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Centre for Process Systems Engineering, Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth, WA 6845, Australia
Department of Imaging and Applied Physics, Curtin University, GPO Box U1987, Perth, WA 6845, Australia
c
School of Chemical Engineering, The University of Queensland, St. Lucia 4072, Australia
b
a r t i c l e
i n f o
Article history:
Received 30 August 2010
Accepted 28 January 2011
Available online 3 February 2011
Keywords:
Carbon aerogel
KOH catalysis
Dye adsorption
a b s t r a c t
Organic carbon aerogels (CAs) were prepared by a solgel method from polymerisation of resorcinol,
furfural, and hexamethylenetetramine catalysed by KOH at around pH 9 using ambient pressure drying. The effect of KOH in the solgel on CA synthesis was studied. It was found that addition of KOH
prior to the solgel polymerisation process improved thermal stability of the gel, prevented the crystallinity of the gel to graphite, increased the microporosity of CA and promoted activation of CA. The
CAs prepared using the KOH catalyst exhibited higher porosity than uncatalysed prepared samples.
Activation in CO2 at higher temperature also enhanced the porosity of CAs. Adsorption tests indicated
that the CAs were effective for both basic and acid dye adsorption and the adsorption increased with
increasing surface area and pore volume. The kinetic adsorption of dyes was diffusion control and
could be described by the second-order kinetic model. The equilibrium adsorption of dyes was higher
than activated carbon.
2011 Elsevier Inc. All rights reserved.
1. Introduction
The pollution of water resources due to the indiscriminate
disposal of toxic organic compounds and heavy metals has been
a worldwide issue in the last few decades. Removal of those contaminants from water is a big challenge. The conventional methods for the removal of toxic compounds include adsorption,
precipitation, coagulation/occulation, ion exchange, reverse
osmosis, complexation/sequestration, electrochemical operation
and biological treatment [18]. Adsorption using activated carbon is the most economic and widely used method. Development of efcient carbon adsorbents is the key to adsorptive
treatment of wastewater and gas cleaning. Dye stuffs from various industries such as textile, food processing, and ink production impose a threat to the environment and ecosystem due to
their blockage of sunlight and toxicity. Several different types
of dye are widely used including basic, acid, reactive, and dispersed dyes. Removal of dyes by adsorption using activated carbon and other low cost adsorbents is the simple and effective
method.
Carbon aerogels (CAs) are novel porous carbon materials and
they are of great signicance in terms of scientic and practical
applications because of their unique properties, such as controlla-
Corresponding author.
E-mail address: shaobin.wang@curtin.edu.au (S. Wang).
0021-9797/$ - see front matter 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2011.01.092
158
S.K. Ling et al. / Journal of Colloid and Interface Science 357 (2011) 157162
2. Experimentals
Fig. 1 shows FT-IR spectra of dry gel of CAs synthesised with and
without KOH. The peak positions were almost the same for the two
samples due to the same composition and the addition of KOH
would not result in a signicant change in chemical structure of
the gels. However, there was an increase in the transmittance (%)
for KOH-catalysed sample, indicating the formation of more porous
structure in the CA catalysed by KOH. The FT-IR spectra showed a
broad peak at 3450 cm1, characteristic of OAH stretching vibrations, ascribed to adsorbed water. The other peaks between 1400
and 1800 cm1 at 1664, 1606, 1503, and 1469 cm1 were associated with aromatic and furfural ring stretching vibrations of
O@C, aromatic ring, OACH2, and CACH2AC, respectively. Meanwhile, the bands at 1012 and 960 cm1 and the bands at
737 cm1 and its accompanying peaks at 803 and 839 cm1 were
assigned to aromatic and furfural CH out-of plane bending vibrations. These IR peaks suggested that the aromatic ring structures
would give rise to the skeleton formation of CAs.
Fig. 2 shows TGA/DTA proles of as-prepared CAs without KOH
and KOH-catalysed. For the two samples, the TG proles were similar showing a three-stage variation. The rst stage of weight loss
was at 25161.2 C, attributing to the evaporation of surface adsorbed water and residual organic reagents. In this stage, KOH-catalysed sample presented less weight loss. At the second stage of
weight loss between 161.2 and 796.6 C, KOH-catalysed sample
exhibited higher weight loss. This stage was the major process of
carbonisation of wet gels. In the last stage, much less weight loss
was observed for both samples compared with the other two processes, which was caused by the further pyrolysis of carbon at high
temperatures. The overall weight loss from the two samples suggested that the gel with KOH would be more stable during the carbonisation process and more organic network would be
transformed to CA. The DTA proles of the two samples also
showed the instability of the uncatalysed gel. A differentiated
curve presented at the top line of Fig. 2 showed the exothermic
and endothermic peaks during the course of carbonisations. In
the second stage of carbonisation, the uncatalysed gel presented
several endothermic and exothermic peaks between 220 and
420 C and also another endothermic peak occurred at 916.6 C
in the last stage, suggesting more violent chemical reactions occurring during the carbonisation, resulting in more loss of carbon.
However, no signicant reaction occurred on KOH-catalysed gel
in the same stages.
Fig. 3 shows the XRD proles of CAs synthesised with or without KOH. Two CAs presented amorphous phase with a broad peak
between 40 and 47. The CA without KOH catalyst also showed
two sharp peaks of graphite (i.e. 21.5 and 23.9). This suggested
that without KOH, amorphous carbon networks would be crystallised to form graphite and the porous structure could be partially
lost. With KOH, no signicant crystallisation to graphite occurred
during carbonisation.
Fig. 4 displays N2 adsorption isotherms of inactivated CA and
activated CAs at varying temperatures prepared by uncatalysed
and KOH-catalysed methods. The surface areas, pore volume and
average pore radius of those samples are presented in Table 1.
The inactivated CA (CA-K-900) had the lowest N2 adsorption. Under the same activation conditions, the uncatalysed CAs also had
lower N2 adsorption than KOH-catalysed CAs. The surface area
and pore volume of the inactivated CA (CA-K-900) were 680 m2/g
and 0.40 cm3/g, respectively. After activation at 900 and 1000 C,
the surface area and pore volume were signicantly increased.
Meanwhile, the activated CAs without KOH also showed higher
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S.K. Ling et al. / Journal of Colloid and Interface Science 357 (2011) 157162
Fig. 1. FT-IR of as-prepared CA samples: (a) noncatalysed sample and (b) KOH-catalysed sample. The full spectra between 400 and 4000 cm1 were shown in (A) and the
spectra between 400 and 2000 cm1 were shown in (B).
Fig. 2. TGA/DTA proles of CAs prepared with KOH and without KOH.
3000
2500
2000
CA-K-900
CA-K-A900
CA-K-A1000
CA-A900
CA-A1000
1500
1000
500
0
0.0
0.2
0.4
0.6
0.8
1.0
p/p0
Fig. 4. N2 adsorption isotherms of various CAs.
Fig. 3. XRD proles of CAs prepared with KOH and without KOH.
surface area and pore volume than the inactivated CAs but the surface area and pore volume were lower than the corresponding
KOH-catalysed samples. The order of surface area and pore volume
of various CAs would be CA-K-A1000 > CA-A1000 > CA-KA900 > CA-A900 > CA-K-900.
The pore size distribution proles of various CAs are illustrated
in Fig. 5. The inactivated CA (CA-K-900) presented microporous
structure with pore size centred at 6 and 10 . CO2 activation could
produce larger pores. The sample CA-A900 exhibited a similar pro-
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S.K. Ling et al. / Journal of Colloid and Interface Science 357 (2011) 157162
Table 1
Textural properties of various CAs prepared.
Table 2
Kinetic parameters of dye adsorption on various CAs.
Sample
SBET
(m2/g)
Vtotal
(cm3/g)
RGmic
(nm)
Vmica
(cm3/g)
Vmicb
(cm3/g)
CA-K-900
CA-K-A900
CA-K-A1000
CA- A900
CA- A1000
680
1403
2796
1280
2139
0.40
0.64
1.89
0.53
1.00
0.62
0.67
0.94
0.61
0.78
0.39
0.58
1.33
0.50
0.81
0.34
0.52
1.06
0.45
0.75
Sample
CA-K-900
CA-K-A900
CA-K-A1000
CA-A900
CA-A1000
CA-K-900
CA-K-A900
CA-K-A1000
CA-A900
CA-A1000
CA-K-900
CA-A900
CA-K-A900
CA-A1000
CA-K-A1000
dV/dR (cc/A)
0.20
6
10 12
0.00
10
20
30
40
well-developed porous structure. This suggested that CA precursors, F and R, could react with KOH as a catalyst to form a crosslinking network at high pH and the pores was dominated by
micropores. The characterisation by TGA/DTA showed that addition of KOH in the precursors would reduce the weight loss and
maintain stable carbonisation. XRD showed that less graphite
would be formed and CA would be more inclined to amorphous
phase. N2 adsorption also indicated that CAs synthesised with
addition of KOH catalyst would have higher surface area and larger
pore volume. These results suggested that the addition of KOH was
important in synthesis of porous CAs. During the synthesis of gels
and carbonisation, KOH would promote the formation of stable
networks and prevent the graphitisation. In addition, it is well
know that KOH is a commonly used reagent for carbon activation
in steam or CO2. Thus, it was also deduced that during the activation of CAs, the presence of KOH in carbon gels would also favour
the development of porous structure, resulting in higher surface
area and larger pore volume.
AR183
8.90 10
4.04 105
2.85 105
7.96 105
5.87 105
1.69 103
1.49 104
4.60 105
2.97 105
2.29 105
q2e k2 t
1 qe k2 t
3000
200
CA-K-900
CA-A900
CA-K-A900
CA-A1000
CA-K-A1000
Second-order kinetics
CA-K-900
CA-A900
CA-K-A900
CA-A1000
CA-K-A1000
Second-order kinetics
2000
1500
1000
500
0
50
100
150
200
250
0.988
0.986
0.998
0.980
0.995
0.923
0.969
0.970
0.960
0.986
(B)
2500
100
232.6
301.6
399.2
360.8
405.6
352.9
490.9
890.1
1262.9
2686.9
R2
(A)
300
0
0
qt
Adsorption (mg/g)
Adsorption (mg/g)
400
5
Fig. 6 shows the adsorption of two dyes on various CAs at varying time. For both dyes, CAs showed a fast increase in dye adsorption within 50 min and the adsorption approached to the
equilibrium at around 300 min. In general, activated CAs exhibited
higher adsorption and KOH-catalysed CAs presented higher
adsorption than uncatalysed samples. The order of adsorption followed
CA-K-A1000 > CA-A1000 > CA-K-A900 > CA-A900 > CA-K900, which was similar to the order of surface area and pore volume. This suggested that dye adsorption was strongly dependent
on the porous structure of CAs. At equilibrium, CA-K-900 would
have BB9 and AR183 adsorption at 200 and 280 mg/g, respectively.
CA-K-A1000 could have adsorption of BB9 and AR183 at 360 and
2650 mg/g, respectively.
In general, adsorption is dependent on porous structure and
surface functional properties. As discussed above, the presence of
KOH in CA gels promoted the formation of stable porosity and
development of larger pores during CO2 activation, which were
evidenced in Table 1. The higher surface area and pore volume of
KOH-catalysed CAs will provide more active sites for adsorption
of dye molecules. Also the presence of KOH could helps to produce
and modify the surface functional groups. These functional groups
with either positive charge or negative charge will favour the
adsorption of charged dye molecules.
The dynamic adsorption of both dyes was also investigated by
pseudo-second-order kinetics, which is presented in the following
equation.
0.10
BB9
K2 (g/mg min)
0.15
0.05
Second-order kinetics
qe (mg/g)
0.25
Dye
300
350
50
100
Time (min)
Fig. 6. Dye adsorption on various CAs. (A) BB9, (B) AR183.
150
200
Time (min)
250
300
350
161
S.K. Ling et al. / Journal of Colloid and Interface Science 357 (2011) 157162
300
3000
(A)
CA-K-900
CA-A900
CA-K-A900
CA-A1000
CA-K-A1000
200
100
(B)
CA-K-900
CA-A900
CA-KA900
CA-A1000
CA-K-A1000
2500
Adsorption (mg/g)
Adsorption (mg/g)
400
2000
1500
1000
500
10
12
14
16
18
20
t1/2 (min1/2)
1/2
10
12
14
16
18
20
1/2
(min )
Fig. 7. Intraparticle diffusion plots of dye adsorption on various CAs. (A) BB9, (B) AR183.
From the curve tting (Fig. 6) and the kinetic parameters (Table
2) obtained from Eq. (1), the dynamic adsorption of two dyes on
various CAs was tted well to the second-order kinetics based on
equilibrium adsorption and regression coefcients. It is known that
the pseudo-second order equation assumes a chemical adsorption
mechanism. For CAs, several functional groups are usually presented such as OH, COOH and they can act as binding sites for
dye adsorption. For BB9 and AR183, the mechanism may be proposed as follows.
qt ki t 1=2
4. Conclusion
Activated CAs were synthesised with addition of KOH catalyst
in a solgel solution and under CO2 activation. The structure and
adsorption properties were compared with CAs without KOH
catalysis. The KOH catalyst was found to play an important role
in improving the gel stability during carbonisation process. The
addition of KOH would also improve the development of porous
structure of CAs by improving larger pores. Activation with CO2
at a high temperature also resulted in higher surface area and
larger pore volume. In adsorption of dyes in aqueous solution,
CAs were much effective for both basic and acid dye adsorption
and the porous structure was the major factor inuencing the
adsorption. The dynamic adsorption of dyes on CAs could be
described by the second-order kinetic model and the equilibrium
adsorption was higher compared with some activated carbons.
Acknowledgement
Partial support from ARC LIEF Grant LE0775551 (XRD) is
acknowledged.
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