Dispersion of Carbon Nanotubes in Water and Non-Aqueous Solvents

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Dispersion of carbon nanotubes in water and

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non-aqueous solvents
Cite this: RSC Adv., 2013, 3, 24812
Oxana V. Kharissova, Boris I. Kharisov* and Edgar Gerardo de Casas Ortiz
Contemporary methods for dispersion of carbon nanotubes in water and non-aqueous media are
discussed. Most attention is paid to ultrasonic and plasma techniques and other physical techniques, as
Received 24th July 2013
Accepted 9th September 2013
well as to the use of surfactants, functionalizing and debundling agents of distinct nature (elemental
substances, metal and organic salts, mineral and organic acids, oxides, inorganic and organic peroxides,
DOI: 10.1039/c3ra43852j
organic sulfonates, polymers, dyes, natural products, biomolecules, and coordination compounds).
www.rsc.org/advances Special studies on CNTs solubilization are examined.
Introduction aggregate easily and therefore make additional processing very

difficult.
Carbon nanotubes (CNTs), classic objects in nanotechnology, Considerable research efforts have already been devoted to
form bundle-like structures with very complex morphologies optimize and develop processes for their effective separation.
with a high number of van der Waals interactions, causing Currently, techniques for separating bundles of carbon nano-
extremely poor solubility in water or organic solvents. It is tubes into homogeneous dispersions are still under develop-
difficult to prepare stable aqueous dispersions of CNTs; their ment, although a few methods have been successful at the
insolubility has been a limitation for the practical applications laboratory scale. One of the main approaches to disperse and
of this unique material. Proper dispersion of CNT materials is exfoliate carbon nanotubes and graphene is based on the use of
important to retaining the electronic properties of the nano- surfactants.1 With their use, tremendous progress has been
tubes. Redissolvable functional compound/CNT composites are made to stabilize CNT dispersions, although many questions
needed for post processing because CNT dispersions usually await answer to design surfactant formulations that selectively
stabilize nanotubes which are monodisperse in diameter and
chirality. Although the efficiencies of anionic, cationic, and
nonionic surfactants have been demonstrated to different
Universidad Autónoma de Nuevo León, Monterrey, Mexico. E-mail: bkhariss@
hotmail.com extents, the exact mechanism by which carbon nanotubes and
Dr Oxana V. Kharissova (born in Dr Boris I. Kharisov (born in

1969 in Ucrania, former USSR) Russia in 1964) is currently a
is currently a professor and professor and researcher at the
researcher at the UANL. Degrees: Universidad Autónoma de
An MS in 1994, in crystallog- Nuevo León (UANL). Degrees: An
raphy from Moscow State MS in 1986, in radiochemistry
University, Russia, and a Ph.D. and a Ph.D. in inorganic chem-
in Materials from the Uni- istry in 1993, from the Moscow
versidad Autónoma de Nuevo State University, Russia; Dr
León, 2001, Mexico. Member- Hab. in physical chemistry in
ships: National Researchers 2006 from Rostov State Univer-
System (Level 2), Materials sity, Russia. He is the co-author
Research Society. She is the co- of six books, 128 articles,
author of three books, 5 book chapters, 61 articles, and has two ve book chapters, and has two patents. Co-editor: Three
patents. Specialities: Nanotechnology (carbon nanotubes, nano- invited special issues of international journals. He is the member
metals, fullerenes), microwave irradiation and crystallography. of the editorial board of four journals. Specialities: Coordination
and inorganic chemistry, phthalocyanines, ultrasound and
nanotechnology.
24812 | RSC Adv., 2013, 3, 24812–24852 This journal is ª The Royal Society of Chemistry 2013
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Fig. 1 Strategies for covalent functionalization of CNTs ((A) direct sidewall functionalization; (B) defect functionalization).
the different surfactants interact is still uncertain. Many ultracentrifugation,11,12 plasma and irradiation techniques, and
researchers worldwide suggest that van der Waals interactions, chromatography13) and chemical (diazonium salts,14 ozonolysis,
p–p stacking, and hydrophobic interactiona are major factors functionalization with porphyrins, bromine, amines, pyrene,
that account for the CNTs dispersion. Nonfunctionalized CNTs DNA, peptides, polymers, etc.) methods. Many of these chemical
can be solubilized in suitably chosen organic solvents and, agents are amphiphiles, known to be suitable molecules to
furthermore, their solubility could be understood in terms of disperse CNTs in water by shielding their highly hydrophobic
the Hansen Solubility Parameters (HSPs).2 surfaces. Tailored anionic, nonionic, and cationic photo-
Recently, several reviews3–5 have been published on partic- polymerizable amphiphiles (objects of permanent attention15,16
ular aspects of CNTs solubilization and stability in solvents. as good dispersants for CNTs) were designed to achieve pro-
In particular, since the CNTs dispersion is most frequently grammed pH-dependent dispersions of CNTs.17 All of these
carried out through functionalization, the main strategies
for covalent functionalization of CNTs were generalized
Table 1 Overview of physical and chemical methods for CNTs dispersion/
(Fig. 1).6 As will be shown below (Table 1 and throughout the
solubilization
text), various dispersion approaches are based on physical
(dielectrophoresis,7,8 gel electrophoresis,9,10 density gradient Technique Observations
Ultrasonication One of the most frequently used

methods. It can be used with or without
use of surfactants, simultaneous
Dr Edgar Gerardo De Casas Ortiz
chemical treatment or dielectrophoresis
(born in 1977 in Durango, Mex- Plasma method RF plasma discharge in O2 or Ar/O2/C2H6
ico). Degrees: Industrial chem- Irradiation Mainly g-irradiation
istry in 1999 and Ph.D. in Ozonolysis Generally by UV/ozone treatment
Polymer Technology from CIQA Functionalization This is carried out with the use of: (a)
inorganic compounds, such as carbon
Saltillo Coahuila, 2009, México.
allotropes (nanodiamonds, graphene
Postdoc in Industrial Physics at oxide), iodine doping, mineral acids and
the UANL, 2012-2013, Mexico. their mixtures, CO2 and SiO2, peroxides,
Co-author of four scientic arti- inorganic salts; (b) organic compounds:
cles and two patents. Specialities diazonium salts, organic acids and salts,
sulfonates, amines, porphyrins, pyrene
in materials chemistry and
and other polyaromatic compounds,
physics, nanotechnology and DNA, biomolecules, polymers, natural
environmental sciences. products, etc.
This journal is ª The Royal Society of Chemistry 2013 RSC Adv., 2013, 3, 24812–24852 | 24813
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methods suffer from problems with scalability, effectiveness,

and oen dissolution sensitivity.
Analyzing the published scientic research articles, it is
evident that there is an important issue or misunderstanding
between the terms “dispersion” and “solubilization”.18 Many
researchers use the terms interchangeably, particularly when
stating the interaction of CNTs with liquids, which causes
confusion. The fundamental question when dealing with
carbon nanotubes in liquids, particularly in water, is: are they

dissolved or dispersed? It has been suggested19 that it is most
appropriate to use the term “dispersion” rather than “solution”.
Also, one of the most problematic issues affecting the CNT
research community is the lack of standards and uniform
characterization methods for CNT dispersions. A 2005 NASA-
NIST workshop aimed to address this issue and made a clear
distinction between “nanodispersion” of individual CNTs and
Fig. 3 Typical double sonication system used for dispersing SWNTs. The system
“macrodispersion” of CNT bundles.20 Unfortunately, this
consists of an ultrasonic bath and an ultrasonic probe on the right.24
distinction has yet to percolate through the CNT dispersion
literature.
The main objective of this review is to summarize the main
recent (2009–2013) methods for CNT dispersion in distinct eld together with mechanical waves from an ultrasonic
media and to represent contemporary trends in this eld. transducer led to faster and better dispersion of threads
formulated from CNTs in the presence of a strong electric eld.
Both the electric eld and ultrasonic transducer had a
Physical methods controllable frequency and power. Both dispersion and
Ultrasonication agglomeration of CNTs can be observed when the parameters of
Ultrasonication is oen used to disperse nanoparticles in the electric eld were changed. Additionally, different uids
aqueous solution. However, good dispersion of nanoparticles in required different frequencies for an optimal dispersion ratio.
aqueous solution is not always achieved, due to the fact that Several studies to increase CNTs dispersibility without the
incoming ultrasonic waves in liquid are usually reected and application of surfactants have been carried out, sometimes
weakened at the gas–liquid interface. In the case of carbon leading to useful CNT applications. Thus, a more efficient
nanotubes, this is a classic debundling method: the MWCNTs cooling cell for probe-type ultrasonication was reported.25
can effectively be ultrasonically dispersed in a water solution.21
A considerable number of the reports below, dedicated to the
use of surfactants and functionalizing agents for CNT disper-
sion/solubilization, imply the simultaneous application of
ultrasound of a distinct power, either weak (Fig. 2, le) or
elevated (Fig. 2, right). A combination of both ultrasonic sources
is also known (Fig. 3). Another combination, designed to
improve the dispersion of CNTs in solvents, represented a
method uniting dielectrophoresis and megasonication.22 This
full system is shown in Fig. 4. Combining an alternating electric
Fig. 4 Diagram of a chamber for efficient CNT dispersion; (1) the chamber made
of stainless steel, (2) the cover made of polytetrafluoroethylene, (3) electrodes, (4)
the power supply, (5) the ultrasonic/megasonic transducer, (6) the control/driver
Fig. 2 Sonicators with different modes for CNT dispersion ((A) water bath unit for the transducer, (7) the fluid with carbon nanotubes, (8) the electric field,
sonicator; (B) probe/horn sonicator).23 (9) the acoustic wave from the transducer, (10) the heater/heat-sink.
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Fig. 5 CNT dispersions in ethanol after (A) 1 min, (B) 3 min, and (C) 5 min sonication. A typical buckypaper produced from 50 mg of CNTs and 10 min sonication time
(D), and SEM images of the cross-section (E) and the surface (F) of the corresponding buckypaper. A typical TEM image of the purified CNTs (inset of F).
Compared with a conventional cylindrical cell, the concentra-

tion of the SWNTs solubilized in water was found to be almost
double in a rosette cooling cell aer ultracentrifugation. The
efficiency of a rosette cell can be attributed to the higher effi-
ciency in circulation and cooling of the SWNT dispersion as well
as an enhancement of the cavitation process. A systematic
calorimetry-based technique was developed to standardize
SWNT dispersion protocol using an ultra-dismembrator.26 The
standardized protocol was used to prepare aqueous SWNT
suspensions by sonicating SWNTs in a varied range of input
energy (18–100 kJ) in water. It was demonstrated that the sus-
pended mass of SWNTs increased up to 18 kJ of energy input
with no further increase upon continued energy input. The
signicant changes observed were limited to the morphological
properties, i.e., shorter length, debundled, and sharp edged
SWNTs and fractal cluster formation (lower Df) with increased
Fig. 6 SEM images of CNT microcapsules prepared with various different CNTs
input energy. In addition, a simple, surfactant-free assembly
contents in O/W Pickering emulsions (water: 10 mL, cyclohexane: 3 mL): (a)
process was used to obtain MWCNTs buckypapers using a 0.0025 g, (b) 0.005 g, (c) 0.01 g, and (d) magnified image of sample (b).
highly efficient purication, sonication, and ltration process
(Fig. 5).27 To achieve effective dispersion of MWCNTs in ethanol,
a minimum of 5 min sonication time was required. By this
method, a buckypaper with a pore size of 41 10 nm and introduced several hydrophilic groups onto the carbon nano-
porosity of 72.9% was fabricated with 10 min of sonication. The tubes resulting in improved aqueous dispersion. The plasma-
as-prepared buckypaper was used as a membrane for humic treated carbon nanotubes were self-assembled at the interface
acid (HA) removal from water. The buckypaper prepared from between water and oil phases.
puried CNTs exhibited excellent removal of HA (>93%) and a CNTs synthesized by direct thermal CVD growth from
long lifetime for ltration. stainless steel mesh were surface functionalized via an
Ar/O2/C2H6 capacitively coupled RF plasma discharge.29 The
open and rigid network of the CNTs allowed for a high degree of
Plasma and irradiation techniques the CNT surface to be treated. As a result, the aqueous nano-
Distinct types of plasma techniques have been applied to uids that were produced by removing the CNTs from the
improve CNTs dispersibility, frequently without surfactants, substrate were found to remain stable for extended periods of
giving different quantitative results. Thus, carbon nanotube time (greater than six months). It was revealed that oxygen
microcapsules were prepared28 by oil in water (O/W) Pickering comprised approximately 21 at.% of the functionalized CNT
emulsions (Fig. 6 and 7) without the use of any surfactants. surface. Poly(vinyl alcohol)/CNT nanocomposites produced
CNTs were treated with oxygen plasma (radio frequency of 13.56 using the plasma functionalized CNTs were observed to be
MHz) at a power of 100 W and a pressure of 200 mTorr for homogenous with excellent dispersion of the CNTs. In a related
several different reaction times. The oxygen plasma treatment work,30 MWCNTs were plasma-treated using glow discharges of
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Fig. 7 Schematic illustration of the preparation of CNT hollow microspheres by O/W Pickering emulsions.
argon, oxygen and methane–oxygen mixtures and then

dispersed into a base uid of water. It was found that proper
plasma treatment of CNTs using nanoscale plasma coatings
signicantly improved the dispersion and stabilized the
suspension of CNTs in the base uid. With 0.01 vol% addition
of plasma-treated CNTs, a 25% initial increase in thermal
conductivity was achieved and a stabilized 20% increase was
observed with the resulting nanouids aer 5 days settling. The
authors pointed out that such a large increase in thermal
conductivity was achieved when plasma-treated CNTs were
stably dispersed in water without adding any dispersing agents Fig. 8 Configuration of the planetary ball mill.
or surfactants. Also, microwave excited Ar/H2O surface-wave
plasma was used31 trying to reach similar objectives. This
treatment greatly enhanced the content of oxygen, and modied signicantly improve the functionalization of SWCNTs with
surface microstructure properties. The integrity of the nanotube DNA.
patterns, however, was not damaged. In addition, CNTs with In addition to the methods above, an interesting approach of
different diameters were treated by plasma and acid.32 The attaining the optimum grinding condition of a planetary ball
CNTs were dispersed in water and the light transmittance of the mill {Fig. 8; the collision medium was monosized (3.00 mm)
CNTs dispersoid (the mixture of CNTs and water) was measured spherical zirconia (ZrO2) balls} and a simple acid-based method
to characterize the dispersibility of the CNTs. It was concluded for purifying MWCNTs to investigate the dispersion character-
that the dispersibility of the CNTs with bigger diameters was istics of MWCNTs was reported.36 This experiment was con-
better. Plasma treatment could improve the dispersibility of ducted under dry and wet grinding conditions at various
CNTs and if the CNTs were acid-treated, plasma treatment rotation speeds (200–500 rpm), with further purication of
could improve their dispersibility further. Also, MWCNTs were MWCNTs and their dispersion use of SDS surfactant (also see
suspended in octylalcohols 2-octanol and 2-ethyl-1-hexanol33 section about SDS use below). It was shown that the structures
using a barrier discharge. Needle to plane electrode congura- of amorphous carbon and carbon particles of MWCNTs were
tions were used in the experiment. The grounded plane elec- completely eliminated and the tips of nanotubes opened.
trode was covered by the solid insulator with or without an Moreover, both dry and wet grinding caused the lengths of the
isolated metallic plate. Successive barrier discharge in the MWCNTs to be shortened with increasing rotation speed.
suspension was obtained by applying a 60 Hz ac high voltage to Purication of MWCNTs removed the impurities and agglom-
the needle electrode. erations of raw materials; consequently, the pure structure
Radiation methods, described in a recent monograph,34 have allowed the MWCNTs to disperse well in the base uid. The
been applied for CNT dispersion too. Thus, a method for highly structure of the MWCNTs remained unchanged aer
efficient functionalization of SWCNTs by DNA wrapping purication.
included exposure of SWCNTs to g-irradiation (50 kGy), which
lowered the amount of single stranded deoxyribonucleic acid Functionalization of CNTs through chemical
(ssDNA) required for SWCNT modication by one order of methods
magnitude.35 While g-irradiation in three different media
signicantly improved the process of SWCNT dispersion, irra- Inorganic compounds
diation in ammonia was the most efficient. The g-irradiated Other carbon allotropes and their derivatives. Among carbon
SWCNTs functionalized with ssDNA were stabilized by electro- allotropes, nanodiamonds (NDs) and graphene oxide have
static forces. The authors suggested that g-irradiation can notably been applied for improvement of CNT dispersion. Thus,
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Fig. 9 Schematic mechanism for the formation of the MWNT–GO complexes.
nanodiamond particles were used37 to disperse CNTs, allowing solubilizing CNTs and opens a new way for GO applications in
the formation of their stable colloidal suspensions. Both colloidal chemistry. Solubility results indicated that the GO
MWCNTs and SWCNTs could be suspended in deionized water sheets lean to stabilizing MWNTs with larger diameters, mainly
using either detonation NDs or high pressure, high temperature depending on whether the CNTs are inclined to form bundles,
NDs. Negatively charged NDs were found to suspend CNTs in twisted structures, or CNT–GO complexes.
deionized water more favorably compared to positively Compounds in elemental form. Chemical functionalization
charged particles, possibly caused by electrostatic interactions. of MWCNTs was carried out39,40 by UV/ozone treatment. The
Graphene oxide (GO) sheets, considered to be “so” 2D presence of oxygen-containing groups (such as carboxylic,
macromolecules containing multiple aromatic regions and quinine, and hydroxyl groups) on the MWCNT surfaces by
hydrophilic oxygen groups, can adsorb the pristine MWNTs UV/ozone treatment was conrmed resulting in better disper-
through p-stacking interactions, thus causing pristine MWNTs sion stability than for pristine MWCNTs in polar solvents. The
to stably disperse and fractionate in aqueous media (Fig. 9 and authors predicted the dispersion states of MWCNTs treated
10).38 The water-soluble and insoluble complexes can be with UV/ozone in 32 different solvents in terms of a Hansen
obtained by changing the initial proportion of MWNTs to GO solubility parameter sphere, which increased as the UV/ozone
sheets, which are important for noncovalent approaches toward exposure time increased. Iodine-doping into SWCNTs can be
effectively done using an electrochemical method41 and can be
easily and nely controlled by changing the polarity. Iodine
molecules were found to be mainly inserted into the hollow
core of SWCNTs and these iodine-doped SWCNTs can be
homogeneously dispersed in water at low temperatures (ca.
<15 C). But, in our opinion, the most intriguing example in
this section is an unusual application of Na–NH3(liq.) system,
well-known in classic inorganic chemistry courses. Thus, an
intrinsically scalable method for SWNT dispersion and sepa-
ration, using reductive treatment in sodium metal–ammonia
solutions was discussed (Fig. 11),42 optionally followed by
selective dissolution in a polar aprotic organic solvent. In situ
small-angle neutron scattering demonstrated the presence of
dissolved, unbundled SWNTs in solution, at concentrations
reaching at least 2 mg mL1; the ability to isolate individual
nanotubes was conrmed by atomic force microscopy. The
soluble fraction contained predominantly large SWCNTs.
Fig. 10 TEM images of interactions formed between MWNTs and GO sheets by
SWNTs can indeed be unbundled to give individual tubes in
changing the initial proportion of MWNTs to GO sheets to 2 : 1 at different
magnifications (a and b) and the initial proportion of MWNTs to GO sheets to 1 : 2
solution by reductive charging in ammonia. This process
at different magnifications (c and d). The insets in (b and d) are the schematic requires control of the metal : carbon (M : C) ratio, to much
descriptions of the MWNT–GO complexes. lower values (approximately 1 : 10) than typically given in the
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Fig. 11 Liquid ammonia reduction of ARC SWNTs. (a) Process scheme for the reduction, solvation, and subsequent dissolution in sodium–ammonia, illustrated by
atomistic models (Na ions in pink) and photographs of the relevant phases (M : C ¼ 1 : 20). (b) SANS pattern from the spontaneously dissolved SWNTs (M : C ¼ 1 : 24) in
sodium–ammonia (Na : ND3). The red and green lines show power-law best fits, giving exponents of 1.0 and 2.65, as marked. The inset shows a schematic of the
corresponding nanotube mesh and associated length scales.
literature (>1 : 1), but does not inherently involve covalent CO2 and SiO2. The dispersion of MWCNTs at the very low
functionalization of the tubes. The initial treatment of SWNTs milligram level was achieved by effervescence due to the in situ
in liquid sodium metal ammonia solution is a key step in the generation of carbon dioxide like in some traditional pharma-
separation. Following the removal of the liquid ammonia, a ceuticals.43 A special tablet containing the effervescence
dry powder of sodium “nanotubide” was formed (where precursors (sodium carbonate as the carbon dioxide source and
“nanotubide” was proposed by authors as a term for a pure sodium dihydrogen phosphate as a proton donor) and the
nanotube anion). On the addition of dry DMF, the nanotubide MWCNTs was applied for MWCNT solubilization. Another
swells and a fraction (approximately 40 wt%) of the reported type of carbon dioxide action was completely different.
SWNTs spontaneously dissolved. It is worth emphasizing that Thus, an efficient method using supercritical (SC) CO2 was used
no stirring and, more importantly, no ultrasound were used at to help a p-type conducting polymer, conjugated polymer
any stage of the process. This spontaneous dissolution is MDMO-PPV, wrap onto CNTs.44 1D CNTs were periodically
presumably driven by the solvation of the cations, leading to decorated with congeries of MDMO-PPV molecular chains to
repulsion between the solvated nanotubide anions and the form functional nanohybrid structures. The solubility and light
formation of an electrostatically stabilized colloid (or poly- emission of the hybrid MDMO-PPV/CNTs can be controlled by
electrolyte molecule). This separation process was shown to varying the SC CO2 pressure. Chemical interactions between
scale consistently to the 100 mg level.
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MDMO-PPV and CNTs were conrmed, and the interactions not increased in polar media like water and methanol. A
only bestowed CNTs with the desired solubility but also added comparison of CNTs treatments with individual acids and
the functionality of light emission to the CNTs. With DMSO as their mixtures also led to interesting conclusions. The effect
the solvent, the higher SC CO2 pressure ensures the excellent of ve different chemical treatments (HNO3, H2SO4, H2O2,
dispersion and solubility of MDMO-PPV/CNTs. Related HNO3 + H2SO4 and HNO3 + HCl) on the homogeneity, surface
research was carried out for a typical piezoelectric polymer, chemistry, structure and dispersibility in water of iron- and
poly(vinylidene uoride) (PVDF), which was wrapped onto iron oxide-lled MWCNT samples was evaluated by a series of
SWCNTs using a simple supercritical carbon dioxide (SC CO2) methods.51 It was indicated that chemical treatments are
antisolvent-induced polymer epitaxy method.45 In case of SiO2,
generally effective in removing non-nanotube carbonaceous

nanoscale silica functional groups were covalently bonded to species present in the sample. Obviously, with the exception of
the CNTs to improve their dispersion in water while providing the H2O2 treatment, the chemical treatments offered good
interfacial bond sites for the proposed matrix material.46 At the removal of free iron species. Besides the increase in the
nanoscale, interparticle spacing was greatly increased and, as a sample homogeneity, the chemical treatments promoted an
result, dramatically improved dispersion stability in water was increase in the carboxyl and hydroxyl groups at the carbon
observed. nanotube surfaces, which directly affects the dispersibility of
Inorganic acids and their mixtures. Mineral acids were these carbon nanotubes in water. In particular, dispersions of
extensively used in the rst attempts to functionalize CNTs, 2.24 101 g L1 were obtained for the samples treated with a
now described in classic books on nanotechnology, and mixture of nitric and sulfuric acid. Also, MWCNT particles
continue to be used now too, generally as a rst simple step of were dispersed in n-hexadecane (used to decrease super-
attachment of polar groups to CNT surfaces before being cooling)52 through surface modication of the MWCNT parti-
further interchanged to other functional groups. Among acids, cles with the strong acids H2SO4 and HNO3, plus the addition
nitric acid is the most common, leading to –OH and –COOH of 1-decanol as a surfactant to the organic liquid. The super-
attachment to CNT surfaces. Thus, the CNTs, CVD-synthesized cooling of n-hexadecane was signicantly decreased at
from heavy petroleum fractions like furnace oil and light diesel concentrations of 0.1% and 0.5% but only slightly with
oil (70 nm in the rst case and 90 nm in the second case), concentrations over 1.0%. The authors suggested that well
were puried, oxidized with dilute nitric acid and dispersed in dispersed nanoparticles provided stable foreign nuclei of
different solvents.47 It was shown that these –COOH- and –OH- proper size to promote the heterogeneous nucleation process
functionalized CNTs were highly dispersed in acetone and and accelerate the crystallization process, thus supercooling
distilled water compared to ethanol and methanol and stable was signicantly reduced.
even up to 60 C. Also, a combination of HNO3 application Inorganic salts. Few examples of salt applications for CNT
with further physical treatments has also been developed. For dispersion are known. The effects of inorganic monovalent
instance, individual electric arc-produced SWNTs were salts (NaCl and NaI) on the dispersion stability of CNTs were
prepared in aqueous solution on a large scale through three studied, performing all-atom molecular dynamics simulations
steps of processing: reuxing in concentrated HNO3, low speed (MDS) using non-polarizable interaction models to compute
centrifugation, and high speed centrifugation.48 The bulk the potential of mean force between two (10,10) SWNTs in the
production (10 g of starting SWNTs) resulted in a concentra- presence of NaCl/NaI and compare to the potential of mean
tion of 0.2 mg mL1 individual SWNTs stably dispersed in DI- force between SWNTs in pure water.53 Addition of salts
H2O without any external protection. It was shown that the enhances the stability of the contact state between two SWNTs
aqueous dispersion contained approximately 80% individual in the order of 4 kcal mol1. The ion-specic spatial distri-
SWNTs with lengths ranging from 500 nm to 1 mcm and an bution of different halide anions gives rise to starkly different
absolute zeta potential value of 72 mV with a concentration contributions to the free energy stability of nanotubes in the
of 0.05 mg mL1 at pH 5. The authors believed that it is this contact state. The iodide anion directly stabilizes the contact
high zeta potential resulting from an electrical double layer state to a much greater extent than the chloride anion. The
which produces the repulsion to overcome the van der Waals enhanced stability arises from the locally repulsive forces
attraction thereby keeping the SWNTs individually dispersed. imposed on nanotubes by the surface-segregated iodide anion.
Additionally, a nondestructive method for the preparation of Within the time scale of these simulations, both NaI and NaCl
stable aqueous colloidal solutions of graphene nanoribbons solutions stabilize the contact state by equivalent amounts. In
and carbon nanotubes including sonication of carbon nano- a related report,54 the effects of salt (NaI) on pristine CNT
materials in hypophosphorous acid (H3PO2), ltration accom- dispersions in N-methyl-2-pyrrolidone (NMP) were also MDS-
panied by washing the solids with water and dispersion of the studied, revealing another group of conclusions. It was
solids in a fresh portion of water to form colloidal solutions, revealed that both ions (Na+ and I) are depleted from the CNT
was described.49 surface in the CNT–NMP dispersions mainly due to two
MWCNTs were puried and functionalized using oxidizing reasons: (1) there is a high energy penalty for the ion partial
acid mixtures (sulfuric and nitric acids).50 It was revealed that desolvation at the CNT surface; (2) NMP molecules form a
the length of MWCNTs decreased when the purication and dense solvation layer at the CNT surface that prevents ions
functionalization times were increased; also, by functionali- from getting close to the CNT surface. An increase of the salt
zation the solubility and colloidal stability of MWCNTs were concentration increases the “osmotic” stress in the CNT–NMP
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uorosilicate modied with an inorganic polyphosphate

dispersing agent) to stabilize aqueous suspensions of
MWCNTs was investigated with the help of analytical centri-
fugation, microscopic image analysis, and measurements of
electrical conductivity of hybrid laponite/MWCNTs suspen-
sions.56 It was observed that sonication of MWCNTs at critical
minimal concentration of laponite Xc z 0.25 0.05 resulted
in efficient dispersion and formation of stabilized suspensions
of individual nanotubes. The stabilization of nanotubes in the

presence of laponite was explained by the adsorption of its
particles and formation of a hydrophilic charged shell on the
surface of the nanotubes (Fig. 12).
Inorganic peroxides. An easy strategy was developed for the
water-soluble MWCNTs without the length cutting of MWCNTs
via the ultrasonic-assisted chemical functionalization with a
Fig. 12 Impact of laponite content and nanotube concentration on the struc- redox couple ammonium persulfate/diethanolamine at r.t.57
ture of hybrid laponite + MWCNT suspensions. Diethanolamino groups were found to be covalently attached
onto the sidewalls of the MWCNTs; the surface functional group
content of the functionalized MWCNTs was 0.66 mmol g1; the
system and, thus, decreases the stability of the CNT disper- MWCNTs were exfoliated into individual nanotubes. The
sions in NMP. Direct experiments conrmed the simulation resultant MWCNTs were dispersed easily in water and the
results: addition of NaI salt into NMP dispersions of pristine dispersion was stable for more than 4 days. In a related
CNTs led to the precipitation of CNTs (bundle formation) even research,58 MWCNTs with improved dispersion properties
at very low salt concentration (103 mol L1). It is necessary (Fig. 13) were prepared by mild and fast hydrothermal treat-
to mention that the MDS method was also used to compute for ment with the use of potassium persulfate. The modied
the potential of mean force as a function of the distance and MWCNTs were highly soluble in polar solvents such as water,
orientation between a pair of SWCNTs in water.55 An adaptive ethanol, dimethylformamide, tetrahydrofuran, dimethylaceta-
biasing force method was applied to speed up the calculations. mide. These treated MWCNTs showed the highest solubility in
Simulation results showed that CNT orientation and the water and the solubility was around 1.16 mg mL1. However,
addition of surfactant can signicantly affect CNT interactions they could not be well dispersed in nonpolar solvents (such as
and, in turn, dispersion. In addition to sodium halides, the hexane and toluene) and eventually precipitated. This indicated
ability of laponite (a synthetic layered magnesium aluminum that various hydrophilic groups were created on the treated
Fig. 13 Typical FESEM images of (a) pristine MWCNTs and (b) treated MWCNTs, with high magnification images in the insets; typical TEM images of (c) pristine
MWCNTs and (d) treated MWCNTs, with the individual MWCNT images in the insets.
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MWCNTs aer hydrothermal modication. We note herein that acylation in an optimized PPA/P2O5 medium. It was shown
hydro(solvo)thermal methods and, in particular, when that the MWCNTs were functionalized effectively and without
combined with microwave heating (MW-hydro(solvo)thermal damaging the CNTs compared to the mineral acid oxidation
technique), is a useful synthesis tool in chemistry and method (using HNO3 and H2SO4), described in the previous
nanotechnology.59 section, and the dispersion and compatibility of the obtained
MWCNTs in organic medium was improved.
Organic acids and salts
A few organic acids have been applied for CNT functionalization
with the objective of increasing their solubility. Thus, the

preparation of a stable dispersion of MWCNTs using carminic
acid (1, CA, 7-D-glucopyranosyl-3,5,6,8-tetrahydroxy-1-methyl-
9,10-dioxo-9,10-dihydroanthracene-2-carboxylic acid)60 as a
dispersing agent revealed that the MWCNTs are well dispersed
in CA aqueous solution and CA was well adsorbed at the
MWCNT walls. The prepared CA/CNTs aqueous dispersion was
found to be highly stable for 4 months (Fig. 14). The p–p-
stacking interactions between CA and MWCNTs provided good
stability to the CA/CNTs dispersion. On the basis of this
composite, a selective amperometric biosensor for H2O2 and
iodate was developed, which exhibited excellent amperometric In a synthesized self-assembled system, namely, hydrogen
response towards H2O2 and iodate in the linear concentration bonded liquid crystal 2, MWCNTs were dispersed.62 This self-
range between 10 M to 3.2 mM and 0.01–2.16 mM. CA/CNTs assembled liquid crystal system was realized by the formation
could be used as an effective platform for immobilizing vital of hydrogen bonds between levotartaric acid and undecyloxy-
proteins and biomolecules to explore their direct electrochem- benzoic acid. A small amount (0.05 wt%) of MWCNTs was
istry. Functionalization of MWCNTs with benzenetricarboxylic dispersed in the liquid crystal and the resultant mixture in its
acid (BTC) was conducted61 by using a direct Friedel–Cra isotropic state is ultrasonicated for 2 h so as to obtain a
monodispersion of MWCNTs without any aggregation.
Another example is the acid yellow 9 (4-amino-1-10 -azo-
benzene-3,40 -disulfonic acid, AY), which was found to be a
good stabilizing agent for MWCNTs.63 MWCNTs dispersed in
an AY solution remained stable for about three months
and even remained stable aer centrifugation at 10 000 rpm
for 30 min.
Among a series of ionic salts of organic acids, sodium
dodecylbenzene sulfonate 3 (SDBS) and sodium dodecyl
sulfate 4 (SDS) are very popular and mostly frequently used64,65
due to their outstanding properties for CNT dispersion,
primarily their dispersion stability in distinct temperature
conditions and solvents. Thus, as a representative example, the
stability of dispersions of SWCNTs stabilized by SDBS in
binary polar solvents “water + antifreeze” (glycerol, poly-
ethyleneglycole) with eutectic compositions was studied.66,67
The absorption spectra of the suspensions demonstrated no
changes during 1 year of storage with temperatures ranging
from 40 to +40 C. Aqueous dispersions of nanotubes
exhibited a considerable enhancement of optical limiting
parameters alongside an increase of the bundled material
populace. Using SDBS, the layered double hydroxide LDH/
CNTs composites with interlayer anions of dodecylbenzene
sulfo-group (DBS–LDH/CNTs) were obtained68 and dispersed in
several organic solvents. The suspension of DBS–LDH/CNTs in
1-butanol, ethanol and xylene were stable for a long duration,
Fig. 14 Photographs of 1 mg mL1 CA/CNTs dispersion taken after (a) 1 h, (c) 1,
while they sedimentated quickly in tetrahydrofuran. In addi-
(e) 2, and (g) 3 weeks; (i) 1, (k) 2, (l) 3, and (m) 4 months; CNT dispersion taken
after: (b) 1 h, (d) 1, (f) 2, and (h) 3 weeks; (j) 1 month. TEM images of (A) CNTs and
tion, the delamination extent for LDH in these solvents ranked
(B–D) CA/CNTs at different magnifications. (B) The yellow dotted circles indicate as follows: 1-butanol > ethanol > xylene > tetrahydrofuran.
the adsorbed CA molecules. Among other important studies, the aggregation kinetics for
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SWNTs and MWNTs carbon nanotubes dispersed using SDBS molecules in which the heads form a compact outer surface,
were investigated69 using time-resolved dynamic light scat- while the tails remain in contact with the nanotube walls. It is
tering (DLS), in the presence of several electrolytes, and humic important to note that the nal conguration can be described
acid (HA). The CNTs could be effectively suspended in aqueous as a cylindrical micelle with a nanotube in the center.
solution using SDBS, and the increased electrolyte concentra- As an example of SDS applications, CNTs were dispersed in
tion induced aggregation. Increases in the solution pH from 3 a SDS/decanol/water nematic uid mixture.72,73 The long-term
to 10 led to a signicant decrease in CNT aggregation, indi- stability of the dispersions was ensured by the small density
cating the presence of functional groups on the CNTs surface. gradients existing between the nanotubes and the nematic
In NaCl solution, the stability of the CNTs was increased. A uid, and also by its viscosity. Presumably, surfactant or
pseudostationary phase of MWCNTs dispersed with SDBS was nematic micelles adsorb onto the nanotubes and stabilize
used70 for the EKC separation of nucleotides. SDBS has a long them. It was quantied how changing the counter-ion (Cs+
hydrophobic chain and a benzylsulfonate group. It suspends instead of Na+) affected the morphology of the dodecyl sulfate
more MWCNTs (about 100-fold) than SDS, and the p–p surfactants adsorbed on the CNTs.74 Using atomistic molec-
interaction between the benzene ring of SDBS and MWCNTs ular dynamics, aqueous cesium dodecyl sulfate (CsDS)
prolongs the slurry suspension time. Using SDBS as a surfac- adsorbed on (6,6), (12,12), and (20,20) SWCNTs at r.t. were
tant can reduce the required amount of MWCNTs and simulated. It was suggested that CsDS should be more effec-
decrease the baseline noise. In addition, in the case of SDBS, it tive than SDS at stabilizing aqueous carbon nanotube
was found71 that during its adsorption on SWNT coulombic dispersions. More importantly, these results were obtained
forces do not play a central role, but are overcome by the only for the (6,6) nanotubes simulated. The analysis of surface
hydrophobic interactions between the surfactant tail and the tension of SDS-stabilized dispersions of CNTs was carried
nanotube walls. The hydrophobic forces between the surfac- out.75 It was shown that surface tension is very sensitive to
tant tail and the nanotubes determine the structure of the small changes in the nanotube and surfactant concentrations.
surfactant-stabilized nanotubes (Fig. 15). In such a structure, It was suggested that, at moderate concentrations, the
each nanotube is covered by a monolayer of surfactant surfactant displaces carbon nanotubes from the air–water
Fig. 15 Model for the surfactant–nanotube interaction. Head cubic packing density ¼ 1.45 molecules per nm2. Head diameter (HD) ¼ 0.69 nm. Chain length
(lc) ¼ 1.5 + 1.265n (Å). n ¼ number of carbons; lc ¼ 24.27 (Å).
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interface and the nanotubes are mostly moved into the

bulk of the liquid. Also, the effect of the CNT diameter
(10–500 nm) and CNT length (1–40 mm) in the presence of 1%
sodium dodecyl sulfate (SDS) on a suspension of CNTs in
water was studied.76
In addition, a series of comparative studies between SDBS
and SDS, as well as with frequently used non-sulfonate surfac-
tants, have been carried out. The SDBS contributed to a better
dispersibility and electrical conductivity of SWCNTs than SDS 4,

sodium cholate 5 (SC, see below), and cetyltrimethyl ammo-
nium bromide 6 (CTAB).77 A similar conclusion was also made78
on the basis of molecular dynamic simulations comparing
SDBS and SDS, concluding that the SDBS surfactant contributed
weaker interactions between CNTs compared with those of SDS
by a factor of about 10. Adsorption isotherms of four different
surfactants, SDBS 3, SDS 4, benzethonium chloride 7 and Triton
X-100 8 were measured on MWCNTs in water.79 The nature of Other sulfonate-containing surfactants are rare;81 among
the polar head had only a small inuence on adsorption which them, we note the water-soluble polyaniline blend poly(sodium
was mainly driven by hydrophobic interactions. However, the 4-styrenesulfonate), (PANI$PSS), which was used82 to disperse
outcome of the dispersion experiment was dependent on MWCNTs by noncovalent surface modication. The anionic
the purity of the carbon nanotubes. Using these results, it PANI$PSS solution was prepared by interfacial polymerization of
was possible to prepare concentrated colloidally stable an aniline monomer in the presence of PSS as the blending
dispersions of MWCNTs in water (c ¼ 32 g L1). Other reagent to provide water solubility. The MWCNTs dispersed with
comparative studies on the interactions and dispersion of PANI$PSS were found to be highly dispersible in water, which
MWNTs using two different surfactants (SDS 4 and poly- opens up new possibilities for the fabrication of composite
oxyethylenesorbitanmonooleate 9, Tween 80)80 showed that, lms. Water-soluble sodium p-aminobenzenesulfonate-graed
for effective dispersion, the minimum weight ratio of MWNTs MWCNTs (MWCNTs-CO-NHC6H5SO3Na) were synthesized by an
to surfactant was 1 : 41 and 1 : 3 for SDS and Tween 80, amidation reaction of sodium p-aminobenzenesulfonate with
respectively. MWCNT-COCl (prepared by MWCNTs oxidation83 by concen-
trated HNO3 and then reaction with SOCl2). The MWCNTs-CO-
NHC6H5SO3Na showed good solubility and dispersion in water,
and had improved adsorptive performance for the removal of low
concentrations of Cu2+ in water. MWCNTs were also function-
alized84 with sodium lignosulfonate (10, SLS) at various SLS/
MWCNT ratios. It was shown that the solubility of the MWCNTs
did not increase signicantly with further increases in SLS aer
the appropriate amount of SLS was employed. Excessive use of
SLS rather decreased the conductivity of the functionalized
MWNTs. Also, the solubility of MWCNTs was inuenced by
dispersing method even when the same amount of SLS was used.
†
The tail groups of SDS, SDBS, and SC contain anionic moieties, Several other organic salts, applied for CNT dispersion, are
while CTAB has a cationic tail group. also known, for instance dodecyl quaternary ammonium
bromides.85 Thus, dodecyl trimethylammonium bromide (11,
DTAB) and sodium octanoate (12, SOCT) were found86 to form
exceptionally stable MWNT dispersions. Stable dispersions were
obtained at low total surfactant concentrations compared to their
concentration when used alone. A waterproof biomaterial, stearic
acid (STA), which is one of components of the wax present on lotus
leaf surfaces, was used as a material with low surface energy to
fabricate superhydrophobic MWCNT hybrids through a solution
method. This method involved preparation87 of a sodium stearate
(SST)-stabilized MWCNT dispersion (Fig. 16), followed by a
precipitating process. STA was assembled on the MWCNT–SST
hybrid surface by a reaction of SST with acetic acid. With
increasing SST/MWCNT weight ratio, the water CA of MWCNT
hybrid increased and then decreased aer a maximum value of
163 C at a ratio of 1 : 1. It was interesting that the wetting property
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of MWCNT hybrids (SST : MWCNT ¼ 0.5 : 1 and 1 : 1) was

tunable between superhydrophobicity and superhydrophilicity by
changing the temperature. In some related research,88 a sol–gel
synthesis was carried out for obtaining MWCNTs/zirconia
composites, where two kinds of surfactants, sodium and ammo-
nium stearates {CH3(CH2)16COOM, M ¼ Na, NH4+} dissolved in
water (1 g per 100 mL), were used as dispersant agents for
MWCNTs. Different quantities of MWCNTs (up to 5 wt%) were
added to the solution of stearate/water and this solution with the
highly dispersed MWCNTs was added to the zirconia sol–gel,
producing composites of MWCNTs/zirconia with different
concentrations of MWCNTs. Finally, the detailed large-scale all-
atomistic molecular dynamics simulation study of the adsorption
and surface self-assembly of a common bile salt surfactant,
sodium cholate 5 (SC, noted above) on a SWNT in aqueous solu-
tion was made.89 The cholate ions wrap around the SWNT like a
ring and have a small tendency to orient perpendicular to the
cylindrical axis of the SWNT, a unique feature that has not been
observed for conventional linear surfactants such as SDS. At the
saturated surface coverages, SC is a better stabilizer than SDS, a
nding that is consistent with the widespread use of SC to
disperse SWNTs in aqueous media. Indeed, the superior disper-
sion-induced stability of SC over SDS results from a higher
repulsive energy barrier and a shallower attractive energy well
induced by SC in the PMF prole. The sodium cholate assisted
CNT dispersion can remain stable and clear for two months.90
Fig. 16 Images of MWCNT aqueous suspensions: (a) MWCNT (2 104 g mL1),

(b) SST : MWCNT (1 : 1), (c) SST : MWCNT (1 : 1) after addition of acetic acid; (d)
image of a MWCNT hybrid (SST : MWCNT ¼ 1 : 1); (e–g) SEM images of MWCNT
hybrids (SST : MWCNT ¼ 1 : 1); (h) image of a water concave formed when a
MWCNT hybrid (SST : MWCNT ¼ 1 : 1) was touched to the water’s surface.
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Other organic and coordination compounds A poly[(4-pyridineoxy)(phenoxy)phosphazene] was prepared96

by sequential treatment of poly(dichlorophosphazene) (–PNCl2–)n
In addition to the organic acids and salts described above, the
with sodium 4-pyridineoxy and sodium phenoxide in THF.
other organic non-biological substances discussed below are
MWCNT/poly(organophosphazene) composites (f-MWCNT/PZS)
mostly aromatic and polyaromatic compounds, frequently
with different feed ratios [Rfeed ¼ 1 : 1, 1 : 3, 1 : 5 and 1 : 10 (w/w)]
containing heterocycles, for instance porphyrin91 or thiophene.
were obtained by the treatment of the functionalized f-MWCNTs
Thus, as an example of an S-heterocycle, the hydrogenation of
with protonated poly(organophosphazene) (PZS), achieving
2-nitrothiophene gave 2-aminothiophene 13 that was used92 for
amidation of SWCNTs functionalized with carboxylic acid excellent dispersions in water and common organic solvents. The
groups (SWCNT-COOH). In these modied carbon nanotubes dispersion of SWCNTs in the presence of water soluble poly-
pyridyl complexes of the general formula [Rux(bpy)yL]2+ (L ¼
(SWCNT-CONHTh), the thiophenes were covalently attached to
dppz, dppn, tpphz) was reported.97 These ligands have extended
the SWCNTs via amide linkages. The modied SWCNTs showed
planar p-systems, which aid in the solubilization of SWCNTs via
enhanced solubility, and thus better dispersion in common
p–p interactions. A series of imidazolinium derivatives have been
organic solvents and were used as dopants in polymer–fullerene
reported to be good surfactants for CNTs, leading to composites
photovoltaic cells. However, N-containing compounds repre-
with useful properties and possible applications. Thus, an
sent the majority of the compounds which have a dispersion
capacity for CNTs. For instance, the classic chemical aniline approach for the stabilization of dispersions based on the use of
(PhNH2) was found to act as a very efficient dispersing agent to cationic surfactants (imidazolinium iodide 15 and imidazoli-
nium bromide 16) synthesized98 from raw materials was offered.
debundle CNTs from 200 to 50 nm at a very low concentration of
The resulting homogeneous dispersions of CNTS with sonication
0.5% in an IPA/water solution.93 The aniline-stabilized CNTs
with imidazolinium iodide were observed to be stable for two
had a larger pore volume and larger amount of mesopores than
months. Polyesters incorporating a variable quantity of imida-
pristine CNTs, and the debundling of CNTs by aniline appears
zolium rings along the backbone were synthesized by Huisgen
to be a physical rather than a chemical process. In addition,
1,3-dipolar cycloaddition99 and revealed an efficient dispersing
aniline is an efficient dispersant and stabilizer for the prepa-
ration of Pt nanoparticles deposited on CNTs. Octadecylamine ability toward the CNTs through supramolecular interactions in
functionalized MWCNT-ODA was used94 as the model organic media. These compounds offered a simple and reliable
strategy to control the quantity of dispersed CNTs as a function of
compound (studying the possibility of antisolvent precipitation
imidazolium content. This approach is particularly suitable for
of hydrophobic, organic soluble functionalized carbon nano-
the elaboration of biosourced and biodegradable materials based
tubes (f-CNTs), where water acts as an antisolvent is presented)
on poly(butylene succinate) with high-performance properties. A
and it was found to form highly stable dispersions in different
core–shell carbon nanotube/conducting polymer hybrid, using
water/solvent systems, and the particle sizes ranged from 170 to
an imidazolium-salt-based ionic liquid as a linker, was devel-
400 nm. Colloidal behavior was studied using dynamic light
scattering and particle aggregation was found to increase with oped100 for large-scale solution processing of CNTs. The water-
the addition of electrolytes, with THF and ethanol showing the soluble shell promotes dispersion of the CNT aggregates and
brings individual CNTs into aqueous solution while maintaining
maximum effect. Based on this reported study, it is evident that
an intact p-conjugated structure, and leads to a reduced charge
hydrophobic f-CNTs are potential water pollutants. Also, the
injection barrier and realizes high photovoltaic performance. In
addition of an azobenzene derivative, Disperse Orange 3 (DO3)
addition, the 1-hexadecyl-3-vinylimidazolium bromide (hvimBr),
14 to dispersions of MWCNTs in THF efficiently helped the
a water-soluble long-chain imidazolium ionic liquid (IL) with
debundling of MWCNTs and made dispersions stable for days.95
surfactant properties, showed the ability to produce stable
homogeneous aqueous dispersions of pristine SWNTs.101 The
improvement of SWNT dispersion ability was suggested to be due
to the effect of different groups in position 3 of the imidazole ring.
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Among other CNT composites with heteroatom-containing dissolved in water by the non-TPP type chiral porphyrins, and
cycles, we note thymine-(17) modied CNTs (CNT-Thy) can be the dissolved chiral porphyrin/SWNTs composites could be
dispersed in solution in the presence of diaminotriazine (18, easily redissolved. Both the dissolved and redissolved SWNT
DAT) end-functionalized polymers, through supramolecular solutions were found to be very stable and did not form
Thy/DAT association.102 Long-term stable supramolecular CNT apparent aggregates even aer being kept for six months.
dispersions were reversibly aggregated by adding a few droplets
of a selective dissociating agent to the Thy/DAT association
(DMSO). CNT-Thy, simply recycled by centrifugation or ltra-
tion, can be redispersed in another solvent in the presence of a

suitable soluble DAT–polymer. Dispersion and aggregation can
also be switched on and off by choosing a polymer for which a
given solvent is close to Q-conditions, e.g., PS in cyclohexane or
PPO/PEO in water. The effect of poly(2-ethyl-2-oxazoline) (PEOX,
[–N(COC2H5)CH2CH2–]n) as a surface modier for MWCNTs in a
poly(vinyl alcohol) (PVA) composite was studied103 through
simple polymer wrapping and melt extrusion processes.
MWCNTs were carboxylated in a reaction with HNO3, followed
by mixing with 10 wt% PEOX in ethanol to produce a MWCNT–
PEOX complex. A PEOX layer existing on the surface of
MWCNTs was identied. Compared with pristine MWCNTs,
MWCNT–PEOX showed improved dispersion in hydrophilic
solvents such as water and ethanol. We emphasize also chiral
porphyrins, whose SWCNT nanocomposites are quite prom-
ising for applications in chiral catalysis and bio-sensing due to
the outstanding electronic, photophysical and photochemical
properties. The porphyrins used for the solubilization of CNTs
are usually tetra-phenyl porphyrin (19, TPP) analogues.
However, TPP analogues do not favor the formation of p–p
interactions because the aryl groups prevent the porphyrin
moiety from approaching the CNT surface due to the perpen-
dicular conformation of the porphyrin moiety and its aryl group
substituents. To avoid this, non-TPP type porphyrins 20, with
chiral and hydrophilic substituents, that make the porphyrins
soluble in water, were synthesized.104 SWNTs were effectively
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Polyaromatic hydrocarbons are also very common for CNT

dispersion purposes. Thus, the synthesis of perylene-based (21)
SWCNT surfactants and the dispersion and exfoliation of
SWCNTs in water by a variety of designed surfactants is inves-
tigated.105 Signicantly, the dispersion efficiency can be
increased at higher pH, as water solubility of the surfactants is
ensured by peripheral derivatization with carboxyl-functional-
ized rst and second-order Newkome dendrimers. Even at very
low perylene concentrations of 0.1 g L1 and a nanotube-to-
surfactant ratio of 1 : 1, the nanotube supernatant aer centri- Fig. 17 Illustration of the noncovalent surface modification of SWCNTs by
fugation contained up to 73% of the pristine material with amphiphilic Trp-TEG molecules.
exfoliation degrees (the number of fractions of individualized
nanotubes N1/NT) of up to 76%. A water-soluble stilbene (22)
either two ionic or non-ionic tails to ensure a large number of
derivative with cationic charges enables tuning of the dis-
supramolecular interactions with the solvent, thereby
persibility of the SWNTs in aqueous solution by photo-
promoting strong solubilization. The surfactants produced
irradiation.106 The nearly coplanar core of the stilbene
stable suspensions in which the SWNTs were dispersed and the
dispersant interacts with the SWNTs via p–p interactions,
surfactant/SWNT complexes formed are stable for more than
resulting in a stable dispersion of the SWNTs. Photoinduced
one year. In a related research,109 supramolecular surface
cyclization for the dispersant-triggered reprecipitation of the
modication of SWCNTs using amphiphilic molecules con-
SWNTs is due to the detachment of the dispersant from the
taining a bent triptycene moiety and a hydrophilic oligo-
SWNT surfaces.
(ethylene glycol) chain 25 and 26 was described. The surface
modication was realized through the binding of the triptycene
moiety onto the sidewall of SWCNTs through p–p stacking
interactions, and the oligo(ethylene glycol) chains extend into
the water and act as dispersing agents, thus yielding an aqueous
SWCNT dispersion. This dispersion was found to be stable for
more than six months and contained a high concentration of
SWCNTs. Based on shape-tting of SWCNTs and the triptycene
moiety, the stacking of triptycene moieties on the SWCNT
sidewall showed nice selectivity for SWCNTs with a diameter of
1.0 nm. The stacking of Trp-TEG molecules onto the SWCNT
sidewall is illustrated in Fig. 17.
A preparation method for individually dispersed SWNTs in

both liquid and dried solid states was developed using triphe-
nylene 23 derivatives.107 On this basis, a highly concentrated
solution of SWNTs (0.7–0.8%) was prepared, and also the
SWNTs were well dispersed aer the addition of methanol (up
to 70%) for a long time. These properties (redispersion ability
and dispersion in the presence of organic solvent) were not
observed in typical dispersing surfactants, such as SFBS and
sodium cholate. A triptycene-24 (Trp) and amphiphilic naph-
thalene-based surfactant was designed with the ability to solu-
bilize SWNTs and C60 in water through non-covalent
interactions.108 The prepared compounds were designed with
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and spacer length between POSS and the MWCNT surface on

MWCNT dispersion. It was found that POSS molecules with
longer spacer lengths and less bulky R groups facilitated the
CNT modication process better, while CNTs modied by POSS
with shorter spacer lengths and less bulky R groups showed
better dispersion in THF.
In addition, pyrene can be used together with coordina-
tion compounds, although the last example below was used
for another purpose, not for increasing solubility. Thus, the

synthesis of a multifunctional block copolymer incorporated
with pyrene and ruthenium terpyridyl thiocyanato complex
moieties by reversible addition–fragmentation chain transfer
polymerization was reported.112 The pyrene block in the
copolymer facilitates the dispersion of MWCNTs in DMF
solution because of the strong p–p interactions between the
pyrene moieties and nanotube surfaces. On the other hand,
the ruthenium complexes greatly enhance the photosensi-
tivity of the functionalized nanotubes in the visible region. An
organogelator, N,N0 -bis(octadecyl)-l-(1-pyrenebutyric acid)-
glutamic diamide (LPG), was designed and its interaction
with pristine SWNTs in the gel state was investigated.113 It
was found that LPG can form organogels with various kinds
Nanohybrid dispersant molecules based on pyrene 27 and
of organic solvents and SWNTs can be well dispersed into
polyhedral oligomeric silsesquioxanes were created for the non-
LPG gel. The gelation process and the properties of the
covalent functionalization of MWCNTs.110 The prepared
resulting nanocomposites were found to be closely related to
dispersant improved the dispersion of MWCNTs in organic
the pyrene group in the gelator. The textures of the nano-
solvents with very different polarities such as tetrahydrofuran,
composites were altered from a layer structure to intertwined
toluene, and n-hexane. The functionalized MWCNTs were
bers upon the incorporation of SWNTs, which also sup-
used to introduce conductivity into polydimethylsiloxane
ported the effective mixing of SWNTs into LPG organogels. In
membranes which can be used for electrostatic discharge
addition to this LPG gel, hybrid organogels, where SWNTs
applications. Silsesquioxanes were also used without pyrene
were incorporated114 into organogel bers, were prepared.
moieties: covalently attaching polyhedral oligomeric silses-
The SWNTs were covalently functionalized with organic
quixoane 28 (POSS) to the surface of MWCNTs can increase111
branches {1,8-bis[3,4,5-tris(decyloxy)benzoylamino]octane
their dispersion both in solution and in polymer matrices.
and N-(8-aminooctyl)-3,4,5-tris(decyloxy)benzamide} (Fig. 18)
Three types of POSS with different organic substituent groups
that had a similar structure to the organogelator. The func-
were used as dispersing agents to study the effect of the R group
tionalized SWNTs in the hybrid organogel formed in decane
were mainly located inside or on the surface of the organogel
bers, while the f-SWNTs in the hybrid organogel formed in
DMF were distributed evenly over the sample. When an
organogelator had a different chemical structure to that of an
organic functional group on the SWNT surface, SWNTs exis-
ted as large aggregates, or long bundles, which were not
incorporated inside the organogel bers. The dispersion
properties of the f-SWNTs in the organogels are greatly
dependent on their relative interactions with the solvent and
the organogelator, and can be exploited to optimize the
properties of hybrid gels bearing CNTs.
Other interesting examples of bifunctional aromatic
molecules are as follows. The large aromatic surfaces of elec-
tron-donor and -acceptor molecules {highly soluble tetrathia-
fulvalene (TTF) derivatives 29 and 30 as the electron donors
and a coronene bisimide (CBI) derivative 31 as the electron
acceptor} direct them onto the surface of the graphene/SWNTs
through p–p stacking interactions whereas the alkyl chains as
well as the glycol chains on the aromatic molecules promote
solubility, thereby giving stable dispersions of SWNT/graphene
composites in non-polar solvents.115 Among other arene
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Fig. 18 Covalent functionalization of a SWCNT with N-(8-aminooctyl)-3,4,5-tris(decyloxy)benzamide}.
derivatives, the capacity of pillar[6]arene 32 host–guest

complexes to disperse MWCNTs, reversibly controlled by
changing the pH, should be noted.116
Representative examples of organic agents for CNT
dispersion are a series of dyes. Thus, uorophore and dye
molecules such as Rhodamine B and uorescein have both
hydrophilic and hydrophobic moieties and also contain
p-conjugated systems that can potentially interact with
SWCNTs to induce their dispersion. It was shown that
SWCNTs can be dispersed117 in aqueous solutions in the thermodynamically stable colloidal system,118 by adding
presence of various uorophore or dye molecules. However, sodium chloride as an electrolyte, SWCNTs occulated and
the ability of a uorophore or dye molecule to disperse settled out due to the destabilization of the colloidal systems
SWCNTs is not correlated with the stability of the uo- initiated by the increase in ionic strength. The dye molecules
rophore/dye–SWCNT complex, suggesting that the on-rate of can be removed by heat treatment at 300 C for 5 h following
uorophore/dye binding to SWCNTs may dominate the effi- washing with water. In addition, bromocresol green 33
ciency of this process. These results could have potential (BCG) and bromophenol blue 34 (BPB) in acidic and basic
applications in the delivery of poor cell-penetrating uo- forms were used119 as dispersing agents to suspend
rophore molecules. In case of another CNT–dye MWCNTs in deionized water. Both these dyes exhibited
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critical concentrations in dispersing MWCNTs; this may result were used. Triton X-series surfactants, compared in the
from the formation of dye micelles, which induces osmotic previous section with SBDS and SDS, with the same hydro-
pressure on MWCNTs and aids nanotube re-aggregation. The phobic functional group {4-(1,1,3,3-tetramethylbutyl)-phenyl}
optimum dye concentration for dispersion was proposed to be and different hydrophilic polyethoxyl chain lengths were
a competing result between the adsorption of dye molecules selected to investigate their adsorption onto CNTs and their
on nanotube surfaces and formation of micelles in water ability to stabilize CNT suspensions.121 The adsorption
(Fig. 19). This critical value is largely related to the balance capacities of the surfactants increased with decreasing
point between the hydrophilicity and hydrophobicity of the hydrophilic chain length: Triton-305 < Triton-165 < Triton-114
dye molecule and its molecular architecture as well. < Triton-100. Electrostatic interactions and hydrogen bonds
MWCNTs were also dispersed120 in water and in a Pluronic could be excluded from the main mechanism because
F108 (2-methyloxirane; oxirane) solution by four different adsorption was not signicantly affected by pH change.
dispersion methods (stirring, bath sonication, stirring Hydrophobic and p–p interactions between the surfactants
followed by bath sonication, and sonication probe). It was and CNTs were the dominant mechanism for adsorption.
shown that, irrespective of the dispersion method used, the Corresponding studies were also carried out for some Tween-
MWCNTs were strongly wrapped with the biocompatible type surfactants. In the case of Tween 65 (compound 35), it
surfactant Pluronic F108, thereby modifying the external could suspend high-loading nanotubes in ethanol.122 MWNT
surface of the MWCNTs. Some shortening of MWCNTs and suspensions in ethanol with Triton X-100 and Tween 65 initial
more wrapping were also observed when sonication methods supernatant concentrations of 1.0 g L1 were prepared and
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Among other organic compounds (for example, poly-

imides)124, we note the microwave-assisted chemical function-
alization of SWCNTs with undecyl groups decomposed from
lauroyl peroxide 36.125 This rapid and efficient procedure
reduced the reaction time to 10 min, and obtained products
with a higher degree of functionalization than those obtained
by the conventional reuxing method. Longer treatment time
leads to partial defunctionalization, and a higher microwave
power (higher than 900 W) can reduce the degree of function-

alization by removing some of the initially attached functional
groups. The resulting SWNTs had enhanced dispersivity in
Fig. 19 Effect of dye content on the formation of dye micelles and dispersion of organic solvents compared to the pristine nanotubes.
CNTs. Red balls represent the hydrophilic groups in the dye molecules.
Polymer-assisted dispersion of CNTs

A lot of reports are dedicated to CNT–polymer composites, used,
in particular, for polymer reinforcement and drug delivery
purposes. Currently, the dispersion processes for CNTs in
polymers are the object of much attention. If a polymer can be
solubilized in solvents, its CNT composites could also be
dispersed; obviously, this is not the only condition for the
possibility of polymer-assisted CNT dispersion. In the case of
most simple polymers, such as poly(vinyl alcohol) (37, PVA), a
low-temperature synthesis method from amorphous carbon
their concentrations were more than 0.50 and 0.35 g L1 aer nanotubes (a-CNTs) and PVA composite thin lms was repor-
240 h, respectively. These concentrations for MWNT suspen- ted.126 Initially the a-CNTs were functionalized by acid treat-
sions, which are stable in the long term in ethanol without ment to improve dispersion in water. The functionalized
polymer or covalent functionalization, are higher than others a-CNTs showed a much enhanced solubility in water. It was
reported in the literature. The slow diffusion of Tween 80 (see revealed that the sheet resistance of the PVA–a-CNT composite
the previous section) surfactant molecules in SWCNT aqueous monotonically decreases with increasing a-CNT concentration
dispersion was directly observed using a pulsed eld gradient in the composites. The composite showed a higher crystallinity
nuclear magnetic resonance method.123 The slow diffusion of with increased a-CNT concentration, compared to pure PVA.
Tween 80 molecules was attributed to the strongly adsorbed The swelling test conrmed that due to the introduction of the
molecules on the SWCNTs in the aqueous dispersion. The carboxylic groups into the a-CNTs' walls, they gradually became
amount of bound Tween 80 molecules was estimated to be hydrophilic. Different polymers can be used for the stepwise
approximately 12% of the total amount of Tween 80 mole- preparation of composites. Thus, PEGylated MWNTs were
cules, contributing to the stability of the SWCNT aqueous prepared for the successive fabrication of poly(vinyl alcohol)
dispersion. This SWCNT/Tween 80 aqueous dispersion was PVA/MWNT nanocomposite lms by solution casting.127 The
found to be very stable for at least 3 weeks. The observed zeta surface modied MWNTs showed a good colloidal stability in
potentials of this SWCNT dispersion are between 10 and water and improved dispersion stability in aqueous PVA solu-
0 mV, indicating that the stability of the SWCNTs in the tion. The electrical conductivity of the PVA/modied MWNT
Tween 80 solution was maintained by steric interactions
between the small amount of adsorbed Tween 80 molecules
on the SWCNTs, while the effect of the electrostatic interac-
tions between adsorbed Tween 80 was minimal.
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composite lm was three-fold higher than that of the PVA/ SWCNT/polymer systems in the presence of water molecules in
pristine MWNTs composite lm due to the much improved solution.133 It was revealed that the hydrophobic nature of PPS
distribution uniformity of the modied MWNTs in the PVA systematically ensures a higher SWCNT surface coverage,
matrix. higher interstitial water depletion and a much lower degree of
Polyethylene glycol 38 (PEG), mentioned above, and its water ordering when compared to the PEG homopolymer.
derivatives are also very common in CNT functionalization Polyethylene oxide (PEO, 39) and its derivatives are also
processes. Thus, a CNT–polyethylene glycol graed copolymer capable of dispersing CNTs. For this process, molecular
was synthesized128 by covalent functionalization of electric arc- dynamics simulations were carried out to investigate CNT
interactions and dispersion in a PEO/water solution.134 A type of
produced SWNTs with monofunctional, tetrahydrofurfuryl-

terminated polyethylene glycol PEG-THFF (molecular weight light-switchable “smart” SWCNTs was developed by the revers-
200), to give a material composed of 80 wt% SWNTs. Sequential ible host–guest interaction between azobenzene-terminal PEO
processing of the resulting material by ultrasonication and (AzoPEO) and pyrene-labeled hosts attached on the sidewalls of
high-shear mixing provided a means to disperse the SWNT– nanotubes via p–p stacking.135 These SWCNT hybrids were not
PEG-THFF macromolecules on two different length scales and only found to be well dispersed in pure water, but also exhibited
leads to highly viscous solutions; at a concentration of 10 mg switchable dispersion/aggregation states upon alternate irradi-
mL1 the kinematic viscosity (v) of an aqueous SWNT–PEG- ation with UV and visible light. Such a reversible host–guest
THFF dispersion reached a value of v > 1000 cSt (for water v 1 interaction system may open up the possibility of controlling
cSt). Analysis of this procedure by means of viscosity measure- the dispersion state of SWNTs by other common polymers.
ments and AFM showed that ultrasonication is effective in Another representative example of PEO–pyrene combination is
disrupting the SWNT bundles, while the high shear mixing “Pluronic F38” (PEO–PPO–PEO) micelles with pendent pyrene
disperses the individual SWNTs. In order to improve the groups, obtained136 via UV-induced crosslinking of pentaery-
biocompatibility of SWNHox (carbon nanohorns, new materials thritol tetraacrylate within the micellar core. The pyrene moie-
that are similar to SWNTs but have more comparative advan- ties were attached to the periphery of the micelles via reacting
tages than SWNTs), carboxyl polyethylene glycol distearoyl OH-groups of F38 with pyrenebutyric acid. Also, various effects
phosphatidylethanolamine (DSPE-PEG-COOH) was chosen129 to on the dispersion of MWCNTs in organic solvents and in poly-
modify them. Different concentrations of DSPE-PEG-COOH mer lms by means of pyrene-containing polymeric surface
were used in water and phosphate buffered solution (PBS) fol- modiers were investigated.137 Gra surface modiers of
lowed by determining the zeta potentials and monitoring the poly(ethylene oxide) and polystyrene with pyrene groups were
coagulation times. It was shown that 0.25 mg mL1 was the synthesized by radical co-polymerization of the corresponding
optimal concentration of DSPE-PEG-COOH to achieve the best macromonomers and a pyrene-containing methacrylate mono-
dispersion in PBS. Without DSPE-PEG-COOH, H2O2 oxidation mer. The dispersibility of MWCNTs in THF was improved with
assisted by Xe lamp for 1 h was found to be the most effective increasing pyrene content in the gra polymer and was also
method because it generates a large amount of oxygenated improved by a branched architecture of the polymeric non-
groups on the surface of SWNHs which are of great help for covalent surface modier.
their dispersion. The stabilizing character of PEG linked
butylpyrene (see previous section on pyrene functionalization
and the report130) in MWCNT dispersion was studied.131 Sepa-
ration of the aromatic group from the polar PEG by an alkyl unit
was found to be a requirement for the effectiveness of the
surfactant. The use of this surfactant led to a stable nanotube
dispersion in water. Discussing drug delivery applications of Water-soluble MWCNTs were prepared138 by in situ polymeri-
PEG/CNTs composites, we note that MWCNTs were modied132 zation of acrylic acid in a poor solvent for poly(acrylic acid) (PAA,
with three types of hydrophilic moieties: phosphatidylcholine 40). The solvent type inuenced the graed density and chain
(PC), PEG, and PC-terminated PEG (PEG-PC). Based on the high length of PAA. MWCNTs with a high graed density of PAA (22
water dispersibility of modied CNTs, the extremely high doses wt%) could be well dispersed in water, NaCl aqueous solution (0.9
of these CNT derivatives were intravenously injected in rats wt%) and cell culture media. The biocompatibility of these
from 12.5 to 200 mg kg1. Based upon the pathologic results, MWCNTs is sufficient for biological applications; in particular,
most of the injected CNT derivatives accumulated in the lungs, PAA-g-MWCNTs were utilized for lymph node tracing. In the case
whereas CNT-PC dispersed throughout the organism compared of PAA derivatives, the SWNTs were homogeneously dispersed in
to CNT-PEG and CNT-PEG-PC, thereby resulting in a broader an aqueous solution of poly(N-isopropylacrylamide-co-acrylic
distribution in the liver and spleen, which may be biologically acid) {P(NIPAm-co-AA), 41} with the assistance of sonication.139
relevant. The modied CNT induced only low acute toxicity, The mixture was sonicated at 25 C for 3 h to form the P(NIPAm-
which may contribute to the biocompatibility of these graed co-AA)–SWNTs or PNIPAm–SWNTs complex, and then centri-
functional groups with mammals. In addition, starting from fuged at 2000 rpm for 30 min. In addition, the SWNTs were
experimental evidence of the ability of poly(ethylene glycol-b- endowed with pH- and thermo-sensitivity at the same time. The
propylene sulde), PEG-PPS, to disperse SWCNTs, atomistic SWNTs switched reversibly between the aggregated and the well-
molecular dynamics simulations were performed to study exfoliated states by using pH or temperature as a stimulus
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(Fig. 20). Moreover, factors including the solvent composition

while preparing P(NIPAm-co-AA), concentration and composition
of P(NIPAm-co-AA) showed an evident inuence on the dispersing
stability of SWNTs. In order to control the level of carbon nano-
tube exfoliation in water, pH-responsive polymers (i.e., weak
polyelectrolytes, PAA, poly(methacrylic acid) (PMAA, 42), poly-
(allylamine) (PAAm, 43), and branched polyethyleneimine (BPEI,
44) were used140 as stabilizers in water. This noncovalent func-
tionalization of SWNTs resulted in suspensions whose dispersion

state can be altered by simply changing the pH (Fig. 21 and 22),
similar to poly(N-isopropylacrylamide) (PNIPAAm, 45) and poly-L-
lysine (PLL, 46).141 The SWNTs stabilized with these polymers
showed pH tailorable exfoliation and bundling in water.
Composite lms prepared by drying these aqueous suspensions
suggest that the nanotube microstructure in the liquid state is
largely preserved in the solid composites, with more bundled/
Fig. 20 Schematic showing the reversible changes in SWNTs between the networked structures showing higher electrical conductivity. In
aggregated and well-exfoliated states with pH and temperature of the P(NIPAm- addition, homogeneous dispersion and functionalization of
co-AA) aqueous solution. At high pH or low temperature, the polymer was in the
pristine MWNTs in various organic solvents was achieved by a
extended state and the SWNTs were homogeneously dispersed in the aqueous
solution. At low pH or high temperature, the polymer was in the coiled state and
simple ultrasonic process in the presence of an azide copolymer,
the SWNTs aggregated or precipitated from the aqueous solution. poly(4-azidophenyl methacrylate-co-methyl acrylate) {P(APM-co-
MA)}.142 The copolymers were noncovalently attached to
the surface of the MWNTs via p–p interactions to form
Fig. 21 Effect of pH on the chain conformations of PAA, PMAA, PAAm and BPEI.
PAA and PMAA are neutral at low pH and become negatively charged at high pH.
PAAm and BPEI are neutral at high pH and are positively charged at low pH.
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Classic polymers, frequently used in nanotechnology, such

as polyaniline, polyurethane, and siloxanes have been also
applied for CNT dispersion. Thus, a straightforward, template-
free chemical oxidative polymerization of aniline was used to
prepare nanobrillar polyaniline (nf-PANI, 47) and a set of
corresponding composites with MWNTs. All the products
showed143 remarkable water dispersibility since they are formed
by hydrophilic particles of nanometre sizes. On one hand, the
presence of MWNTs affects neither the chemical structure nor

the crystallinity of polyaniline. On the other hand, even small
amounts of MWNTs have a signicant effect on the morphology
MWNT-P(APM-co-MA) composites. The solution dispersion of the of polyaniline in composites. MWCNT–polyurethane (PU, 48)
MWNT–P(APM-co-MA) composites were used to prepare super- composites were obtained144 by an in situ polycondensation
hydrophobic cotton fabric by a facile dip-coating approach. approach. The functionalized MWNTs had more advantages for
MWNTs were covalently attached to the surface of the cotton improving the dispersion and stability in water and N,N0 -
fabric through chemical reactions between the azide groups of dimethylformamide. The tensile strength and elongation at
P(APM-co-MA) with both MWNTs and cotton bers. Due to this break of the composites exhibited obvious increases with the
interaction “MWCNTs/cotton fabric”, highly-stable and chemi- addition of MWNT content below 1 wt% and then decreases
cally durable superhydrophobic composites were obtained. with addition above 1 wt%.
Fig. 22 Images of aqueous nanotube suspensions after centrifugation at different pHs. All suspensions contained 0.11 wt% of SWNT in 1 wt% of the aqueous
polymer solution.
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To endow sufficient water affinity to MWCNTs, dendritic was reported,149 showing that P4VP stabilized SWCNTs displayed
hyperbranched poly(ether-ketone) (HPEK) was rst covalently good dispersion in both organic solvents and aqueous solution
graed to the surface of a MWCNT via a Friedel–Cras acylation (pH ¼ 2). The ability to manipulate the dispersion state of CNTs in
reaction.145 The resultant HPEK-graed MWCNT (HPEK-g- water with P4VP will likely benet many biological applications,
MWCNT) was subsequently sulfonated in chlorosulfonic acid to such as drug delivery and optical sensors. Among a series of other
produce sulfonated HPEK-g-MWCNT (SHPEK-g-MWCNT), which polymers, whose CNT composites could be successfully dispersed
was found to be dispersible in water showing a zeta potential in solvents, we note poly(vinyl chloride)150 (PVC) 52, carboxy-
value of 57.8 mV. The SHPEK-g-MWCNT paper simply formed methylcellulose151 53, heteroarm star block terpolymer on poly-
by ltration of aqueous dispersion has a sheet resistance as low as styrene basis,152 branched block copolymer Tetronic 1107 (ref.
63 U sq1. Its thin lm showed a high electrocatalytic activity for 153) 54, polyamides,154 phenolic resins,155 phenylene vinylene
the oxygen reduction reaction (ORR). Also, the ability of a mixture conjugated polymers,156 polymers with azobenzene units,157 etc.
of an ethoxy-modied trisiloxane (a silicone surfactant, named
Ag-64) and a block copolymer F127 to disperse CNTs was inves-
tigated, showing that dispersions with large amounts of indi-
vidual CNTs were obtained.146 The quantity of dispersed CNTs
was obviously larger than each quantity of the dispersions with
individual surfactants at the same concentration, even exceeding
the sum of them. It can be inferred that Ag-64 and some F127
could wrap onto the surface of CNTs to separate clusters into
individuals, and the other F127 interact with adsorbed Ag-64 and
F127 to generate stronger steric stabilization, showing a syner-
gistic effect on dispersing CNTs by the mixture of Ag-64 and F127.
Two kinds of polyuorenes 49 bearing two lateral pyrene

terminated alkyl chains and two alkyl chains per repeating unit
were synthesized by Suzuki polycondensation and used to
disperse SWCNTs in organic solvents.147 A stable polymer–SWCNT
complex can be formed via the multivalent stacking interactions
of the lateral pyrene functional groups and the polyuorene
backbone with the outer surface of the carbon nanotubes;
meanwhile the lateral alkyl chains can impart good solubility to
the complex. Polyuorenes bearing lateral pyrene functional
groups and octyl chains exhibited much higher CNT solubility in
common organic solvents than the corresponding polyuorenes
bearing only octyl chains. The selective dispersion of SWCNT
species (n,m) with conjugated polymers such as poly(9,9-dioctyl-
uorene) (PFO, 50) and its analogue poly(9,9-dioctyluorene-co-
benzothiadiazole) (F8BT) in organic solvents depends not only on
the type of solvent but also on the molecular weight of the poly-
mer.148 The solution viscosity was found to be one of the factors
inuencing the apparent selectivity by changing the reaggregation
rate of the SWNTs. Poly(4-vinylpyridine) (P4VP 51) is a widely
studied polymer with applications in catalysis, humidity sensitive
and antimicrobial materials due to its pyridine group exhibiting
coordinative reactivity with transition metals. The non-covalent
functionalization of SWCNTs with P4VP in CO2-expanded liquids
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Natural products
Among a few natural products, whose composites with CNTs
could be dispersed, gum arabic (GA, a natural gum made of
hardened sap taken from two species of the acacia tree; Sene-
galia senegal and Vachellia seyal) is most frequently used. Thus,
stable homogeneous suspensions of MWCNTs were prepared
using GA as a dispersant.158 The concentration measurement of
MWCNTs showed that the optimum concentration of GA is
0.45 g L1. Measurement of their viscosity and thermal

conductivity159 showed that thermal conductivity ratios
increased strongly with temperature, especially above 45 C.
Relative viscosities also increased with temperature above 45 C
at relatively higher MWCNTs concentration indicating the
potential role of Brownian motion. Also, MWCNTs/epoxy
nanocomposites were fabricated with 0.3 wt% unmodied,
oxidized and GA-treated MWCNTs.160 The gum treatment
produced better dispersion of the MWCNTs in distilled water
and the gum treated MWCNT/epoxy nanocomposites had a
better tensile strength and elastic modulus than the unmodi-
ed and acid-treated MWCNT/epoxy nanocomposites.
Biopolymer dispersant gellan gum (a water-soluble poly-
saccharide produced by Sphingomonas elodea, a bacterium) was
used to achieve aqueous dispersion of highly concentrated
SWCNTs, which can be used to form the SWCNT liquid crystal
phase.161 To achieve alignment of SWCNTs, purication of
SWCNTs was found to be very important and it was achieved by
a facile and nondestructive physical method that can prepare
large volumes of SWCNTs in high yield for experimental use.
Composite membranes of aligned SWCNTs could be obtained
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by simple evaporation of SWCNT liquid crystals. Co-dispersion Sugars and biomolecules

of native cellulose and SWCNTs in water was demonstrated,162
A covalent microwave-assisted functionalization of pristine
showing that the pH of the water should be between 6 and 10 for
SWCNTs directly with three sugar azides (Fig. 23), 2,3,4,
better dispersion. The co-solubility is likely caused through
6-tetra-O-acetyl-b-D-glucopyranosyl, 2,3,4,6-tetra-O-acetyl-b-
disruption of intramolecular hydrogen bonds in the cellulose by
D-galactopyranosyl or 2,3,4,6-tetra-O-acetyl-b-D-mannopyranosyl
hydroxyl groups present on nanotubes surface and the creation
azide170 was carried out for SWCNTs prepared by the HiPCO
of intermolecular hydrogen bonds between cellulose and
method (high-pressure carbon monoxide process). Deacetyla-
carbon nanotubes. MWCNTs can be stably dispersed in water tion of the functionalized tubes by sodium methoxide yielded
with a small amount of lignin.163 One-step dispersion in the
nitrogen-linked, sugar-functionalized CNTs that formed stable

20.0 g L1 concentration range was achieved at r.t. with excel-
dispersions in water. The water solubility was found to be
lent electrical properties of MWCNTs. Lignin was depicted to
highest for galactopyranosyl and lowest for gluco- and man-
act as an anti-static agent. In addition, MWNTs and SWNTs
nopyranosyl derivatives varying between 0.6 and 1.3 mg mL1.
were surface modied164 with humic acids HA 55 {the major
Based on the water solubility it was calculated that ca. 16–35%
organic constituents of soil (humus), peat, coal, many upland
of functionalized SWCNTs dispersed in water depending on the
streams, dystrophic lakes, and ocean water} from different
reactant sugar azide from which galactopyranosyl azide was
sources and with surfactants of different ionic types. Both most reactive. These functionalized SWCNTs were not soluble
humic acid and surfactant could effectively disperse MWNTs, in ethanol, methanol or ethyl acetate and thereby showed
but not SWNTs, into stable suspensions under the studied
similar solubility properties as the corresponding untreated
conditions. The inhibitory effect of peat humic acid was rela-
sugars.
tively stronger than that of soil humic acid, but the two
A single, yet multifunctional, hyaluronic acid (57, HA, an
surfactants had a similar inhibitory effect on atrazine adsorp-
anionic, nonsulfated glycosaminoglycan)-based biosurfactant
tion by the two CNT types. Increases in surfactant concentration
was used to simultaneously disperse nanocarbons and target
resulted in rapid decreases in the adsorption of atrazine by
SWCNTs to CD44 receptor positive tumor cells with prompt
CNTs when the surfactant concentration was less than 0.5 uptake.171 In vivo photoacoustic, uorescence, and positron
critical micelle concentration. The tribological behavior of emission tomography imaging of coated SWCNTs displayed
CNTs in aqueous HA solutions was studied using a surface
high tumor targeting capability while providing long-term,
forces apparatus and showed promising lubricant additive
uorescence molecular imaging of targeted enzyme events. A
properties.165 Adding CNTs to the solution changes the friction
HA derivative, pyrene-conjugated hyaluronan (Py-HA) facilitated
forces between two mica surfaces from “adhesion controlled” to
the exfoliation of low-dimensional nanomaterials including
“load controlled” friction. Lateral sliding promotes a redistri-
graphite, hexagonal boron nitride (h-BN) and molybdenum
bution or accumulation, rather than squeezing out, of nano-
disulde (MoS2), and the dispersion of CNTs172 and carbon
tubes between the surfaces. Also, green tea (tea extracts as nano-onions (CNOs) in water with the assistance of sonication.
sources of polyphenols are widely used in “greener chemistry”
approaches for obtaining nanoparticles166) was reported167,168 to
be a good dispersant of SWCNTs in aqueous media and organic
solvents. Dimethylsulfoxide (DMSO) was found to be a good
solvent of green tea extract for dispersing SWCNTs. A combi-
nation of green tea (dispersant)/DMSO (solvent)/polyvinyl
alcohol (PVA) (nanotube wrap) was obtained that resulted in the
dispersion of SWCNTs almost to individual nanotubes or to very
thin nanotube bundles. Dispersions of SWNTs in various
surfactant solutions were also evaluated using natural products
catechins 56, phenolic acids, and avonoids (a class of plant
secondary metabolites).169 A dispersion of SWCNTs in an aqueous medium was
prepared173 by functionalizing the SWCNT with D-glucosamine
58. The graing resulted in a good dispersion of the SWCNTs
in water of an amount less than 1 mg mL1. b-1,3-Glucan
polysaccharides have the potential to produce gene carriers and
bio-nanomaterials. Carboxylic curdlan (CurCOOH) bearing the
b-1,3-polyglucuronic acid structure was prepared174 from one of
them, b-1,3-glucan polysaccharide curdlan (Cur), by one-step
oxidation using a 4-acetamido-TEMPO/NaClO/NaClO2 system
as the oxidant. Its further complexation with SWNTs resulted in
a water-soluble 1D architecture, which formed a dispersion in
aqueous solution, stable for several months, and much more
stable than SWNTs complexes of the similar negatively-charged
polyacrylic acid (PAA) and polymethacrylic acid (PMAA). It was
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Fig. 23 Functionalization of HiPCO SWCNTs by sugar azides under microwave conditions yielding nitrogen-linked functionalized CNTs. Deacetylation of the product
with sodium methoxide produces water-dispersible nitrogen-linked b-D-pyranosyl-functionalized carbon nanotubes.
shown that in the complex, SWNTs are effectively wrapped by a lms because of the hydrophilic polysaccharide structure of
small amount of CurCOOH, enabling them to avoid electro- starch components. CCNT–starch containing 12.8 wt% starch
static repulsion. Also, MWCNTs were well dispersed in an in water could form homogeneous solutions without obvious
aqueous solution of the cyanobacterial polysaccharide, sacran, aggregation of CCNTs. In addition, phase transfer of MWNTs
with an ultra-high molecular weight >10 million g mol1.175 from an aqueous phase into an organic phase was achieved
MWCNT powder was put into aqueous solutions of various using the hydrogen-bonding interactions between the disac-
polysaccharides including sacran and was dispersed under charide groups of a sugar-based amphiphile and the oxygenated
sonication. Cryogenic transmission electron microscopic (Cryo- functional groups on the surface of MWNTs.177 The dispersion
TEM) studies directly demonstrated the existence of MWCNTs of MWCNTs in a wide range of organic solvents was enabled.
in the supernatant, and high-resolution TEM observation
revealed that MWCNTs covered by sacran chains were efficiently
dispersed in water. A starch (59)/carboxylated multiwall carbon
nanotube (CCNT) composite (CCNT-starch) was prepared176 by
covalently graing a natural polymer starch onto the surfaces of
CCNTs. It was revealed that the covalent bonds between –OH
groups of soluble starch and CCNTs were formed in CCNT–
starch; CCNTs were covered with the graed starch about 7.7
and 12.8 wt% in CCNT–starch, respectively. The graed starch
facilitated the dispersion of CCNT–starch in water and chitosan
Chitosan 60, a very popular object in the nanotechnology,

has been used to improve CNTs solubility. Thus, the dispersion
of CNTs in water at different pHs and in chitosan aqueous
solutions of three acids, acetic acid, formic acid, and hydro-
chloric acid, was investigated.178 Chitosan was soluble in water
at pH # 3 and could disperse untreated CNT and acid-treated
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aqueous solution.180 A so-called wet-grinding assisted ultra-

sonication (GU) method was reported,181 in which wet-grinding
of MWCNTs in chitosan solution was carried out before ultra-
sonication. Interestingly, the dispersion quality of chitosan/
MWCNT suspension prepared by wet-grinding assisted ultra-
sonication is much better than that by ultrasonication or wet-
grinding alone. The authors also found that wet-grinding could
improve the water wettability of MWCNTs and eliminate the
barrier of the air layer around MWCNTs to ultrasonic waves.

An environmentally friendly group of dispersants, cyclodex-
trins 62–64 (CD), was revealed as a preferable alternative to
functionalize CNTs without changing their pristine structure
and properties.182 MWCNTs were functionalized using b-CD 63.
Different concentrations of b-CD served as the dispersant, and
different non aqueous media (ethanol, acetic acid, and water)
were studied to achieve the required degree of functionalization
Fig. 24 Controlled N-acetylation of chitosan using acetic anhydride. for MWCNTs, showing that the degree of functionalization
increases with increasing b-CD ratio. Its derivative, diamino-
functionalized b-CD, was covalently bound183 with carboxylic
CNT, both of which had poor dispersion in water at pH # 3. acid-functionalized MWNTs via amide linkages using a water-
Among the three acids, hydrochloric acid gave the smallest soluble condensation agent at r.t. The obtained product, in
particle sizes in the CNT dispersion. Without chitosan, the which 70 wt% b-cyclodextrin was attached on the surface of
dispersibility of the acid-treated CNT in aqueous solutions of MWNTs, denoted as b-cyclodextrin-modied MWNTs was also
three acids was in the order of acetic acid > formic acid > highly dispersible in an aqueous medium.
hydrochloric acid. Debundling and selective dispersion of MWCNTs were rst functionalized with lysine 65 under
semiconducting SWNTs was demonstrated179 using a neutral microwave irradiation184 and then the water-dispersed CNTs
pH water soluble chitosan derivative, N-acetylated chitosan 61 were obtained by diazonium-assisted functionalization. A dia-
(NACHI), which was synthesized by controlled N-acetylation of zonium reaction occurred between lysine molecules and CNTs,
chitosan using acetic anhydride (reactions in Fig. 24). The resulting in the attachment of lysine to the nanotubes surfaces,
SWNT–NACHI supernatant solution demonstrated semi- so this covalent functionalization procedure could signicantly
conductor-enriched properties owing to the preferential increase aqueous solubility. A lysine analogue, poly(3-benzy-
adsorption of N-groups of the NACHI on semiconducting loxycarbonyl-L-lysine) (PZLL), prepared by ring-opening
nanotubes with a fairly weak charge transfer. Another chitosan polymerization of 3-carbobenzoxy-L-lysine N-carboxyanhydride
derivative, neutral pH water-soluble chitosan-hydroxyphenyl (Z-L-Lys NCA),185 aer the removal of the benzyloxycarbonyl
acetamide (CHPA), prepared by functionalizing the amino group, led to water-soluble poly-L-lysine (66, PLL). When the
groups of chitosan with 4-hydroxyphenyl acetic acid, was also mass ratio of MWCNTs to PLL was 1 : 50 and the pH of the water
found to be an efficient biocompatible dispersant to effectively solution of PLL is 5, MWCNTs could be well dispersed in water.
debundle and individually disperse SWNTs in a neutral A composite material was developed with SWCNTs and
articially designed peptides,186 which were designed to form a
b-sheet structure that would be suitable for wrapping SWCNTs.
The composite SWCNT–peptide showed good dispersibility in
aqueous media and was considerably stable even in the absence
of an excess amount of peptide in the media. The authors
suggested the potential of the SWCNT–peptide composite as a
molecular platform on which a desirable structure and/or
function can be constructed for biomedical and industrial
applications. In some related research,187 the noncovalent
modication of MWNTs immersed in aqueous solution using
the ionic-complementary peptide EFK16-II orients hydrophilic
functional groups toward the solution phase and enables them
to form highly stable dispersions in water. This stability can be
attributed to the electrostatic repulsion between self-assembled
peptides on the MWNTs. Tissue culture plates previously con-
tacted with EFK16-II-modied MWNTs were shown to have
enough biocompatibility for the growth and attachment of cells.
The biocompatibility and enhanced electrical conductivity that
should result from modication with these EFK16-II-MWNT
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containing two stretches of cytosine 67 (C) rich domains are

covalently linked to carbon nanotubes. At pH 8.0, the DNA is in
a random coil state, which enhances the dispersion of MWCNTs
in water; aer changing pH to 5.0, the intermolecular i-motif
structures formed by the C-rich ssDNA on neighboring carbon
nanotubes could drive the MWCNTs to aggregate.
The dispersion stability, viscosity, shear stress, and thermal
conductivity of MWCNTs in the presence of gum arabic
(MWCNT–GA, see previous section) as well as functionalized
MWCNTs with cysteine 68 (MWCNT–Cys) and silver (MWCNT–
Ag), were investigated.190 To realize good dispersibility and
high thermal enhancement, MWCNTs were rst functionalized
by cysteine and then silver ions were covalently attached
through the thiol group of cysteine. For the enhancement of
thermal conductivity, the results suggest that covalent
functionalization by Ag is more effective than noncovalent
functionalization. Polyhistidine (Polyhis)191 was also used to
efficiently disperse MWCNTs. The optimum dispersion
MWCNT–Polyhis was obtained by sonicating 1.0 mg mL1
MWCNTs in 0.25 mg mL1 Polyhis solution prepared in 75 : 25
suspensions opens up their use in a number of potential (v/v) ethanol–0.200 M acetate buffer solution at pH 5.00 for 30
biomedical applications such as the design of bioelectrode min. The glassy carbon electrode modied with MWCNT–
interfaces and the fabrication of biosensors with high sensi- Polyhis dispersion was used to quantify dopamine or uric acid
tivity. Cholesterol based peptide carboxylates were also found to at nanomolar levels, even in the presence of a large excess of
be efficient dispersing agents for SWNTs as well as graphene in ascorbic acid.
water.188 The dipeptide carboxylate comprising two alanine Double stranded calf-thymus DNA (deoxyribonucleic acid
residues showed 80% SWNTs dispersion which is 2 fold from calf thymus, dsDNA) was used to disperse bamboo-like
higher than that obtained by using the common surfactant, MWCNTs (bCNT).192 The drastic treatment for dispersing the
SDBS. The dipeptide amphiphiles also efficiently dispersed the bCNT (45 min sonication in a 50% (v/v) ethanol–water solution),
2D-allotrope of carbon, graphene, in water. Acidication of the produced a partial denaturation and a decrease in the length of
nanohybrids with HCl converted the carboxylates to the water dsDNA that facilitates the dispersion of CNTs and made
insoluble carboxylic acids leading to the precipitation of carbon possible an efficient electron transfer of guanine residues to the
nanomaterials. Most importantly, addition of an equivalent electrode. The electron transfer of redox probes and guanine
amount of NaOH resulted in the restoration of stable aqueous residues was more efficient at GCE modied with bCNT
dispersion of SWNT/graphene. In addition, an intriguing dispersed in dsDNA than at GCE modied with hollow CNT
strategy to manipulate reversibly the aggregation and disper- (hCNT) dispersed in dsDNA, demonstrating the importance of
sion of CNTs in solution via the formation of intermolecular the presence of bCNT. Stable dispersions of single-walled and
i-motif (four-stranded C-quadruplex) structures in a pH non-associated carbon nanotubes in aqueous lysozyme solution
dependent manner.189 Firstly, single-stranded (ss) DNA were investigated193 by analyzing the stabilizing effect of both
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protein concentration and pH. Lysozyme is presumably adsor- The dynamics of protein-assisted CNT dispersion in water
bed onto the SWNT surface through hydrophobic and p–p were studied.199 It was found that in equilibrium, only a small
interactions. It was observed that electrophoretic mobility and fraction of the dispersant is indeed adsorbed to the nanotubes
dielectric increment increase with the amount of added lyso- surface, while there is a fast exchange process between the
zyme, up to saturation. This occurs at a denite LYS/SWNT adsorbed and free protein molecules. A noncovalent approach
mass ratio. At higher lysozyme content, depletion phenomena, was developed200 for the functionalization of MWNTs using the
opposing to the stabilization process, occurred. hydrophobin, HFBI. Owing to the amphipathic nature, HFBI
Functionalization of MWCNTs with amino acid molecules can be adopted onto the surface of MWNTs to form HFBI–
using microwave irradiation, followed by reaction with a MWNT nanocomposites with good dispersion in water.
carboxylic acid moiety allowed direct attachment by an amide Furthermore, a glucose biosensor was developed based on
bond.194 The process resulted in a high degree of functionali- HFBI–MWNTs by a one-step casting method. The resulting
zation as well as dispersibility in organic solvents like N,N0 - biosensor displayed high sensitivity, a wider linear range, low
dimethylacetamide. Complexes composed of poly-L-tyrosine 69 detection limit, and fast response for glucose detection, which
(pLT) and SWCNTs were produced.195 It was found that the implied that the HFBI–MWNTs nanocomposite lm holds great
complexes remained stably dispersed in the water at least for promise in the design of electrochemical devices, such as
two weeks. A stable aqueous SWNT dispersion up to 92% was sensors and biosensors.
also achieved using amino acid based amphiphiles through a
structure–property investigation.196 The nanohybrids showed
remarkable serum stability and biocompatibility to mamma- Special comparative studies and techniques for
lian cells. The ability of N-(uorenyl-9-methoxycarbonyl) understanding CNT dispersion
(Fmoc) amino acids to disperse CNTs was demonstrated.197 Dispersion of CNTs in solvents. A series of studies have been
Four Fmoc-protected aromatic amino acids, W, H, tyrosine (Y), carried out for pristine and, in some cases, OH-MWCNTs in
and phenylalanine (F), were selected, with glycine (G) as a distinct protic and aprotic solvents and their mixtures, generally
nonaromatic control. The interactions of these molecules with without surfactants. As a representative example, the dispersion
SWNTs and MWNTs were studied by examining their ability to of hydroxylated MWCNTs was modied in non-protic acetoni-
disperse CNTs in phosphate buffered saline (PBS). In addition, trile solvent using treatment by ethanol.201 Either the MWCNT-
all-atom molecular dynamics simulations were carried out for OH powder was used as it is or previously treated by EtOH.
aqueous avin mononucleotide 70 (FMN), which was found These two types of powders were diluted by acetonitrile and the
experimentally to efficiently separate SWNTs based on diam- solvation was followed by photoluminescence and Rayleigh-
eter and chirality.198 Several important conclusions had been scattering methods. Despite the well-known very low solubility
made by authors: to stabilize carbon nanotubes in water it is of nanotubes, the results showed the presence of nanotube
necessary to employ dispersing agents that (1) strongly adsorb dimers in the solution at a considerable concentration.
on the nanotubes surfaces, (2) present hydrophilic groups, Applying a qualitative model, DH ¼ 46.6 12 kJ mol1 and DS
better if rigid, that extend toward the aqueous phase, (3) are ¼ 29.9 7 J K1 mol enthalpy and entropy changes were
not very mobile on the nanotube surface, and (4) show obtained during the formation of nanotube dimers. This highly
aggregates with structure dependence on the nanotube diam- negative entropy term is of great importance for the deposition
eter and chirality. We note that these conditions can be obvi- of carbon nanotubes by liquid phase epitaxy to enlarge the
ously applied not only for the FMN case, but can be considered surface coverage.
as universal requirements in the development of dispersion The analysis of the reported data202–204 clearly show that
techniques. N-methyl-2-pyrrolidinone (NMP), N-dodecyl-pyrrolidinone
(N12P), acetone, tetrahydrofuran (THF), N,N-dimethylforma-
mide (DMF), N,N-dimethylacetamide (DMA), cyclohexyl-pyrro-
lidinone (CHP), and dichloromethane are good solvents to
debundle and disperse the MWCNTs. In contrast, much
precipitation can be obviously observed for systems of the CNTs
in water, ethanol and toluene. Tyndall effect tests suggested
that the upper dispersions of the carbon nanotubes in acetone,
tetrahydrofuran and dichloromethane with a concentration of
0.1 mg mL1 and the dispersion of carbon nanotubes in
N-methyl-2-pyrrolodone with a concentration of 0.05 mg mL1
are colloidal systems rather than solutions. If similar amounts
of carboxylic acid and phenolic groups were introduced205 to
mostly already existing defects, the presence of acid oxygenated
groups increased the SWNTs dispersibility in NMP, DMF and
DMA, but decreased in N12P and CHP. The absorption coeffi-
cients, however, decreased for all the above solvents aer
oxidation, reecting the weakening of the effective transition
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dipole of the p–p transition with even limited extension func- TX-100, sodium cholate (bile salt) and dipalmitoyl phosphati-
tionalization and solvent interactions. In the case of mixtures of dylcholine (DPPC, a clinical pulmonary surfactant preparation
organic solvents such as DMF and NMP,206 it was shown that called Survanta), were used210 in a wide range of concentrations
mixing DMF and NMP can yield dispersion stabilities that are (0.01 CMC to 2 CMC) to probe the dispersion mechanism. It was
60–115% greater than the pure solvents with a 50/50 mixture revealed that the adsorption of surfactant molecules on the
(v/v). Additionally, the inuence of zeta potential on CNT nanoparticle surface was an interplay of ionic, hydrophobic and
dispersion in solvents is a permanent object for discussion. p–p stacking forces. The CTAB molecules (cationic) formed a
Thus, the correlation between the electrokinetic potential, dis- bilayer on the carbon nanoclusters providing robust dispersion
persibility in solvents, surface energy and oxygen content of stability whereas SDS molecules (anionic) were poorly adsorbed
CNTs affected by functionalization was studied.207 Colloidal through hydrophobic interactions. TX-100 molecules (neutral)
systems consisting of CNTs with varying degrees of dispersion stabilized the dispersion via hydrophobic and p–p stacking
were prepared and characterized to evaluate CNT dispersibility interactions. Sodium cholate was adsorbed on nanoclusters
and suspension stability in solvents with different polarities. It mostly through hydrophobic interactions and generated large
was revealed that an absolute value of zeta potential at about asymmetric complexes. DPPC, a gemini surfactant, formed a
25 mV is closely related to the micro- and macroscopic disper- rigid monolayer around the carbon nanocluster even at nano-
sion of CNTs, whereas a high absolute value of 40 mV is molar concentrations and provided excellent stability to the
regarded as an indication of high quality CNT dispersion with dispersion. In some related research,211 to test the dispersion of
much enhanced suspension stability in solvents. The absolute CNTs in biocompatible solutions, ve known biocompatible
zeta potential value increases consistently with increasing dispersants were selected that are widely used for nanomaterial
degree of CNT functionality, the increase being most toxicity evaluation studies. SWCNTs and MWCNTs were both
pronounced in a hydrophilic liquid such as water. The CNT dispersed in these dispersants and their macrodispersion
dispersibility in a liquid is determined not only by their physical evaluated using a light absorbance method. Distilled water and
states, but also by the hydrophilicity and surface functionality of dimethylsulfoxide (DMSO) both showed a poor macro-
CNTs, all of which are reected by the zeta potential. Also, the dispersion of only 1–13% for the various CNT concentrations. In
dispersion and solubilization of CNTs in solvents is obviously 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), the 0.02
related with the terms of Hildebrand and Hansen solubility and 0.1% MWCNTs showed macrodispersions of 11 and 74%,
parameters. As an example of such study, dispersions of respectively, while the 0.02 and 0.1% SWCNTs showed macro-
produced HiPco SWNTs in a series of organic solvents were dispersions of 15 and 16%, respectively. In 0.5% bovine serum
prepared208 by dilution with the aid of tip sonication. Mild albumin (BSA), the 0.02, 0.1, and 0.5% MWCNTs showed very
centrifugation (945 g) was carried out to remove large bundles. good macrodispersions of 32, 53, and 70%, respectively, yet the
AFM studies revealed that the bundle size decreased as the 0.02% SWCNTs only showed a macrodispersion of 17%. In 1%
dispersion was diluted. SWNTs are easily dispersed in solvents Tween 80, the 0.02–0.5% SWNCTs exhibited good macro-
with a Hildebrand solubility parameter in the range 22–24 dispersions of 27–81%, whereas the 0.02–05% MWCNTs only
MPa1/2 and Hansen polarity component (P) 12–14 MPa1/2. It showed macrodispersions of 13–23%. Also, SWCNTs were
was found that the degree of dispersion depends critically on dispersed212 in water using a range of natural (gum arabic,
the sample preparation conditions and in particular the soni- amylose, Suwannee River natural organic matter) and synthetic
cation time; however, increased sonication also induces (polyvinyl pyrrolidone, Triton X-100) dispersing agents that
discernible changes to the SWNTs themselves and in itself attach to the CNT surface non-covalently via different phys-
inuences their solubility, under which conditions no clear isorption mechanisms. The charge and the average effective
solubility parameters can be determined. In related research,209 hydrodynamic diameter of the suspended SWCNTs as well as
the dispersion behavior of graphene oxide (GO) and oxidized the concentration of exfoliated SWCNTs in the dispersion were
carbon nanotubes (o-CNT) in a polar solvent, as well as the found to remain relatively stable over a period of 4 weeks. A
differences in the behavior related to the Hansen solubility strong dependence of the toxicity of SWCNT suspensions on the
parameter windows was studied. In polar aprotic solvents, GO toxicity of the dispersant and point to the potential of non-
and o-CNT showed similar dispersion behavior. On the other covalent functionalization with non-toxic dispersants was sug-
hand, in polar protic solvents, such as ethanol and isopropanol, gested as a method for the preparation of stable aqueous
GO did not show dispersion stability whereas the o-CNTs did. suspensions of biocompatible CNTs.
This difference in the dispersion behavior between GO and o- Combinations of surfactants. An intriguing approach
CNTs resulted from the stronger hydrogen bonding between the (Fig. 25) for the stabilization of double-walled carbon nanotubes
GO interlayer induced by a large amount of oxygen functional (DWNT) in aqueous media was developed.213 A low molecular
groups and exible 2D morphology with a large surface area. weight surfactant was used in the rst stage for the debundling
Comparison of surfactant abilities. Comparative studies of of the nanotubes followed by substitution with a higher
surfactants belonging to distinct groups of compounds have molecular weight surfactant or non-ionic surfactants. A
been carried out. Thus, a systematic study was carried out to combination of different types of surfactants {SDS, Tween 20
establish the surfactant assisted dispersion mechanism of (71), Surope 1216 {sucrose ester of lauric acid (C12 fatty
carbon nanoclusters (size z 150 nm, zeta potential z 15 mV), chain)}, Montanov 82 (emulsifying alkylpolyglucoside),
obtained from soot in water. An array of surfactants, SDS, CTAB, cholates} and a polymer surfactant (gum arabic, high molecular
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production was conrmed by observing enhanced FFA decay in

deuterium oxide, attenuated decay of FFA in the presence of
azide ions, and the lack of decay of FFA in deoxygenated solu-
tions. Also, SWCNTs were functionalized by the covalent
attachment of 2-propanol-2-yl radicals, generated by the
photolysis of 2-hydroxy-2-methyl-1-phenyl-1-propanone under
UV light, to their surface in THF solution.215 A loss of Van Hove
singularities and decrease of the intensity ratio of the G band
and D band (IG/ID) were observed. The solubility in common

organic solvents was improved and the original electronic
structure of the SWCNTs was retained without severe modi-
cation that damaged the nanotubes.
Selected studies on carboxylated and amine-functionalized
CNTs. The size dependent colloidal behavior of aqueous
Fig. 25 Schematic illustration of the mechanisms of stabilization with different
surfactants: (a) LMW surfactant; (b) HMW surfactant; (c) substitution of LMW dispersions of carboxylated multiwall carbon nanotubes
surfactant by HMW surfactant. (c-MWCNTs) was discussed.216 The presence of carboxylic
groups provided electrostatic stabilization in water, where the
size affected agglomeration. While the aspect ratio did not show
weight (HMW) surfactant) were used for the aqueous dispersion any denite correlation, the hydrophobicity indices (HI), zeta
of DWNTs. The surfactant SDS was rst used for exfoliation and potential and aggregation kinetics showed dependences on the
surface coating of the carbon nanotubes. It can penetrate easily length of the c-MWCNTs where the shorter c-MWCNTs showed
inside aggregates of carbon nanotubes and is useful for signicantly lower HI values, smaller particle aggregates, higher
improving the dispersibility; however, it does not protect indi- zeta potential values and higher critical coagulation concen-
vidual nanotubes from agglomeration during lm drying. In trations (ccc) in the presence of electrolytes. Two cell culture
order to achieve better stabilization, wrapping of CNTs with systems, human A549 pneumocytes and D384 astrocytoma
more or less amphiphilic polymers chains was used. The cells, were used217 to assess the cytotoxicity of MWCNTs with
hydrophobic part of the polymer is strongly anchored to the varying degrees of functionalization and to understand their
hydrophobic nanotube surfaces with a polymer layer of suffi- potential harmful effects. Laboratory-made highly functional-
cient thickness, while the hydrophilic parts, when fully ionized, ized hf-MW-NH2 and less functionalized CNTs (MW-COOH and
impart sufficient ionic charge to the CNT surfaces. The resulting MW-NH2) were tested in comparison with pristine MWCNTs,
dispersions showed better stability aer centrifugation carbon black and silica (SiO2) by MTT assay and calcein/propi-
compared to regular dispersions with each surfactant alone. dium iodide (PI) staining. hf-MW-NH2 were found to be water
Low molecular weight surfactant molecules were shown to be soluble and easily dispersible in medium; they presented lower
successfully removed during the substitution process and were aggregate size ranges as well as considerably lower length to
not found in dispersions. diameter ratios and low tendencies to form aggregates
compared to the other CNTs tested. The properties obtained by
chemical functionalization, such as water solubility, high dis-
persibility and low agglomeration tendencies were relevant
factors in modulating cytotoxicity.
Other particular studies. A simple model describing the
solubility of rods in solvents, expressing the nal result
explicitly in terms of the surface entropy and the enthalpy of
mixing, was used to describe the experimental results for the
concentration of dispersed nanotubes in various solvents.218
Qualitative agreement with these predictions is observed
UV- and visible-light inuence. Photochemical reactions experimentally. However, the authors suggested that the fact
involving colloidal dispersions of carboxylated SWNT-COOH in that quantitative agreement is not found may be explained by
sunlight were examined.214 Production of reactive oxygen solvent ordering at the nanotube surface. Also, the potential of
species (ROS) during irradiation occurs and is evidence for asymmetrical ow eld-ow fractionation (A4F) coupled to
potential further phototransformation and may be signicant ultraviolet spectrometry (UV) and multi-angle light scattering
in assessing their overall environmental impacts. In aerated (MALS) for the study of SWCNT dispersions in aqueous solu-
samples exposed to sunlight or to lamps that emit light only tions containing a surfactant was demonstrated.219 This tech-
within the solar spectrum, the probe compounds, furfuryl nique is a powerful analytical tool that is able to evaluate
alcohol (FFA), tetrazolium salts (NBT2+ and XTT), and p-chlor- SWCNT dispersion states in aqueous media and determine
obenzoic acid (pCBA), were used to indicate the production of the presence or absence of aggregates, the numbers and
1
O2, O2_, and _OH, respectively. All three ROS were produced in sizes of different SWCNT populations and the SWCNT size
the presence of SWNT-COOH and molecular oxygen (3O2). 1O2 distribution.
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Conclusions tetrahydrofuran, toluene, and n-hexane. Several special studies

have been carried out in the areas of inuence of solvent and
Carbon nanotubes continue to be one of the hottest topics in light on CNTs dispersibility, combinations and abilities of
nanoscience and nanotechnology, so the development of their surfactants, CNTs cytotoxicity, etc.
functionalization and dispersion methods is and will be an
important research area, at least for next 5 years. A series of
contemporary techniques are being used for CNTs solubiliza- Acknowledgements
tion, from physical (classic ultrasound or plasma treatment) to
The authors are very grateful to Mr Daniel Hutchinson Flores
chemical and biological, applying inorganic (other carbon
(FIME-UANL, Mexico) for technical assistance in the prepara-

allotropes, iodine, metallic sodium in liquid ammonia, CO2,
tion of this manuscript.
peroxides, metal salts and mineral acids) and organic (acids,
salts, polymers, dyes, natural products and biomolecules)
compounds, as well as some metal complexes. Frequently,
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Dispersion of Carbon Nanotubes in Water and Non-Aqueous Solvents

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Dispersion of Carbon Nanotubes in Water and Non-Aqueous Solvents

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Dispersion of carbon nanotubes in water and

Oxana V. Kharissova, Boris I. Kharisov* and Edgar Gerardo de Casas Ortiz

Introduction aggregate easily and therefore make additional processing very

Dr Oxana V. Kharissova (born in Dr Boris I. Kharisov (born in

Review RSC Advances

Ultrasonication One of the most frequently used

RSC Advances Review

methods suﬀer from problems with scalability, eﬀectiveness,

carbon nanotubes in liquids, particularly in water, is: are they

Review RSC Advances

Compared with a conventional cylindrical cell, the concentra-

RSC Advances Review

argon, oxygen and methane–oxygen mixtures and then

Review RSC Advances

Fig. 9 Schematic mechanism for the formation of the MWNT–GO complexes.

RSC Advances Review

Review RSC Advances

generally eﬀective in removing non-nanotube carbonaceous

RSC Advances Review

uorosilicate modied with an inorganic polyphosphate

of individual nanotubes. The stabilization of nanotubes in the

Review RSC Advances

with the objective of increasing their solubility. Thus, the

RSC Advances Review

Review RSC Advances

interface and the nanotubes are mostly moved into the

dispersibility and electrical conductivity of SWCNTs than SDS 4,

RSC Advances Review

of MWCNT hybrids (SST : MWCNT ¼ 0.5 : 1 and 1 : 1) was

Fig. 16 Images of MWCNT aqueous suspensions: (a) MWCNT (2  104 g mL1),

Review RSC Advances

Other organic and coordination compounds A poly[(4-pyridineoxy)(phenoxy)phosphazene] was prepared96

RSC Advances Review

tion, can be redispersed in another solvent in the presence of a

Review RSC Advances

Polyaromatic hydrocarbons are also very common for CNT

A preparation method for individually dispersed SWNTs in

RSC Advances Review

and spacer length between POSS and the MWCNT surface on

for another purpose, not for increasing solubility. Thus, the

Review RSC Advances

Fig. 18 Covalent functionalization of a SWCNT with N-(8-aminooctyl)-3,4,5-tris(decyloxy)benzamide}.

derivatives, the capacity of pillar[6]arene 32 host–guest

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Among other organic compounds (for example, poly-

power (higher than 900 W) can reduce the degree of function-

Polymer-assisted dispersion of CNTs

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produced SWNTs with monofunctional, tetrahydrofurfuryl-

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(Fig. 20). Moreover, factors including the solvent composition

tionalization of SWNTs resulted in suspensions whose dispersion

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Classic polymers, frequently used in nanotechnology, such

presence of MWNTs aﬀects neither the chemical structure nor

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Two kinds of polyuorenes 49 bearing two lateral pyrene

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0.45 g L1. Measurement of their viscosity and thermal

Fig. 16 Images of MWCNT aqueous suspensions: (a) MWCNT (2 104 g mL1),