Materials Science and Engineering B 194 (2015) 62–67

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Materials Science and Engineering B

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

3D hierarchical porous graphene aerogels for highly improved

adsorption and recycled capacity
Caixia Chi a,b , Hongbo Xu a , Ke Zhang a,∗ , Yibo Wang a , Shuanghu Zhang b , Xusong Liu a ,
Xin Liu a , Jiupeng Zhao a , Yao Li c,∗
a
School of Chemical Engineering and Technology, Harbin Institute of Technology, Xida Zhi street 92, Harbin 150001, China
b
Food and Pharmaceutical Engineering College, Suihua University, Suihua 152061, China
c
Center for Composite Materials, Harbin Institute of Technology, Harbin 150001, China

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

Article history: This article demonstrates the fabrication of 3D hierarchical porous graphene aerogels (HGAs) with tun-
Received 30 September 2014 able porous architecture by a “fishing” process with polystyrene (PS) particles as sacrificial templates.
Received in revised form 2 December 2014 Structure and morphology were characterized by X-ray diffraction (XRD), Raman spectroscopy, and scan-
Accepted 23 December 2014
ning electron microscopy (SEM), respectively. The 3D HGAs exhibits low density, super hydrophobicity,
Available online 8 January 2015
high porosity and good thermal stability, which were used as adsorbents for removal of oils and organic
solvents, showing highly efficient adsorption. In addition, they could be regenerated by heat treatment
Keywords:
to release the adsorbates. After eight toluene-adsorbing and drying recycles, the adsorption capacity of
3D hierarchical porous graphene aerogel
Polystyrene particle
HGAs reaches 93% of the initial uptake.
Self-assembly © 2015 Elsevier B.V. All rights reserved.
Pore size tunable
Oil adsorption
Recycled capacity

1. Introduction
Graphene, a single layer of graphite, has been attracted much
attention due to its excellent mechanical [1,2], electrical [3,4], ther-
mal [5,6] and optical properties [7,8]. Since the first discovery
of isolated graphene by mechanical exfoliation of graphite crys-
tals [9], numerous approaches were developed for fabrication of
graphene, such as micromechanical cleavage [9], crystal epitaxial
growth [10,11], chemical vapor deposition [12–14] and chemical
reduction of graphene oxide (GO) [15–23]. Relative to other tech-
niques, chemical reduction of GO, is considered to be an efficient
approach to produce processable graphene on a large scale [15],
in which it is usually prepared by oxidation of graphite powder
with strong oxidants such as a mixture of concentrated sulfuric acid
and potassium permanganate via Hummer’s method. The abundant
oxygen-containing groups on GO endow it with excellent aqueous
dispersion and make it easy to modify [17–24].
Recently, efforts have been made to fabricate 3D graphene
through self-assembly of well-dispersed GO or functionalized
graphene sheets [4,18–23]. The former was prepared by Wang
et al. [20], being promoted by a noble-metal nanocrystal (Au, Ag,
∗ Corresponding authors. Tel.: +86 451 86403767; fax: +86 451 86403767.
E-mail addresses: zhangke@hit.edu.cn (K. Zhang), yaoli@hit.edu.cn (Y. Li).
Pd, Ir, Rh, or Pt, etc.) and treated hydrothermally at 120 ◦ C for
20 h. The samples had excellent mechanical properties, and had
been utilized as fixed-bed catalysts for a Heck reaction resulting in
both 100% selectivity and conversion. Yan et al. [23] demonstrated
different kinds of reducing agents (NaHSO3 , Na2 S, HI, etc.) to be
effective in preparing 3D architectures of graphene which exhibited
high mechanical, thermal and electrical properties; furthermore, by
incorporating Fe3 O4 nanoparticles [22], the obtained composites
showed a high performance as an anode for lithium-ion batter-
ies. Yu et al. [25] reported a one-step fabrication of graphene/iron
oxide hydrogels which is induced by ferrous ions, and revealed their
excellent capabilities for removal of oil and heavy metal ions in
water. Spongy graphene was made by reducing a suspension of
GO at 180 ◦ C for 24 h in Ruoff’s paper [26]. The samples possessed
highly efficient adsorption of fats and petroleum products, but also
toxic solvents such as toluene and chloroform. Hu et al. [27] pre-
pared 3D structures of graphene via the chemical reduction of GO
in the presence of a range of environmentally-friendly phenolic
acids at 95 ◦ C for 8 h without stirring. These products were used
as electrode materials for supercapacitors, as well as adsorbents
for removal of oils, organic solvents and dyes from contaminated
water. In addition, an ice-templating method was used to prepare
the macroporous and hydrophobic prGO-PDMS structure through
vapor deposition of PDMS on GO scaffolds, which exhibits a great
improvement in both the adsorption capacity and reusability [28].

http://dx.doi.org/10.1016/j.mseb.2014.12.026
0921-5107/© 2015 Elsevier B.V. All rights reserved.
 C. Chi et al. / Materials Science and Engineering B 194 (2015) 62–67
Moreover, Ahn et al. [29] reported a novel and practical technol-
ogy to form 3D interconnected foam-like graphene layer and base
graphene multi-layer on heater surface to effectively eliminate the
sudden and rapid increase of wall temperature at critical heat flux
(CHF).
Many literature reported integration of graphene sheets into
3D structures by different strategies and investigated the advanced
properties as aforementioned, nonetheless the 3D interconnected
frameworks of graphene with a tunable hierarchically porous archi-
tecture has not been reported. Enlightened by the studies on
preparation of a 3D graphene hydrogel [22–24], it is possible to
prepare composites of 3D graphene embedded nanoparticles if
some of the nanoparticles are dispersed homogeneously in a GO
aqueous suspension during the reduction and self-assembly. In this
paper, it is proposed that the capture of PS particles is similar to a
“fishing process with “fish net , where the “fish is the PS par-
ticle and the “fish net is composed of graphene/graphene oxide
nanosheet, leading to a network during reduction via self-assembly.
Polystyrene spheres are polymeric particles which are easily syn-
thesized by different approaches such as emulsifier-free emulsion
polymerization [30] and dispersion polymerization [31]. Normally,
PS particles as close-packed colloidal crystal templates (CCT) that
are used for preparation of three-dimensionally ordered macro-
porous (3DOM) nanostructures by chemically removed after the
deposition of the desired material [30]. Here, the 3D self-assembly
architecture of PS/graphene hydrogels were fabricated owing to the
electrostatic repulsions between the negative charged graphene
oxide and PS particles at pH = 5–7 in water during the reduction.
PS particles are employed as sacrificial templates that yield porous
structure when removed by organic solvent to obtain HGAs. The
microstructure (porosity and pore size distribution) of HGAs can be
controlled by varying the size of PS particles, and the macroscopic
structure of HGAs (shape and size) can be dominated by changing
the shape and volume of vessel. Particularly, both the microscopic
and macroscopic structure of HGAs can be easily carried out in one
step.
2. Experimental
2.1. Preparation of GO
GO was prepared by an improved Hummer’s method as
described in Ref. [32]. The as-prepared GO was dispersed in water
(2 mg mL−1 ) and sonicated for 30 min in an ultrasonic bath. The
resulting brown dispersion was subjected to centrifugation for
30 min at 5000 rpm to remove un-exfoliated GO.
2.2. Preparation of PS particles
The nano-sized PS particles were synthesized by an emulsifier-
free emulsion polymerization [30]. Firstly, styrene monomer and
initiator K2 S2 O8 were dispersed in aqueous solution under a rapid
stirring of 400 rpm and it was initiated at 70 ◦ C after removing
oxygen by nitrogen purging. The PS particles with different size
(256 nm, 356 nm, 410 nm and 598 nm) were obtained by increase of
monomer content. On the other hand, the micro-sized PS particles
with average diameters of 1000 nm, 1200 nm and 1580 nm were
prepared by dispersion polymerization and then they are treated
in sulfuric acid to obtain the sulfoated PS particles [31].
2.3. Preparation of HGHs and HGAs
GO aqueous dispersion (∼2 mg mL−1 ) was mixed with PS par-
ticle solution (1.44 wt%), and 30 mg ascorbic acid was added
as reducing agent. The homogeneous red-brown dispersion was
obtained after sonication for 15 min to dissolve the ascorbic acid.
63
Successively, the as-prepared dispersion was heated at 80 ◦ C for
1.5 h to produce the PS/graphene hydrogels. Then, they were
immersed in tetrahydrofuran (THF) to remove PS particles to obtain
the hierarchical porous graphene hydrogels (HGHs). The porosity
and pore size distribution of graphene can be controlled by vary-
ing the size of PS particles. Finally, the product was dialyzed with
ultrapure water for three days, and followed by freeze-drying for
further use.
2.4. Characterization
The morphology of samples was observed using a field emis-
sion scanning electron microscope (SU8000). The X-ray diffraction
(XRD) data were obtained on a Rigaku D/max-rb (12 KW) with Cu
K␣ radiation ( = 0.15418 nm). X-ray photoelectron spectroscopy
(XPS) data were obtained using a PHI 5700 ESCA system with an Al
K 1486.6 eV as the X-ray source. Thermogravimetric analysis (TGA)
was carried out using a ZRY-2P thermal analysis station with a ramp
rate of 5 ◦ C min−1 . Raman spectra were obtained with a Renishaw
Raman system model 1000 spectrometer. The 514.5 nm radiation
from a 20 mW air-cooled argon ion laser was used as an exciting
source. The N2 adsorption–desorption isotherms of the samples
were measured at 77 K using specific surface porosity analyzer 3H-
2000PS1.
2.5. Oil-uptake experiments
Oil-uptake capacity of the HGAs was determined by measuring
the weight. The aerogel samples were put into various kinds of
oils and organic solvents labeled with Sudan III dye, and taken out
until they were fully adsorbed. Then the samples were weighed
after removing the surface oils with filter papers. The oil-uptake
performance was reflected by the saturated adsorption capacity
per unit mass of the aerogel samples, which is defined as follows:
(Ws − Wi )
Q = (1)
Wi
Here, Q is the adsorption capacity at saturated state. Wi and Ws
are the initial and final weight (at adsorption saturation) of HGAs,
respectively.
3. Results and discussion
The proposed mechanism for fabrication of HGAs is shown in
Fig. 1. PS particles are well dispersed in GO solution (Fig. 2(a) – left)
under controlled pH between 5 and 7 due to electrostatic repul-
sion, where zeta potential values are measured to be −42 ± 1.5 mV
for GO and −50 ± 5.2 mV for PS. At early-stage reduction, partially
reduced GO sheets come up, and graphene/GO nanosheets that
can be self-assembled together to form network. Then PS particles
are spontaneously captured into the network in a simple one-step
process. Some sheets of reduced GO assemble together in parallel,
but others may assemble at any angle during the reduction. At the
end, much water was expelled out from the aggregates to obtain
the compact 3D architectures (Fig. 2(a) – right, 3(a)).When PS are
removed, a certain hydrogel with hierarchical porous structure is
formed (Fig. 3(b)). The as-prepared graphene hydrogels still con-
tain plenty of water (above 97 wt%) and the corresponding aerogels
are obtained by removing the water via a freeze-drying method
(Figs. 2(b) and 3(c)). Moreover, HGAs can be molded into any shape
(Fig. 2(b)), thus it could be placed directly in polluted areas and
dredged intact afterwards, leading to simpler recovery.
Fig. 4 shows XRD patterns of pristine graphite, GO and HGAs. The
XRD pattern of pristine graphite exhibits a basal reflection (0 0 2)
peak at 2 = 26.6◦ (d-spacing = 0.34 nm) [33]. For GO, the 0 0 2 reflec-
tion peak shifts to the lower angle of 8.66◦ which corresponds to
64 C. Chi et al. / Materials Science and Engineering B 194 (2015) 62–67

Fig. 1. Illustration of the process for preparation of HGAs.

Fig. 2. Photographs of (a) an aqueous mixture of GO, PS (dPS = 410 nm) and ascorbic acid before (left) and after (right) chemical reduction at 80 ◦ C (b) the HGAs with different
shape and size.

Fig. 3. SEM images of (a) HGHs with PS (b) HGHs without PS (c) HGAs.

increase of the interlayer spacing (1.02 nm) during the oxidation.
This peak completely disappears after GO was reduced to HGAs;
instead, a new peak appears at 19.4◦ , which attributes to a decrease
interlayer spacing of 0.44 nm. In addition, the broad peak of HGAs
is different from the narrow peak of pristine graphite, suggesting
that the disordered stacked graphene sheets in the microscopic
scale.
Raman spectra of the graphite, GO and HGAs are shown in
Fig. 5. Raman spectrum is highly sensitive to the electronic structure
and has proven to be an essential tool for the characterization of
carbon-based materials (especially for C C bands) [34]. The Raman
spectrum of graphite, displays a prominent G peak as the feature at
1574.7 cm−1 , corresponding to the first-order scattering of the E2g
mode [35]. In the Raman spectrum of GO, the G band is broadened

Fig. 4. XRD pattern of (a) graphite, (b) GO and (c) HGAs. Fig. 5. Raman spectra of (a) graphite, (b) GO and (c) HGAs.
 C. Chi et al. / Materials Science and Engineering B 194 (2015) 62–67 65

Fig. 6. XPS spectra of C1s of (a) GO and (b) HGAs.

and shifted to 1585 cm−1 . In addition, the D band at 1353.8 cm−1

becomes prominent, indicating the reduction in size of the in-plane
sp2 domains, possibly due to the extensive oxidation. After reduc-
tion, the G band appears at 1574.7 cm−1 and with an increased
ID /IG intensity ratio of 1.06 compared to that in GO (0.80). This
change suggests a degree of disorder in the carbon arrangement
upon reduction of the exfoliated GO [36].
Fig. 6 shows the C1s XPS spectra of GO and HGAs. For GO
(Fig. 6(a)), four different peaks centered at 284.6 eV, 286.5 eV,
288.2 eV, and 290.0 eV are detected, which correspond to C C/C–C
in aromatic rings, C–O (epoxy and alkoxy), C O, and COOH groups, Fig. 8. Image of water droplet on HGAs surface.
respectively. After the reduction, the intensities of all C1s peaks of
the carbons binding to oxygen decrease dramatically, especially the
starting mass loss temperature (∼350 ◦ C) of the HGAs is roughly
peak of C–O (epoxy and alkoxy). These results reveal that most oxy-
250 ◦ C higher than that of GO. This is attributed to the removal of
gen containing functional groups were removed and the majority
oxygen functionalities from the surface of GO during the reduction
of the conjugated graphene networks have been restored after the
process. On the other hand, the adsorbed liquids can be readily
reduction.
recycled by heating in air without destroying the porous structures
To confirm the reduction effect, TGA was carried out from
due to the fine thermal stability of HGAs.
25 ◦ C to 700 ◦ C under an air atmosphere, as shown in Fig. 7. GO
The HGAs (9.22∼23.05 mg cm−3 ) is of highly hydrophobic (the
is thermally unstable and starts to lose mass (10%) upon heating,
contact angle is 139 ± 0.5◦ , as shown in Fig. 8), which has a
even below 100 ◦ C, which is attributed to the rapid evaporation
maximum surface area of 237.47 m2 g−1 with tunable pore size
of the intercalated water. The main mass loss (80%) takes place
(N2 adsorption–desorption isotherms, as shown in Fig. 9). The
at around 180 ◦ C [15] due to the decomposition of the oxygen
isotherms in Fig. 9 are characteristic of type III isotherms, which
functional groups, yielding CO, CO2 , and steam. The gases produced
suggest the multilayer adsorption on a macroporous solid at the
by thermal paralysis’ of the oxygen-containing functional groups
relatively high pressure region (P/P0 of 0.9–0.95) [38,39]. The dis-
accelerate GO expansion and delimitation [37]. In contrast, the
tribution of pore size computed using the BJH method (Fig. 9 insert),
thermal stability of HGAs is much higher than that of GO. The

Fig. 9. N2 adsorption–desorption isotherms and pore size distribution (insert) of

Fig. 7. TGA plot of (a) GO and (b) HGAs. HGAs (dPS = 410 nm).
66 C. Chi et al. / Materials Science and Engineering B 194 (2015) 62–67
Fig. 10. Adsorption of soya oil in HGAs at intervals of 30 s.
Fig. 11. Adsorption efficiency of HGAs for different oils and organic solvents.
finding that HGAs possess hierarchical porous structure. The max-
imum pore size is about 120 nm. The progress of adsorption for
soybean oil is shown in a series of photos in Fig. 10. To further
reveal the adsorption performance of HGAs, it was tested in various
kinds of oils and organic solvents on the HGAs with different density
and pore diameters. As shown in Fig. 11, the maximum adsorption
capacities are obtained to be from 21 to 77 times as heavy as the
weight of the aerogel samples for different oils and organic solvents,
which may be related to the density of the oils and organic solvents.
The adsorption capacities are different on the HGAs with various
PS size as template for identical oils and organic solvents, which
may be related not only to the molecular dimension of the oils and
Fig. 12. Surface area, pore size and pore volume of the HAGs samples as function of the added PS partciels.
organic solvents, but also to the pore size, specific surface area and
pore volume of adsorbent. Its adsorption efficiency is much higher
than that of previously reported adsorptive materials, e.g., macro-
scopic multifunctional graphene-based aerogels [25]. In addition,
although the adsorption capacity is close to spongy graphene [26],
the preparation process of HGAs is much simpler, in which HGAs
could be obtained without long-time treatment. In comparison
with commercial adsorbents, the generated HGAs exhibit better
performance than that of sisal, coir fiber, sponge-gourd [40] and
polypropylene nonwoven web [41].
As shown in Fig. 11, the adsorption capacities of HGAs for identi-
cal oils and organic solvents decrease after first increasement with
the increase of particle size, i.e. there is the optimum particle size
existed for the adsorption. Microporous zeolites and polymers have
been used to remove organics and oil from water due to their
large specific surface area and hydrophobicity [42,43]. In liquid
chromatography, the adsorption value of organics will generally
increase with the increase of molecular weight unless the molec-
ular is too big to enter the pore. The ideal condition is that the
adsorbent has large numbers of pores with the suitable size for
adsorbate to enter. Too small pores will block the entry of adsor-
bate; too large pores will cause low specific area. Normally, bigger
BET will bring stronger adsorption affinity, but this theory has its
limitation in practical applications. The surface area, pore size and
pore volume were analyzed for the HGAs with addition of PS par-
ticles (Fig. 12). The pore size as opposed to the surface area shows
an increasing trend with increasing particle size (Fig. 12a). In addi-
tion, regarding the effect of particle size on the pore volume, it is
found that the pore volume reaches the maximum value when the
added PS particles is 410 nm, revealing that accumulative total pore
volume of HGAs does not increase with increasing pore size. From
this, it is confirmed that the pore volume may be the principal factor
determining the oil adsorption in HGAs. Therefore, it can be used
 C. Chi et al. / Materials Science and Engineering B 194 (2015) 62–67
Fig. 13. Recyclability of HGAs (dPS = 410 nm) repetitively adsorbed toluene and
released its vapor under heat treatment (105 ◦ C) for 8 cycles.
to explain why the adsorption capacity declines after reaching one
peak (Fig. 11).
Furthermore, it is found that the HGAs had an excellent regener-
ation capacity through releasing the adsorbed organics by heating.
As shown in Fig. 13, the HGAs maintained a high adsorption capac-
ity (93% of the initial uptake) after eight toluene-adsorbing and
drying recycles.
4. Conclusion
In summary, 3D HGAs with tunable pore sizes has been suc-
cessfully prepared by a wet chemical self-assembly technique, i.e.
“fishing” process during the reduction of GO in aqueous suspension,
PS was removed by subsequent treatment with THF. The prepared
HGAs exhibit low density, super hydrophobicity, high porosity and
good thermal stability, which could be promising candidates for
adsorption of oils and organic solvents with good adsorption and
regeneration capacity. This study suggests a facile, low cost and
scalable route to prepare graphene based aerogels in application of
water purification.
Prime novelty statement
This work reports a facile, low cost and scalable route to prepare
3D hierarchical porous graphene aerogels (HGAs) by using of
polystyrene (PS) as sacrificial templates for the first time. It exhibits
highly improved adsorption and recycled capacity for different oils
and organic solvents than that of previously reported.
Acknowledgements
This research were supported by National Natural Science Foun-
dation of China (Nos. 51010005, 90916020, 51174063, 21201128),
the Program for New Century Excellent Talents in University
(NCET-08-0168), Natural Science Funds for Distinguished Young
Scholar of Heilongjiang province, the project of International
Cooperation supported by Ministry of Science and Technol-
ogy of China (2013DFR10630), the project of Natural Scientific
67
Research Innovation Foundation in Harbin Institute of Technol-
ogy (XWQQ5750013113) and Heilongjiang Post-doctoral Science
Foundation (AUGA4110029613).
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