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Materials Chemistry
Cite this: J. Mater. Chem., 2012, 22, 8767
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Green synthesis of carbon nanotube–graphene hybrid aerogels and their use as
versatile agents for water purification†
Zhuyin Sui,a Qinghan Meng,b Xuetong Zhang,*a Rui Mab and Bing Caob
Received 4th January 2012, Accepted 15th March 2012
DOI: 10.1039/c2jm00055e
Carbon nanotube–graphene hybrid aerogels have been fabricated by
supercritical CO2 drying of their hydrogel precursors obtained from
heating the aqueous mixtures of graphene oxide and carbon nano-
tubes with Vitamin C without stirring. The resulting hybrid aerogels
show very promising performance in water purification including
capacitive deionization of light metal salts, removal of organic dyes
and enrichment of heavy metal ions.
The increasing human population combined with exploitation of
water resources has resulted in a shortage of fresh water supply in
many regions of the world because a growing number of contami-
nants including organic dyestuffs, heavy metal ions, light metal salts,
etc. are entering water supplies due to human activity.1 Gradually
water scarcity has become one of the most serious global concerns of
our time as it strongly affects the health and living of human beings,
energy and food production, industrial output, quality of our envi-
ronment, as well as economies of both developing and industrialized
nations.2 Ever-increasing public health and environmental concerns
drive efforts to increase water supply, beyond what is available from
the hydrological cycle, by means of either desalination of brackish
water or decontamination of wastewater.2 The promising future is
that, through focusing on the science of the interface between
constituents in water and the materials used for treatment, novel,
sustainable, affordable, secure and robust technologies for increasing
supplies and purifying water can be developed and implemented to
serve people throughout the world.1
On the other hand, graphene sheets and carbon nanotubes (CNTs)
have attracted tremendous attention because of their extraordinary
electronic, thermal, and mechanical properties, and their potential
application in many fields.3 Attempts to combine graphene and CNT
have been made to prepare electrode materials for lithium ion
batteries and transparent conductors.4 CNTs have bridged the defects
a
School of Materials Science & Engineering, Beijing Institute of
Technology, Beijing, 100081, P. R. China. E-mail: zhangxtchina@yahoo.
com
b
College of Materials Science and Engineering, Beijing University of
Chemical Technology, Beijing, 100029, P. R. China
† Electronic supplementary information (ESI) available: Experimental
details, TEM images and UV spectra of the GO stabilized CNTs,
Raman spectra, XRD patterns, stress–strain curves, I–V curves,
sorption kinetic curves and controllable desorption figures of the
resulting carbon nanotube/green hybrid aerogels. See DOI:
10.1039/c2jm0005e
This journal is ª The Royal Society of Chemistry 2012
COMMUNICATION
for electron transfer as well as increased the layer spacing between
graphene sheets, and what’s more, a unique synergistic effect of one-
dimensional CNTs and two-dimensional graphene sheets has been
observed for these hybrid materials. Aerogels, composed of a tenuous
network of nanoparticles or filaments, are ultralight, highly porous
nanomaterials with large surface area.5 Assembling graphene and
CNT hybrid aerogels, which may integrate the intriguing properties
of graphene sheets and CNTs and unique characteristics of aerogels,
would create new bulk materials with desired structures and
charming properties. To date, although aerogels have been fabricated
with silica, pyrolized organic polymers, metal oxides and carbon-
based materials,5 fabricating graphene and CNT hybrid aerogels is
still a great challenge due to the lack of an appropriate sol–gel
chemistry to make the hybrid gel precursors.
In this communication, we report a green approach to fabricate
ultralight graphene–CNT hybrid aerogel monoliths for the first time
obtained from aqueous gel precursors processed by supercritical CO2
drying. The resulting ultralight graphene–CNT hybrid aerogels
have shown large surface area (435 m2 g 1), ample pore volume
(2.58 cm3 g 1) and high conductivity (7.5 S m 1). The resulting gra-
phene–CNT hybrid aerogels have been investigated in desalination of
brackish water as capacitive deionization (CDI) electrodes and
a maximum desalination capacity of 633.3 mg g 1 has been obtained
in 35 000 mg L 1 NaCl aqueous solution. To the best of our
knowledge, this value is 15.8 times higher than the reported
maximum capacity (40.1 mg g 1)6 among various materials used as
electrodes for CDI application. Furthermore, the resulting graphene–
CNT hybrid aerogels also exhibit excellent scavenging capability for
basic dyes and heavy metal ions as sorbents and binding species.
The synthetic procedure for the graphene–CNT hybrid aerogels is
shown in Fig. 1. Graphene oxide (GO) used in this case was
synthesized and reported in our previous studies.7 The CNTs
employed here are directly applicable to pristine (MWCNTs) or acid
treated (c-MWCNTs) multi-walled CNTs.8 Pre-dispersed GO sheets
and CNTs were mixed and sonicated further to obtain homogeneous
GO–MWCNT and GO–c-MWCNT complexes. TEM images (see
the ESI† Fig. SI1) indicated that the CNTs have attached randomly
to the GO sheets without obvious aggregation. Absorption peaks (see
Fig. SI2†) of the GO–MWCNT and GO–c-MWCNT turned up at
233 nm and 235 nm, respectively, indicative of interaction between
GO sheets and CNTs.9 After that, an appropriate amount of Vitamin
C (VC) and a catalytic amount of hydrochloric acid were added to
the GO–CNT mixtures and sonicated for a short while to dissolve
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Fig. 1 Schematic diagram for green synthesis of the graphene–CNT
hybrid aerogels: (a) pre-dispersed GO solution, (b) pre-dispersed CNT
suspension; (c) the mixture of GO and CNT after sonication; (d) the
graphene–CNT hybrid hydrogel and (e) the graphene–CNT hybrid aer-
ogel. In each subdivision graph, the left part is the digital photo of the real
substance and the right part is the drawing photo of the imaginary
substance. The CNTs employed here are directly applicable to pristine
(MWCNTs) or acid treated (c-MWCNTs) multi-wall CNTs.
VC completely. The purpose of HCl addition is to lower the pH value
of the reaction mixtures for speeding up the reaction between GO and
VC and thus shortening the gelation time of the mixtures.7 The
graphene–MWCNT and graphene–c-MWCNT hydrogel precursors
were obtained by heating the mixtures without stirring for 12 hours
and then the resulting hybrid hydrogels were dried supercritically
with CO2 to obtain the corresponding hybrid aerogels. The VC used
in this case has served as a reducing agent for reduction of GO to
graphene. The use of the environmentally friendly reducing agent
VC, together with the environmentally friendly CO2 drying, has made
our synthesis a green one only if we leave the energy requirements for
the CO2 drying process out of consideration.
The porous structure of the resulting graphene–CNT hybrid aer-
ogels was revealed by SEM images as shown in Fig. 2, XRD patterns
as shown in Fig. SI3† and Raman spectra as shown in Fig. SI4†. It
can be clearly seen in Fig. 2a and b that the graphene–MWCNT
Fig. 2 SEM images of the resulting graphene–MWCNT (a and b) and
graphene–c-MWCNT (c and d) hybrid aerogels. Arrows in (b) and (d) are
the indication of the CNTs.
8768 | J. Mater. Chem., 2012, 22, 8767–8771
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hybrid aerogels exhibit a three-dimensional network structure
composed of hierarchical pores: the macropores with the diameter in
the range of several micrometres are embedded in the monolithic
aerogel matrix and their solid walls are composed of randomly
oriented CNTs, wrinkled graphene sheets and a lot of mesopores in
the range of several tens of nanometres enclosed by CNTs and gra-
phene sheets. Either CNTs or graphene sheets are dispersed
uniformly in the monolithic aerogel matrix because CNTs can be well
dispersed and stabilized in GO dispersions before reduction revealed
by TEM images in Fig. SI1†. The similar morphology and network
structure can be found for the graphene–c-MWCNT hybrid aerogel
as shown in Fig. 2c and d. The hierarchically porous structure may
favor mass transfer and reduce transport limitation for these hybrid
aerogels in some particular applications.10 XRD patterns of the
graphene–CNT hybrid aerogels in Fig. SI3† present crystalline peaks
consistent with those of both CNT powder and graphene aerogel,
which indicates that graphene–CNT hybrid aerogels are essentially
composed of graphene sheets and CNTs and no additional crystalline
order has formed in these hybrid aerogels. It is noteworthy that the
values of the intensity ratio of D to G band are in the order of gra-
phene aerogel (1.34) > graphene–MWCNT aerogel (1.18) > gra-
phene–c-MWCNT aerogel (1.17) > c-MWCNT powder (0.94) >
MWCNT powder (0.84), Fig. SI4†, indicating that the hybrid aero-
gels are a composite of graphene sheets and CNTs again. In addition,
the G band of graphene–CNT hybrid aerogels shifts to some extent in
comparison with MWCNT and c-MWCNT powder, reflecting
a significant interaction between CNTs and graphene sheets.
The porous attribute of the resultant graphene–CNT hybrid aer-
ogels was also confirmed by the nitrogen sorption investigation as
shown in Fig. 3a and b. For the graphene–MWCNT hybrid aerogel,
the nitrogen adsorption–desorption isotherm exhibits an IUPAC
type IV curve characteristic, indicating that there are many meso-
pores existing in this hybrid aerogel. The surface area of the gra-
phene–MWCNT hybrid aerogel is 435 m2 g 1 obtained by fitting the
isotherm to the Brunauer–Emmett–Teller (BET) model. The porous
property of the graphene–MWCNT hybrid aerogel can be further
Fig. 3 Typical nitrogen sorption isotherms of both graphene–MWCNT
(a) and graphene–c-MWCNT (b) hybrid aerogels and XPS spectra of
both graphene–MWCNT (c) and graphene–c-MWCNT (d) hybrid aer-
ogels. Insets in (a) and (b) are the pore size distribution curves of the
corresponding hybrid aerogels.
This journal is ª The Royal Society of Chemistry 2012

confirmed by pore size distribution analysis determined by the Bar-
ret–Joyner–Halenda method,11 from which we can see that there are
two distributed peaks of mesopores respectively centered at 3.6 and
29.7 nm, and the total pore volume is up to 2.58 cm3 g 1. The sorption
isotherm of the graphene–c-MWCNT hybrid aerogel resembles that
of the graphene–MWCNT hybrid aerogel, indicating that the
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morphology and structure of the graphene–c-MWCNT hybrid aer-
ogel are similar to those of the graphene–MWCNT hybrid aerogel.
The specific surface area and total pore volume of the graphene–c-
MWCNT hybrid aerogel are 365 m2 g 1 and 1.90 cm3 g 1, respec-
tively, which are lower than those of the graphene–MWCNT hybrid
aerogel.
Regardless of their porous attribute, the graphene–CNT hybrid
aerogels exhibit high mechanical and electrical properties. The linear
I–V relationship was observed as shown in Fig. SI5† for the gra-
phene–CNT composite monoliths, indicating high conductivity of
these hybrid aerogels. The graphene–MWNCT hybrid aerogel with
a density of 41.1 mg cm 3 has an electrical conductivity of 7.5 S m 1,
while the graphene–c-MWCNT aerogel with a density of 32.2 mg
cm 3 has an electrical conductivity of 2.8 S m 1. The difference in
electrical conductivity is primarily determined by the aerogel density
because the sample with higher density is easier to transfer electrons,
as well as the attribute of MWCNTs and c-MWCNTs in the hybrid
aerogels because c-MWCNTs have underwent an extra oxidation
process which results in the reduction in the conductivity in
comparison with MWCNTs. The compressive stress–strain curves of
the graphene–CNT hybrid aerogels as shown in Fig. SI6† contain
three regions: an elastic region, a yield region and a densification
region. The elastic region at less than 3% strain records the elastic
bending of pore walls of the hybrid aerogels, indicating that the
graphene–CNT hybrid aerogels are linearly elastic under low stress
level. The yield region (until 50% strain) may result from the
gradual pore collapse with the increase of stress. The densification
region (until 70% strain) indicates that these pore walls begin to
collide each other. The compress moduli of the resulting graphene–
MWNCT aerogel with a density of 54.4 mg cm 3 and the graphene–
c-MWCNT aerogel with a density of 31.8 mg cm 3 are approximately
2.9 MPa and 1.2 MPa, respectively.
The chemical attribute of the graphene–CNT aerogels has been
investigated by X-ray photoelectron spectroscopy (XPS) as shown
in Fig. 3c and d. XPS analysis reveals that surface O contents
(atomic %) were 10.24 for the graphene–c-MWCNT hybrid aerogel
and 7.14 for the graphene–MWCNT hybrid aerogel, respectively.
The GO shows C1s XPS peaks at 284.5, 286.5, 287.8, and 289.0 eV
reported in our previous study,7 corresponding to C]C/C–C in
aromatic rings, C–O (epoxy and alkoxy), carbonyl, and carboxyl
groups, respectively. Although the graphene–CNT hybrid aerogels
exhibit the same oxygen-containing functionalities, the intensities of
the carbon attached to oxygen (primary C–O) become sharply
weakened in comparison with original GO sheets, indicating that
removal of O happened during reduction with VC. The residue O in
these hybrid aerogels mainly results from carbonyl and carboxyl
groups, which cannot be removed during VC reduction. The differ-
ence in surface O content between graphene–MWCNT and gra-
phene–c-MWCNT hybrid aerogels comes from the difference
in chemical composition between MWCNT and c-MWCNT as
c-MWCNTs have underwent an oxidation process which results in
the extra carboxylic acid groups introduced on the side walls of the
nanotubes in comparison with MWCNTs.
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To investigate desalination capacity of the graphene–CNT hybrid
aerogels, batch-mode experiments were conducted in a continuously
recycling system including an electrosorptive unit cell and a conduc-
tivity monitor as shown in Fig. 4a. Figure 4b presents a digital photo
of a representative CDI electrode made by pressing hybrid aerogel
powder into nickel foam. To investigate electrosorption behavior
of the graphene–CNT hybrid aerogel electrodes, desalination
experiments at different initial concentrations ranging from 100 to
4000 mg L 1 were conducted at a bias potential of 1.6 V, higher than
the water decomposition potential due to existence of cell internal
resistance. As shown in Fig. 4c, when the initial concentration of
NaCl aqueous solution was 4000 mg L 1, the removal capacities of
salt were 75.6 and 79.4 mg g 1 for the graphene–c-MWNCT and
graphene–MWCNT hybrid aerogels, respectively. The experimental
data on the NaCl electrosorption to the graphene–CNT hybrid aer-
ogels can be fitted well with the Freundlich isotherm, rather than the
Langmuir isotherm reported elsewhere.6,12 The Freundlich isotherm
was also observed for the graphene electrode in CDI, but removal
capacity is only 1.6 mg g 1 at the salt concentration of 500 mg L 1.13
Further experiments were conducted to compare the removal
capacity of the graphene–MWCNT and graphene–c-MWCNT
hybrid aerogels at increased NaCl concentration up to 35 000
mg L 1, which corresponds to the salinity of seawater. It should be
noted that the applied voltage should be decreased from 1.6 to 1.0 V
when the initial 35 000 mg L 1 NaCl was used. Otherwise a lot of air
bubbles are observed due to gas evolution. This may result from the
sharp decrease in cell internal resistance when such a high concen-
tration of NaCl was used. It has been observed that, when the initial
NaCl concentration is 35 000 mg L 1, the removal capacities are
633.3 and 521.6 mg g 1 for the graphene–MWCNT and graphene–c-
MWCNT hybrid aerogels, respectively. To the best of our
Fig. 4 Schematic diagram for CDI cell set-up used in our case: 1 and 7
stand for polypropylene plates; 2, 4, and 6 stand for silicone gaskets with
a hole and 3 and 5 stand for working electrodes (a), the digital photo of
one CDI working electrode made by pressing graphene–CNT hybrid
aerogel powder into nickel foam (b), the relationships between salt
concentration and removal capacity during the desalination process using
the graphene–CNT hybrid aerogels as electrode materials, fitted well with
Freundlich isotherms (c) and the real time monitoring of the conductiv-
ities for the investigated salt-containing solutions before and after
applying the electric field between the hybrid aerogel electrodes (d). For
comparison, the related data collected with graphene alone aerogel
electrode and MWCNTs powder electrode were also shown in (c) and (d).
J. Mater. Chem., 2012, 22, 8767–8771 | 8769

knowledge, the former is 15.8 times and the latter is 13.0 times higher
than the maximum CDI capacity (40.1 mg g 1) reported so far.6
To investigate the CDI mechanism of these hybrid aerogels, the
change in conductivity of the NaCl solution during the desalination
process has been monitored as shown in Fig. 4d. During the first 10
minutes without applying the potential, the conductivity decreased
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significantly, which indicates that both Na+ and Cl have strong
affinity to either graphene–MWCNT or graphene–c-MWNCT
hybrid aerogels. The adsorption equilibrium can be reached after 20
minutes. Once the electric field was applied, the conductivity
decreased dramatically again due to electrosorption of NaCl onto the
surface of either graphene–MWCNT or graphene–c-MWCNT
hybrid aerogels. These results show that, for the graphene–CNT
hybrid aerogels as the CDI electrodes, the desalination process can be
recognized as two different ones, namely physical- and electro-
adsorption, similar to the desalination process observed for the
carbon aerogel electrode.14 The favorable factors, including the
hierarchically porous structure10 of the hybrid aerogels, the functional
groups15 attached to the surfaces of graphene sheets or CNTs, the
high conductivity resulted from the interconnection among graphene
and CNTs, together with large surface areas of these hybrid aerogels,
have resulted in the especially high desalination capacity due to
combination of physical- and electro-adsorption. In addition, in
comparison with the graphene–c-MWCNT hybrid aerogel, the
desalination capacity of the graphene–MWCNT hybrid aerogel is
higher. This may result from larger specific surface area and higher
electrical conductivity of the latter. It also can be clearly seen from
either Fig. 4c or d that, at each salt concentration, the removal
capacities of the hybrid graphene–CNT aerogels are higher
than either graphene alone aerogel7b or MWCNT powder,8a indi-
cating that significant synergistic effect exists if graphene sheets are
integrated with carbon nanotubes into graphene–CNT hybrid
aerogels.
Fig. 5 Adsorption of dyes (A: methylene blue, B: fuchsin, C: rhodamine
B, D: acid fuchsin) by graphene–CNT hybrid aerogels (a) and binding of
heavy metal ions with graphene–CNT hybrid aerogels (b). For compar-
ison, the related data collected with graphene alone aerogel were also
shown in (b).
8770 | J. Mater. Chem., 2012, 22, 8767–8771
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Fig. 5a presents adsorption curves of three basic dyes (methylene
blue, rhodamine B and fuchsin) and one acid dye (acid fuchsin) with
the graphene–CNT hybrid aerogels. The removal of dyes has attained
equilibrium in 10 hours and a plateau is gradually reached thereafter.
For the graphene–c-MWCNT hybrid aerogel, the adsorption
capacity for methylene blue is 190.9 mg g 1, which is much larger
than those of the same dye with most conventional adsorbents under
similar conditions.16 For the graphene–MWCNT hybrid aerogel, the
adsorption capacity for rhodamine B is 145.9 mg g 1, which is larger
than those of the same dye with substances such as magnetically
separable porous graphitic carbon (73.0 mg g 1),17 O-carbox-
ymethylchitosan-N-lauryl (38.5 mg g 1) and Rhizopus oryzae biomass
(39.08 mg g 1).18 Obviously, in all cases, the graphene–CNT hybrid
aerogels have a large adsorption capacity for basic dyes. In addition,
the adsorption capacity of the graphene–c-MWCNT hybrid aerogel
is larger than that of the graphene–MWCNT hybrid aerogel because
of the higher O content (mainly carboxyl groups revealed by previous
XPS analysis) present in the former, which is favorable for the basic
dye adsorption. The adsorption of acid fuchsin with the graphene–
MWCNT and graphene–c-MWCNT hybrid aerogels is 66.4 and
35.8 mg g 1, respectively, relatively lower capacities due to existence
of electrostatic repulsion between hybrid aerogels and adsorbed
acidic dyes. However, still appropriate amount of acidic dye can be
adsorbed with the hybrid aerogels, indicating that strong p–p
interaction existed between hybrid aerogels and adsorbed dyes. Thus,
the adsorption behavior of dyes with the graphene–CNT hybrid
aerogels is the result of the synergistic effect of electrostatic and p–p
interactions. The adsorption process of dyes with the graphene/CNT
hybrid aerogels fitted well with the pseudo-second-order kinetic
model as shown in Fig. SI7†, indicative of existence of these inter-
actions. By the way, in comparison with the graphene–MWCNT and
graphene–c-MWCNT hybrid aerogels, our previously reported gra-
phene aerogel7b has intermediate adsorption capacities for some dyes
as shown in Table SI1†. Furthermore, the more the surfactant cetyl
trimethylammonium bromide added, the more the dyes desorbed
from the loaded graphene–CNT hybrid aerogels as shown in
Fig. SI8†, indicative of the controlled release of the adsorbed dyes.
Fig. 5b presents binding capacities of the graphene–c-MWCNT
hybrid aerogel with 104.9 mg g 1(0.51 mmol g 1) for Pb2+, 93.3
mg g 1 (0.46 mmol g 1) for Hg2+, 64 mg g 1(0.59 mmol g 1) for Ag+
and 33.8 mg g 1 (0.53 mmol g 1) for Cu2+, and those of the graphene–
MWCNT hybrid aerogel with 44.5 mg g 1 (0.21 mmol g 1) for Pb2+,
75.6 mg g 1(0.38 mmol g 1) for Hg2+, 46 mg g 1 (0.43 mmol g 1) for
Ag+ and 9.8 mg g 1 (0.15 mmol g 1) for Cu2+, respectively. In
comparison with the graphene–MWCNT hybrid aerogel, the gra-
phene–c-MWCNT hybrid aerogels have respectively higher binding
capacities for the same heavy metal ions. This is because the binding
of the various metal ions to porous hosts in aqueous solution is
mainly controlled by the electrostatic interaction19 and the graphene–
c-MWCNT hybrid aerogel has more oxygen-containing groups
revealed in previous XPS analysis, which is favorable for binding the
above heavy metal ions.20 This is also the reason that, in comparison
with the graphene–MWCNT and graphene–c-MWCNT hybrid
aerogels, our previously reported graphene aerogel7b has intermediate
binding capacities for various metal ions as shown in Fig. 5b.
Furthermore, the difference in binding capacity for these metal ions
probably ascribes to their different affinity to carboxyl groups
attached to the end edges of the graphene sheets and the side walls of
the CNTs (for c-MWNTs only).
This journal is ª The Royal Society of Chemistry 2012

In conclusion, we report a green method to fabricate graphene–
CNT hybrid aerogels prepared by supercritical CO2 drying of the
graphene–CNT hybrid hydrogel precursors obtained from heating
the aqueous mixtures of GO and CNTs with VC without stirring.
The resulting graphene–CNT hybrid aerogels show light weight, high
conductivity, large BET surface area, and ample volume with hier-
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archically porous structure. The resulting graphene–CNT hybrid
aerogels show extremely high desalination capacity (633.3 mg g 1)
with the NaCl concentration up to 35 g L 1, which is 15.8 times
higher than the reported maximum capacity (40.1 mg g 1) among
various materials used as electrodes for CDI application. The
resulting graphene–CNT hybrid aerogels also exhibit high binding
capacities to some heavy metal ions including Pb2+, Ag+, etc., and
high adsorption capacities for dyestuffs, especially for basic dyes with
well-controlled desorption behavior. These investigations have indi-
cated that the synthesized graphene–CNT hybrid aerogels reported
here may have promising application in the field of water purification
including CDI of light metal salts, removal of waste dyes, enrichment
of heavy metal ions, etc.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (20903009) and the Science Foundation for the
Excellent Youth Scholars of Beijing Institute of Technology
(2010YS0903).
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