Adsorption behavior of methylene blue on carbon nanotubes

Yunjin Yao
*
, Feifei Xu, Ming Chen, Zhongxiao Xu, Zhiwen Zhu
School of Chemical Engineering, Hefei University of Technology, Hefei 230009, China
a r t i c l e i n f o
Article history:
Received 7 September 2009
Received in revised form 6 December 2009
Accepted 10 December 2009
Available online 8 January 2010
Keywords:
Adsorption
Carbon nanotube
Isotherm
Methylene blue
Thermodynamics
a b s t r a c t
The effect of temperature on the equilibrium adsorption of methylene blue dye from aqueous solution
using carbon nanotubes was investigated. The equilibrium adsorption data were analyzed using two
widely applied isotherms: Langmuir and Freundlich. The results revealed that Langmuir isotherm t
the experimental results well. Kinetic analyses were conducted using pseudo-rst and second-order
models and the intraparticle diffusion model. The regression results showed that the adsorption kinetics
were more accurately represented by pseudo-second-order model. The activation energy of system (Ea)
was calculated as 18.54 kJ/mol. Standard free energy changes (DG
0
), standard enthalpy change (DH
0
), and
standard entropy change (DS
0
) were calculated using adsorption equilibrium constants obtained from the
Langmuir isotherm at different temperatures. All DG
0
values were negative; the DH
0
values and DS
0
val-
ues of CNTs were 7.29 kJ/mol and 64.6 J/mol K, respectively. Results suggested that the methylene blue
adsorption on CNTs was a spontaneous and endothermic process.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Dyes are colour organic compounds which can colorize other
substances. These substances are usually present in the efuent
water of many industries, such as textiles, leather, paper, print-
ing, and cosmetics. The complex aromatic structures of dyes
make them more stable and more difcult to remove from the
efuents discharged into water bodies (Crini, 2006). There are
several methods to remove dyes such as physical and chemical
processes to treat wastewaters including organic pollutant and
dyes. The most commonly used methods for color removal are
biological oxidation and chemical precipitation. However, these
processes are effective and economic only in the case where
the solute concentrations are relatively high. The adsorption
technique has proven to be an effective and attractive process
for the treatment of these dye-bearing wastewaters. The adsorp-
tion characteristics of dyes on various adsorbents have been
extensively investigated for many purposes involving separation
and purication.
Carbon nanotubes (CNTs), with nano-sized diameter and tubu-
lar microstructure, have been the worldwide hotspot of study since
their discovery because of their unique morphologies and various
potential applications. Because of their relatively large specic sur-
face areas and easily modied surfaces, much attention has been
paid to the adsorption by CNTs of contaminants such as Zn
2+
(Lu
and Chiu, 2006), Cd
2+
(Li et al., 2003), Pb
2+
(Kabbashi et al.,
2009), Cu
2+
(Wu, 2007), Cr
6+
(Di et al., 2006), uoride (Li et al.,
2003), and dioxin (Long and Yang, 2001). Therefore, CNTs might
be ideal sorbents for the removal of dyes from water. The reactive
dye, methylene blue (MB) has wide applications, which include
coloring paper, temporary hair colorant, dyeing cottons, wools,
and coating for paper stock. Although MB is not extremely hazard-
ous, it can cause some harmful effects. MB was employed as the or-
ganic pollutant to be treated by CNTs in this work.
Earlier studies have obtained only equilibrium adsorption
data and few works have measured the kinetics and thermody-
namic parameters of adsorption on CNTs. Peng et al. (Peng
et al., 2003) measured those of the adsorption of 1,2-dichloroben-
zene and Li et al. (Li et al., 2005) examined the thermodynam-
ics of the adsorption of Pb
2+
on CNTs. Few investigations
focused on the adsorption of organic pollutants on CNTs and
simultaneously determined the kinetics equilibrium and
thermodynamic parameters. Hence, this study elucidates the
kinetics equilibrium and thermodynamics of the adsorption of
MB onto CNTs.
In this study CNTs were used and evaluated as a possible sor-
bent for the removal of a cationic dye (methylene blue, MB) from
aqueous solution. The objective of this study is to investigate the
effect of MB concentration, temperature, and contact time on the
adsorption process. Kinetics and thermodynamics studies have
been performed and the results have been analyzed by applying
conventional theoretical methods. Thermodynamic parameters,
such as DG
0
, DH
0
, and DS
0
, were calculated.
0960-8524/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.12.042
* Corresponding author. Tel.: +86 551 2901458; fax: +81 551 2901453.
E-mail address: yaoyunjin@gmail.com (Y. Yao).
Bioresource Technology 101 (2010) 30403046
Contents lists available at ScienceDirect
Bioresource Technology
j our nal homepage: www. el sevi er . com/ l ocat e/ bi or t ech
2. Methods
2.1. Materials
CNTs were produced by chemical vapor deposition using the car-
bon from acetylene cracking; iron nanoparticles embedded in mes-
oporous silica, prepared by mixing iron nitrate solution and
tetraethoxysilane in a solgel process, were employed as the cata-
lyst. The method of synthesis had been described before (Yao
et al., 2008a,b). The rawproduct contains the aerogel support, cata-
lyst particles, and a fewamorphous carbons (mostly as a coating on
the catalyst nanoparticles) as impurities. The as-grown CNTs were
puried using a two-step purication procedure involving acid
washingandoxidationindilutedair. TheBETsurfacearea was deter-
mined fromadsorption isotherms using a Micromeritics ASAP 2020
Surface Area Analyzer. The BET surface area, average pore diameter,
andpore volume was 160 m
2
/g, 20 nm, and0.67 cm
3
/g, respectively.
MB (C
16
H
18
ClN
3
S3H
2
O, molecular weight 373.9) were obtained
from Shanghai Reagents Co. and used without further purication.
All MB solutions used in this study were prepared by weighing and
dissolving the required amounts MB in distilled water.
2.2. MB absorption
Batch adsorption experiments were performed using 100 ml
glass bottles with addition of 15 mg puried CNTs and 50 ml of
MB solution of increased initial concentrations (C
0
) from 5 to
40 mg/l. The glass bottles were sealed and placed within a temper-
ature control box to maintain water temperature. The pH of the
samples was adjusted by adding 2 M HCl or 0.5 M NaOH to each
200 ml of the prepared solution to pH 7. The pH of solutions was
measured with a pH meter. In the experiments on the effect of
temperature, the temperature was held at 273, 298, and 333 K
and the pH was xed at 7. At the end of the equilibrium period,
the suspensions were separated for later analysis of the dye con-
centration. The amount of MB adsorption at equilibrium q
e
(mg/
g) was calculated from the following equation:
q
e
VC
0
C
e
=W 1
where C
0
and C
e
(mg/L) are the liquid-phase concentrations of dye
at initial and equilibrium, respectively, V (L) the volume of the solu-
tion and W (g) is the mass of adsorbent used. The concentration of
MB after and before adsorption was determined using a spectropho-
tometer (k
max
= 665 nm).
The procedures of kinetic experiments were identical with
those of equilibriumtests. The effect of contact time on the amount
of dye adsorbed was investigated at 20 mg/l initial concentration of
dye and at different temperatures (273, 298, and 333 K).The
amounts of dye adsorbed on CNTs at any time, t, were calculated
from the concentrations in solutions before and after adsorption.
At any times, the amount of MB adsorbed (mg/g) (q
t
) onto CNTs
was calculated from the mass balance equation as follows:
q
t
VC
0
C
e
=W 2
where q
t
is the amount of adsorbed dye on CNTs at any time (mg/g);
C
0
and C
t
are the initial and liquid-phase concentrations of MB at
any time (mg/L), respectively; V (L) is the volume of MB solution,
and W (g) is the mass of CNTs sample used.
3. Results and discussion
3.1. Adsorption isotherms
The adsorption equilibrium isotherm is important for describ-
ing how the adsorbate molecules distribute between the liquid
and the solid phases when the adsorption process reaches an equi-
librium state. The adsorption isotherms of MB on CNTs at 273, 298,
and 333 K are shown in Fig. 1, respectively. As seen from Fig. 1,
equilibrium uptake increased with the increasing of equilibrium
MB concentrations at the range of experimental concentration.
This is a result of the increase in the driving force from the concen-
tration gradient. In the same conditions, if the concentration of MB
in solution was bigger, the active sites of CNTs were surrounded by
much more MB ions, and the process of adsorption would carry out
sufcient. Therefore, the values of q
e
increased with the increase of
equilibrium MB concentrations. From Fig. 1, the adsorption capac-
ity of MB onto CNTs 35.0 mg/g
1
at 298 K, compared to other
adsorbents, the quantity of MB adsorption onto CNTs is not high,
but as natural materials, it is vast and cheap, so CNTs can be used
to remove MB from solution. The increase of the equilibrium
adsorption with increased temperature indicated that the adsorp-
tion of MB ions onto CNTs was endothermic in nature.
The analysis of the isotherm data by seeing how well different
models can accommodate them is an important step in establish-
ing a model that can be successfully used for design purposes.
Adsorption equilibrium is a dynamic concept achieved when the
rate at which molecules adsorb onto a surface is equal to the rate
at which they desorb. At equilibrium, no change can be observed
in the concentration of the solute on the solid surface or in the bulk
solution, a situation characteristic of the entire system, including
solute, adsorbent, solvent, temperature, pH, and so on. The equilib-
rium adsorption isotherm is vital to the design of adsorption sys-
tems, and its shape provides information about the homogeneity
and heterogeneity of the adsorbent surface. Moreover, the correla-
tion of the equilibrium data with either theoretical or empirical
equations is essential to practical operation. The isotherm data
were tted to the Langmuir and Freundlich.
The Langmuir model assumes that there is no interaction be-
tween the adsorbate molecules and the adsorption is localized in
a monolayer. The Langmuir isotherm (Langmuir, 1918) is repre-
sented by the following linear equation:
C
e
q
e

1
q
0
K
L

1
q
0
C
e
3
where C
e
(mg/L) is the equilibrium concentration, q
e
(mg/g) the
amount of adsorbate adsorbed per unit mass of adsorbate, and q
0
and K
L
are the Langmuir constants related to adsorption capacity
and rate of adsorption, respectively. When C
e
/q
e
was plotted against
C
e
, straight line with slope 1/q
0
was obtained (Fig. 2a), indicating
that the adsorption of MB on CNTs follows the Langmuir isotherm.
Fig. 1. Adsorption isotherms of MB onto CNTs at different temperatures.
Y. Yao et al. / Bioresource Technology 101 (2010) 30403046 3041
The Langmuir constants K
L
and q
0
were calculated from this iso-
therm and their values are listed in Table 1. Furthermore, the effect
of the isotherm shape is considered with a view to predict whether
an adsorption system is favorable or unfavorable. Another impor-
tant parameter, R
L
, called the separation factor or equilibrium
parameter, also evaluated in this study, is determined fromthe rela-
tion (Hall et al., 1966):
R
L

1
1 bC
0
4
where K
L
is the Langmuir constant and C
0
(mg/L) is the highest dye
concentration. The value of R
L
indicates the type of the isotherm to
be either unfavorable (R
L
> 1), linear (R
L
= 1), favorable (0 < R
L
< 1) or
irreversible (R
L
= 0). R
L
values for MB adsorption onto CNTs were
less than 1 and greater than zero indicating favorable adsorption
(Table 1).
The Freundlich isotherm model is an empirical relationship
describing the adsorption of solutes from a liquid to a solid surface,
and assumes that different sites with several adsorption energies
are involved. The linear form of the Freundlich equation is
lnq
e
lnK
F

1
n
lnC
e
5
where q
e
is the amount adsorbed at equilibrium(mg/g) and C
e
is the
equilibrium concentration of the MB. K
F
and n are Freundlich con-
stants, n giving an indication of how favorable the adsorption pro-
cess and K
F
(mg/g (L/mg)
1/n
) is the adsorption capacity of the
adsorbent. It is generally stated that values of n in the range 210
represent good, 12 moderately difcult, and less than 1 poor
adsorption characteristics. The studied materials are good adsor-
bents for MB (n > 2). The slope 1/n ranging between 0 and 1 is a
measure of adsorption intensity or surface heterogeneity, becoming
more heterogeneous as its value gets closer to 0 (Haghseresht and
Lu, 1998). The plot of ln q
e
versus ln C
e
(Fig. 2b) gives straight lines
with slope 1/n. Fig. 2b shows that the adsorption of MB also follows
the Freundlich isotherm. Accordingly, Freundlich constants (K
F
and
n) were calculated and listed in Table 1.
The validity of models was determined by calculating the stan-
dard deviation (S.D., %) using
S:D:

P
q
exp
q
cal
=q
exp

n 1
r
6
where the subscripts exp and cal refer to the experimental and the
calculated data, and n is the number of data points. The S.D. values
are smaller than 15% for both the Langmuir and the Freundlich
models, suggesting that both models closely tted the experimental
results (Table 1). As also seen in Table 1, the adsorption capacities of
CNTs for MB are varied in the range of 35.464.7 mg/g. Previously
some researchers investigated several adsorbents such as wheat
shells (Bulut and AydIn, 2006), rice husk (Vadivelan and Kumar,
2005), Indian rosewood sawdust (Garg et al., 2004), neem leaf pow-
der (Bhattacharyya and Sharma, 2005), pyrophyllite (Gucek et al.,
2005), jute processing wastes (Banerjee and Dastidar, 2005), egg-
shells (Tsai et al., 2006), y ash (Wang et al., 2005), and activated
carbon (Legrouri et al., 2005) for the removal of MB from aqueous
solutions. By comparison of the results obtained in this study with
those in the previously reported works (Table 2) on adsorption
capacities of various adsorbent and activated carbon in aqueous
a
b
Fig. 2. Langmuir (a) and Freundlich (b) isotherms for MB dye adsorption onto CNTs
at different temperatures.
Table 1
Isotherm parameters for removal of MB by CNTs different temperatures.
Isotherms Parameters Temperatures (K)
273 298 333
Langmuir q
0
(mg/g) 35.4 46.2 64.7
K
L
(L/mg) 0.326 0.213 0.564
K
L
(L/mol) 122 79.6 211
R
2
0.996 0.995 0.995
R
L
0.0712 0.105 0.0425
S.D. (%) 2.50 7.10 11.8
Freundlich K
F
(mg/g (L/mg)1/n) 14.0 13.6 30.8
n 3.63 2.86 4.45
R
2
0.984 0.979 0.992
S.D. (%) 1.49 14.1 18.0
Table 2
Previously reported adsorption capacities of various adsorbents for methylene blue
(Bulut and Aydin, 2006).
Adsorbent q
0
, mg/g Ref.
Indian rosewood sawdust 11.851.4 Garg et al. (2004)
Rice husk 40.58 Vadivelan and Kumar (2005)
Neem leaf 8.76
19.61
Bhattacharyya and Sharma
(2005)
Pyrophyllite 70.42 Gucek et al. (2005)
Jute processing waste 22.47 Banerjee and Dastidar (2005)
Eggshell and eggshell
membrane
0.800.24 Tsai et al. (2006)
Fly ash 13.42 Wang et al. (2005)
Activated carbon 435 Legrouri et al. (2005)
Wheat shells 16.56
21.50
Bulut and Aydin (2006)
Carbon nanotubes 35.464.7 This study
3042 Y. Yao et al. / Bioresource Technology 101 (2010) 30403046
solution for MB it can be stated that our ndings are extremely
good.
3.2. Kinetic analyses
It is important to be able to predict the rate at which contami-
nation is removed from aqueous solutions in order to design an
adsorption treatment plant. The effect of temperature on the
adsorption rate of MB on CNTs was investigated at 273, 298, and
333 K. Increasing the temperature is known to increase the rate
of diffusion of the adsorbate molecules across the external bound-
ary layer and in the internal pores of the adsorbent particle, owing
to the decrease in the viscosity of the solution. In addition, chang-
ing temperature will change the equilibrium capacity of the adsor-
bent for a particular adsorbate. Fig. 3 shows the results of contact
time experiments carried out at different temperatures for MB
adsorption on CNTs. The 90 min adsorption capacity at 273, 298,
and 333 K was 26.14, 27.73, and 41.63 mg/g, respectively, indicat-
ing the process to be endothermic. This kind of temperature depen-
dence of the adsorbed amount of the dyes may reect the increase
in the case with which the dye penetrates into CNTs because of its
larger diffusion coefcient. The adsorption is initially (contact time
<45 min) rapid, and then slows (Fig. 3), perhaps because a large
number of vacant surface sites were available for adsorption dur-
ing the initial stage, and then, the remaining vacant surface sites
were difcult to occupy because of the repulsive forces between
the dye molecules on the CNTs and the bulk phase (ChungHsin,
2007).
In order to investigate the adsorption processes of MB dyes on
CNTs, kinetic analysis were conducted using pseudo-rst and sec-
ond-order models and the intraparticle diffusion model. These
models are most commonly used to describe the sorption of dyes
as well as other pollutants (heavy metals) on solid sorbents.
The Lagergren rate equation is one of the most widely used
adsorption rate equations for the adsorption of solute from a liquid
solution. The pseudo-rst-order kinetic model of Lagergren may be
represented by
dq
t
dt
k
1
q
e
q
t
7
Integrating this equation for the boundary conditions t = 0 to
t = t and q = 0 to q = q
t
, gives:
lnq
e
q lnq
e
k
1
t 8
where q
e
and q
t
are the amounts of MB adsorbed (mg/g) at equilib-
rium and at time t (min), respectively, and k
1
is the rate constant of
pseudo-rst-order adsorption (min
1
). The validity of the model
can be checked by linearized plot of ln(q
e
q
t
) versus t. The rate
constant of pseudo-rst-order adsorption is determined from the
slope of the plot. The values of k
1
and q
e
at different temperatures
are presented in Table 3.
The pseudo-second-order equation based on adsorption equi-
librium capacity can be expressed as (Wu, 2007)
dq
dt
k
2
q
e
q
2
9
Rearranging the variables in Eq. (9) gives
dq
q
e
q
2
k
2
dt 10
Taking into account, the boundary conditions t = 0 to t = t and q = 0
to q = q
t
, the integrated linear form of Eq. (10) can be rearranged to
obtain Eq. (11):
t
q

1
k
2
q
2
e

t
q
e
11
Since neither the pseudo-rst-order nor the second-order model
can identify the diffusion mechanism, the kinetic results were ana-
lyzed by the intraparticle diffusion model to elucidate the diffusion
mechanism, which model is expressed as: (Kavitha and Namasiva-
yam, 2007)
q
t
k
i
t
1=2
C 12
where C is the intercept and k
i
is the intraparticle diffusion rate con-
stant (mg/g min
1/2
), which can be evaluated from the slope of the
linear plot of q
t
versus t
1/2
.
The results of Fig. 3 are tted using pseudo-rst- and second-or-
der models and intraparticle diffusion model. Fig. 4(ac) displays
the linear regressions. Table 3 presented the coefcients of the
pseudo-rst and second-order adsorption kinetic models and the
intraparticle diffusion model. The linear plots of t/q
t
versus t show
good agreement between experimental (q
e
(exp)) and calculated
(q
e
(cal)) values. Furthermore, the correlation coefcients for the
second-order kinetics model (R
2
) are greater than 0.99. As a result,
it can be said that MB adsorption onto CNTs takes place according
to second-order kinetic model. Similar phenomena have been ob-
served for MB adsorption on coir pith carbon (Kavitha and Namas-
ivayam, 2007), perlite (Doan et al., 2004), and wheat shells (Bulut
and AydIn, 2006). The values of k
2
, q
e,exp
and q
e,cal
all increased with
the temperature. zcan et al. (zcan et al., 2006) proposed that the
Fig. 3. Kinetic analysis of temperature effect (MB = 20 mg/l,CNTs = 15 mg and pH
7.0).
Table 3
Coefcients of pseudo-rst and second-order adsorption kinetic models and intrapar-
ticle diffusion model (dye concentration = 20 mg/l, CNTs = 15 mg and pH 7.0).
Temperature (K) q
e,exp
(mg/g) k
1
(min
1
) q
e,cal
(mg/g) R
2
Pseudo-rst-order model
273 26.14 0.03286 22.07 0.9830
298 27.73 0.02938 21.51 0.9919
333 41.63 0.05615 14.75 0.9910
Temperature (K) q
e
,
exp
(mg/g) k
2
(min
1
) q
e,cal
(mg/g) R
2
Pseudo-second-order model
273 26.14 0.00182 31.37 0.99396
298 27.73 0.00254 31.09 0.9951
333 41.63 0.0078 43.02 0.99929
Temperature (K) k
i
(mg/g min
0.5
) C (mg/g) R
2
Intraparticle diffusion model
273 3.086 1.935 0.9597
298 2.907 4.723 0.9758
333 1.969 27.30 0.9351
Y. Yao et al. / Bioresource Technology 101 (2010) 30403046 3043
adsorption of Acid Blue 93 by natural sepiolite proceeds by physi-
sorption, in which increasing the temperature increases the
adsorption rate but reduces adsorption capacity. However, this
study suggested that the thermodynamic analyses were more
appropriate for determining whether the adsorption was a physi-
sorption or a chemisorption process, as would be discussed in
the following section.
The removal of MB by adsorption on CNTs was found to be rapid
at the initial period and then to become slow and stagnate with the
increase in contact time. The removal of MB by adsorption on sur-
face of CNTs was due to MB as MB
+
cationic form. Typically, various
mechanisms control the adsorption kinetics; the most limiting
were the diffusion mechanisms, including external diffusion,
boundary layer diffusion and intraparticle diffusion (zcan et al.,
2006). Hence, the intraparticle diffusion model was utilized to
determine the rate-limiting step of the adsorption process. If the
regression of q versus t
1/2
was linear and passes through the origin,
then intraparticle diffusion was the sole rate-limiting step. The
regression was linear, but the plot did not pass through the origin
(Fig. 4(c)), suggesting that adsorption involved intraparticle diffu-
sion, but that was not the only rate-controlling step. Other kinetic
models may control the adsorption rate, which nding was similar
to that made in previous works on adsorption. The values of C were
helpful in determining the boundary thickness: a larger C value
corresponded to a greater boundary layer diffusion effect (Kannan
and Sundaram, 2001). The C values (1.93527.296 mg/g) increased
with the temperature (273333 K). The results of this study dem-
onstrated increasing the temperature promoted the boundary
layer diffusion effect. The k
i
Values calculated from Fig. 4 were
3.09, 2.91, and 1.97 mg/g min
0.5
at 273, 298, and 333 K, respec-
tively. From Table 3, it was observed that k
i
decreased with
increasing temperature.
3.3. Thermodynamic analyses
To estimate the effect of temperature on the adsorption of MB
onto CNTs, the free energy change (DG
0
), enthalpy change (DH
0
),
and entropy change (DS
0
) were determined. The Langmuir iso-
therm was used to calculate thermodynamic parameters using
the following equations:
DG
0
RT lnK
L
13
lnK
L

DS
0
R

DH
0
RT
14
where K
L
is the Langmuir equilibrium constant (l/mol); R is the gas
constant (8.314 J/mol K) and T is the temperature (K). Considering
the relationship between DG
0
and K
L
, DH
0
and DS
0
were determined
from the slope and intercept of the vant Hoff plots of ln(K
L
) versus
1/T. Table 4 presents the thermodynamic parameters at various
temperatures. The negative values conrmthe feasibility of the pro-
cess and the spontaneous nature of the adsorption. The values
a
b
c
Fig. 4. Regressions of kinetic plots at different temperature: (a) pseudo-rst-order model, (b) pseudo-second-order model and (c) intraparticle diffusion model.
3044 Y. Yao et al. / Bioresource Technology 101 (2010) 30403046
ofDG
0
, were found to decrease 10.9 to 14.8 kJ/mol using the
equilibrium constant, K
L
. The decrease in the negative value of
DG
0
with an increase in temperature indicates that the adsorption
process of MB on CNTs becomes more favorable at higher tempera-
tures. The values of DH
0
and DS
0
calculated from the plot of ln(K
L
)
versus 1/T were given as 7.29 kJ/mol and 64.6 J/mol K, respectively.
Kara et al. (Kara et al., 2003) suggested that the DH
0
of physisorp-
tion is smaller than 40 kJ/mol. Based on DH
0
, this study suggested
that the adsorption of MB onto CNTs was a physisorption process.
The value of DH
0
was positive, indicating that the adsorption reac-
tion was endothermic. The positive value of DS
0
reects the afnity
of CNTs for MB and suggests some structural changes in dye and
CNTs.
The pseudo-second-order model was identied as the best ki-
netic model for the adsorption of MB onto CNTs. Accordingly, the
rate constants (k
2
) of the pseudo-second-order model were
adopted to calculate the activation energy of the adsorption pro-
cess using the Arrhenius equation (Wu, 2007):
lnk
2
lnk
o

E
a
RT
15
where k
2
, k
o
, E
a
, R, and T are the rate constant of the pseudo-second-
order model (g/mg min), the Arrhenius factor, the activation energy
(kJ/mol), the gas constant (8.314 J/mol K) and the temperature (K),
respectively. The activation energy could be determined from the
slope of the plot of ln (k
2
) versus 1/T. The activation energy was
18.54 kJ/mol at pH 7.0. The magnitude of activation energy might
give an idea about the type of sorption. There are two main types
of adsorption: physical and chemical. Activated chemical adsorp-
tion means the rate varies with temperature according to nite acti-
vation energy (8.483.7 kJ mol
1
) in the Arrhenius equation. In non-
activated chemical adsorption, the activation energy is near zero
(Han et al., 2009). Therefore, DH
0
, DG
0
, and E
a
all suggested the
same fact: the adsorption of MB onto CNTs was a physisorption pro-
cess. The positive values of Ea suggested that rise in temperature fa-
vor the adsorption and adsorption process may be an endothermic
in nature. Lazaridis and Asouhidou (Lazaridis and Asouhidou, 2003)
stated that the activation energy of adsorption was less than 25
30 kJ/mol in a diffusion-controlled process. Based on the results of
activation energy and the intraparticle diffusion model (Table 4
and Fig. 4(c)), this study proposed that the adsorption involved
intraparticle diffusion was not the only rate-controlling step, and
the other kinetic models might control the adsorption rate.
4. Conclusion
This investigation examined the equilibrium and the dynamic
adsorption of MB onto CNTs. The results suggested the adsorption
capacity increased with increasing temperature. The equilibrium
data were analyzed using the Langmuir, and Freundlich isotherm
models. Equilibrium data tted very well with Langmuir isotherm
equation. Adsorption data were modeled using the rst and sec-
ond-order kinetic equations and intraparticle diffusion models.
The second-order kinetic equation could best describe the sorption
kinetics. Thermodynamic analyses indicated that the adsorption of
MB direct dyes onto CNTs was endothermic and spontaneous;
additionally, the adsorption of direct dyes onto CNTs was via a
physisorption process.
References
Banerjee, S., Dastidar, M.G., 2005. Use of jute processing wastes for treatment of
wastewater contaminated with dye and other organics. Bioresource Technology
96, 19191928.
Bhattacharyya, K.G., Sharma, A., 2005. Kinetics and thermodynamics of methylene
blue adsorption on neem (Azadirachta indica) leaf powder. Dyes and Pigments
65, 5159.
Bulut, Y., AydIn, H., 2006. A kinetics and thermodynamics study of methylene blue
adsorption on wheat shells. Desalination 194, 259267.
ChungHsin, W., 2007. Adsorption of reactive dye onto carbon nanotubes:
equilibrium, kinetics and thermodynamics. Journal of Hazardous Materials
144, 93100.
Crini, G., 2006. Non-conventional low-cost adsorbents for dye removal: a review.
Bioresource Technology 97, 10611085.
Di, Z.C., Ding, J., Peng, X.J., Li, Y.H., Luan, Z.K., Liang, J., 2006. Chromium adsorption
by aligned carbon nanotubes supported ceria nanoparticles. Chemosphere 62,
861865.
Doan, M., Alkan, M., Trkyilmaz, A., zdemir, Y., 2004. Kinetics and mechanism of
removal of methylene blue by adsorption onto perlite. Journal of Hazardous
Materials 109, 141148.
Garg, V.K., Amita, M., Kumar, R., Gupta, R., 2004. Basic dye (methylene blue)
removal from simulated wastewater by adsorption using Indian Rosewood
sawdust: a timber industry waste. Dyes and Pigments 63, 243250.
Gucek, A., Sener, S., Bilgen, S., Mamano, M.A., 2005. Adsorption and kinetic studies
of cationic and anionic dyes on pyrophyllite from aqueous solutions. Journal of
Colloid and Interface Science 286, 5360.
Haghseresht, F., Lu, G., 1998. Adsorption characteristics of phenolic compounds
onto coal-reject-derived adsorbents. Energy and Fuels 12, 11001107.
Hall, K., Eagleton, L., Acrivos, A., Vermeulen, T., 1966. Pore-and solid-diffusion
kinetics in xed-bed adsorption under constant-pattern conditions. Industrial
and Engineering Chemistry Fundamentals 5, 212223.
Han, R., Zhang, J., Han, P., Wang, Y., Zhao, Z., Tang, M., 2009. Study of equilibrium,
kinetic and thermodynamic parameters about methylene blue adsorption onto
natural zeolite. Chemical Engineering Journal 145, 496504.
Kabbashi, N.A., Atieh, M.A., Al-Mamun, A., Mirghami, M.E., Alam, M.D., Yahya, N.,
2009. Kinetic adsorption of application of carbon nanotubes for Pb(II) removal
from aqueous solution. J. Environ. Sci. (China) 21, 539544.
Kannan, N., Sundaram, M., 2001. Kinetics and mechanism of removal of methylene
blue by adsorption on various carbons a comparative study. Dyes and
Pigments 51, 2540.
Kara, M., Yuzer, H., Sabah, E., Celik, M.S., 2003. Adsorption of cobalt from aqueous
solutions onto sepiolite. Water Research 37, 224232.
Kavitha, D., Namasivayam, C., 2007. Experimental and kinetic studies on methylene
blue adsorption by coir pith carbon. Bioresource Technology 98, 1421.
Langmuir, I., 1918. The adsorption of gases on plane surfaces of glass, mica and
platinum. J. Am. Chem. Soc 40, 13611403.
Lazaridis, N.K., Asouhidou, D.D., 2003. Kinetics of sorptive removal of chromium(VI)
from aqueous solutions by calcined MgAlCO(3) hydrotalcite. Water Research
37, 28752882.
Legrouri, K., Khouya, E., Ezzine, M., Hannache, H., Denoyel, R., Pallier, R., Naslain, R.,
2005. Production of activated carbon from a new precursor molasses by
activation with sulphuric acid. Journal of Hazardous Materials 118, 259263.
Li, Y.-H., Di, Z., Ding, J., Wu, D., Luan, Z., Zhu, Y., 2005. Adsorption thermodynamic,
kinetic and desorption studies of Pb
2+
on carbon nanotubes. Water Research 39,
605609.
Li, Y.-H., Wang, S., Luan, Z., Ding, J., Xu, C., Wu, D., 2003. Adsorption of cadmium(II)
from aqueous solution by surface oxidized carbon nanotubes. Carbon 41, 1057
1062.
Li, Y.-H., Wang, S., Zhang, X., Wei, J., Xu, C., Luan, Z., Wu, D., 2003. Adsorption of
uoride from water by aligned carbon nanotubes. Materials Research Bulletin
38, 469476.
Long, R., Yang, R., 2001. Carbon nanotubes as superior sorbent for dioxin removal. J.
Am. Chem. Soc. 123, 20582059.
Lu, C., Chiu, H., 2006. Adsorption of zinc(II) from water with puried carbon
nanotubes. Chemical Engineering Science 61, 11381145.
zcan, A., nc, E., zcan, A., 2006. Adsorption of Acid Blue 193 from aqueous
solutions onto DEDMAsepiolite. Journal of Hazardous Materials 129, 244252.
zcan, A., nc, E., zcan, A., 2006. Kinetics, isotherm and thermodynamic studies
of adsorption of Acid Blue 193 from aqueous solutions onto natural sepiolite.
Colloids and Surfaces A: Physicochemical and Engineering Aspects 277, 9097.
Peng, X., Li, Y., Luan, Z., Di, Z., Wang, H., Tian, B., Jia, Z., 2003. Adsorption of 1, 2-
dichlorobenzene from water to carbon nanotubes. Chemical Physics Letters
376, 154158.
Tsai, W.T., Yang, J.M., Lai, C.W., Cheng, Y.H., Lin, C.C., Yeh, C.W., 2006.
Characterization and adsorption properties of eggshells and eggshell
membrane. Bioresource Technology 97, 488493.
Vadivelan, V., Kumar, K.V., 2005. Equilibrium, kinetics, mechanism, and process
design for the sorption of methylene blue onto rice husk. Journal of Colloid and
Interface Science 286, 90100.
Wang, S., Boyjoo, Y., Choueib, A., 2005. A comparative study of dye removal using y
ash treated by different methods. Chemosphere 60, 14011407.
Wu, C.-H., 2007. Studies of the equilibrium and thermodynamics of the adsorption
of Cu
2+
onto as-produced and modied carbon nanotubes. Journal of Colloid and
Interface Science 311, 338346.
Table 4
Values of thermodynamic parameters (kJ/mol) for the adsorption of dyes onto CNTs.
T, K
DG
0
(kJ/mol) DH
0
(kJ/mol) DS
0
(J/mol K)
273 10.9 7.29 64.6
298 11.0
333 14.8
Y. Yao et al. / Bioresource Technology 101 (2010) 30403046 3045
Wu, C., 2007. Adsorption of reactive dye onto carbon nanotubes: equilibrium,
kinetics and thermodynamics. Journal of Hazardous Materials 144, 93100.
Wu, C.H., 2007. Adsorption of reactive dye onto carbon nanotubes: equilibrium,
kinetics and thermodynamics. J. Hazard. Mater. 144, 93100.
Yao, Y., Zhang, S., Yan, Y., 2008a. CVD synthesis and hydrogen storage properties of
multi-walled carbon nanotubes 2008 2nd IEEE International Nanoelectronics
Conference, INEC 2008, March 24, 2008 March 27, 2008. Inst. of Elec. and Elec.
Eng. Computer Society, Shanghai, China. pp. 140143.
Yao, Y., Zhang, S., Yan, Y., 2008b. CVD synthesis and purication of multi-walled
carbon nanotubes 2008 2nd IEEE International Nanoelectronics Conference,
INEC 2008, March 24, 2008 March 27, 2008. Inst. of Elec. and Elec. Eng.
Computer Society, Shanghai, China. pp. 562565.
3046 Y. Yao et al. / Bioresource Technology 101 (2010) 30403046