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Separation and Purification Technology 58 (2007) 224231

Sorption of divalent metal ions from aqueous solution by

carbon nanotubes: A review
Gadupudi Purnachadra Rao, Chungsying Lu , Fengsheng Su
Department of Environmental Engineering, National ChungHsing University,
250 Kuo Kuang Road, Taichung, Taiwan

Abstract
In this article, the technical feasibility of various kinds of raw and surface oxidized carbon nanotubes (CNTs) for sorption of divalent metal ions
(Cd2+ , Cu2+ , Ni2+ , Pb2+ , Zn2+ ) from aqueous solution is reviewed. The sorption mechanisms appear mainly attributable to chemical interactions
between the metal ions and the surface functional groups of the CNTs. The sorption capacities of CNTs remarkably increased after oxidized by
NaOCl, HNO3 and KMnO4 solutions and such surface oxidized CNTs show great potential as superior sorbents for environmental protection
applications. Effects of process parameters, such as CNT characterizations (surface area, pore size distribution, sorbent mass, and surface total
acidity), solution properties (ionic strength, pH, initial sorbate concentration and temperature) and competition for sorption sites by multiple metal
ions, on the performance of CNTs are addressed in some detail. The recovery of metal ions and the regeneration of CNTs can be achieved using
acid elution with little effect on the CNT performance. The utilization of CNTs for the treatment of water and wastewater containing divalent metal
ions is gaining more attention as a simple and effective means of pollution control. Future research works on developing a cost-effective way of
CNT production and testing the toxicity of CNTs and CNT-related materials are recommended.
2007 Elsevier B.V. All rights reserved.
Keywords: Carbon nanotubes; Chemical treatment; Heavy metal ions; Sorption

1. Introduction
The pollution of water resources due to the indiscriminate
disposal of metal ions has been causing worldwide concern.
Wastewater from many industries such as metallurgical, tannery,
chemical manufacturing, mining, battery manufacturing industries, etc. contains one or more toxic metal ions. It is necessary to
remove these metal ions from the wastewaters before releasing
into the environment, because there is possibility of entry of toxic
metal ions into food chain through waste discharges into water
bodies. There are many conventional methods that are being
used to remove the metal ions including oxidation, reduction,
precipitation, membrane filtration, ion exchange and adsorption. Among the above methods, the promising process for the
removal of metal ions from water and wastewater is adsorption,
because the employed adsorbent can be regenerated by suitable
desorption process and it is highly effective and economical.
Several adsorbents which have been studied for adsorption of
metal ions such as activated carbon [1,2], fly ash [3,4], peat [5],

Corresponding author. Tel.: +886 4 2284 0441; fax: +886 4 2286 2587.
E-mail address: clu@nchu.edu.tw (C. Lu).

1383-5866/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2006.12.006

sewage sludge ash [6], zeolite [7], biomaterials [8,9], recycled

alum sludge [10], manganese oxides [11], peanut hulls [12],
kaolinite [13] and resins [14]. However, these adsorbents suffer
from low adsorption capacities or removal efficiencies of metal
ions. Therefore, researchers carried out investigation for new
promising adsorbents.
Carbon nanotubes (CNTs) had been discovered by Iijima
[15], has led research to new area in many interdisciplinary
investigations as the advantages of CNTs are unique structural,
electronic, optoelectronic, semiconductor, mechanical, chemical and physical properties [16]. CNT would impact future
nanoscience and nanotechnology since it is a highly potential
material and has became available in macroscopic quantities
[1720].
Synthesis methods are quickly improved year to year, to
produce large amount of size-controlled CNTs for commercial
applications. CNTs could be visualized as a sheet of graphite
that has been warped to a tube. Chemical synthesis methods
control diameter of nanotube, chirality and wall number are significant challenge. Presently three main methods employed for
CNTs synthesis are arc-discharge, laser ablation, and chemical vapor deposition (CVD) [21]. CNTs are divided into two
types: (1) single-walled CNTs (SWCNTs) and (2) multi-walled

G.P. Rao et al. / Separation and Purification Technology 58 (2007) 224231

CNTs (MWCNTs) [22,23]. CNTs walls are not reactive, but

their fullerene-like tips are known to be more reactive, so end
functionalization of CNTs is used relatively often to generate
functional groups (e.g., COOH, OH, or C O) [24].
CNTs have attracted great attention in latent applications
such as nanodevices [25], field emission [26], gas adsorption
[27], composite reinforcement [28], metal (ion) nanocomposites [29] and as catalyst supports [30] as they possess exceptional
mechanical properties, unique electrical properties, high chemical and thermal stability and a large specific surface area.
The applications of CNTs have been extensively employed
in the various detection devices, for example in electrochemical detectors, gas sensors [31,32], biosensors with immobilized
biomolecules [24]. Their applications are favorable in voltammetric and electrochemical stripping methods [3335] and
also have been employed for determination of metal ions
[3638].
CNTs have been proven to possess great potential as superior
adsorbents for removing many kinds of organic and inorganic
pollutants such as dioxin [39], volatile organic compounds
[40,41] from air stream or fluoride [42], 1,2-dichlorobenzene
[43], trihalomethanes [44], soil organic matters [45] and various
divalent metal ions from aqueous solution [4657].
This review surveyed recent publications on the sorption
of various divalent metal ions (Cd2+ , Cu2+ , Ni2+ , Pb2+ , Zn2+ )
from aqueous solution by raw and surface oxidized CNTs and
discussed their sorption capacities, mechanisms, process parameters, desorption and further research works.

225

2. Sorption performance
2.1. Isotherm equation
The metal ion sorption equilibrium data are commonly correlated with the Langmuir or the Freundlich equations [1,2,4].
The Langmuir equation is valid for dynamic equilibrium sorption process on completely homogenous surfaces while the
Freundlich equation is applicable to heterogeneous surface. Several researchers reported that the metal ion sorption onto CNTs
can be described by both Langmuir and Freundlich equations
[4648]. Li et al. [55] depicted that the sorption of Pb2+ onto asgrown CNTs can be well correlated by the Freundlich equation.
Some other researchers stated that the metal ions sorption onto
CNTs follows the Langmuir equation [50,51,56,57].
2.2. Sorption capacity
Maximum metal ion sorption capacities of raw and surface
oxidized CNTs and other sorbents calculated by the Langmuir
equation are given in Tables 1 and 2, respectively. It is apparent
that the sorption uptakes of metal ions to different CNTs follow roughly the order: Pb2+ > Ni2+ > Zn2+ > Cu2+ > Cd2+ . The
sorption capacities of metal ions by raw CNTs are very low
but significantly increase after oxidized by HNO3 , NaOCl, and
KMnO4 solutions. This could be explained by the fact that the
tips of CNTs were opened and the fractures took place at the
location where defects such as pentagons and heptagons existed

Table 1
Maximum sorption capacities of divalent metal ion with CNTs
Sorbents

qm
Cd2+

CNTs
CNTs(HNO3 )
SWCNTs
SWCNTs(NaOCl)
MWCNTs
MWCNTs(NaOCl)
CNTs
CNTs(H2 O2 )
CNTs(KMnO4 )
CNTs(HNO3 )
SWCNTs
SWCNTs(NaOCl)
MWCNTs
MWCNTs(NaOCl)
CNTs(HNO3 )a
XyleneFe
BenzeneFe
PropyleneNi
MethaneNi
MWCNTs(HNO3 )
CNTs(HNO3 )
MWCNTs(HNO3 )
MWCNTs(HNO3 )

Cu2+

Ni2+

Pb2+

Conditions

Ref.

pH: 7.0, T: room, S/L: 0.05/100, C0 = 214 mg/L

[46]

pH: 7.0, T: 25, S/L: 0.05/100

[48]

pH: 5.5, T: 25, S/L: 0.05/100, C0 = 9.50 mg/L

[49]

pH: 7.0, T: 25, S/L: 0.05/100, C0 = 1080 mg/L

[50]

pH: 5.0, T: room, S/L: 0.02/100, C0 = 1060 mg/L

[52]

(Column study)
pH: 8.0, T: room, C0 = 1
pH: 5.0, T: 25, S/L: 0.05/100, C0 = 1080 mg/L
pH: 5.0, T: room, S/L: 0.05/100, C0 = 215 (Cd2+ ),
530 (Cu2+ ), 1080 (Pb2+ )
pH: 6.55, T: 60, S/L: 0.15/500, C0 = 620 mg/L

[54]

Zn2+

1.00
49.95
9.22
47.85
7.53
38.46
1.1
2.6
11.0
5.1
11.23
43.66
10.21
32.68
14.8
11.2
59.8
82.6
7.42

10.86

6.89
35.6
97.08

24.49
9.80
( C),

qm = maximum sorption capacity (mg/g), T = temperature

S/L = solid/liquid (g/mL), C0 = initial concentration (mg/L).
a Raw CNTs were fabricated by catalytic decomposing of following volatile organic compounds.

[55]
[56]
[57]

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G.P. Rao et al. / Separation and Purification Technology 58 (2007) 224231

Table 2
Maximum sorption capacities of various divalent metal ions with other sorbents
Sorbents

qm
Cd2+

Cu2+

Fly ash
Inactivated lichen
GAC
PAC
Crab shell
Green macroalga
Palm shell AC
AC cloths: CS 1501
RS 1301
Kaolinite
Pinus sylvestris
Iron slag
Modified chitosan

8.00

8.10
7.69

38.50

88.50
109.00

9.60

Granular biomass
Sugar beet pulp

60.00
24.39

55.00
21.16

26.00
11.86

Ni2+

Pb2+

20.55
13.50
198.97
4.70

62.28
5.57
15.30
11.50
11.04

5.80
5.10
2.79

267.29
28.72
95.20
17.30
17.20

2.66

11.38
95.24

255.00
73.76

Conditions

Ref.

pH: 5.0, T: room, S/L: 0.25/300, C0 = 335 (Cu2+ ), 320 (Cd2+ )

pH: 5.0, T: 15, S/L: 0.5/30, C0 = 100
pH: 7.0, T: 25, S/L: 0.05/100, C0 = 60
pH: 7.0, T: 25, S/L: 0.05/100, C0 = 1080 mg/L
pH: 5.0, T: 30, S/L: 40/1000, C0 = 1000
pH: 5.0, S/L: 0.5/100, C0 = 100
pH: 5.0, T: 27, S/L: 0.5/100, C0 = 10700
pH: 5.0, T: 20, S/L: 0.5/250, C0 = 40

[3]
[9]
[48]
[50]
[64]
[65]
[66]
[67]

pH: T: 40, S/L: 1/100,

pH: 4.0, T: room, S/L: 4/100, C0 = 50
pH: 5.5, S/L(g/ml): 2/1000, C0 = 200
pH: 6.0(Cu), 2.0-3.0(Cd2+ , Ni2+ ), T: 25, S/L: 0.1/100, C0 = 100 (Cu2+ ),
50(Cd2+ , Ni2+ )
pH: 4.05.5, T: 21 S/L: 0.5/50, C0 = 10
pH: 4.7, T: 20, C0 = 2.5 103 M

[68]
[69]
[70]
[71]

Zn2+

17.79

[72]
[73]

qm = maximum sorption capacity (mg/g), T = temperature ( C), S/L = solid/liquid (g/mL), C0 = initial concentration (mg/L).

after oxidation with oxidizing agents. Therefore, oxidation process improves their dispersivity and increases a large amount
of oxygen-containing functional groups like COOH, OH, or
C O on the surface site of CNTs [58]. These functional groups
cause a rise in negative charge on carbon surface and the oxygen atoms in functional groups donate single pair of electrons
to metal ions, consequently increasing their cation exchange
capacity [46].
The SWCNTs have better performance on the Ni2+ and Zn2+
sorption than the MWCNTs. There are two possible reasons
to explain the greater Ni2+ and Zn2+ sorption onto SWCNTs.
First, the oxidized SWCNTs contain more surface total acidic
sites than the oxidized MWCNTs. Second, the zeta potential
of oxidized SWCNTs is more negative than that of oxidized
MWCNTs at a solution pH of 7, in which Ni2+ and Zn2+ sorption
has a greater electrostatic attraction for the SWCNTs than for
the MWCNTs.
Maximum sorption capacities of Cd2+ , Cu2+ , Pb2+ by crab
shell and granular biomass, Cu2+ by iron slag and Cd2+ ,
Cu2+ by modified chitosan were higher than those by CNTs.
However, the maximum sorption capacities of metal ions
by surface oxidized CNTs are higher as compared to green

macroalga, palm shell activated carbon, activated carbon cloths,

inactivated lichen, fly ash, kaolinite, pinus sylvestris, pine needles, sugar beet pulp (except Cd2+ ), granular activated carbon
(GAC), powdered activated carbon (PAC). These comparisons
suggest that the surface oxidized CNTs are promising sorbents for the removal of divalent metal ions from water and
wastewater.
2.3. Sorption mechanism
The mechanisms by which the metal ions are sorbed onto
CNTs are very complicated and appear attributable to electrostatic attraction, sorptionprecipitation and chemical interaction
between the metal ions and the surface functional groups of
CNTs.
It is commonly believed that the chemical interaction between
the metal ions and the surface functional groups of CNTs is the
major sorption mechanism [48,51] (see schematic diagram presented in Fig. 1). Protons in the carboxylic and phenolic groups
of CNTs exchange with the metal ions in the aqueous phase.
The solution pH dropped after sorption of metal ion onto CNTs
reached equilibrium, which could be explained by the release

Fig. 1. Schematic diagram of the major mechanism for sorption of divalent metal ions onto CNT surface.

G.P. Rao et al. / Separation and Purification Technology 58 (2007) 224231

of H+ from the CNT surface where metal ions are sorbed, consequently decreasing the solution pH. The drop in pH value
increased with a rise in initial metal ion concentration, which
clearly indicates that sorption of more metal ion onto CNTs
causes the release of more H+ ions from the surface site of CNTs
into the solution. Li et al. [56] have found evidence that surface
oxidized CNTs take up metal ions by sorptionprecipitation and
electrostatic attraction. Lu and Chiu [50] investigated the Zn2+
sorption onto purified CNTs and reported that more electrostatic
attraction occurs at a higher solution pH and leads to an increase
in sorption of more Zn2+ ions onto CNTs.

3. Process parameters
3.1. CNT characterization
Characterization of sorbents plays a key role in influence sorption rate of aqueous metal ions. Li. et al. [52]
studied four kinds of HNO3 oxidized CNTs with different
morphologies produced by CVD method for the removal of
Pb2+ from aqueous solution. As can be seen in Table 1,
the methaneNiCNTs possess the greatest sorption capacity of Pb2+ , followed by the propyleneNiCNTs, the
xyleneFeCNTs, and then the benzeneFeCNTs. The large
sorption capacity of methaneNiCNTs is mainly attributable
to their surface defects, which can be easily introduced functional groups after treatment by HNO3 solution and thus provide
numerous chemical sorption sites.
A modification of CNTs with specific physicochemical properties can be achieved by chemical treatments to make CNTs
that possess the best performance for metal ion removal. Chiu
[53] modified MWCNTs with various kinds of chemical agents

227

including HCl, H2 SO4 , H2 O2 , O3 , 30 ml HNO3 + 10 ml H2 SO4 ,

HNO3 , KMnO4 and NaOCl. These chemical agents have been
used to modify surface property of carbon sorbents for the
removal of metal ions from aqueous solution [49,50,59,60]. The
Zn2+ sorption capacities of different oxidized MWCNTs follow
the order: NaOCl, KMnO4 , HNO3 , 30 ml HNO3 + 10 ml H2 SO4 ,
O3 , H2 O2 , H2 SO4 , and HCl. Li et al. [49] modified CNTs with
KMnO4 , HNO3 and H2 O2 solutions for the removal of Cd2+
from aqueous solution. The CNTs(KMnO4 ) have the best performance on Cd2+ sorption, followed by the CNTs(HNO3 ), and
then the CNTs(H2 O2 ).
Table 3 lists the comparisons of CNT characterization and
their sorption capacity of various divalent metal ions (Cd2+ ,
Cu2+ , Ni2+ , Pb2+ , Zn2+ ). It is evident that the metal ion sorption
capacity of CNTs does not have a direct correlation with their
specific surface area, pore specific volume and mean pore diameter but strongly depends upon their surface total acidity. The
metal ion sorption capacity of CNTs increased as a rise in the
amount of surface total acidity (including carboxyls, lactones
and phenols) present on the surface site of CNTs. This reflects
that the sorption of metal ions onto CNTs is chemisorption process rather than physisorption process. The oxidized CNTs have
more surface total basicities, which are responsible for sorption
of anions from aqueous solution, than the raw CNTs.
3.2. pH
The removal of Ni2+ and Zn2+ increased with solution pH
in the range 18, fluctuated little and reached maximum in
the range 811, and steeply decreased at a pH of 12 [48,50].
A favorable pH range 811 can be thus noted for sorption of
Ni2+ and Zn2+ from aqueous solution. The effect of solution
pH can be explained by considering the surface charge of the

Table 3
Comparisons of CNT characterization and maximum sorption capacity of various divalent metal ions
Metal ions

Sorbents

SA

PV

MPD

STA

STB

qm

Ref.

Ni2+

SWCNTs
SWCNTs(NaOCl)
MWCNTs
MWCNTs(NaOCl)

577
397
448
307

1.15
0.46
1.10
0.39

7.98
4.62
8.26
5.21

0.54
4.42
0.44
3.06

0.23
0.35
0.19
0.31

9.22
47.85
7.53
38.46

[48]

Pb2+

CNTs(HNO3 )*
XyleneFe
BenzeneFe
PropyleneNi
MethaneNi

47
62
154
145

0.18
0.26
0.58
0.54

3.40
2.43.2
3.60
3.60

1.63
1.65
4.04
4.31

Zn2+

SWCNTs
SWCNTs(NaOCl)
MWCNTs
MWCNTs(NaOCl)

590
423
435
297

1.12
0.43
0.91
0.38

7.60
4.12
8.35
5.17

Cd2+

As-grown CNTs
CNTs(H2 O2 )
CNTs(KMnO4 )
CNTs(HNO3 )

122
130
128
154

0.28
0.36
0.32
0.58

3.60
3.60
3.60
3.60

[49]

2.52
3.36
4.04

14.80
11.20
59.80
82.60
11.23
43.66
10.21
32.68

[50]

1.10
2.60
11.00
5.10

[52]

SA = BET surface area (m2 /g), PV = pore volume (cm3 /g), MPD = mean pore diameter (nm), STA = surface total acidity (mmol/g), STB = surface total basicity
(mmol/g), qm = maximum sorption capacity (mg/g).
* Raw CNTs were fabricated by catalytic decomposing of following volatile organic compounds.

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G.P. Rao et al. / Separation and Purification Technology 58 (2007) 224231

CNT and the degree of ionization and speciation of the sorbates

[46,50,56,57]. It is known that divalent metal ions (M2+ ) can
be present in deionized water in the forms of M2+ , M(OH)+1 ,
M(OH)2 0 , M(OH)3 1 , etc. [57]. At a pH 8, the predominant
nickel species is always M2+ and the M2+ removal is mainly
accomplished by sorption process. Thus, the fact that more M2+
sorption took place at a higher pH could be attributed to a
decrease in competition between H+ and M2+ at the same sorption site of CNTs. Furthermore, the surface of CNTs is more
negatively charged at a higher pH, which causes a more electrostatic attraction of M2+ . In the pH range 811, the maximum
M2+ removal was observed, which might be explained by the
formation of hydrolysis ion species [M(OH)+1 and M(OH)2 0 ].
Low solubilities of these species contribute in part to maximum
M2+ removal. At a pH of 12, the predominant nickel species
is M(OH)3 1 . Thus, the decrease in M2+ removal taking place
at a pH of 12 could be attributed in part to a rise in competition between OH1 and M(OH)3 1 at the same sorption site of
CNTs. Additionally, the negatively charged CNT surface may
cause an electrostatic repulsion of M(OH)3 1 .
3.3. Ionic strength
Ionic strength, which is a general property of the solution
affecting the affinity between the solute and the aqueous phase,
has a negative effect on the metal ion sorption onto CNTs.
Lu and Liu [48] found that the Ni2+ sorption decreases with
increasing solution ionic strength. However, the effect became
small for solution ionic strength >0.05 mol/L as NaClO4 . Li et
al. [56] reported that the sorption capacities of Pb2+ , Cu2+ and
Cd2+ ions by CNTs decreased with an increase in solution ionic
strength. The decrease in sorption capacity of metal ions by
CNTs can be attributed to the increase in activity coefficients of
these metal ions, which retards their transfer to the surface site
of CNTs.
3.4. CNT mass
The amount of Ni2+ sorbed per unit mass of CNTs at a given
C0 decreased with a rise in CNT mass [48]. However, the sorption percentage of Ni2+ , Pb2+ , Cu2+ and Cd2+ increased with an
increase in CNT mass [48,56], which could be due to the availability of more sorption sites. Up to a certain value, no further
increase in percent sorption of metal ion occurred as an increase
in CNT mass.
3.5. Contact time and initial metal ion concentration
Li et al. [55] found that the sorption capacity of Pb2+ onto
CNTs increased quickly with contact time and then slowly
reached equilibrium in 20, 50 and 60 min at a C0 of 10, 20 and
30 mg/L, respectively. Lu et al. [48] reported that the Ni2+ sorption reached equilibrium in 60 and 120 min with a C0 of 10 and
60 mg/L, respectively. It is apparent that the equilibrium would
be reached faster at a lower C0 , probably because the sorption
site sorbed the available metal ions more rapidly at a lower C0
[61].

3.6. Temperature and sorption kinetics

The temperature at which a sorption process is carried out
will influence both the sorption rate and the degree to which
sorption takes place. The sorption capacity of Pb2+ and Zn2+
ions remarkably increased with a rise in temperature [51,55],
indicating an endothermic reaction. The time required to uptake
50% of the maximum Zn2+ sorption capacity (t50 ) would be
reached faster at a higher temperature.
The kinetic sorption process of Pb2+ and Zn2+ ions onto CNTs
could be well described by the pseudo-second-order rate law and
the rate constants increased with a rise in temperature [51,55].
This could be explained by the fact that increasing temperature
results in a rise in diffusion rate of metal ions across the external
boundary layer and within the pores of CNTs due to the result
of decreasing solution viscosity.
Activation energy of sorption (Ea ) is the free energy required
for metal ions sorbed onto CNTs. The faster the rate of sorption
process, the lower the Ea . Lu et al. [51] determined the Ea for
Zn2+ sorption onto CNTs and found that the Ea is less for the
SWCNTs than for the MWCNTs, which could be explained by
the fact that a SWCNT has no multiple atomic layers structure
like a MWCNT requiring more energy for the diffusion of Zn2+
ions. The Ea is also less with a higher C0 . This could be explained
by the fact that the diffusion driving force would be greater at
a higher C0 , which causes a faster diffusion rate of Zn2+ ions
and thus requires less energy for the progress of the sorption
process.
3.7. Competition
Competitive sorption is important in water and wastewater
treatment because most metal ions to be sorbed exist in solution
with other sorbable metal ions. Li et al. [56] studied the individual and competitive sorption of Pb2+ , Cu2+ and Cd2+ ions onto
HNO3 oxidized CNTs. The sorption capacities of CNTs for the
three metal ions are in the order of Pb2+ > Cu2+ > Cd2+ and the
competitive sorption of metal ions also follows the same order.
The sorption capabilities of CNTs without competition are much
better than those with competition because the CNT surface is
utilized by competing metal ions.
3.8. Thermodynamics
The thermodynamic parameters for Pb2+ , Zn2+ , and Ni2+ ions
onto CNTs, which provide useful information concerning the
inherent energetic changes of sorption process, revealed that
the enthalpy change (H ) is positive indicating the endothermic nature of the sorption process [51,55,57]. The negative
free energy change (G ) suggests that the sorption process
is spontaneous with a high preference of Pb2+ , Zn2+ and Ni2+
ions for the CNTs. The positive entropy change (S ), which
may be due to the release of water molecules produced by
ion-exchange reaction between the metal ions and the surface
functional groups of CNTs [55], reflects the affinity of the CNTs
for the Pb2+ , Zn2+ and Ni2+ , ions and the increase of randomness
at the solid/liquid interface during the sorption process [51,57].

G.P. Rao et al. / Separation and Purification Technology 58 (2007) 224231

4. Sorption/desorption study
Testing the repeated availability performance of metal ion
sorption onto CNTs to reduce the cost for the replacement of
CNTs in water and wastewater treatment is important before
practical use of CNTs for environmental protection applications
can be realized.
Desorption of metal ions from CNTs surface depends on pH
of the regeneration solution. Lu et al. [51] studied Zn2+ recovery from SWCNTs and MWCNTs using different pH values of
regeneration solution ranging from 1 to 5 and found that the Zn2+
recovery of SWCNTs and MWCNTs, respectively, reached 91.1
and 90.7% at a solution pH of 1 and decreased to 62.3 and 43.3%
at a solution pH of 5. The sorption capacity was maintained
after 10 cycles of sorption/desorption process. Liang et al. [54]
reported that the Cd2+ , Mn2+ and Ni2+ ions could be effectively
desorbed from the MWCNTs by a 1.0 mol/L HNO3 solution and
the performance was stable up to 50 adsorptionelution cycles
without obvious decrease in the recoveries for the studied ions.
Li et al. [55] reported that desorption of the Pb2+ increased with
decreasing pH of the regeneration solution and reached 100%
Pb2+ desorption from CNTs using HCl or HNO3 solutions at
a pH of 2.0. Chen and Wang [57] found that the Ni2+ desorption was 9% at pH > 5.5, then sharply increased with decreasing
pH of the regeneration solution and ultimately reached 93% at
pH < 2.0. Lu et al. [62] conducted a statistical analysis on the
replacement cost of SWCNTs, MWCNTs and PAC based on
the best-fit regression of the measured Zn2+ equilibrium capacity of each water treatment cycle and revealed that SWCNTs
and MWCNTs could be reused through a large number of water
treatment cycles and thus appear cost-effective in spite of their
high unit cost at the present time. The above results demonstrate that the CNTs are regenerable sorbents for the removal of
divalent metal ions in water and wastewater treatment.
5. Need for further research
Although the CNTs have been proven to possess potential as
superior sorbents for removing divalent metal ions from aqueous
solution, the relatively high unit cost restricts their practical use
at the present time [56]. Furthermore, the raw CNTs may possess
some degree of toxicity due to the presence of metal catalysts
while chemically functionalized CNTs have not demonstrated
any toxicity so far. As a result, the practical use of CNTs as
sorbents in water and wastewater treatment depend upon the
continuation of research into the development of a cost-effective
way of CNT production and the toxicity of CNTs and CNTrelated materials [63].
6. Conclusions
This review summarized the removal of divalent metal ions
(Cd2+ , Cu2+ , Ni2+ , Pb2+ , Zn2+ ) from aqueous solution using
various kinds of CNTs. Most sorption works adopted either
the Langmuir isotherm or the Freundlich isotherm (or both)
for equilibrium sorption data correlation. The sorption capacities of metal ions to different CNTs follow roughly the order:

229

Pb2+ > Ni2+ > Zn2+ > Cu2+ > Cd2+ . Oxidation of CNTs with acid
solution can considerably improve the sorption capacity of metal
ions. The sorption mechanism appears mainly attributable to
chemical interaction between the metal ions and the surface
functional groups. Process parameters such as surface total acidity, pH and temperature play a key role in determining sorption
rate of metal ion onto CNTs. Sorption/desorption study elucidated the possibility to reuse the spent CNTs for the removal of
divalent metal ions in water and wastewater treatment. The superior sorption capacity and effective desorption of divalent metal
ions suggest that the CNTs are promising sorbents for environmental protection applications. Further research works on
developing a cost-effective way of CNT production and testing
toxicity of CNTs and CNT-related materials are recommended.
Acknowledgement
Support from the National Science Council, Taiwan, under
a contract no. NSC 94-2211-E-005-038 is gratefully acknowledged.
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