors, gas sensors, and other
fields.12−16 More interestingly, the excellent hydrophobicity
of the 3D carbon-based network makes it promising for the
oil−water separation. Generally speaking, there were several
types of carbon-based frameworks in the 3D network,
including organic aerogels that can be pyrolyzed in an inert
atmosphere,17,18 carbon nanotube (CNT) sponges,19 and self-
gelating graphene aerogel.4,20,21 However, the obtained organic
aerogel is brittle, dense, and less efficient for oil absorption.17,18
Furthermore, the preparation of CNT sponges requires
complex equipment and expensive precursors, which hinders
graphene-based aerogels have high adsorption performance
and excellent recyclability for oils and organic solvents.4
However, in the process of preparing graphene oxide, a large
amount of acid waste will be produced, which seriously
restricts the industrial production. Therefore, it is urgent to
develop a simple, economical, and efficient method to
synthesize the large-scale carbon-based aerogel.
Natural materials are attracting more and more attention
because of their advantages. These include abundant sources,
low cost, and nontoxicity.12,23,24 Cellulose is abundant in
natural storage, which has the advantages of sustainability and
environmental protection. In recent years, carbon nanofiber
aerogels with good oil absorption and organic solvent
properties were prepared from synthetic bacterial cellulose.12
However, the complex production process and high cost limit
its industrial application. Raw cotton is a typical natural
material at a low price. It contains 90−95% cellulose and is
Received: September 5, 2019
Accepted: December 31, 2019
Published: December 31, 2019

© 2019 American Chemical Society https://dx.doi.org/10.1021/acsnano.9b07063

595 ACS Nano 2020, 14, 595−602
ACS Nano www.acsnano.org
regarded as the most promising candidate material for making
carbon-based aerogels.25,26 Although raw cotton fiber has been
widely used in the adsorption of dyes,27,28 heavy metals,29 and
heavy oils,30,31 it has apparent disadvantages of hydrophobicity,
low adsorption capacity, poor buoyancy, and unsatisfactory
recyclability. Thus, it hinders further application in oil−water
separation. Herein, a light, hydrophobic, and porous carbon
microtube aerogel (CMA) was fabricated via a facile method
using kapok fiber as the starting material. It is worth
mentioning that CMA displays high absorption capacity with
various organic solvents and oils, and its maximum adsorption
capacity can be up to 348 times the weight of the original
CMA. In addition, the CMA also had good recyclability, even
after distillation, combustion, or squeezing for 10 times. These
characteristics make CMA a promising candidate for oil−water
separation.
RESULTS AND DISCUSSION
The cylindrical kapok fiber underwent pyrolysis at 800 °C for 6
h in an inert atmosphere of argon to obtain the carbon
Figure 1. Optical photograph of the synthesis of a carbon
microtube by carbonization of kapok fiber. (a) Kapok fiber. (b)
Carbon microtube. (c) SEM image of the kapok fiber. Inset:
Optical photograph of a kapok fiber. (d) SEM image of the carbon
microtube. Inset: Optical photo of CMA.
microtube (Figure 1a,b). After pyrolysis, the size of the
cylindrical kapok fiber is changed, with a decrease from 3 to 2
cm in diameter and from 2 to 1 cm in height (insets in Figure
1c,d, respectively). As shown in Figure 1c,d, the kapok fibers
have an interconnected 3D porous structure. After the kapok
fibers were pyrolyzed into carbon microtubes, their tubular
structures were retained and show a length of several microns.
Meanwhile, the diameter of the kapok fiber was reduced from
15 to 30 μm to 10−20 μm after carbonization (Figure S1,
Supporting Information). High-magnification scanning elec-
tron microscopy (SEM) images show kapok fiber with a
diameter of 15−30 μm and length of 80−200 μm (Figure
S2a,c, Supporting Information). The diameter of the carbon
microtube is 10−20 μm with a length of 60−150 μm (Figure
S2b,d, Supporting Information).
Figure 2a shows the thermogravimetric analysis (TGA)
curves of the kapok fiber. The weight of the kapok fiber
decreased slightly (∼5%) in the temperature range of 20 to 78
°C, which contributed to the loss of moisture. After that, the
weight of the kapok fiber decreased sharply (∼77%) from 235
to 405 °C, indicating that the major reactions happened in this
section. As a result, ∼11% weight of the original materials
596
Article
Figure 2. (a) TGA curve of the kapok fiber. (b) Raman spectra of
the kapok fiber and carbon microtubes that are carbonized at the
temperatures of 600, 700, and 800 °C. (c) Peak density ratio of D-
band over G-band of samples carbonized at different temperatures.
(d) Nitrogen adsorption (blue circles) and desorption (red circles)
isotherm of the carbon microtubes carbonized at 800 °C.
remained, and this value is unchanged even when the
temperatures increase to ∼800 °C, suggesting no more
chemical reactions occurred at this stage. The TGA result of
the kapok fiber shows that the carbonization process mainly
occurred in the temperature windows of 235−405 °C. It has
been shown that the high temperature was beneficial to obtain
the high specific area and porous carbon structures.32 Hence,
we tried to improve the adsorption performance of carbon
microtubes by increasing the carbonization temperature. The
chemical structures of the carbon microtubes were investigated
using Raman spectroscopy. Figure 2b show two peaks found at
1595 cm−1 (G-band) and 1340 cm−1 (D-band) due to the
stretching of in-plane C−C bonds and the defect of the carbon
crystallite that is attributed to form amorphous carbon in the
fiber.33,34 The intensity ratio (ID/IG) increased from 0.97 to 1
(Figure 2c), suggesting structural defects of the carbon
microtubes grew with the increase of carbonization temper-
ature.35 Figure 2d and Figure S3 show the N2 adsorption−
desorption isotherms. The Brunauer−Emmett−Teller (BET)
surface areas are 206, 276, and 324 m2/g at 600, 700, and 800
°C, respectively (Table S1, Supporting Information). These
results show that the high temperature can improve the
porosity density and specific surface areas of carbon micro-
tubes.
Figure 3 shows the X-ray photoelectron spectroscopy (XPS)
spectra of the kapok fiber and the carbonized samples. These
composites consist of C and O elements. The C 1s peaks are
divided into two peaks which can be attributed to CC/C−C
(284.31 eV) and C−O (285.13 eV) groups.36 These results
indicate the CC/C−C bonds increase and the C−O bonds
decrease with the increase of carbonization temperature.
Energy-dispersive spectroscopy results are shown in Table
S2; the oxygen content decreased with the increase of the
carbonization temperature, and the content was ∼2.4% at 800
°C, indicating the decarboxylation and dehydration occurred
during the reaction process.37 However, the oxygen still exists
after the carbonization, which may be caused by the absorption
of oxygen from air or partial carbonization.
https://dx.doi.org/10.1021/acsnano.9b07063
ACS Nano 2020, 14, 595−602
ACS Nano www.acsnano.org
Figure 3. XPS of kapok fiber and carbon microtubes. XPS survey
spectra and related C 1s spectra for the kapok fiber (a,b) and the
kapok fiber carbonized at 600 °C (c,d), 700 °C (e,f), and 800 °C
(g,h).
Therefore, we carbonized the carbon microtubes at 800 °C
to ensure a good performance, and the as-treated sample was
selected as the building unit. According to Archimedes’
principle, the density of CMA is measured to be 20 mg
cm−3; it can stand on the top of a Boehmeria nivea stably
(Figure 4a). Kapok fiber is hydrophilic and can effectively
absorb water (Figure S4, Supporting Information). However,
the CMA can support water droplets due to its hydrophobicity
after the pyrolysis treatment (Figure 4b). The wettability test
of the carbon microtube was carried out with a contact angle
measurement system (Figure 4c). The CMA showed a contact
angle of about 134°, indicating the hydrophobic surface of
CMA. Herein, in order to further investigate the hydro-
phobicity of the CMA, it was clamped and completely
immersed into water. As shown in Figure 4d, the uniform
mirror reflection was ascribed to a new interface formation
between trapped air in the aerogel and surrounding water.38
Fourier transform infrared spectrometry (FTIR) was further
employed to study the wettability of kapok fiber and CMA. It
can be observed that the kapok fiber has several characteristic
peaks of hydrophilic functional groups, including the character-
597
Article
Figure 4. (a) CMA standing on a Boehmeria nivea, indicating its
ultralight property. (b) Optical photograph of a water droplet on
the CMA surface. (c) Photographs demonstrating the contact
angle of CMA with water. (d) Optical photograph of mirror
reflection can be observed, which provides strong evidence for the
hydrophobicity of the CMA.
Figure 5. Absorption of organic solvents and oils by the CMA. (a)
Photographs showing pump oil was absorbed by a CMA
completely in 10 s. (b) Absorption efficiency of the CMA for
various organic solvents and oils.
istic peaks at 3347, 2910, 1734, 1648 and 1560, 1373 and
1240, and 1034 cm−1, corresponding to the O−H stretching
vibration, CH2 and CH3 stretching vibration, CO stretching
vibration of carboxylic and ketones groups, aromatic ring
carbon skeletal stretching, C−H and C−O bending vibration,
and the region of carbohydrate or polysaccharide, respectively
(Figure S5, Supporting Information). However, all of these
peaks have disappeared in the CMA, which indicates that
CMA has converted into hydrophobic.
Moreover, the CMA has excellent mechanical properties and
is expected to be an excellent candidate for practical
https://dx.doi.org/10.1021/acsnano.9b07063
ACS Nano 2020, 14, 595−602
ACS Nano www.acsnano.org Article

Table 1. Comparison of Various Sorbent Materialsa

sorption sorption
capacity capacity
sorbent materials absorbed substances (g g−1) cost ref sorbent materials absorbed substances (g g−1) cost ref
wool-based diesel, crude oil, SN 9−15 low 6 CNF aerogels oils and organic 106−312 low 12
nonwoven 150 solvents
vegetable fiber crude oil 1−100 low 8 TCF aerogel oils and organic 50−192 low 65
polymers oils and organic 5−25 medium 10 solvents
solvents CMB aerogel oils and organic 56−188 low 53
nanowire oils and some organic 4−20 low 40 solvents
membrane solvents GMF aerogel oils and organic 60−140 low 54
exfoliated graphite heavy oil 60−90 low 41 solvents
activated carbons benzene, toluene <1 low 42 OCA aerogel oils and organic 81−171 low 55
solvents
CNT sponges oils and organic 80−180 high 19
solvents MCF aerogel oils and organic 88−228 low 56
solvents
magnetic oils 30−50 high 43
exfoliated CNF aerogels oils and organic 52−139 low 57
graphite solvents
graphene/a- cyclohexane, toluene, 10−30 high 44 SMS sponges oils and organic 82−159 low 58
FeOOH vegetable oil, etc. solvents
composite MCGA oils and organic 80−197 high 59
graphene/CNT compress oil, organic 80−140 high 45 solvents
foam solvents HAP nanowire oils and organic 83−156 low 60
graphene-based oils and organic 60−160 high 38 aerogel solvents
sponges solvents silylated wood oils and organic 16−41 low 61
carbonaceous carbonaceous 40−115 high 46 sponge solvents
nanofiber nanofiber aerogel graphene foams oils and organic 120−250 high 62
aerogel solvents
graphene sponge oils and organic 60−160 high 47 EVOH NFAs oils and organic 45−102 low 63
solvents solvents
reduced graphite oils and organic 5−40 high 48 GCTs oils and organic 250−400 high 64
oxide foam solvents solvents
nitrogen-doped oils and organic 200−600 high 49 CMA oils and organic 78−348 quite low this
graphene foam solvents solvents work
marshmallow-like oils and organic 6−15 high 50 a
UFAs, ultra-flyweight aerogels; TCF, twisted carbon fibers; CMB,
gels solvents
carbon microbelt; GMF, graphene-modified foam; OCA, oleophylic
boron-doped oils and organic 25−125 high 51
MWCNT solvents
carbon aerogel; MCF, microfibrillated cellulose fibers; SMS, super-
sponge oleophilic MOS2 nanosheet; MCGA, modified cellulose/graphene
UFAs oils and organic 215−913 high 52 aerogels; HAP, hydroxyapatite; EVOH NFAs, poly(vinyl alcohol-co-
solvents ethylene) nanofiber aerogels; GCTs, giant carbon tubes.

applications. The compressive tests of the CMA with different
densities of carbon microtubes were conducted (Figure S6,
Supporting Information). The result show that CMA has a
well-shaped hysteresis loop curve under 50% strain, which is
consistent with the typical behavior of the porous structure
material.39 As shown in Figure S7a−d, weights of 20 and 50 g
were placed on kapok fiber and CMA, respectively. Kapok fiber
was deformed by ∼90% in height (Figure S7b), whereas the
CMA was only deformed by ∼10% in height (Figure S7d),
indicating the CMA has excellent mechanical properties. In
addition, the CMA also has impressive fire resistance when
exposed to flame (Figure S8 and Movie S1, Supporting
Information).
The CMA is an ideal candidate for oil−water separation due
to its excellent hydrophobicity and outstanding mechanical
stability. Figure 5a and Supporting Information Movie S2 show
the strong adsorption capacity of the CMA. When the CMA
came into contact with the oil−water mixture, it could
completely and rapidly absorb the pump oil on the water
surface (Figure 5a and Movie S2, Supporting Information). As
an adsorbent, due to the low density and excellent hydro-
phobicity of CMA, it can float on the water surface, indicating
its great applications in removing oil spills and chemical leaks
with easy utilization and recovery.
In order to quantitatively study the adsorption capacity of
CMA, the weight increase (wt %) is defined as the weight of
598
the absorbed substances per unit weight by the dried aerogel.
Various types of oils and organic solvents have been selected,
which are common pollutants produced from the industrial
processes and are the main components of crude oil, such as
industrial petroleum products (pump oil), lipids (olive oil,
canola oil), and ketones.
In addition, the adsorption capability of CMA on toluene,
ethanol, acetone, and other organic solvents was tested. These
results show that the CMA can absorb all of these organic
solvents and oils with a high adsorption capacity as mentioned
above. Typically, the CMA can absorb the liquid 78−348 times
its weight (Figure 5b).
Impressively, the CMA exhibited an adsorption capacity
higher than those reported previously (Table
1),6,8,10,12,19,38,40−65 such as CNT sponges (80−180 times),19
graphene sponges (60−160 times),38 boron-doped multiwalled
carbon nanotube (MWCNT) sponges (25−125 times),51
twisted carbon fiber aerogel (50−192 times),65 oleophilic
carbon aerogels (81−171 times),55 and modified cellulose/
graphene aerogels (80−197 times).59 The adsorption capacity
of CMA is still lower than that of freestanding giant carbon
tubes,64 nitrogen-doped graphene foam,49 and ultralight
carbon aerogel.52 However, among all of these adsorbents,
the method to prepare the CMA is relatively simple, and its
precursor, kapok fiber, is relatively cheap. Therefore, our CMA
https://dx.doi.org/10.1021/acsnano.9b07063
ACS Nano 2020, 14, 595−602
ACS Nano www.acsnano.org
Figure 6. Recycling of CMA. (a) Squeezing and (b) combustion of ethanol-immersed CMA. (c) Distillation was used to recycle the CMA for
the absorption of heptane. (d) Squeezing was used to recycle the CMA for the absorption of octadecene. (e) Combustion was applied to
recycle the CMA for the absorption of ethanol.
should be one of the most promising adsorbents for pollutant
removal.
Figure S9 shows that the highest adsorption capacities of
CMA to ethanol, pump oil, and phenoxin reached 78, 248, and
348 g g−1, respectively. Moreover, the adsorption capacity to
phenoxin significantly enhanced from 283 to 348 g g−1 when
the carbonized temperature increased from 600 to 800 °C.
This is mainly due to the obtained high porosity with an
increase of carbonization temperature,32 resulting in the
enhancement of the adsorption performance.
The critical criteria for oil/chemical cleaning are adsorbent
recyclability as well as the recoverability of pollutants, as most
contaminants are either valuable materials or harmful wastes,
such as toluene and crude oil. There are three common ways to
recover pollutants: combustion, distillation, and squeezing.
Combustion is a great selection for those flammable and trashy
pollutants; distillation is preferred for those with low boiling
points and valuable pollutants, whereas squeezing is the best
useful method for those nonflammable, high-boiling-point,
valuable pollutants. The recovery process of CMA is
demonstrated in Figure 6a,b. The octadecene absorbed by
the CMA can be removed by squeezing, and the CMA retains
its original shape after squeezing (Figure 6a). As can be seen
from Figure 6b, ethanol absorbed by the CMA can be
eliminated by combustion, and the CMA maintains its original
shape and size after combustion.
599
Article
In addition, repeated recycle tests of CMA were carried out
by distillation (Figure 6c), squeezing (Figure 6d), and
combustion (Figure 6e). Heptane have a boiling point (98.5
°C) was absorbed by the CMA to study the cyclic distillation
performance. The vapor of heptane was released by heating the
material to 95 °C. This absorption−evaporation process was
repeated for 10 cycles. Figure 6c shows that the residual
heptane remained in the CMA is less than 3 wt % after each
cycle, and the sorption capacity of CMA does not change
significantly after 10 cycles, indicating its good recyclability.
Furthermore, there is no structural damage to the CMA after
cyclic distillation (Figure S10a,b, Supporting Information). For
the absorption−squeezing cycle test, the CMA with absorbed
octadecene, which has a high boiling point of 314 °C, is
targeted. In the first cycle, the CMA absorbs 8.1 g of
octadecene. As the CMA cannot be completely compressed,
the compressed residual mass reaches 2 g after squeezing.
From the second cycle, the absorption weight remains
unchanged and the absorption capacity of CMA tends to be
stable (Figure 6d) because the 3D porous structure of CMA
remains unchanged throughout the absorption−squeezing
process (Figure S11a,b, Supporting Information). We used
ethanol as the absorbent during the process of combustion
recovery. Compared to the first cycle, the absorption capacity
of CMA is decreased only 5% after 10 cycles (Figure 6e),
which may be ascribed to the deposition of residue after
combustion with ethanol. Notably, after repeated adsorption−
https://dx.doi.org/10.1021/acsnano.9b07063
ACS Nano 2020, 14, 595−602
ACS Nano www.acsnano.org
combustion cycles, the 3D network structure of CMA still
exists (Figure S12a,b, Supporting Information). Therefore,
ascribed to the excellent thermal stability and outstanding
mechanical properties of aerogel, whether with distillation,
squeezing, combustion, or a combination of them, all can be
used to recover the CMA according to the type of pollutant.
CONCLUSIONS
In summary, the CMA with hydrophobicity, strong adsorption
capacity, and excellent recyclability was obtained by a feasible
approach with economical raw material, such as kapok fiber.
The adsorption capacity of CMA reached 78−348 times its
weight. Ascribed to its excellent thermal stability and
outstanding mechanical properties, the CMA can be recycled
by distillation, squeezing, and combustion. Furthermore, the
availability of raw materials and a simple preparation method
for CMA make it practical for industrial applications.
Therefore, the obtained CMA has a broad application prospect
as an economical and safe adsorbent for environmental
protection. Furthermore, the CMA can be employed as a 3D
electrode material for energy storage or as a building unit for
other functional composites.
EXPERIMENTAL SECTION
Preparation of the Carbon Microtube. Cylindrical kapok fiber
was washed with deionized water several times and vacuum dried at
80 °C for 24 h. Then it was moved to a tubular furnace for pyrolysis.
The furnace was heated from 25 to 800 °C with 10 °C min−1 and kept
at 800 °C for 6 h. Finally, after being cooled naturally, the carbon
microtube was obtained.
Preparation of 3D CMA. 3D network CMA was fabricated
according to the unidirectional freezing method.66−70 Briefly, different
concentrations of carbon microtube solution were poured into the
silicone rubber mold, which was frozen by adding liquid nitrogen kept
at a certain temperature. The frozen samples were further freeze-dried
to obtain a target sample.
Characterization. The morphologies of samples were obtained by
SEM (Zeiss Supra 40), and the samples were freeze-dried before SEM
imaging. FTIR spectra were collected at room temperature using a
Nicolet 6700 instrument. X-ray photoelectron spectroscopy was
performed with a PHI-5400 photoelectron spectroscopy system.
Thermogravimetric analysis (Q600SDT) was performed under a N2
gas atmosphere at a rate of 10 °C/min. The contact angle
measurements were performed on a OCA 15 Pro. The BET surface
area was measured by an ASAP 2020 instrument. Compression tests
of CMA were performed on an Instron 5565A with a speed of 0.1
mm/min.
Absorption of Organic Solvents and Oils. During the
adsorption test, the CMA was required to contact various solvents
until the aerogels are completely filled with the solution and then
quickly removed for measurement. Weight measurements should be
made as soon as possible to avoid evaporation of organic liquids with
low boiling points. The weight of CMA before and after adsorption
was recorded, and the weight increment was calculated.
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsnano.9b07063.
Figures S1−S12, Tables S1 and S2; additional
supporting data include pore distribution graph of
kapok fiber and carbon microtube; N2 adsorption−
desorption isotherm at different temperature; FTIR
spectrum of kapok fiber and CMA; compressive stress−
strain curves of CMA with different contents of carbon
600
Article
microtube; photographs of the burning process of a
CMA using a lighter; summary of adsorption capacity of
the CMA with different carbonization temperatures;
SEM images of CMA after being recycled 10 times for
sorption−distillation, sorption−squeezing, and sorp-
tion−combustion process (PDF)
Movie S1 (MP4)
Movie S2 (MP4)
AUTHOR INFORMATION
Corresponding Author
Zheng Liu − Nanyang Technological University,
Singapore; orcid.org/0000-0002-8825-7198;
Email: z.liu@ntu.edu.sg
Other Authors
Pin Song − Nanyang Technological University, Singapore
Jiewu Cui − Hefei University of Technology, Hefei, P.R.
China; orcid.org/0000-0003-4613-4795
Jun Di − Nanyang Technological University, Singapore;
orcid.org/0000-0002-6232-6466
Daobin Liu − University of Science and Technology of
China, Hefei, P.R. China; orcid.org/0000-0002-8811-
7646
Manzhang Xu − Nanyang Technological University,
Singapore; orcid.org/0000-0001-6752-5299
Bijun Tang − Nanyang Technological University,
Singapore
Qingsheng Zeng − Nanyang Technological University,
Singapore
Jun Xiong − Jiangsu University, Zhenjiang, P.R. China
Changda Wang − University of Science and Technology of
China, Hefei, P.R. China
Qun He − University of Science and Technology of China,
Hefei, P.R. China
Lixing Kang − Nanyang Technological University,
Singapore
Jiadong Zhou − Nanyang Technological University,
Singapore
Ruihuan Duan − Nanyang Technological University,
Singapore
Bingbing Chen − Nanyang Technological University,
Singapore
Shasha Guo − Nanyang Technological University,
Singapore
Fucai Liu − University of Electronic Science and
Technology of China, Chengdu, P.R. China
Jun Shen − Chinese Academy of Sciences, Chongqing City,
P.R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsnano.9b07063
Author Contributions
P.S., J.C., J.D., and D.L. contributed equally. P.S. and Z.L.
designed the research. P.S. and J.C. finished the synthesis and
XPS measurement. J.D. performed FTIR, TGA measurements,
and data analysis. D.L. performed compressive tests and
contact angle measurements. M.X., B.T., Q.Z., J.X., C.W., Q.H.,
https://dx.doi.org/10.1021/acsnano.9b07063
ACS Nano 2020, 14, 595−602
ACS Nano www.acsnano.org
L.K., J.Z., R.D., B.C., S.G., F.L., and J.S. contributed to data
analysis and discussions. Z.L. directed the research.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was financially supported by Singapore National
Research Foundation under NRF RF Award No. MOE2016-
T2-1-131, Tier 1 2017-T1-001-075.
REFERENCES
(1) Toyoda, M.; Inagaki, M. Sorption and Recovery of Heavy Oil by
Using Exfoliated Graphite. Spill Sci. Technol. Bull. 2003, 8, 467−474.
(2) Choi, H. M.; Cloud, R. M. Natural Sorbents in Oil Spill Cleanup.
Environ. Sci. Technol. 1992, 26, 772−776.
(3) Dalton, T.; Jin, D. Extent and Frequency of Vessel Oil Spills in
US Marine Protected Areas. Mar. Pollut. Bull. 2010, 60, 1939−1945.
(4) Bi, H. C.; Xie, X.; Yin, K. B.; Zhou, Y. L.; Wan, S.; He, L. B.; Xu,
F.; Banhart, F.; Sun, L. T.; Ruoff, R. S. Spongy Graphene as a Highly
Efficient and Recyclable Sorbent for Oils and Organic Solvents. Adv.
Funct. Mater. 2012, 22, 4421−4425.
(5) Bastani, D.; Safekordi, A. A.; Alihosseini, A.; Taghikhani, V.
Study of Oil Sorption by Expanded Perlite at 298.15 K. Sep. Purif.
Technol. 2006, 52, 295−300.
(6) Radetić, M. M.; Jocić, D. M.; Jovančić, P. M.; Petrović, Z. L. J.;
Thomas, H. F. Recycled Wool-Based Nonwoven Material as an Oil
Sorbent. Environ. Sci. Technol. 2003, 37, 1008−1012.
(7) Bayat, A.; Aghamiri, S. F.; Moheb, A.; Vakili-Nezhaad, G. R. Oil
Spill Cleanup from Sea Water by Sorbent Materials. Chem. Eng.
Technol. 2005, 28, 1525−1528.
(8) Annunciado, T. R.; Sydenstricker, T. H. D.; Amico, S. C.
Experimental Investigation of Various Vegetable Fibers as Sorbent
Materials for Oil Spills. Mar. Pollut. Bull. 2005, 50, 1340−1346.
(9) Atta, A. M.; El-Ghazawy, R. A. M.; Farag, R. K.; Abdel-Azim, A.
A. A. Crosslinked Reactive Macromonomers Based on Polyisobuty-
lene and Octadecyl Acrylate Copolymers as Crude Oil Sorbers. React.
Funct. Polym. 2006, 66, 931−943.
(10) Li, A.; Sun, H. X.; Tan, D. Z.; Fan, W. J.; Wen, S. H.; Qing, X.
J.; Li, G. X.; Li, S. Y.; Deng, W. Q. Superhydrophobic Conjugated
Microporous Polymers for Separation and Adsorption. Energy Environ.
Sci. 2011, 4, 2062−2065.
(11) Farag, R. K.; Elsaeed, S. M. Synthesis and Characterization of
Oil Sorbers Based on Docosanyl Acrylate and Methacrylates
Copolymers. J. Appl. Polym. Sci. 2008, 109, 3704−3713.
(12) Wu, Z. Y.; Li, C.; Liang, H. W.; Chen, J. F.; Yu, S. H. Ultralight,
Flexible, and Fire-Resistant Carbon Nanofiber Aerogels from Bacterial
Cellulose. Angew. Chem., Int. Ed. 2013, 52, 2925−2929.
(13) Hüsing, N.; Schubert, U. Aerogels-Airy Materials: Chemistry,
Structure, and Properties. Angew. Chem., Int. Ed. 1998, 37, 22−45.
(14) Elkhatat, A. M.; Al-Muhtaseb, S. A. Advances in Tailoring
Resorcinol-Formaldehyde Organic and Carbon Gels. Adv. Mater.
2011, 23, 2887−2903.
(15) Pierre, A. C.; Pajonk, G. M. Chemistry of Aerogels and Their
Applications. Chem. Rev. 2002, 102, 4243−4266.
(16) Wan, S.; Bi, H. C.; Sun, L. T. Graphene and Carbon-Based
Nanomaterials as Highly Efficient Adsorbents for Oils and Organic
Solvents. Nanotechnol. Rev. 2016, 5, 3−22.
(17) Wu, D. C.; Fu, R. W.; Zhang, S. T.; Dresselhaus, M. S.;
Dresselhaus, G. Preparation of Low-Density Carbon Aerogels by
Ambient Pressure Drying. Carbon 2004, 42, 2033−2039.
(18) Fu, R.; Zheng, B.; Liu, J.; Dresselhaus, M.S.; Dresselhaus, G.;
Satcher, J.H.; Baumann, T.F. The Fabrication and Characterization of
Carbon Aerogels by Gelation and Supercritical Drying in Isopropanol.
Adv. Funct. Mater. 2003, 13, 558−562.
(19) Gui, X. C.; Wei, J. Q.; Wang, K. L.; Cao, A. Y.; Zhu, H. W.; Jia,
Y.; Shu, Q. K.; Wu, D. H. Carbon Nanotube Sponges. Adv. Mater.
2010, 22, 617−621.
601
Article
(20) Xu, Y. X.; Sheng, K. X.; Li, C.; Shi, G. Q. Self-Assembled
Graphene Hydrogel via a One-Step Hydrothermal Process. ACS Nano
2010, 4, 4324−4330.
(21) Bi, H. C.; Yin, K. B.; Xie, X.; Zhou, Y. L.; Wan, N.; Xu, F.;
Banhart, F.; Sun, L. T.; Ruoff, R. S. Low Temperature Casting of
Graphene with High Compressive Strength. Adv. Mater. 2012, 24,
5124−5129.
(22) Shin, M. K.; Oh, J.; Lima, M.; Kozlov, M. E.; Kim, S. J.;
Baughman, R. H. Elastomeric Conductive Composites Based on
Carbon Nanotube Forests. Adv. Mater. 2010, 22, 2663−2667.
(23) Hu, B.; Wang, K.; Wu, L. H.; Yu, S. H.; Antonietti, M.; Titirici,
M.-M. Engineering Carbon Materials from the Hydrothermal
Carbonization Process of Biomass. Adv. Mater. 2010, 22, 813−828.
(24) Yang, H. R.; Zhu, H. J.; Hendrix, M. M. R. M.; Lousberg, N. J.
H. G. M.; De With, G.; Esteves, A. C. C.; Xin, J. H. Temperature-
Triggered Collection and Release of Water from Fogs by a Sponge-
Like Cotton Fabric. Adv. Mater. 2013, 25, 1150−1154.
(25) Wakelyn, P. J.; Bertoniere, N. R.; French, A. D.; Thibodeaux, D.
Cotton Fiber Chemistry and Technology; CRS Press (Taylor and
Francis Group): Boca Raton, FL, 2007; pp 77−80.
(26) Carmody, O.; Frost, R.; Xi, Y.; Kokot, S. Surface Character-
isation of Selected Sorbent Materials for Common Hydrocarbon
Fuels. Surf. Sci. 2007, 601, 2066−2076.
(27) Jabli, M.; Baouab, M. H. V.; Roudesli, M. S.; Bartegi, A.
Adsorption of Acid Dyes from Aqueous Solution on a Chitosan-
Cotton Composite Material Prepared by a New Pad-Dry Process. J.
Eng. Fibers Fabr. 2011, 6, 1−12.
(28) Kaewprasit, C.; Hequet, E.; Abidi, N.; Gourlot, J. P. Application
of Methylene Blue Adsorption to Cotton Fiber Specific Surface Area
Measurement: Part I. Methodology. J. Cotton Sci. 1998, 2, 164−173.
(29) Nada, A. M. A.; El-Wakil, N. A.; Hassan, M. L.; Adel, A. M.
Differential Adsorption of Heavy Metal Ions by Cotton Stalk Cation-
Exchangers Containing Multiple Functional Groups. J. Appl. Polym.
Sci. 2006, 101, 4124−4132.
(30) Hussein, M.; Amer, A. A.; Sawsan, I. I. Heavy Oil Spill Cleanup
Using Law Grade Raw Cotton Fibers: Trial for Practical Application.
J. Pet. Technol. Altern. Fuels 2011, 2, 132−140.
(31) Adebajo, M. O.; Frost, R. L.; Kloprogge, J. T.; Carmody, O.;
Kokot, S. Porous Materials for Oil Spill Cleanup: A Review of
Synthesis and Absorbing Properties. J. Porous Mater. 2003, 10, 159−
170.
(32) Shultz, J. M.; Walsh, L.; Garfin, D. R.; Wilson, F. E.; Neria, Y.
The 2010 Deepwater Horizon Oil Spill: The Trauma Signature of an
Ecological Disaster. J. Behav. Health. Ser. R. 2015, 42, 58−76.
(33) Dresselhaus, M. S.; Dresselhaus, G.; Saito, R.; Jorio, A. Raman
Spectroscopy of Carbon Nanotubes. Phys. Rep. 2005, 409, 47−99.
(34) Ferrari, A. C.; Robertson, J. Interpretation of Raman Spectra of
Disordered and Amorphous Carbon. Phys. Rev. B: Condens. Matter
Mater. Phys. 2000, 61, 14095−14107.
(35) Park, Y. S.; Choi, Y. C.; Kim, K. S.; Chung, D.-C.; Bae, D. J.;
An, K. H.; Lim, S. C.; Zhu, X. Y.; Lee, Y. H. High Yield Purification of
Multiwalled Carbon Nanotubes by Selective Oxidation during
Thermal Annealing. Carbon 2001, 39, 655−661.
(36) Roldan, L.; Santos, I.; Armenise, S.; Fraile, J. M.; García-
Bordejé, E. The Formation of a Hydrothermal Carbon Coating on
Graphite Microfiber Felts for Using as Structured Acid Catalyst.
Carbon 2011, 50, 1363−1372.
(37) Ishimaru, K.; Hata, T.; Bronsveld, P.; Meier, D.; Imamura, Y.
Spectroscopic Analysis of Carbonization Behavior of Wood, Cellulose
and Lignin. J. Mater. Sci. 2007, 42, 122−129.
(38) Nguyen, D. D.; Tai, N. H.; Lee, S. B.; Kuo, W. S.
Superhydrophobic and Superoleophilic Properties of Graphene-
Based Sponges Fabricated Using a Facile Dip Coating Method.
Energy Environ. Sci. 2012, 5, 7908−7912.
(39) Tang, Y.; Yeo, K. L.; Chen, Y.; Yap, L. W.; Xiong, W.; Cheng,
W. Ultralow-Density Copper Nanowire Aerogel Monoliths with
Tunable Mechanical and Electrical Properties. J. Mater. Chem. A 2013,
1, 6723−6726.
https://dx.doi.org/10.1021/acsnano.9b07063
ACS Nano 2020, 14, 595−602
ACS Nano www.acsnano.org
(40) Yuan, J.; Liu, X.; Akbulut, O.; Hu, J.; Suib, S. L.; Kong, J.;
Stellacci, F. Superwetting Nanowire Membranes for Selective
Absorption. Nat. Nanotechnol. 2008, 3, 332−336.
(41) Toyoda, M.; Inagaki, M. Heavy Oil Sorption Using Exfoliated
Graphite: New Application of Exfoliated Graphite to Protect Heavy
Oil Pollution. Carbon 2000, 38, 199−210.
(42) Lillo-Ródenas, M. A.; Cazorla-Amorós, D.; Linares-Solano, A.
Behaviour of Activated Carbons with Different Pore Size Distribu-
tions and Surface Oxygen Groups for Benzene and Toluene
Adsorption at Low Concentrations. Carbon 2005, 43, 1758−1767.
(43) Wang, G. L.; Sun, Q. R.; Zhang, Y. Q.; Fan, J. H.; Ma, L. M.
Sorption and Regeneration of Magnetic Exfoliated Graphite as a New
Sorbent for Oil Pollution. Desalination 2010, 263, 183−188.
(44) Cong, H. P.; Ren, X. C.; Wang, P.; Yu, S. H. Macroscopic
Multifunctional Graphene-Based Hydrogels and Aerogels by a Metal
Ion Induced Self-Assembly Process. ACS Nano 2012, 6, 2693−2703.
(45) Dong, X.; Chen, J.; Ma, Y.; Wang, J.; Chan-Park, M. B.; Liu, X.;
Wang, L.; Huang, W.; Chen, P. Superhydrophobic and Super-
oleophilic Hybrid Foam of Graphene and Carbon Nanotube for
Selective Removal of Oils or Organic Solvents from the Surface of
Water. Chem. Commun. 2012, 48, 10660−10662.
(46) Liang, H. W.; Guan, Q. F.; Chen, L. F.; Zhu, Z.; Zhang, W. J.;
Yu, S. H. Macroscopic-Scale Template Synthesis of Robust Carbona-
ceous Nanofiber Hydrogels and Aerogels and Their Applications.
Angew. Chem., Int. Ed. 2012, 51, 5101−5105.
(47) Zhao, J. P.; Ren, W. C.; Cheng, H. M. Graphene Sponge for
Efficient and Repeatable Adsorption and Desorption of Water
Contaminations. J. Mater. Chem. 2012, 22, 20197−20202.
(48) Niu, Z. Q.; Chen, J.; Hng, H. H.; Ma, J.; Chen, X. D. A
Leavening Strategy to Prepare Reduced Graphene Oxide Foams. Adv.
Mater. 2012, 24, 4144−4150.
(49) Zhao, Y.; Hu, C. G.; Hu, Y.; Cheng, H. H.; Shi, G. Q.; Qu, L. T.
A Versatile, Ultralight, Nitrogen-Doped Graphene Framework. Angew.
Chem. 2012, 124, 11533−11537.
(50) Hayase, G.; Kanamori, K.; Fukuchi, M.; Kaji, H.; Nakanishi, K.
Facile Synthesis of Marshmallow-Like Macroporous Gels Usable
Under Harsh Conditions for the Separation of Oil and Water. Angew.
Chem., Int. Ed. 2013, 52, 1986−1989.
(51) Hashim, D. P.; Narayanan, N. T.; Romo-Herrera, J. M.; Cullen,
D. A.; Hahm, M. G.; Lezzi, P.; Suttle, J. R.; Kelkhoff, D.; Muñoz-
Sandoval, E.; Ganguli, S.; et al. Covalently Bonded Three-Dimen-
sional Carbon Nanotube Solids via Boron Induced Nanojunctions.
Sci. Rep. 2012, 2, 363−370.
(52) Sun, H. Y.; Xu, Z.; Gao, C. Multifunctional, Ultra-Flyweight,
Synergistically Assembled Carbon Aerogels. Adv. Mater. 2013, 25,
2554−2560.
(53) Bi, H. C.; Huang, X.; Wu, X.; Cao, X. H.; Tan, C. L.; Yin, Z. Y.;
Lu, X. H.; Sun, L. T.; Zhang, H. Carbon Microbelt Aerogel Prepared
by Waste Paper: An Efficient and Recyclable Sorbent for Oils and
Organic Solvents. Small 2014, 10, 3544−3550.
(54) Zhu, H.; Chen, D.; An, W.; Li, N.; Xu, Q.; Li, H.; He, J.; Lu, J.
A Robust and Cost-Effective Superhydrophobic Graphene Foam for
Efficient Oil and Organic Solvent Recovery. Small 2015, 11, 5222−
5229.
(55) Gao, S. Y.; Li, X. G.; Li, L. Y.; Wei, X. J. A Versatile Biomass
Derived Carbon Material for Oxygen Reduction Reaction, Super-
capacitors and Oil/Water Separation. Nano Energy 2017, 33, 334−
342.
(56) Wang, S.; Peng, X. W.; Zhong, L. X.; Tan, J. W.; Jing, S. S.;
Cao, X. F.; Chen, W.; Liu, C. F.; Sun, R. C. An Ultralight, Elastic,
Cost-Effective, and Highly Recyclable Superabsorbent from Micro-
fibrillated Cellulose Fibers for Oil Spillage Cleanup. J. Mater. Chem. A
2015, 3, 8772−8781.
(57) Wu, Z. Y.; Li, C.; Liang, H. W.; Zhang, Y. N.; Wang, X.; Chen,
J. F.; Yu, S. H. Carbon Nanofiber Aerogels for Emergent Cleanup of
Oil Spillage and Chemical Leakage Under Harsh Conditions. Sci. Rep.
2014, 4, 4079−4084.
602
Article
(58) Gao, X. J.; Wang, X. F.; Ouyang, X. P.; Wen, C. Flexible
Superhydrophobic and Superoleophilic MoS2 Sponge for Highly
Efficient Oil-Water Separation. Sci. Rep. 2016, 6, 27207−27214.
(59) Mi, H. Y.; Jing, X.; Politowicz, A. L.; Chen, E.; Huang, H. X.;
Turng, L.-S. Highly Compressible Ultra-Light Anisotropic Cellulose/
Graphene Aerogel Fabricated by Bidirectional Freeze Drying for
Selective Oil Absorption. Carbon 2018, 132, 199−209.
(60) Zhang, Y. G.; Zhu, Y. J.; Xiong, Z. C.; Wu, J.; Chen, F.
Bioinspired Ultralight Inorganic Aerogel for Highly Efficient Air
Filtration and Oil-Water Separation. ACS Appl. Mater. Interfaces 2018,
10, 13019−13027.
(61) Guan, H.; Cheng, Z. Y.; Wang, X. Q. Highly Compressible
Wood Sponges with a Spring-Like Lamellar Structure as Effective and
Reusable Oil Absorbents. ACS Nano 2018, 12, 10365−10373.
(62) Shi, L. R.; Chen, K.; Du, R.; Bachmatiuk, A.; Rummeli, M. H.;
Xie, K. W.; Huang, Y. Y.; Zhang, Y. F.; Liu, Z. F. Scalable Seashell-
Based Chemical Vapor Deposition Growth of Three-Dimensional
Graphene Foams for Oil-Water Separation. J. Am. Chem. Soc. 2016,
138, 6360−6363.
(63) Lu, J. W.; Xu, D. D.; Wei, J. K.; Yan, S.; Xiao, R.
Superoleophilic and Flexible Thermoplastic Polymer Nanofiber
Aerogels for Removal of Oils and Organic Solvents. ACS Appl.
Mater. Interfaces 2017, 9, 25533−25541.
(64) Chen, J. F.; Shen, X. C.; Pan, Y. B.; Liu, C.; Hwang, S. Y.; Xu,
Q.; Peng, Z. M. Synthesis of Freestanding Amorphous Giant Carbon
Tubes with Outstanding Oil Sorption and Water Oxidation
Properties. J. Mater. Chem. A 2018, 6, 3996−4002.
(65) Bi, H. C.; Yin, Z. Y.; Cao, X. H.; Xie, X.; Tan, C. L.; Huang, X.;
Chen, B.; Chen, F. T.; Yang, Q. L.; Bu, X. Y.; et al. Carbon Fiber
Aerogel Made From Raw Cotton: A Novel, Efficient and Recyclable
Sorbent for Oils and Organic Solvents. Adv. Mater. 2013, 25, 5916−
5921.
(66) Gao, H. L.; Xu, L.; Long, F.; Pan, Z.; Du, Y. X.; Lu, Y.; Ge, J.;
Yu, S. H. Macroscopic Free-Standing Hierarchical 3D Architectures
Assembled from Silver Nanowires by Ice Templating. Angew. Chem.,
Int. Ed. 2014, 53, 4561−4566.
(67) Deville, S.; Saiz, E.; Nalla, R. K.; Tomsia, A. P. Freezing as a
Path to Build Complex Composites. Science 2006, 311, 515−518.
(68) Deville, S.; Maire, E.; Bernard-Granger, G.; Lasalle, A.; Bogner,
A.; Gauthier, C.; Leloup, J.; Guizard, C. Metastable and Unstable
Cellular Solidification of Colloidal Suspensions. Nat. Mater. 2009, 8,
966−972.
(69) Song, P.; Qin, H. L.; Gao, H. L.; Cong, H. P.; Yu, S. H. Self-
Healing and Superstretchable Conductors from Hierarchical Nano-
wire Assemblies. Nat. Commun. 2018, 9, 2786−2794.
(70) Song, P.; Di, J.; Kang, L. X.; Xu, M. Z.; Tang, B. J.; Xiong, J.;
Cui, J. W.; Zeng, Q. S.; Zhou, J. D.; He, Y. M.; et al. Enhancing the
Cycling Stability of Na-Ion Batteries by Bonding MoS2 on Assembled
Carbon-Based Materials. Nano Materials Science 2019, 1, 310−317.
https://dx.doi.org/10.1021/acsnano.9b07063
ACS Nano 2020, 14, 595−602