Advances in Colloid and Interface Science 193–194 (2013) 24–34

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Advances in Colloid and Interface Science

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Adsorptive removal of dyes from aqueous solution onto carbon

nanotubes: A review
Vinod Kumar Gupta a, b,⁎, Rajeev Kumar c, Arunima Nayak a, Tawfik A. Saleh b, M.A. Barakat c, d
a
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, 247 667, India
b
Chemistry Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
c
Department of Environmental Sciences, Faculty of Meteorology, Environment and Arid Land Agriculture, King Abdulaziz University, Jeddah, 21589, Saudi Arabia
d
Central Metallurgical R & D Institute, Helwan 11421, Cairo, Egypt

a r t i c l e i n f o a b s t r a c t

Available online 25 March 2013 Adsorption is a widely used technique for the separation and removal of pollutants from wastewaters. Carbon
nanotubes (CNTs) are emerging as potential adsorbents because of its well defined cylindrical hollow structure,
Keywords: large surface area, high aspect ratios, hydrophobic wall and easily modified surfaces. In this review, dye adsorp-
Carbon nanotubes tion capability of CNTs and CNT based composites from aqueous system has been compiled. This article provides
Active sites
the information about the defect, adsorption sites on CNTs and batch adsorption studies under the influence of
Dyes
various operational parameters such as contact time, solution pH, temperatures etc. and deals with mechanisms
Adsorption
Desorption
involved in adsorption of dyes onto CNTs. From the literature reviewed, it is observed that single walled carbon
nanotubes (SWCNTs) show higher adsorption capacity than multi walled carbon nanotubes (MWCNTs) and
functionalized and CNT composite have better sorption capacity than as grown CNTs. It is evident from the liter-
ature that CNT based nanosorbents have shown good potential for the removal of dyes from aqueous solution.
However, still more research work should be focused on the development of cost effective, higher efficient
and environmental friendly CNT based nanosorbents for their commercial applications.
© 2013 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2. Morphology, defect and active site of CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3. Adsorption of dyes onto CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.1. Effect of physical properties of CNTs on adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.2. Effect of nature of adsorbates on dye adsorption onto CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.3. Effect of chemical treatment of CNTs on dye adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4. Adsorption of dyes onto CNTs based composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.1. CNT–chitosan composites as adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.2. CNT–ACF as adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.3. CNTs–Fe3O4 as adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.4. CNTs–dolomite as adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.5. CNTs–cellulose as adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.6. CNTs–graphene as adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5. Dyes adsorption mechanism onto CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
6. Regeneration of saturated CNTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
7. Conclusions and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

1. Introduction

⁎ Corresponding author at: Department of Chemistry, Indian Institute of Technology

Contamination of surface and ground water with synthetic dyes is
Roorkee, Roorkee, 247 667, India. Fax: +91 1332286202. a serious environmental problem and is a threat to human being and
E-mail address: vinodfcy@gmail.com (V.K. Gupta). aquatic life [1–4]. Synthetic dye stuffs are extensively used as coloring

0001-8686/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cis.2013.03.003
 V.K. Gupta et al. / Advances in Colloid and Interface Science 193–194 (2013) 24–34 25

agents in the textile, paper, leather, gasoline, pharmaceutical, and 2. Morphology, defect and active site of CNTs
food industries. Their discharge into the hydrosphere possess a signif-
icant source of pollution due to their visibility even at very low con- Morphology, defects and active sites of CNTs played an important role
centrations and due to their recalcitrance nature, giving undesirable in the adsorption of the dyes onto CNTs. CNTs consist of graphitic sheets
color to the water, reducing sunlight penetration, resisting photo- or graphene, which have been rolled up into a cylindrical shape and
chemical and biological attack, and their degradation products being exhibiting a special sidewall curvature and possessing a π-conjugative
toxic or even mutagenic, carcinogenic and increased COD and BOD structure with a highly hydrophobic surface. When CNTs have one
levels of aquatic sources [5,6]. Dyes have an aromatic molecular struc- graphitic shell then these are called single-walled carbon nanotubes
ture which possibly comes from coal tar-based hydrocarbons such as (SWCNTs) while having several concentric graphitic shells, these are
benzene, anthracene, toluene, naphthalene, xylene etc. [7,8]. Till date, known as multi-walled carbon nanotubes (MWCNTs). The length of
more than 100,000 commercial dyes are known with an annual pro- CNTs can be from 10s of nm to 10s of mms with diameters up to
duction of > 7 × 10 5 tonnes/year [9,10]. The total dye consumption 100 nm and has a large specific surface area, high porosity, hollow
in textile industry worldwide is more than 10,000 tonnes/year and and layered structures [42–45]. These unique properties and the hexag-
approximately 100 tonnes/year of dyes are discharged into waste onal arrays of carbon atoms in graphite sheets of CNT surface have
streams [11,12]. Due to toxicity of dyes, it is necessary to eliminate strong interactions which allow them to interact with other molecules
dyes from wastewater before its discharge to aqueous bodies. The or atoms through π–π electronic and hydrophobic interactions which
complex aromatic structure and synthetic origin of the dyes make make CNTs a promising adsorbent material [46–49]. The adsorption
them stable to the heat, oxidizing agents, photodegradation and bio- on CNTs is relatively higher as compared to such widely used materials
degradation [7,13–15]. as activated carbons due to the unique properties exhibited by CNTs as
Numerous technologies such as membrane separation, flocculation– discussed earlier [50,51].
coagulation, electrochemical techniques and aerobic or anaerobic treat- Geometrically, CNTs especially SWCNTs have four different spaces
ment have been developed and applied worldwide for the scavenging which act as possible adsorption sites for binding of foreign compo-
of dyes [16]. Despite the development of various technologies for dye nents as shown in Fig. 1 [32,52,53].
waste water treatment, economic, effective and rapid water treatment
1) Internal sites — these sites are found within the hollow structure of
at a commercial level is still a challenging problem. Previous research
tubes and available only when ends of the tube are open.
efforts have focused on the adsorption technology for the dye remedia-
2) Interstitial channels — these sites are easily accessible for the ad-
tion from waste water [17]. This technique can handle fairly large flow
sorbate species and found in the interior space of the bundle be-
rates, producing a high-quality effluent that does not result in the for-
tween individual nanotubes.
mation of harmful substances, such as ozone and free radicals [18,19].
3) External grooves — the grooves present on the periphery of a nano-
Moreover, it can remove or minimize different types of organic and
tube bundle and the exterior surface of the outer most nanotubes,
inorganic pollutants and thus has a wider applicability in pollution
where two adjacent parallel tubes meet.
control. Adsorption is hence recognized as the most versatile process
4) Exposed surface site or outside surface — outside surface site is highly
used in lesser developing countries and is currently being used exten-
accessible for the adsobate (external surface adsorption) and found
sively for the removal of organic pollutants from the aqueous media
on the curved surface of individual nanotubes on the outside of the
[20–23]. Activated carbon is one of the best adsorbent for effluent treat-
nanotube bundles.
ment containing dyes [24–26]. The higher adsorption capacity of the ac-
tivated carbons is due to high porosity and large surface area. But the The layer-to-layer spacing in SWNTs is 0.34 nm which is smaller
high cost and low regeneration of activated carbon restrict its use [6]. than the radius of gyration of organic vapors and common organic
Several researchers investigated the dye adsorption ability on a large molecules are too large to be adsorbed between the SWNT layers
variety of low cost non-conventional adsorbents such as industrial [54]. Therefore, adsorption can occur on the external wall surface or
waste, agricultural waste etc. [6,21–23]. However, non-conventional through capillary condensation in the SWNT pores [55]. The inner
adsorbents showed mixed results and in very few cases the adsorption sites would also be inaccessible for adsorbate molecules because
capacity of these low cost adsorbents is higher than activated carbons. these cavities would be blocked and as-produced CNTs contains a
Therefore, the search to develop efficient adsorbents having the higher
adsorption capacity and better regeneration capacity is still going on.
Since their discovery by Wiles and Abrahamson [27] and re-discovery
by Iijima [28], carbon nanotubes (CNTs) have been intensively studied as
a potential material to be used in a variety of applications based on their
unusual physical and chemical properties [29]. In last decade, the appli-
cation of the CNTs for the removal of organic pollutants and inorganic
pollutant has been investigated [30–40], which is comparable to other
carbon-based adsorbents that are used for commercial applications
[41]. Several reviews have been written on the environmental pollution
management application of CNTs [32,39,40] and this review is an exten-
sion of literature work on the dye scavenging property of CNTs as
adsorbent.
In this paper, we reviewed the use of as grown, treated and CNT
based composites as adsorbents for dye removal from aqueous solu-
tions. The main aim of this review is to provide a summary of recent in-
formation concerning the use of CNT based adsorbents for the removal
of dyes since its discovery. The effect of various parameters such as CNTs
and dyes characteristics, experimental conditions (i.e. contact time, so-
lution pH, initial concentration, temperature) on the adsorption process
Fig. 1. Different adsorption sites in a homogeneous bundle of SWCNTs with tube diameter
has been presented and discussed. The review also summarizes the ki- D: (1) intratubular, (2) interstitial channel, (3) external groove, and (4) exposed surface of
netics, thermodynamic and adsorption isotherm studies, to understand peripheral tube. Sites 1 and 2 comprise the internal porous volume of the bundle, whereas
the mechanism of dye adsorption onto CNTs. sites 3 and 4 are both located on the external surface of the bundle [52].
26 V.K. Gupta et al. / Advances in Colloid and Interface Science 193–194 (2013) 24–34
lot of impurities such as graphite (wrapped up) sheets, amorphous
carbon, metal catalyst and the smaller fullerenes[56]. Although the
blocked inner pores or sites and impurities can be removed by using
several treatment methods like acid, base, heat treatment and so
forth. Acid, base treatment methods are good ways to remove carbo-
naceous impurities or to clear the metal surface while thermal treat-
ment causes the graphitic carbon and the short fullerenes to pyrolyse
[57,58]. Acid treatment of CNTs depends on the acid type experimen-
tal conditions of treatment. It was found that CNTs treated with
non-oxidizing acids like HCl contained very low amount of graphitic
nanoparticles bearing oxygen functionalities. Oxidation with nitric acid
under extreme conditions (reflux) increased the defect population/
formation on the CNTs due to length shortening [59]. The purity of
the CNTs depends on the exposure time of acid treatment. When
the tubes are exposed to the acid for a short time, only the metal
dissolves, but for a longer exposure time, the tubes will chemically
cut functionalization and introduce new defect sites in nanotubes
[58,60]. Mild acid treatment preferentially attacks the end caps
with minimum or no oxidation of the side walls [61]. While, harsh
acid treatment causes oxidation not only on the ends but also on
the side walls of the nanotubes. This can be attributed to the fact
that end caps of CNTs are more reactive than that of side walls be-
cause of highly curved hemispherical fullerene like structure of the
end caps [62]. During the reaction, acid oxidants attack not only
the existing active defect sites but also perfect sites in CNT sidewalls
Fig. 2. Schematic illustration of the oxidation and defect creation mechanism in mild H2SO4/HNO3 mixture [63].
and damage them to induce additional defect sites (Fig. 2) [63,64].
Generally, the surface with various defects is able to exhibit relative-
ly high surface reactivity toward the adsorption and activation of adsor-
bates. The introduction of defects in the carbon network is thus an
interesting way to tailor its intrinsic properties and to create new
potential material. In addition, from experimental point of view, it
is quite difficult to accurately study the adsorption process at defect
sites of solid surface [65,66].
3. Adsorption of dyes onto CNTs
Adsorption of dyes from aqueous solution has been widely inves-
tigated by the scientists onto various kinds of adsorbents such as ac-
tivated carbons, agricultural by products, minerals, polymers, metal
oxides and so forth. Adsorption of dyes onto CNTs and CNT based
composites has been receiving great attention for environmental ap-
plication of CNTs in water treatment. The list of CNTs and CNT based
composites that have been used to remove dyes is summarized in
Tables 1 and 2. In the following sections, the applications of CNTs
for the removal of dyes will be discussed separately.
3.1. Effect of physical properties of CNTs on adsorption
Adsorption capacity of dyes depends on the physical properties
of CNTs as is evident from the works of Yao et al. [67,68] and
 V.K. Gupta et al. / Advances in Colloid and Interface Science 193–194 (2013) 24–34 27

Shahryari et al. [69]. Yao et al. [68] reported an adsorption capacity
of 41.63 mg/g at 333 K for removal of methylene blue (MB) onto
CNTs. Shahryari et al. [69] performed the same batch of experiments
on MWCNTs having a higher surface area of 280 m 2/g as compared
to that of CNTs (160 m 2/g) used by Yao et al. and reported a higher
MB adsorption of 132.6 mg/g at 310 K. Furthermore, we can say that
the adsorption capacity also depends on the experimental condi-
tions and nature and type of the adsorbent. In the above mentioned
study, Shahryari et al. [69] used MWCNTs as adsorbent while Yao et
al. [68,55] reported the use of CNTs.
The comparative adsorption of cationic methylene blue (MB) and
anionic orange II (OII), from aqueous solution by using MWNTs and
carbon nanofibers (CNF) as adsorbents was studied in batch experi-
ments by Rodríguez and coworkers [70]. The adsorption of MB onto
CNF was slightly higher than adsorption onto MWCNTs while for
OII, the adsorption capacity of CNF was (66.12 ± 2.11) mg/g and
that of MWCNTs was 77.83 ± 1.6 mg/g.
Reverse adsorption capacity was observed for the removal of Re-
active Red M-2BE onto MWCNTs and powdered activated carbon
(PAC) while PAC had a higher surface area of 728.7 m 2/g than that
of MWCNTs (180.9 m 2/g) [71]. The maximum amounts of Reactive
Red M-2BE (RRM) uptake were 335.7 and 260.7 mg/g for MWCNT
and PAC, respectively. Here we can justify the higher adsorption capac-
ity on the basis of higher average pore diameter of MWCNTs which was
7.62 nm as compared to 3.52 nm of PAC. Due to larger pore size dye
molecules easily diffused from surface to pores of MWCNTs.
A comparative study of MWCNTs and SWCNTs as nano-adsorbents
for the removal of reactive blue 4 (RB4) textile dye from aqueous
solutions was performed as a function of effects of pH, shaking time
and temperature [72]. The optimum adsorption was found to be at
pH 2.0 and at 4 h contact time for both adsorbents. The equilibrium
data were best fitted to the Langmuir isotherm model with the max-
imum sorption capacity for RB4 occurring at 323 K being 502.5 and
567.7 mg/g for MWCNT and SWCNT, respectively. SWCNTs showed
higher adsorption capacity for RB4 than MWCNTs because the spe-
cific surface area and total pore volume of SWCNTs were 114.3%
and 91.9% higher than that for MWCNTs, respectively. Furthermore,
we can explain the higher adsorption of ARB by SWCNTs than MWCNTs,
on the basis of the probability of molecular sieving effect (the effect
of average pore diameter and volume) in MWCNTs. This could be
explained by the fact that a SWCNT has no multiple atomic layer struc-
ture like a MWCNT, which requires more energy for the diffusion of ad-
sorbate and thus, leads to slower adsorption rate [73,74]. Similar trends
for the removal of acid red B (ARB), by SWCNTs and MWCNTs were
reported by Jia et al. [75]. The results showed that SWCNTs have higher
adsorption capacity for ARB than MWCNTs, and were 585 and 85 mg/g,
respectively.
3.2. Effect of nature of adsorbates on dye adsorption onto CNTs
The nature of adsorbates also played a crucial role in the adsorp-
tion onto CNTs. A comparative adsorptive study of two direct azo
dyes namely C.I. Direct Yellow 86 (DY86) and C.I. Direct Red 224
(DR224) was conducted onto MWCNTs by Kuo et al. [76]. The affinity
between DR224 and MWCNTs was stronger than that between DY86
and MWCNTs reflecting the nature of the dye to have a contributory
influence on the binding mechanism. The instructing result reported
by the authors, is that DR86 was best fitted to the Freundlich isotherm
and that of DR224 was best fitted to the D–R isotherm, suggesting
that adsorption process may change with the adsorbate species.
While the other results ware similar i.e. both dyes followed pseudo sec-
ond order kinetics and endothermic and spontaneous physiosorption
process. Wang et al. [77] conducted a synergistic adsorption studies of
cationic methylene blue (MB) and anionic acid red 183 (AR183) on
MWCNTs from aqueous solution in single and binary dye system. In sin-
gle dye systems, the maximum adsorption capacities of MB and AR183

Table 1
Property and maximum dye adsorption capacity of CNTs.

CNTs CNT preparation method Treatment SA (m2/g) pHzpc Dye adsorbed qe (mg/g) qe/SA (mg/m2) Ref.

MWCNTs CVD 4.9 Procion red MX-5B 44.68 9.11 [13]

MWCNTs HCl Sufranine O 43.48 8.87 [35]
MWCNTs CVD 270 Acid red 18 166.67 0.62 [36]
Oxidize MWCNTs HCl, NaClO, HNO3 96.8 1.5 Bromothymol blue 55 0.57 [37]
MWCNTs na Methyl violet 71.76 – [38]
CNTs CVD 160 methylene blue 64.7 0.40 [67]
CNTs CVD na Methyl violet, 46.2 – [68]
Methylene blue 53.74
MWNTs 280 Methylene blue 132.6 0.47 [69]
MWNTs CVD 162.2 7.8 Orange II, 66.12 + 2.11 0.41 [70]
Methylene blue 54.54 + 0.61 0.37
MWNTs CVD 180.9 6.85 Reactive red M-2BE 335.7 1.86 [71]
MWNTs CVD 82.2 4.98 C.I. Direct Yellow 86 56.2 0.68 [76]
C.I. Direct Red 224 61.3 0.75
MWNTs na Alizarin red S, 161.290 – [78]
Morin 26.247
MWCNTs CVD HCl 180.9 6.85 Reactive blue 4 502.5 2.78 [72]
SWCNts 397.66 6.73 567.7 1.43
f-MWNTs CVD Air oxidation and HNO3 91.96 Congo red, 148 1.61 [79]
Reactive green 152 1.65
HE4BD, 141 1.53
Golden yellow MR
MWNTs CVD Acid wash and oxidation in diluted 160 Methyl orange 52.86 0.33 [81]
air. (acid name not reported)
CNTs/activated carbon fiber CVD 565 Basic violet 10 220 0.39 [82]
Magnetic MWCNTs HNO3 na 6.5 Methylene blue 48.06 – [83]
MWCNTs/Fe3C CVD 38.7 Direct Red 23 172 4.44 [84]
Calcium alginate/MWCNTs CVD na Methylene blue, 606.1 [85]
Methyl orange 12.5
Chitosan/Fe2O3/MWCNTs na Methyl orange 66.90 [107]
G–CNTs H2SO4, HNO3, NaNO3, H2O2 78.9 2.7 Methylene blue, 81.79 1.04 [110]
MWCNTs/Fe2O3 HCl, H2SO4 + HNO3 114 Methylene blue, 42.3 0.37 [127]
Natural red 77.5 0.68

na = not available CVD = chemical vapor deposition, SA = surface area, pHzpc = point of zero charge qe = maximum adsorption capacity,
28 V.K. Gupta et al. / Advances in Colloid and Interface Science 193–194 (2013) 24–34

Table 2
Kinetics, adsorption isotherm and thermodynamics behavior of dye adsorption onto CNTs.

CNTs Dye adsorbed Applied kinetic Followed kinetic Applied isotherm Followed isotherm Nature of Ref.
models model models model process

MWCNTs Procion red MX-5B PFO, PSO PSO Lm, Fd Lm En [13]

MWCNTs Sufranine O PFO, PSO, EM PSO Lm, Pd, Tm, DR Tm En [35]
MWCNTs Acid red 18 PFO, PSO PSO Lm, Pd, Tm, Lm [36]
Oxidized MWCNTs Bromothymol blue PFO, PSO, EM PSO Lm, Pd, Tm, Lm En [37]
MWCNTs Methyl violet PFO, PSO, EM PSO Lm, Pd, Tm, Lm En [38]
CNTs Methylene blue PFO, PSO PSO Lm, Fd Lm En [67]
CNTs Methyl violet, methylene blue PSO PSO Lm, Lm [68]
MWNTs Methylene blue PFO, PSO, EM PSO Lm, Fd, Tm, Sp Sp En [69]
MWNTs Orange II, methylene blue Lm, Fd Lm Ex [70]
MWNTs Reactive red M-2BE PFO, PSO, AFO AFO Lm, Fd, Lu Lu En [71]
MWNTs C.I. Direct Yellow 86, C.I. Direct Red 224 PSO, BM PSO Lm, Fd, Tm, D-R Fd, D-R En [76]
MWNTs PSO PSO Lm, Fd, Lm [77]
MWNTs Alizarin red S, morin PFO, PSO, EM PSO Lm, Fd, Tm, D-R, H-J Tm, Tm En [78]
f-MWNTs Congo red, reactive green HE4BD, PFO, PSO PFO, PFO Lm, Fd, Tm Lm, Fd, Tm [79]
golden yellow MR
MWNTs Methyl orange PFO, PSO, PSO Lm, Fd, Tm Lm En [81]
MWCNTs/Fe3C Direct red 23 PFO, PSO PSO Lm, Fd Fd En [84]
Calcium alginate/ Methylene blue, methyl orange PFO, PSO PSO Lm, Fd Lm [85]
MWCNTs
Chitosan/MWNTs Congo red PFO, PSO PFO Lm, Fd, Sp Lm [99]
Magnetic MWCNTS Methylene blue, beutral red, brilliant PSO PSO Fd Fd [103]
cresyl blue
Chitosan/Fe2O3/MWCNTs Methyl orange PFO, PSO PSO Lm, Fd Lm Ex [107]

Pseudo-first-order = PFO, Pseudo-second-order = PSOK, Avrami fractional-order = AFO, Elovich Model = EM, Bangham's Model = BM, Langmuir = Lm, Freundlich = Fd,
Temkin = Tk, Sips = Sp, Dubinin and Radushkevich = D–R, Liu = Lu, Harkins-Jura = H-J, En = Endothermic, Ex = Exothermic.

were 59.7 and 45.2 mg/g, respectively while in binary system, the
adsorption equilibrium of MB and AR183 reached 80 and 53 mg/g, re-
spectively. In single dye system, the Langmuir model better fitted the
equilibrium data while in binary system, Freundlich model fitted well.
In a binary dye system, the adsorption of MB on MWCNTs was higher
due to electrostatic and hydrophobic effect and π–π interaction at
low AR183 concentration (10 mg/L) and forms MWCNTS-AR183-MB
complex. However, MB adsorption got reduced at higher AR183 con-
centration (>20 mg/L) due to a strong electrostatic attraction between
MWCNT-AR183. Furthermore, AR183 was larger in size than that of MB
which in turn produced space hindrance at higher AR183 concentra-
tion. Removal of acidic dyes alizarin red S (ARS) and morin from waste-
water in batch method using MWCNTs has been investigated [78]. It
was found that the adsorption capacity of both morin and ARS de-
creased with increasing pH over the pH range 1 to 5. This is because
at lower pH values, the increased MWCNT functional group protonation
was electrostatically attracted to the highly negative dyes. Thus electro-
static attraction played an important role in enhancing the dye uptake
in the MWCNTs. The adsorption of ARS and morin has been found to
be endothermic and feasible in nature. The kinetic studies suggest the
process following pseudo second-order kinetics and involvement of
the particle-diffusion mechanism. For the removal of both dyes the
adsorption density of dyes decreased with the increase in adsorbent
dosage. The adsorption capacities for the dyes were not significantly
affected by increasing the KCl concentration from 0 to 4 mol/L. This
indicates that Cl− ions did not compete with the functional groups of
the dye molecules for MWCNTs. The result of the proposed research in-
dicates that the MWCNTs can be used for the removal of acidic dyes
from water containing salt.
3.3. Effect of chemical treatment of CNTs on dye adsorption
Adsorption capacity of CNTs can increase after functionalization/
treatment with acids or oxidizing agents. Surface functionalization
of CNTs improves their dispersion in aqueous solutions and decreases
aggregate formation. Functionalized CNTs are hydrophilic in nature
resulting in the high affinity for the adsorption of ionic species from
the aqueous solution due to the presence of oxygen containing func-
tional groups at the surface. Mishra et al. [79] used functionalized
MWCNTs (f-MWCNTs) for the removal of three azo dyes namely direct
congo red, reactive green HE4BD and golden yellow MR. Pristine
MWNTs were purified by air oxidation followed by acid treatment to
remove amorphous carbon and catalytic impurities. Purified MWNTs
were further functionalized to make them hydrophilic by stirring
MWCNTs in conc. HNO3 acid (16 M) for 2 h. FT-IR study of f-MWNTs
confirms the defective sites at the surface of f-MWNTs and the presence
of >C_C, >C_O, CH2 and \OH functional groups at the surface of
MWNTs. Cluster of adsorbed CR dye can be seen from TEM images
(Fig. 3). The maximum adsorption capacity of 148, 152 and 141 mg/g
was obtained for direct congo red, reactive green HE4BD and golden
yellow MR dyes, respectively.
Three different structural carbonaceous materials, activated carbon
(AC), graphene oxide (GO), and MWCNTs were modified by nitric
acid modified, and were used as adsorbents for the removal of methy-
lene blue (MB) dye from aqueous solution by batch process [80]. The
adsorption of MB onto AC, GO and MWCNTs was found to be 270.27,
243.9 and 188.68 mg/g, respectively. In this case, the adsorption of
MB was not surface area dependent. MWCNTs had a much larger sur-
face area (177 m2/g) than that of GO (32 m2/g), but was found to ad-
sorb MB lesser as compared to GO because of its higher surface area
accessibility for MB caused by its unique single atom layered structure.
However, the adsorption of MB onto modified MWCNTs was found to
be much higher than that of the virgin MWCNTs (Table 1).
The adsorption of methyl orange (MO) onto functionalized MWCNTs
from aqueous solutions was investigated as a function of contact time,
dosage, temperature, pH, and MO concentration in the solution [81].
The as-grown MWCNTs were purified using a two-step purification pro-
cedure involving acid washing and oxidation in diluted air to remove the
raw product containing the aerogel support, catalyst particles and amor-
phous carbons. After treatment both ends of MWCNTs were opened and
only a small amount of metal catalysts remained in the MWCNTs. The
maximum removal of MO was observed at pH 2.3. With an increase in
pH from 4 to 10, adsorption capacities decrease from 30.4 mg/g to
24.8 mg/g. This may be attributed to the electrostatic interaction be-
tween anionic dyes and partially negative charged MWCNT surface due
to the presence of oxygen containing functional groups.
From the above literature study, it is clear that modified CNTs have
a higher dye removal efficiency as compared to the pristine CNTs. This
 V.K. Gupta et al. / Advances in Colloid and Interface Science 193–194 (2013) 24–34
is because of the defects and functional groups generated by the
chemical treatment of CNTs. These defects and functional groups act
as active sites which are easily accessible to the dye molecules.
4. Adsorption of dyes onto CNTs based composites
Although, several reports demonstrated that CNTs have good ad-
sorption capacities for dyes due to their hollow and layered nanosized
structures which in turn have a large specific surface area but their
high cost restricts their use from industrial application. Furthermore,
separation of CNTs from aqueous solution is very difficult because of
its smaller size and high aggregation property [82]. The problem of
cost and separation of CNTs from aqueous medium can be overcome
by making composites of CNTs with polymers, metal oxide, carbon
etc. Such materials act as a stable matrix to the CNTs. Recently the
CNTs have been used as a promising nano-filler for the preparation
of CNT based nanocomposites because of their excellent improved
adsorption, mechanical, electrical and thermal properties [83–96].
CNT based composites are expected to be excellent adsorbent because
CNTs provide not only the additional active sites but also larger sur-
face area, which in turn makes them good adsorbents compared to
their parent materials.
4.1. CNT–chitosan composites as adsorbent
Chitosan (CS) is one of the best adsorbents for the removal of dyes
due to its multiple functional groups, biocompatibility and biodegrad-
ability [97], but its low mechanical strength limits its commercial
applications. Impregnation of CS hydrogel beads with CNTs (CS/CNT
beads) resulted in significant improved mechanical strength [98]. In
CS/CNT composite, CNTs and CS are like a symbiosis, CNTs help to im-
prove the mechanical strength of CS while CS help to reduce the cost
of CNTs for adsorption [99], while the resulted composite solves the
problem of separating CNTs from aqueous medium. Impregnation of
0.05 wt.% cetyltrimethylammonium bromide (CTAB) increased the max-
imum adsorption capacity of CS beads from 223.25 to 433.12 mg/g [100].
The small difference in maximum adsorption capacity of CS/CNT beads
(450.4 mg/g) and CS/CTAB beads (433.12 mg/g) indicated that CTAB
molecules played a significant role in enhancing the adsorption perfor-
mance of both varieties of beads. However, higher maximum adsorption
capacity of CS/CNT beads than CS/CTAB beads suggested that CNTs itself
in the beads adsorb CR during adsorption. This work suggests that surfac-
tant played an important role in the removal of dyes.
In his further studies on CS/CNTs, Chatterjee at al [101] investigated
the effect of anionic and cationic surfactants as dispersant on impreg-
nated MWCNTs/CS for the removal of CR dye. The adsorption capacity
Fig. 3. TEM images of (a) f-MWNTs and (b) direct congo red adsorbed f-MWNTs [79].
29
of CNT-impregnated CSBs was found to be dependent on the nature of
dispersant for CNTs. CNT-impregnated CSBs were prepared by four differ-
ent strategies for dispersing CNTs: (a) in CS solution (CSBN1), (b) in sodi-
um dodecyl sulfate (SDS) solution (CSBN2), (c) in CS solution containing
cetyltrimethylammonium bromide (CTAB) (CSBN3), and (d) in SDS
solution for gelation with CTAB-containing CS solution (CSBN4). The
adsorption capacities of composite for CR were in the order of: CSBN4
(375.94 mg/g) > CSBN1 (200 mg/g) > CSBN2 (188.32 mg/g) > CSBN3
(121.07 mg/g). The adsorption capacity of CSBN1 was slightly higher
than CSBN2 for CR. This could be due to the dispersion in SDS molecules
resulting in negatively charged CNTs as a result of adsorption of SDS mol-
ecules onto CNTs. The CR adsorption onto CSBN4 increased as the concen-
tration of CNTs increased because of better dispersion of CNTs in SDS
solution than in CTAB solution. CSBN3 showed poor adsorption capacity
because CNTs were dispersed in CTAB and aggregates of CNTs blocked
the adsorption sites on CS, CTAB, and SDS molecules in the beads. In addi-
tion, unlike CNTs in CS solution for CSBN1 and CSBN3, CNTs were incorpo-
rated into CSBN4 from the SDS solution possibly causing less blocking of
the binding sites of CS molecules in CSBN4. Furthermore we can say, elec-
trostatic interaction between anionic CR and cationic CTAB, also played an
important role for higher adsorption capacity of CSBN4.
4.2. CNT–ACF as adsorbent
To resolve the aggregation and dispersion problem of CNTs, Wang
et al. [82] prepared the CNTs/activated carbon fabric (CNTs/ACF)
composite and its application was investigated for the removal of
phenol and basic violet 10 (BV10). CNTs/ACF was prepared via direct-
ly growing nanoscaled CNTs on microscaled carbon matrix. Polyacry-
lonitrile was used as a source of carbon. From the results, it was
observed that dye adsorption equilibrium time for CNTs/ACF is
shorter as compared to ACF and monolayer adsorption capacity
does not display a linear increase with increasing the BET surface
area. The decoration of CNTs tends to lower the porosity of the ACF
from 1065 to 565 m 2/g. The adsorption of BV10 onto ACF and CNTs/
ACF was 162.4 and 220 mg/g, respectively. This finding indicates
that the total microporosity of ACF cannot be fully accessed by the
dye molecules. However, as-produced CNTs offer more attractive
sites, including grooves between adjacent tubes on the perimeter of
the bundles, accessible interstitial channels, and external nanotube
walls. Therefore, the appearance of CNTs plays a positive role in (i) fa-
cilitating the pore accessibility to adsorbates and (ii) providing more
adsorptive sites for the liquid-phase adsorption. This reflects that
CNTs/ACF contains a large number of mesopore channels, thus preventing
the pore blockage from the diffusion path of micropores for adsorbates to
penetrate.
30 V.K. Gupta et al. / Advances in Colloid and Interface Science 193–194 (2013) 24–34

4.3. CNTs–Fe3O4 as adsorbent
Incorporation of magnetic property in CNTs is another good tech-
nique to separate CNTs from solution. The magnetic adsorbent can be
well dispersed in the water and easily separated magnetically [102].
Magnetic-modified MWCNTs were used for removal of cationic dye crys-
tal violet (CV), thionine (Th), janus green B (JG), and methylene blue
(MB) [103]. To find the optimum adsorption, effect of various parameters
including initial pH, dosages of adsorbent and contact time have been in-
vestigated. The optimum adsorption was found to be at pH 7.0 for all
dyes. The maximum predicted adsorption capacities for CV, JG, Th and
MB dyes were obtained as 227.7, 250.0, 36.4 and 48.1 mg/g, respectively.
Yan et al. [104] prepared guar gum grafted Fe3O4/MWCNTs (GG/
MWCNT/Fe3O4) ternary composite for the removal of natural red (NR)
and methylene blue (MB). The adsorption of both dyes followed the
pseudo second kinetics. The maximum adsorption of MB and NR reached
61.92 and 89.85 mg/g. The removal efficiency of cationic dyes using GG/
MWCNT/Fe3O4 is higher as compared with other adsorbents such as
MWCNTs and MWCNT/Fe3O4. Gong et al. [105] reported that the maxi-
mum monolayer adsorption capacities of MB and NR by MWCNT–
Fe3O4 were 15.87 and 20.51 mg/g. The higher adsorption capacity of
GG/MWCNT/Fe3O4 could be related to the hydrophilic property of GG,
which improved the dispersion of GG–MWCNT–Fe3O4 in the solution,
which facilitated the diffusion of dye molecules to the surface of CNTs.
The magnetic GG/MWCNT/Fe3O4 possesses the high adsorption proper-
ties and magnetic separation and can therefore be used as magnetic ad-
sorbents to remove the contaminants from aqueous solutions.
Starch-functionalized MWCTs/iron oxide composite was prepared
to improve the hydrophilicity and biocompatibility of MWCNTs [106].
Synthesized magnetic MWCNT–starch–iron oxide was used as an ad-
sorbent for removing anionic methyl orange (MO) and cationic meth-
ylene blue (MB) from aqueous solutions. MWCNT–starch–iron oxide
exhibits super paramagnetic properties with a saturation magnetiza-
tion (23.15 emu/g) and better adsorption for MO and MB dyes than
MWCNT–iron oxide. The specific surface areas of MWCNT/iron
oxide and MWCNT–starch–iron oxide were 124.86 and 132.59 m 2/g,
respectively while The BET surface areas of MWCNT–COOH and
MWCNT–starch were 184.3 and 155.36 m 2/g respectively. However,
surface area of the composite was small but adsorption capacity was
higher compared to the parent one, the adsorption capacities of MB
and MO onto MWCNTs–starch–iron oxide were 93.7 and 135.6 mg/g,
respectively while for MWCNTs–iron oxide were 52.1 and 74.9 mg/g.
This is again confirming that ternary composite has the higher removal
capacity than the binary composite and as grown CNTs.
A novel magnetic composite bioadsorbent composed of chitosan
wrapping magnetic nanosized γ-Fe2O3 and multi-walled carbon nano-
tubes (m-CS/γ-Fe2O3/MWCNTs) was prepared for the removal of methyl
orange [107]. The adsorption capacity of MO onto m-CS/γ-Fe2O3/
MWCNTs was 2.2 times higher than m-CS/γ-Fe2O3. The adsorption ca-
pacity of MO onto m-CS/γ-Fe2O3/MWCNTs (66.90 mg/g) was also
higher than MWCNTs (52.86 mg/g) [81]. Kinetics data and adsorption
isotherm data were better fitted by pseudo-second-order kinetic model
and by Langmuir isotherm, respectively. The results from thermodynam-
ic studies indicated that the adsorption was feasible, spontaneous and
exothermic process in nature. On the comparison of nature of adsorption
of MO onto MWCNTs and m-CS/γ-Fe2O3/MWCNTs, we observed that ad-
sorption of MO onto MWCNTs was endothermic. We think CS is respon-
sible for the exothermic adsorption process because with the increase in
bromide, acridine orange, methylene blue, eosin B, and eosin Y dyes
from wastewater. Polyurethane polymer was used as binder to pro-
duce the foam line CNTs/dolomite adsorbent. Adsorptions reached
equilibrium within 30 min for the cationic dyes, acridine orange,
ethidium bromide, and methylene blue while it was about 60 min
for the anionic dyes, eosin B and eosin Y. The maximum adsorption
of all studied dyes is reported in Table 3. Foam like ternary composite
PUF/diatomite/dispersed-MWCNTs, gave the highest capacities for
adsorption of these dyes, followed by PUF/agglomerated-MWCNTs,
and then PUF/dispersed-MWCNTs. Langmuir adsorption isotherm
was best fitted to the equilibrium data.
4.5. CNTs–cellulose as adsorbent
The removal of methylene blue onto natural tentacle type walem
gum grafted CNTs/cellulose beads was investigated by Deng et al.
[109]. The maximum adsorption of MB was observed at pH 5 and
150 min. Adsorption isotherm study revealed the monolayer adsorp-
tion at higher concentration and multilayer adsorption at lower con-
centration. The equilibrium adsorption capacity onto the adsorbent
was determined to be 302.1 mg/g at pH 6.0 from Sips model. Pseudo
first order kinetics gives the best fitted results compared to the pseu-
do second order. From the results, it is evident that carboxylic group
on the adsorbent plays the important role for the removal of MB as
ionized to \COO − at higher pH and bind with MB through electro-
static force.
4.6. CNTs–graphene as adsorbent
Self-assembled cylindrical graphene–MCNT (G–MCNT) hybrid, syn-
thesized by the one pot hydrothermal process was used as adsorbent for
the removal of methylene blue in batch process [110]. G–MCNT hybrid
showed good performance for the removal of MB from aqueous solution
with a maximum adsorption capacity of 81.97 mg/g. The kinetics of
adsorption followed the pseudo-second-order kinetic model and equi-
librium data were best fitted to Freundlich adsorption isotherm. The ad-
sorption capacity of G–MCNTs is much higher than MCNTs (Table 1).
Therefore, G–CNTs hybrid could be utilized as an efficient adsorbent for
environmental remediation.
5. Dyes adsorption mechanism onto CNTs
Adsorption process generally depends on three parameters i.e. so-
lution conditions, nature of adsorbent and adsorbate. Furthermore,
the factors that affect the adsorption process are size of adsorbent
and adsorbate, charge of the adsorbate and adsorbent surface, pH
and temperature of solution and so forth [40,111]. Generally, hydro-
phobic interaction, π\π bond, hydrogen bond, and covalent and elec-
trostatic interactions are responsible for the adsorption of organic
chemicals on carbon nanoparticles [40]. The sidewall of CNTs has
Table 3
Capacity (μmol-dye/g-MWCNTs) of dye adsorptions for the agglomerates of the entire
MWCNTs (MWCNTsa), PUF/agglomerated-MWCNTs (PUF/MWCNTsa), PUF/dispersed-
MWCNTs (PUF/MWCNTsb), PUF/diatomite/dispersed-MWCNTs (PUF/MWCNTsc), and
the diatomite and PUFs (the positive controls), respectively[108].
Dyes MWCNTsa PUF/ PUF/ PUF/ Diatomite PUF
MWCNTsa MWCNTsb MWCNTsc

the temperature, polymeric network of CS changed/deshaped, which re- Acridine 394.41 276.13 252.65 421.73 8.45 3.75
duced the porosity of the biosorbent and hindered the diffusion of dye orange
Methylene 346.88 249.38 177.19 378.38 12.1 4.98
molecules at high temperature.
blue
Ethidum 188.4 145.09 110 296.11 2.78 1.67
4.4. CNTs–dolomite as adsorbent bromide
Eosin Y 158.78 102.43 57.75 234.2 12.3 3.29
Yu and Fugetsu [108] developed a novel adsorbent by inserting Eosin B 137.69 97.93 48.3 202.71 13.7 2.68

MWCNTs into the cavities of dolomite for scavenging of ethidium Unit = μmol-dye/g-MWCNTs.
 V.K. Gupta et al. / Advances in Colloid and Interface Science 193–194 (2013) 24–34 31

Fig. 4. Schematic illustration of the possible interaction between MWCNTs and methylene blue: (a) electrostatic attraction and (b) π–π stacking [83].

highly hydrophobic property because of high π electron density of sp 2

carbons. Dyes may interact with side wall of CNTs through hydropho-
bic interactions [49]. π\π bonding generally takes place between
bulk π system of CNTs and dye molecules with C_C or benzene
rings. A schematic presentation of dye interaction with the CNTs is
shown in Figs. 4 and 5. The functional groups such as \COOH, \OH,
and \NH2 are the main groups involved in the hydrogen bond forma-
tion between dye molecules and the CNTs [112–114]. Electrostatic in-
teractions greatly control the adsorption of ionic compounds because
of the charged CNT surface [113].

6. Regeneration of saturated CNTs

To make the process more economical and recycle the adsorbent

and adsorbate, desorption of dyes and regeneration of saturated ad-
sorbent should be performed. For regeneration of adsorbents several
methods have been used such as thermal treatment [115], chemical ex-
traction [115], bio-regeneration [116], supercritical regeneration [117],
microwave irradiation [118,119], ultrasonic regeneration [120] and ox-
idative regeneration [121,122]. Thermal and chemical treatments are
the most applied methods for the regeneration of exhausted adsorbent.
The regeneration efficiency of saturated CNTs has been tabulated in
Table 4 and discussed in the following section.
Peang and coworker [106] applied microwave irradiation for the
regeneration of reactive red 3BS saturated MWCNTs and 92.8% regener- Fig. 5. Schematic illustration of the possible interaction between graphene and dyes
ation efficiency was achieved after four cycles. In microwave irradiation (methylene blue and methylene violet) [113].
32 V.K. Gupta et al. / Advances in Colloid and Interface Science 193–194 (2013) 24–34

Table 4 The adsorption and desorption of the dyes is highly influenced by

Regeneration of dye saturated CNTs. the solution pH. Generally, negatively charged dyes are adsorbed in
Adsorbent Dye Desorbent/ No. of Desorption/ Ref. the acidic and desorbed in basic medium. Reversibly cationic dyes
treatment cycles readsorption show maximum adsorption at higher solution pH (electrostatic inter-
efficiency (%) action) and desorb in acidic pH. Desorption of anionic methyl orange
MWCNTs Reactive red M-2BE Ethanol, 1 13.74, [71] (MO) and cationic methylene blue from saturated MWCNTs was car-
n-Heptane, 0.50, ried out at pH 2.0–13 [85]. At the fixed pH, desorption of both dyes
n-Propane, 12.54
was found reverse to the adsorption (Fig. 6) i.e. maximum desorption
Methanol, 10.96,
NaOH, 8.67, of MO and MB were observed at pH 13.0 and 2, respectively, while
NaOH + methanol 87.50 optimum adsorption of MO and MB was found at pH 2.0 and 4–12,
Calcium Methyl orange, pH-13, 1 79.7, [85] respectively.
alginate/ Methylene blue pH-2 1 80.2, Gong et al. [105] also performed desorption of three cationic dyes
MWCNTs
namely, methylene blue, neutral red, and brilliant cresyl blue by varying
Magnetic Crystal violet, Acetonitrile 5 99 ± 4, [102]
MWCNTs Thionine, 98 ± 1, the pH of the ethanol. Maximum desorption was found to be at pH 2 for
Janus green B, 98 ± 2, all thee cationic dyes. Yu and Fugetsu [108] also used ethanol/water
Methylene blue 99 ± 1 (50/50) solution in an ultrasonic generator to regenerate dye exhausted
Magnetic Methylene blue, Ethanol (pH-2) 1 45.47, [105]
PUF/diatomite/dispersed-MWCNTs. The model dyes used in this study
MWCNTs Neutral red, 44.39,
Brilliant cresyl 45.75, are ethidium bromide, acridine orange, methylene blue, eosin B, and
blue eosin Y. After three adsorption/regeneration cycles, the adsorbed dye
MWCNTs Reactive red 2 NaOH, m 44, [117] was mostly released after the regeneration, and the capacity for the
microwave 64 dye absorption remained unchanged.
MWCNTs Reactive red 3BS Microwave 4 92.8 [120]
In chemical regeneration, generally, dye molecules dissolved in
the eluent or replaced from the adsorbent surface by ion-exchange
process. The solubility/desorption of dyes depends upon the nature
and strength of the solvent [123]. Desorption of cationic dyes crystal
heating, organic compound decomposes and these decomposed or-
violet, thionine, janus green B, and methylene blue from magnetic
ganics form coke deposits, which will block the porosity of the carbon
MWCNTs was conducted by washing methanol, N,N-dimethyl formam-
and decrease the adsorption capacity. After four regeneration, CNTs
ide and acetonitrile [102]. For all studied dyes, the desorption equi-
have as good graphite structure as the original CNTs, with no obvious
librium time was 2 min and the desorption efficiency was found in the
graphite-to-amorphous transformation of CNT outer walls during MW
order: methanol b N,N-dimethyl formamide b acetonitrile (Table 4).
irradiation treatment, which indicated that the regeneration process
After five successive cycles, no change in the sorption behavior was ob-
did not damage CNT graphite structure.
served. Therefore, the MMMWCNTs can be a good reusable and eco-
A comparative study was performed using 1 mM NaOH and micro-
nomical sorbent.
wave irradiation to regenerate reactive red 2 from exhausted MWCNTs
To evaluate the possibility of regeneration of Reactive Red M-2BE
[119]. Microwave assisted regeneration was more effective than the de-
(RRM) saturated MMWCNT adsorbent, desorption experiments were
sorption agent of NaOH. The regeneration efficiency using 1 mM NaOH
carried-out using, ethanol; n-heptane; n propanol; methanol; NaOH
in 24 h was 28, 30, 35 and 44% at 18, 28, 38 and 48 °C, respectively. The
aqueous solutions (1.0–3.0 mol/L); and mixture of methanol + NaOH
microwave regeneration was 64% at the input microwave power of
(1.0–7.0 mol/L) [71]. The eluents such as NaOH, ethanol, methanol,
1000 W for 20 min. This study reveals that microwave irradiation mark-
n-propanol and n-heptane showed up to 14% recovery of dye. The
edly decreases the time required for regenerating CNTs, moreover, regen-
best elution efficiency up to 87.5% was obtained with the mixture
eration efficiency with microwave irradiation substantially exceeded that
methanol + 4.0 mol/L NaOH. The maximum adsorption of RRM dye
of desorption using NaOH.
was observed at pH 2.0 due to electrostatic interaction between RRM
and MWCNTs. This interaction was corrupted with the NaOH solution
and methanol act as a solvent dissolves the dye. Therefore, the mixture
of methanol + NaOH improves the elution of RRM.
From the literature, we find only seven articles in which desorp-
tion and regeneration studies have been studied. However, micro-
wave treatment and mixture of organic and inorganic compounds
showed good potential for the regeneration of CNTs. But the data
(above mentioned) is not sufficient to make a clear conclusion. There-
fore, more research work is required and should be focused on the re-
generation of CNTs.

7. Conclusions and future prospects

In this review, the application of CNTs as adsorbents for the re-

moval of dyes from aqueous solution has been presented. CNTs
show the great potential for the removal of dyes and could be used
for commercial purpose. From the literature reviewed, following con-
clusions have been made:

I) CNTs synthesized by chemical vapor deposition method have

been used mostly for the removal of dyes.
II) Functionalized CNTs and CNT based composite demonstrated ex-
Fig. 6. Effect of solution pH on desorption of methyl orange and methylene blue for cellent dye adsorption capacities than the pristine one. But there
saturated calcium alginate/MWCNT composite fiber [85]. have been exceptions when a pristine CNT has demonstrated
 V.K. Gupta et al. / Advances in Colloid and Interface Science 193–194 (2013) 24–34 33

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