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Water Research 39 (2005) 605609

www.elsevier.com/locate/watres

Adsorption thermodynamic, kinetic and desorption

studies of Pb2+ on carbon nanotubes
Yan-Hui Lia,b,, Zechao Dib, Jun Dingb, Dehai Wub,
Zhaokun Luanc, Yanqiu Zhua
a

Advanced Materials, School of Mechanical, Materials and Manufacturing Engineering, the University of Nottingham,
University Park, Nottingham NG7 2RD, UK
b
Department of Mechanical Engineering, Tsinghua University, Beijing 100084, China
c
State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences,
Chinese Academy of Sciences, Beijing 100085, China
Received 19 December 2003; received in revised form 2 November 2004; accepted 6 November 2004

Abstract
Adsorption thermodynamics of Pb2+ on carbon nanotubes has been studied at various temperatures of 280, 298 and
321 K and the thermodynamic parameters, such as equilibrium constant (K0), standard free energy changes (DG0),
standard enthalpy change (DH0) and standard entropy change (DS0), have been obtained. A pseudo-second-order rate
model has been employed to describe the kinetic adsorption processes. Desorption studies reveal that Pb2+ can be easily
removed from carbon nanotubes by altering the pH values of the solution using both HCl and HNO3, indicating that
carbon nanotubes are a promising absorbent for wastewater treatment.
r 2004 Elsevier Ltd. All rights reserved.
Keywords: Adsorption; Carbon nanotubes; Desorption; Kinetics; Lead; Thermodynamics

1. Introduction
Recently, an increasing interest has been focused on
removing Pb2+ ions from drinking water due to its
supreme toxicity to our health. Drinking those that
contain Pb2+ ions for a long term, even if in a very low
concentration, could lead to a wide range of spectrum
health problems, such as nausea, convulsions, coma,
renal failure, cancer and subtle effects on metabolism
and intelligence (Friberg et al., 1979; Rashed, 2001).
Corresponding author. Advanced Materials, School of
Mechanical, Materials and Manufacturing Engineering, the
University of Nottingham, University Park, Nottingham NG7
2RD, UK. Tel.: +44 115 846 7257; fax: +44 115 951 3800.
E-mail address: yanhui.li@nottingham.ac.uk (Y.-H. Li).

Different approaches to remove Pb2+ ions from

wastewater, including chemical precipitation, ion exchange, reverse osmosis and adsorption, have been
reported. One of which, adsorption method, is simple
and cost-effective, thus has been widely used. Various
adsorbents such as activated carbon (Lee et al., 1998;
Reed et al., 1996), iron oxides (Liu and Huang, 2003),
lamentous fungal biomass (Lo et al., 1999) and natural
condensed tannin (Zhan and Zhao, 2003) have been
explored and the results are promising.
Carbon nanotubes (CNTs), a new member of the
carbon family, have attracted special attentions to many
researchers after their discovery in 1991 (Iijima, 1991)
because they possess unique morphologies and have
showed excellent properties and great potential for
engineering applications such as composite reinforce-

0043-1354/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2004.11.004

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Y.-H. Li et al. / Water Research 39 (2005) 605609

ment (Wagner et al., 1998), eld emission element

(Wang et al., 1998), nanodevice component (Collins et
al., 1997), gas adsorption materials (Dillon et al., 1997)
and catalyst support phases (Planeix et al., 1994). CNTs
are also good anion and cation adsorption materials for
wastewater treatment, as they exhibit exceptionally large
specic surface areas which are easy to decorate (Li et
al., 2001, 2002, 2003). We have previously demonstrated
that CNT supported alumina is a good uoride
adsorbent whose adsorption capacity is 1525 times
higher than that of the activated carbon (Li et al., 2001).
CNTs oxidized with nitric acid showed very good cation
adsorption capability, e.g., their lead and cadmium (II)
adsorption capacities being 15.6 and 3.6 mg/g, separately, at metal ion equilibrium concentration of 2.7 mg/
L (Li et al., 2002, 2003).
In this paper, we will investigate the thermodynamic
and kinetic of the Pb2+ absorption onto CNTs, in order
to obtain the thermodynamic parameters, to establish
the adsorption rate equation and to assess the reuse
capacity of CNTs in wastewater treatment.

where C0 and Ct are the Pb2+concentrations contained

in the original solution and after time t, respectively; V is
the volume of the solution and W represents the weight
of the CNT used.
In order to investigate the desorption capacity of
Pb2+ from CNTs, 0.05 g CNTs were introduced to
100 ml solution whose initial Pb2+ concentration is
55 mg/L and pH is 5.0. As the adsorption reaches
equilibrium, the Pb2+ concentration of the solution was
measured, and then the solution was ltrated using a
membrane to recover the CNT sample. These CNTs
were dried at 60 1C and dispersed into 100 ml deionized
water. The pH values of the solution were adjusted,
from 1.6 to 5.4, using HCl and HNO3 solutions,
respectively. After the solutions reach equilibrium, the
Pb2+ concentrations were remeasured and, the desorption results were then obtained. These adsorption/
desorption processes were repeated for three times, to
further ascertain the desorption capability of CNTs.

3. Results and discussion

2. Experimental
CNTs were prepared by Ni nanoparticle catalysed
pyrolysis of propylene in a hydrogen ow at 750 1C. The
as-grown CNTs were dispersed in concentrated HNO3
and were reuxed for 30 min at 140 1C, to remove the
catalyst. By dissolving lead nitrate in deionized water,
we obtained the lead containing stock solution
(1000 mg/L), which was further diluted to the required
concentrations before being used.
To evaluate the thermodynamic properties, we rst
prepared various solutions with initial Pb2+ concentration ranging from 10 to 80 mg/L (10 mg/L interval,
100 ml, pH 5), and then added 0.05 g CNTs to each
solution. These samples were then mounted on a shaker
(HZQ-C) and shaken continuously for 6 h at 280, 298
and 321 K, respectively. The suspensions were ltered
using a 0.45 mm membrane, and the ltrates were
immediately measured using an atomic adsorption
spectroscopy. The differences between the initial and
the equilibrium Pb2+ concentrations determine the
amount that Pb2+ adsorbed by CNTs.
Adsorption kinetics samples were prepared by adding
1 g of CNTs into 2000 ml solution (pH 5.0), and the
Pb2+ concentration was 10, 20 and 30 mg/L, separately,
at 298 K. At predetermined time intervals, samples were
collected utilizing a 0.45 mm membrane lter and then
analyzed by an atomic adsorption spectroscopy. The
Pb2+ adsorption amount at time t, qt (mg/g), was
calculated by
qt C 0  C t V =W ;

(1)

The CNT starting materials usually exhibit curved

features, with ca. 30 nm o.d. and 10 nm i.d., and
hundreds of nm to mm long. Their specic surface areas
are 122 and 153 m3/g, respectively, before and after
oxidation treatment by nitric acid.
Fig. 1 shows the adsorption isotherms of Pb2+ on
CNTs at 280, 298 and 321 K. These data could be
approximated by the Freundlich isotherm model, which
depicts the relationship between the amount of Pb2+
adsorbed by per unit mass of CNTs (qe, mg/g) and the
equilibrium concentration of Pb2+ (Ce, mg/L) in
solution:
qe K F C l=n
e ;

(2)

where KF and n are Freundlich constants related to the

adsorption capacity and adsorption intensity, respec-

Fig. 1. Adsorption isotherms of Pb2+ onto CNTs at different

temperatures.

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Y.-H. Li et al. / Water Research 39 (2005) 605609

tively. The Freundlich equation is applicable to highly

heterogeneous surfaces, and an adsorption isotherm
lacking a plateau indicates a multi-layer adsorption
(Daifullah et al., 2004). The parameter KF refers to the
relative adsorption capacity, i.e., CNTs exhibit higher
Pb2+ adsorption capacity at 321 K than that at 280 K,
according to the KF data shown in Table 1.
Based on Eq. (2), we obtained a straight line when
plotting ln qe vs. ln Ce (Fig. 2). The constants, KF and n,
are then dened by the intercepts and slopes of the line,
respectively. It appears that the Freundlich model agrees
well with our experimental data (Table 1), with the
correlation coefcient values being close to 1 at different
temperatures.
The Pb2+ adsorption capacity increases with the rise
of temperatures, indicating an endothermic reaction.
Thermodynamic parameters can be calculated from the
variation of the thermodynamic equilibrium constant K0
with the change in temperature (Niwas et al., 2000). For
adsorption reactions, K0 is dened as follows:
K0

as vs C s

ae ve C e

(3)

where as is the activity of adsorbed Pb2+, ae is the

activity of the Pb2+ in solution at equilibrium, Cs is the
amount of Pb2+ adsorbed by per mass of CNTs (mmol/
g) and Ce is the Pb2+ concentration in solution at
equilibrium (mmol/ml), vs is the activity coefcient of
the adsorbed Pb2+ and ve is the activity coefcient of the
Pb2+ in solution. As the Pb2+concentration in the

607

solution decreases and approaches to zero, K0 can be

obtained by plotting ln(Cs/Ce) vs. Cs (Fig. 3) and
extrapolating Cs to zero (Niwas et al., 2000). The
straight line obtained is tted to the points based on a
least-squares analysis. Its intercept with the vertical axis
gives the values of K0.
The adsorption standard free energy changes (DG0)
can be calculated according to
DG0 RT ln K 0 ;

(4)

where R is the universal gas constant (1.987 cal/deg/mol)

and T is the temperature in kelvin.
The average standard enthalpy change (DH0) is
obtained from Vant Hoof equation


DH 0 1
1
;
(5)

ln K 0 T 3  ln K 0 T 1
R
T3 T1
where T3 and T1 are two different temperatures. The
standard entropy change (DS0) can be obtained by
DS0 

DG 0  DH 0
:
T

(6)

The thermodynamic parameters are listed in Table 2.

A positive standard enthalpy change suggests that the
interaction of Pb2+ adsorbed by CNTs is endothermic,
which supported by the increasing adsorption of Pb2+
with the increase in temperature; a negative adsorption

Table 1
Parameters of Freundlich adsorption isotherm models for Pb2+
on CNTs
Temperature (K)

KF

R2

280
298
321

12.4100
15.5646
16.1448

4.5269
4.4802
4.3440

0.9869
0.9659
0.9755

Fig. 3. Plots of ln Cs/Ce vs. Cs at various temperatures.

Table 2
Values of various thermodynamic parameters for adsorption of
Pb2+ on CNTs
Thermodynamic constant

Fig. 2. Linearized Freundlich isotherms for Pb2+ adsorption

by the CNTs at different temperatures.

K0
DG0 (  1000 cal mol1)
DH0 (  1000 cal mol1)
DS0 (cal mol1 K1)

Temperature (K)
280

298

321

10.891
1.329
0.441
6.321

11.628
1.453
0.441
6.356

12.052
1.588
0.441
6.321

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Y.-H. Li et al. / Water Research 39 (2005) 605609

608

standard free energy change and a positive standard

entropy change indicate that the adsorption reaction is a
spontaneous process (Niwas et al., 2000). The positive
standard entropy change may be due to the release of
water molecule produced by ion exchange reaction
between the adsorbate and the functional groups on
the surfaces of CNTs (Liang and Chen, 2004; Li et al.,
2002).
Adsorption kinetics, demonstrating the solute uptake
rate, is one of the most important characters which
represent the adsorption efciency of the CNTs and
therefore, determines their potential applications. According to Fig. 4, the Pb2+ adsorption rates increase
dramatically in the rst 10 min for various initial
concentrations, and they reach equilibrium gradually
at 20, 50 and 60 min, corresponding to Pb2+ initial
concentrations of 10, 20 and 30 mg/L, respectively.
To analyze the adsorption rate of Pb2+ onto the
CNTs, the pseudo-second-order rate equation was
evaluated based on the experimental data (Benguella
and Benaissa, 2002)
t=qt

1=2K 0 q2e

t=qe ;

(7)

where K0 stands for the pseudo-second-order rate

constant of adsorption (g/(mg min)).
Linear plot feature of t/qt vs. t (Fig. 5) was achieved
and the K0 values calculated from the slopes and
intercepts were summarized in Table 3. The correlation
coefcients of the pseudo-second-order rate model for
the linear plots are very close to 1, thus suggesting that
kinetic adsorption can be described by the pseudosecond-order rate equation.
The repeated availability is an important factor for an
advanced adsorbent. Such adsorbent not only possess
higher adsorption capability, but also shows better
desorption property, which will signicantly reduce the
overall cost for adsorbent. Fig. 6 shows the Pb2+
desorption curves with regard to various solutions of pH
values. It is apparent that the Pb2+ desorption increases

Fig. 5. Test of pseudo second-order rate equation for adsorption of different concentrations of Pb2+ by CNTs (pH 5.0,
at 298 K).

Table 3
Kinetic parameters of Pb2+ adsorbed on CNTs at different
initial Pb2+ concentrations
Initial Pb2+
concentration
(mg/L)

10
20
30

Pseudo-second order

qe

K0

R2

17.09
23.41
30.32

0.0092
0.0116
0.0053

0.9989
0.9999
0.9987

Fig. 6. Desorption of Pb2+ from CNTs by adjusting the pH

values of the solution using HCl and HNO3 solutions.

Fig. 4. Effect of contact time on Pb2+ absorption rate for

different concentrations (pH 5.0, at 298 K).

when the pH value of the solution is reduced using HCl

and HNO3. The desorption percentages for the two
acids are ca. zero at pH 5.4, increases sharply at
pH 4.0, and eventually reaches 100% at pH 2.0.
These results show that the Pb2+ adsorbed by CNTs can
easily be desorbed, thus the CNTs can be employed
repeatedly in heavy metal adsorption.

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4. Conclusion
Adsorption thermodynamics and kinetics of Pb2+ on
CNTS have been studied. A positive value of the
standard enthalpy change suggests that the interaction
of Pb2+ adsorbed by CNTs is endothermic. The
negative adsorption standard free energy changes and
positive standard entropy changes indicate that the
adsorption reaction is spontaneous process. The kinetic
adsorption process can be well described by the pseudosecond-order rate model. Pb2+ can be easily desorbed
from CNTs by adjusting the solution pH values, thus
CNTs exhibit promising application potentials as an
adsorbent in wastewater treatment.
Acknowledgements
This work was funded by the State Key Project for the
Fundamental Research of MOST of China (Grant No.
20000264-04) and by the open funds of State Key
Laboratory of Environmental Aquatic Chemistry.
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