Progress in Polymer Science 39 (2014) 707–748

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Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Carbon nanotube–polyaniline composites

Cynthia Oueiny, Sophie Berlioz, François-Xavier Perrin ∗
Laboratoire MAPIEM, EA 4323, Université du Sud Toulon Var, ISITV, Avenue George Pompidou, BP 56, 83162 La Valette du Var, France

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

Article history: The last decade has seen a growing interest in hybrid electrically conducting nanocom-
Received 20 March 2013 posites. This article aims to provide a detailed overview of the present status of research
Received in revised form 18 August 2013 in carbon nanotube–polyaniline (CNT/PANI) composites, from processing to structural and
Accepted 22 August 2013
property evaluations. CNT/PANI are synthesized by electrochemical and chemical process-
Available online 27 September 2013
ing. When chemical methods are used, the main challenge is to obtain processable CNT/PANI
in the emeraldine salt (ES) form composites. Stable dispersions of ES–CNT in organic media
Keywords: are prepared using the post doping method, inverse emulsion polymerization, or ex situ
Carbon nanotubes polymerizations. On the contrary, stable water dispersions of CNT/ES are prepared using
Polyaniline hydrophilization of a preformed CNT/ES composite, direct synthesis of micelle–CNT hybrid
Nanoparticles templates, interfacial polymerization, covalent functionalization of CNT with a water solu-
Synthesis ble polymer, or using electrostatic interactions between two oppositely charged ES and CNT
Application aqueous colloids. Moreover, the strategies for the synthesis of ternary CNT/PANI composites
incorporating noble metal nanoparticles, metal oxide, or graphene sheets are also presented
and analyzed in depth. Finally, we give a review of potential applications, including chemical
sensors, capacitors, fuel cells and electronic devices.
© 2013 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 708
2. CNT/PANI binary composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
2.1. CNT/PANI interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
2.1.1. PANI interactions with non functionalized CNT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
2.1.2. PANI interactions with functionalized CNT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 710
2.2. Synthetic methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 710
2.2.1. Electrochemical processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 712
2.2.2. Surfactant free aqueous polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 713

Abbreviations: a-CNT, acylchloride functionalized CNT; AChE, acetylcholine esterase; AsOx, ascorbate oxidase; APS, ammonium peroxydisulfate; Ani,
Aniline; ␤ CD, ␤-cyclodextrin; CNT, carbon nanotubes; c-MWCNT, carboxylized-carbon nanotubes; S-CNT, sulfonized-carbon nanotubes; CNTA, CNT array;
CDI, 1,4-carbonyldiimidazole; ChOd, choline oxidase; ChOx, cholesterol oxidase; CS-CNT, chitosan-coupled CNT; CS-GA, chitosan coupled glutaraldehyde;
CTAB, cetyltrimethyl ammonium bromide; CTA, cetyltrimethylammonium; CV, cyclic voltage; CE, carbon electrode; CPE, carbon paste electrode; Cyt c,
cytochrome c; DBSA, dodecyl benzene sulfonic acid; DNNDSA, dinonylnaphthalene disulfonic acid; DMPU, N,N -dimethyl propylene urea; ES, emeral-
dine salt; EB, emeraldine base; ECD, enzyme catalytic deposition; EDC, N-ethyl-N (3-dimethylaminopropylcarbodiimide); EP, electropolymerization; EPh,
electrophoretic method; FTIR, Fourier transform infrared; GA, glutaraldehyde; GO, graphite oxide; GOD, glucose oxidase; GSHOx, glutathione oxidase;
GCE, glassy carbon electrode; GN, graphene; HCSA, (S)-(+)-10-camphorsulfonic acid; HA, hexanoic acid; HRTEM, high resolution transmission electron
microscopy; IL, ionic liquid; IP, interfacial polymerization; ITO, indium tin oxide; MIP, molecularly imprinted polymer; MWCNT, multi-wall carbon
nanotubes.
∗ Corresponding author. Tel.: +33 0494142737.
E-mail address: perrin@univ-tln.fr (F.-X. Perrin).

0079-6700/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.progpolymsci.2013.08.009
708 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748

2.2.3. Micelle–CNT hybrid template directed synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717

2.2.4. Inverse emulsion pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 718
2.2.5. Interfacial polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 721
2.2.6. Plasma polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 721
2.2.7. Ex situ polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 721
2.2.8. Preparation of micrometric CNT/PANI fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 724
3. CNT/PANI ternary composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 726
3.1. CNT/PANI incorporating noble metal nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 726
3.1.1. Electrochemical deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 726
3.1.2. Chemical reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 726
3.1.3. Physical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 727
3.2. CNT/PANI incorporating metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 727
3.3. CNT/PANI graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 728
4. Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 729
4.1. Thermal stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 729
4.2. Electrical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
4.3. Mechanical properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
5. Applications of CNT/PANI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 731
5.1. Non-enzymatic sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 731
5.2. Enzymatic sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 732
5.2.1. Covalent immobilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 732
5.2.2. Non-covalent immobilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
5.3. Actuators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
5.4. Capacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 737
5.4.1. Binary composite capacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 737
5.4.2. Ternary composite capacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
5.5. Fuel cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 739
5.6. Electronic devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 740
5.7. Electromagnetic waves absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 740
5.8. Depollution/extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 740
5.9. Electrochromic devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
5.10. CNT/PANI with optical activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
5.11. Other applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
6. Conclusions and challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 742
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 742

1. Introduction chemical and electrochemical methods has been reviewed

[6]. The typical chemical oxidative polymerization meth-
In 2000, Heeger, MacDiarmid and Shirakawa were ods of aniline include solution blending [7,8], emulsion
awarded the Nobel Prize in chemistry for their discovery [9], dispersion [10,11], in situ polymerization [12,13] and
and development of the conducting polymers [1–3]. Among enzymatic polymerization [14,15]. The genesis of nanos-
the conducting polymers, polyaniline (PANI) and polypyr- tructures (granules, nanofibers, nanotubes, nanospheres,
role (PPy) are the most popular. According to the Web of . . .) produced during the preparation of PANI has been
Science, more than 10,000 papers appeared in the past 30 recently reviewed [16,17].
years on various aspects of chemistry, physics, and engi- Soft micellar template [18,19], the in situ formation of
neering of PANI. This is due to the cheapness and easy anilinium-peroxydisulfate ion clusters aggregates [20] and
availability of raw materials, ease of synthesis, good envi- the model of phenazine nucleates are generally offered to
ronmental stability, high electrical conductivity and simple explain the various supramolecular nanostructures pro-
doping/dedoping chemistry [4]. PANI has the general for- duced by PANI. Carbon nanotubes (CNT), discovered by
mula [( B NH B NH )n ( B N Q N )1−n ]m in which B Iijima [21] in 1991, are one of the four well-known orga-
and Q denote the rings in the benzenoid and quinonoid nized carbon states on Earth, with graphite, diamond
forms, respectively. PANI is found in three idealized oxi- and fullerenes. CNT are cylindrical shells made by rolling
dation states: the fully reduced form, leucoemeraldine graphene sheets of sp2 bonded carbon atoms into a
(n = 1) and the fully oxidized form, pernigraniline (n = 0) seamless cylinder. Single-wall carbon nanotubes (SWCNT)
are poor conductors. In contrast, emeraldine which cor- consist of a single graphite sheet wound on itself that can
respond to the partially oxidized polymer (n = 0.5) is the be closed at both ends with a semi-fullerene molecule.
most attractive form due to tunable states: emeraldine Multi-wall carbon nanotubes (MWCNT) comprise a cen-
salt (ES) and emeraldine base (EB). The conductive salt tral tube of nanometric diameter surrounded by graphitic
form of PANI (ES, green color) is not soluble, however layers that are concentrically nested like the rings of a tree
dedoping the salt form with ammonium hydroxide yields trunk with an intertube spacing roughly equal to the van
the soluble EB, blue color [5]. The PANI synthesis by de Waals graphite interplane distance, 0.34 nm [22]. The
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
morphology of an individual CNT is described by the chi-
ral vector which defines the way the hexagonal sheet of
graphene is rolled to form a CNT, armchair and zigzag nano-
tubes being the two limiting configurations.
Due to their unique structural, chemical, mechanical,
thermal, optical and electronic properties, the interest in
the fundamental properties of carbon nanotubes and their
exploitation through a wide range of applications contin-
ues to increase. It is obvious that CNT are rarely as perfect as
they were once thought to be [23–25]. Ebbesen and Takada
[26] classified the defect structures into three groups: topo-
logical, rehybridization, and incomplete bonding defects.
The large majority of the nanotube properties, such as their
conductivity and band gap, are strongly affected by such
defects.
Several reviews have explained the different meth-
ods to synthesize CNT [27,28]. Arc-discharge, chemical
vapor decomposition and laser ablation are the three main
techniques which have been developed. Whatever the syn-
thesis method used, the implementation of a process of
purification is necessary to remove graphitic nanoparti-
cles, amorphous carbon, multishell carbon nanocapsules,
fullerenes and residues of metals from catalyst that are
often obtained together with CNT [29]. The purification
methods were reviewed [29] and can be classified in two
major categories: chemical techniques as chemical oxi-
dation [30–32], liquid phase oxidation [30,33–36], and
physical techniques like filtration [37–39], centrifugation
[40], chromatography [41], ultrasonication [42] and high-
temperature annealing [43–46]. It is essential to mention
that a large number of reported purification methods for
MWCNT [31,47] and SWCNT [48,49] either totally destroy
or are ineffective at purifying the present SWCNT or
MWCNT materials in large amounts. Multistep methods
have been adopted to limit the damage of CNT [35,42,50].
Several papers have been devoted to review CNT applica-
tions [51–53], the field of polymer-based composites being
one of the most appealing applications of CNT. The main
idea is to transfer the electrical properties of CNT to insulat-
ing polymer matrices with the aim of obtaining conducting
composites.
Several review articles have been published on vari-
ous aspects of polymer–CNT composites [54–60]. In the
last decade, a growing number of researchers worldwide
1600
1400
mes cited
number of arcles
1200
Times cited
1000
800
600
400
200
0 0
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012
Fig. 1. Evolution of CNT/PANI: number of articles and times cited with
carbon nanotubes and polyaniline in title (source: web of science).
709
have shown an interest in the combination of CNT with
conducting polymer especially PANI (Fig. 1).
One of the main reasons for this fact is that the common
applications of the two components offer the possibility to
observe synergetic effects.
The aim of this review is to provide an updated report
about the progress in the different synthesis methods of
binary and ternary CNT/PANI composites. The identifica-
tions methods, the properties of the final product and,
finally, the progress toward technological applications will
be discussed.
2. CNT/PANI binary composites
2.1. CNT/PANI interactions
A stumbling block in developing polymer-carbon nan-
otube composites is the difficulty in dispersing the CNT
and controlling their orientation [61] as a result of their
strong van der Waals interactions [62]. Functionalization
of CNT through noncovalent and covalent reactions with
organic molecules is the preferred strategy to well-disperse
CNT in organic media. Modifications of CNT with polymers
have been reviewed by Spitalsky et al. [63]. In this part,
we will address successively the PANI interactions with
non-functionalized and with functionalized CNT.
2.1.1. PANI interactions with non functionalized CNT
Non-covalent methods to disperse CNT show the advan-
tage of leaving electronic structure of CNT intact [64]. The
structural integrity and the ␲ conjugation system of the
outer surface of CNT are preserved. Its disadvantage con-
cerns weak forces between wrapped/coupled molecules
that may lower the load transfer in CNT–polymer compos-
ites [57].
Several methods have been reported to make solu-
bilized CNT through noncovalent reactions with organic
molecules [58]. CNT are electron-rich molecules that form
␲–␲ interactions with electron-rich molecules and CH–␲
interactions with CH donor molecules including poly-
mers such as poly(methyl methacrylate) or polybutadiene
and small molecules such as 1-octadecanethiol [52,59]. A
unique compatibility between CNT and aromatic amines
such as aniline has been reported, exemplified by a solubil-
ity of SWCNT in aniline being up to 8 mg/ml. The formation
of a charge-transfer complex between CNT and aniline, a
80 good electron donor, was evidenced by the appearance of
70
a new absorption in the visible region (at 530 nm). This is
followed by proton transfer from aniline to the CNT [65].
60
The three PANI amine-benzenoid units acquire certain
Number of articles
ring-torsion angles with respect to its flat imine-quinoid
50
units. The non-planar chain architecture [66] of PANI
40
should, in principle, reduce opportunities for strong inter-
30 actions with CNT [67]. However, all studies with CNT/PANI
20 composites reveal good interactions between both com-
ponents [5,68,69]. Aromatic structures, in general, are
10
known to interact strongly with the basal plane of graphitic
surfaces via ␲-stacking [58]. The enhanced electrical con-
ductivity of the CNT-Cl− doped PANI composite over neat
PANI was explained by the dopant effect of CNT as sug-
gested by the low Cl/N ratio in the composite. It was
710 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
Fig. 2. CNT/PANI interactions showing that CNT competes with chloride ion to dope PANI [5].
proposed that the doping effect of CNT was due to a charge
transfer from the quinoid unit of PANI to the CNT (Fig. 2).
The new bands that appeared at 362, 455, 510 and
550 nm in ultraviolet–visible (UV–vis) absorption spec-
trum [69] and the intensity increase of the N = Q = N band
at 1137 cm−1 in Fourier transform infrared (FTIR) spectrum
[70] evidence the strong interactions between PANI and
CNT. A more polaronic organization of PANI, induced by
CNT was found from resonant Raman spectroscopy results
[71]. Near-edge X-ray absorption and X-ray photoelectron
spectroscopy showed that PANI developed on the CNT sur-
face was mainly protonated while the PANI developed in
the pores of ordered mesoporous carbon material contains
a marked portion of emeraldine base [72].
It is to be noted that the enhanced conductivity effect
was also related to the fact that CNT may serve as a con-
ducting bridge between the PANI ES domains due to their
large aspect ratio and surface area [73,74].
Abalyaeva et al. [75] used the noncovalent modification
of MWCNT by the anionic co-oxidant hexachloroiridate and
the redox mediator 2,2 -azino-bis(3-ethyl-benzthiazolin-
6-sulfonate) ABTS2− controlled by the electrostatic interac-
tion [76]. An intensification of the polymerization of aniline
on the surface of MWCNT has been observed associated to
the ability of sorbed co-oxidants to accelerate the oxida-
tive dimerization of aniline immediately on the surface
of MWCNT, thereby promoting formation of oligomer and
PANI intermediates directly on the MWCNT.
2.1.2. PANI interactions with functionalized CNT
CNT are essentially reactive at their end caps and are
notably more reactive than flat graphene sheets. This arises
from local strain in CNT, particularly pronounced at these
caps, due to pyramidalization and misalignment of the ␲-
orbitals of the sp2 -hybridized carbon atoms [3,4]. A notable
disadvantage of covalent functionalization is the disrup-
tion of the extended ␲ conjugation in nanotubes which is
expected to have a profound impact on the electrical prop-
erties of CNT. Different methods were developed to prepare
amino functionalized CNT, NH2 -CNT, which are reactive
sites to graft PANI via chemical oxidation polymerization
of aniline (Fig. 3).
The main route to prepare NH2 -CNT uses acylchlo-
ride functionalized CNT (a-CNT) as an intermediate.
Phenylamine [77] and poly(ethyleneglycol)aminopropyl
[78] groups were introduced on the surface of a-CNT
via amide bonding [79] while NH2 -CNT were pre-
pared via ester bonding by the reaction of a-CNT with
N-(tert-butoxycarbonyl)-4-aminophenol followed by the
deprotection of the N-tert-butoxycarbonyl groups by
washing with trifluoroacetic acid [80].
The chemical modification of CNT with 4-Aminobenzoic
acid in polyphosphoric acid/phosphorous pentoxide as a
direct Friedel Crafts acylation reaction medium has been
developed by Jeon et al. [81–83]. The gentle conditions
result in little or no damage of the CNT framework contrary
to conventional Friedel–Craft acylation, chemical treat-
ments with strong acids or physical methods such as
sonication [84]. 4-Aminobenzene groups were grafted onto
the surface of MWCNT via C C covalent bonds by reaction
with p-iodoaniline in liquid ammonia.
Sulfonated PANI (SPANI) was covalently attached to
SWCNT to form water-soluble graft copolymers from an
acyl chloride intermediate [85]. On the basis of FTIR spec-
troscopy, SPANI is covalently bonded to the SWCNT via
amide functionalities [86].
The chemical treatment of MWCNT with phenyldiazo-
nium tetrafluoroborate in presence of sodium hypophos-
phite increases their compatibility with PANI (Fig. 4).
The reduction of the phenyldiazonium cation first
results in diazonium radicals. These primary radicals dis-
sociate to give highly reactive phenyl radicals, leading to
the formation of a phenyl surface layer to the side walls
of CNT [87]. As a result of modification, the PANI chains
become less twisted and the contacts between the redox
site of PANI and CNT increase. This provides more effective
electron transport between the electrode and redox sites of
PANI and, consequently, an increase in the redox currents
of PANI by a factor of an order.
Electrostatic interactions were also used to prepare
MWCNT/PANI composites by rapidly mixing a positively
charged PANI ES nanofibers aqueous colloid and a neg-
atively charged oxidized MWCNT aqueous colloid [88]
(Fig. 5).
Wu and Lin [73] suggest that hydrogen bonding interac-
tions, rather than electrostatic interactions, occur between
the amino groups of aniline monomers and the car-
boxylic acid/acylchloride groups of functionalized MWCNT
together with the ␲–␲ interactions.
2.2. Synthetic methods
Several methods of synthesis of CNT/PANI have been
reported in the literature and considerable progress has
been made in designing and fabricating these composites.
CNT/PANI composites can be synthesized by electrochem-
ical or chemical processing. The processing of micrometric
CNT/PANI fibers by spinning methods will be also dis-
cussed.
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 711

O O
O

C OH C Cl H
M M M M C N R NH2
HNO3 SOCl2 Poly(ethylene
W W
CNT

CNT
W glycol)bis (3- W
CNT
a

CNT
N N O O O
65 C, 24h N
0
aminopropyl) N
T T T terminated
T H
C OH C Cl C N R NH2

O
H
H2 N NH 2 M C N NH2
W

CNT
N O
CH3 (CH2 )17 NH 2 Pyridine, DMAc, 1200C H
T C N NH2

HO NH Boc

THF/pyrridine, reflux
O O
H
M C O N Boc M C O NH2
W TFA/CH 2Cl2
CNT

CNT
O hydrolysis O
N N
H
T C O N Boc T C O NH2

H
M C N (CH 2 )17 CH3
CNT

W O
N
H
T C N (CH 2 )17 CH3

O
Friedel-Crafts acylation
M H2 N COOH M NH2
CNT

W
CNT

W
O
N Isoamyl nitrite N
T Polyphosphoric acid
T NH2
PPA/phosphorous
pentoxide P2O5

- I NH2 NH2
Li/NH3
CNT

Li+
CNT

CNT

NH2

a R= (CH2)3 (O CH2 CH2)n O (CH2)3

Fig. 3. Preparation of amine functionalized CNT.

712 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748

delocalization and the protonation of the amine nitrogen

Phenyldiazonium
tetrafluoroborate atoms.
CNT

CNT
+
N N +e
- °
N N
° + N2°
Fig. 4. Grafting of a thin phenyl layer on CNT [87].
2.2.1. Electrochemical processing
The different methods to prepare CNT/PANI compos-
ite films by electrochemical processing are summarized in
Fig. 6.
2.2.1.1. One step codeposition method. In 1999, Downs et al.
[89] were the first to prepare CNT/PANI composites by
electropolymerization of aniline on nanotube electrodes
constructed with whiskers of loosely packed multiwalled
carbon nanotubes (arc-derived). A comparison with the
conventional electrodes such as Pt showed that PANI films
on nanotubes are oxidized more readily and produce a
higher current density during the anodic oxidation. This
was attributed to the unusual topology and large surface
area of the nanotube electrodes. Nanoporous composite
films of MWCNT and PANI were grown by galvanos-
tatic polymerization from acidic aqueous solutions of
aniline and MWCNT, such that the constituents were
deposited simultaneously onto graphite electrodes. Scan-
ning electron microscopy revealed that the composite films
consisted of nanoporous networks of MWCNT coated with
PANI [90].
SWCNT/PANI composites with good uniformity can be
formed by electrochemical polymerization of aniline con-
taining well-dissolved SWCNT [69]. Higher electroactivity
over neat PANI has been observed due to the charge trans-
fer between SWCNT and PANI that promotes the electron
A film of PANI grafted multiwall nanotube was
deposited over the surface of a glassy carbon electrode by
electrochemical polymerization of a mixture of aniline and
amine functionalized MWCNT, MWCNT-NH2 . The authors
hypothesize that the oxidation of NH2 groups in MWCNT-
NH2 and in aniline occur simultaneously in the potential
beyond 700 mV [77]. The cation radicals site generated at
MWCNT-NH2 participate and interact with aniline cation
radicals/aniline molecules to nucleate grafting of PANI
chains onto MWCNT.
Donor–acceptor dyad SWCNT/PANI and MWCNT/PANI
were prepared by electropolymerization of aniline in
1-butyl-3-methyl-imidazolium hexafluorophosphate con-
taining 1 M trifluoroacetic acid as a ionic liquid (IL) medium
[53,91]. CNT are well separated in IL due to ‘cation–␲’ inter-
actions. This method gives the possibility to functionalize
large amounts (15 mg/ml) of SWCNT electrochemically.
2.2.1.2. Two step deposition method. CNT/PANI composites
were prepared by galvanostatic [92] or pulsed [93] elec-
tropolymerization of aniline on MWCNT–gold electrode in
sulfuric acid solution. Electrodeposition has been used to
produce chiral MWCNT/PANI composite films whose opti-
cal activity can be tuned by the choice of electrode material
and nanotube concentration [94].
A layer-by-layer methodology was used to assemble
homogeneous and stable MWCNT and PANI multilayer
films on glassy carbon electrodes (GCE) [95]. A partial oxi-
dation of MWCNT produced carboxylic acid groups that
are negatively charged in aqueous solution and which can
interact with positively charged polyelectrolytes like PANI-
ES. The MWCNT/PANI multilayer films were formed by
alternately casting a carboxylic acid modified MWCNT dis-
persion and electrodeposition of the aniline.

*
HN
NH
*
n

O
O
O HN
NH HN
O
O
O
O O n
Electrostatic adsorption * NH
O

H H O
N N O HN

HN N * O
H n
H H NH
N N
*
*
N N *
H H n

Fig. 5. Schematic of electrostatic adsorption between a negatively charged MWCNT and positively charged PANI [88].
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
Fig. 6. Electrochemical preparation methods of CNT/PANI films: (a) one step co-deposition process, (b) two step process and (c) electrophoretic deposition
process.
2.2.1.3. Electrophoretic deposition process. Electrophoretic
deposition is a unique electrochemical strategy to pre-
pare nanostructured conjugated polymer films from a
colloidal suspension of preformed polymer. The colloidal
suspension for electrophoretic deposition of MWCNT/PANI
film was prepared by mixing a PANI/formic acid solu-
tion with a carboxyl group functionalized MWCNT
(c-MWCNT) dispersion in acetonitrile [96]. ␲-Stacking,
hydrogen bonding and electrostatic interactions facili-
tate wrapping of c-MWCNT with the positively charged
PANI-ES. These positively charged colloidal spheres, sta-
bilized by symmetrically distributed negatively charged
formate ions, were electrophoretically deposited on a
negatively biased indium tin oxide (ITO) electrode to
give uniform, homogeneous and thin (200 nm) composite
film.
A nanostructured CNT array (CNTA)/PANI composite
electrode was prepared by the combination of a vertically
aligned CNTA framework and electrodeposition technique
[97].
The morphology of the CNTA/PANI composites was
visualized after different cyclic voltage (CV) cycles. At the
initial stage (100 CV cycles), the deposited PANI is uni-
formly wrapped around the CNT (Fig. 7a). As the number
of CV cycles increases, the PANI layer’s thickness increases
continuously (200 CV cycles) leading to a decrement of the
pores between CNT (Fig. 7b). A compact PANI shell begins
to form outside the composite (Fig. 7c and d). Beyond
300 cycles, PANI is no longer deposited around the CNT
but tends to be deposited independently around the sur-
face of the composite electrode, and form worm-like PANI
agglomerates (Fig. 7e and f).
713
2.2.2. Surfactant free aqueous polymerization
The typical surfactant free polymerization method con-
sists to polymerize aniline with an oxidant (ammonium
peroxydisulfate APS [98], FeCl3 [99], PPS [100], . . .) in
an aqueous acidic dispersion (HCl, HClO4 [101], . . .) of
MWCNT or SWCNT in concentrations ranging from 2 to
70 wt% at low temperature (0–4 ◦ C) [5,102] or at room tem-
perature [103]. Different methods have been proposed to
facilitate the dispersion of hydrophobic non-functionalized
CNT in the aqueous medium: addition of ethanol in the
aqueous reaction medium [104] or use of a SWCNT solu-
tion by refluxing in aniline [105] is two possibilities
among others. Chemical modification of the carbon nan-
otube surface is another possibility to disrupt the rope
structure and adding reactive species to the nanotube
to improve interfacial bonding in CNT/PANI composites.
Carboxylic acid [73,106–108] and amine-functionalized
[79,80,106,107,109] CNT (Fig. 3) have been commonly used
for that purpose. The oxidation of amino groups covalently
linked to CNT in aminobenzoyl functionalized CNT gen-
erates radical cations that initiate polymerization on the
surface [108,110] (Fig. 8).
This facilitates the formation of PANI at the surface, and
thus the formation of tubular CNT/PANI composite, relative
to the formation of PANI in the bulk.
The morphology of CNT/PANI composites depends on
the content of CNT [111]. At a 2.7 wt% MWCNT loading,
MWCNT/PANI are formed as individual nanofibers, simi-
lar to that of the neat PANI. Increasing MWCNT loading
at 10 wt% and over 20%, a granular form and a continu-
ous porous matrix formed of cross-linked smooth-surface
nanofibers are obtained respectively (Fig. 9).
714 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
Fig. 7. SEM images of the CNT/PANI composite electrodes synthesized by (a) 100, (b) 200, (c) and (d) 300, (e) and (f) 500 CV cycles at 100 mVs−1 between
−0.2 and 0.8 V [97].
Yang et al. found that when the content of PANI
increased to 80 wt% in the binary system, PANI could fully
encapsulate CNT [112].
Li and Kim [113] found that for a high mass ratio of
aniline/MWCNT (4:1), some aniline monomers can form
nanofibers with a diameter between 10 nm and 15 nm,
instead of polymerizing on MWCNT, as presented in Fig. 10.
It was shown that the use of even smaller amounts of
SWNT (<1%) (or other nanostructured seed template such
as PANI or vanadium oxide nanofibers) can orchestrate bulk
formation of doped PANI nanofibers [114].
Non-covalent (with 1-pyrenesulfonic acid [115] and cal-
cium lignosulfonate [116]) and covalent (with polystyre-
nesulfonic acid [117], prepared through radical polymer-
ization of sodium 4-styrene sulfonate in presence of CNT
and with benzene sulfonic functionalization prepared via
diazonium protocol [118,119]) strategies were used to
functionalize CNT with aromatic sulfonic acids or its salts,
S-CNT. S-CNT were employed as template to lead anilinium
monomers directly aligned on the surface thus directing
the growth of PANI from the side walls of CNT resulting
in a uniform polymer coating. Functionalization in S-CNT
avoids the agglomeration of CNT and gives sulfonate groups
as efficient dopant of PANI [116] (Fig. 11).
The presence of CNT in the reaction medium signifi-
cantly accelerates the rate of aniline oxidation [104,120].
Two explanations for the acceleration of oxidation by CNT
have been proposed, CNT playing the role of an efficient
heterogeneous catalyst due to its large surface area and/or,
as a conducting material, mediating the electron transfer
between aniline and oxidant. Wei et al. [121] have reported
the use of sulfonated MWCNT, MWCNT-(OSO3 H)n , as the
self-assembled template for the formation of PANI nanos-
tructures. The polymerization of aniline on the surface of
CNT giving PANI-coated MWCNT-(OSO3 H)n was observed
when the ratio aniline/MWCNT-(OSO3 H)n ≤ 1. When the
ratio aniline/MWCNT-(OSO3 H)n ≥ 2, supramolecular-type
MWCNT-(OSO3 H)n doped-PANI nanotubes are formed
from a self-assembly process induced by the interaction
between MWCNT-(OSO3 H)n and PANI (Fig. 12).
A microwave-assisted method was developed for the
fabrication of thick PANI layers (50–70 nm) within short
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 715

Fig. 8. Mechanism for the formation of tubular composite of PANI and CNT from aminobenzoyl functionalized MWCNT [110].

reaction time (3 min) coated on the surface of MWCNT
[122].
The polymerization process usually renders PANI in
its insoluble ES form but dedoping by stirring CNT/ES
composite with aqueous ammonium hydroxide results in
a processable CNT/EB composite which is soluble in N-
methylpyrrolidinone (NMP) [66]. It must be noted that
the dopant nature can be readily tuned by a post-doping
method where an initially formed Cl− doped CNT/PANI
composite is first dedoped with ammonium hydroxide and
then re-doped by immersion in a protonic acid solution.
This method was used to prepare dodecyl benzene sul-
fonic acid (DBSA) doped MWCNT/PANI composites that are
soluble and stable in NMP [123].
Substitution of aromatic rings of PANI on preformed
MWCNT/PANI is another method to change the physical
properties of the composite. Such a strategy was used to
prepare water soluble sulfonated PANI (SPAN) function-
alized MWCNT composites by sulfonation with chlorosul-
fonic acid in an inert solvent and by hydrolysis in water of
a chloride doped MWCNT/PANI composite (Fig. 13) [124].
A simple and reproducible way to synthesize ordered
CNT/PANI films consists in polymerizing aniline on a pre-
aligned MWCNT film [125]. The growth process of MWCNT
was carried out by catalytic pyrolysis of xylene on a quartz
glass sheet placed in the middle of a horizontal quartz tube
housed in a muffle furnace gradually heated to 800 ◦ C. The
aligned MWCNT film was dipped in aniline/hydrochloric
acid for 12 h at 0 ◦ C and then a solution of APS dissolved in
1 M hydrochloric acid was added dropwise to polymerize
the aniline monomer adsorbed on the surface of carbon
nanotubes.
716 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748

Fig. 9. HRSEM images of MWCNT/PANI-ES composite with (a) and (b) 10 wt% MWCNT and (c) and (d) 20 wt% MWCNT [111].

The fabrication of patterned CNT/PANI composite on sil-
icon was reported by Flavel et al. [126,127] utilizing low
energy solution chemistry and a scanning probe method
called atomic force anodization lithography (Fig. 14).
Anodization lithography is one of the many dif-
ferent forms of scanning probe lithography and it is
proving to be particularly promising for nano-scale pat-
terning, as it can be readily used to produce features
with sizes below 100 nm [128]. The technique relies
upon the use of a self-assembled monolayer (hexade-
cyltrichlorosilane on silicon [126]), a conductive atomic
force microscope cantilever and the ability to selectively
oxidize and remove molecules on the surface. A mono-
layer of methyl terminated hexadecyltrichlorosilane was
self-assembled onto a p-type silicon (1 0 0) substrate
to provide a resist for electrochemical oxidation with
an atomic force microscope cantilever. Through pre-
cise control of the cantilever’s position on the surface
and the voltage applied, a variety of different patterns
were etched into the substrate. To these etched regions,
amine terminated 3-aminopropyltrimethoxysilane was
self-assembled, which provided a point of attachment
between carboxylic acid functionalized SWCNT and the sil-
icon surface through amide linkage. AFM images showed
that CNT were vertically aligned, with no adsorption of
CNT to the CH3 terminated silane monolayer (Fig. 14A).
Then, PANI was deposited onto this patterned array of
CNT by in situ chemical oxidative polymerization of ani-

Fig. 10. SEM images of MWCNT and MWCNT/PANI composites: (a) MWCNT, (b) MWCNT/PANI (4:1), (c) MWCNT/PANI (1:1), (d) MWCNT/PANI (1:4). The
average diameter of the PANI coated MWCNT is up to 80 nm [113]. The scale bar in each picture is 200 nm.
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 717

MWCNT
Hydrophilic group

SO3 SO3 SO3 SO3

Self-Assembly Process

SO3 SO3 SO3 SO3

SO3 SO3 SO3 SO3
Hydrophobic backbone
LGS-Ca chain
SO3 SO3 SO3 SO3

NH3 NH3 NH3 NH3

SO3 SO3 SO3 SO3

Add aniline

SO3 SO3 SO3 SO3

NH3 NH3 NH3 NH3

H H H H
N N N N

Cl SO3 SO3 SO3 SO3

Chemical oxidation

SO3 SO3 SO3 SO3

H H
N N N N
H H
Cl

Fig. 11. Synthetic route developed for the self-assembly of PANI/LsCa-MWCNT [116].

line. AFM image showed that PANI covered the entire
surface (Fig. 14B). After deposition of PANI, a piece of adhe-
sive tape was pressed to the silicon surface before being
slowly peeled off, hence creating the patterned carbon
nanotube/PANI composite upon removal of PANI from sur-
rounding hydrophobic regions (Fig. 14C).
The length of attached CNT is significantly less than
the expected average length of 380 nm, with most having
lengths between 8 and 20 nm. This dramatic decrease in
the observed height was attributed to two reasons; first,
the adsorption kinetics facilitates the assembly of shorter
carbon nanotubes over their slower moving longer coun-
terparts. Second, the interaction of AFM cantilever as it
scans across the surface may cause the nanotube to bend
and sway, hence providing underestimates in the vertical
height.
2.2.3. Micelle–CNT hybrid template directed synthesis
It is well-known that the use of surfactants can improve
nanotube dispersions in solvent and polymers. Contrary to
covalent functionalization of CNT, this approach preserves
the integrity of CNT without disrupting the extended ␲ con-
jugation of CNT [129,130,131]. When CNT are dispersed in
aqueous solutions containing surfactants, each individual
nanotube (or small bundle) is encased in its own micelle
like envelope with hydrophobic groups of the surfactant
oriented toward the nanotube and hydrophilic groups ori-
ented toward the solution. The insertion of aniline in the
hydrophobic region within the micelle/CNT hybrid tem-
plate will guide the growth of PANI to the CNT surface
(Fig. 15).
Anionic (like sodium dodecylsulfate (SDS) [132], dode-
cylbenzene sulfonic acid sodium salt [133] and DBSA
718 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
Fig. 12. SEM, TEM and electron diffraction patterns of PANI-coated MWCNT-(OSO3 H)n (a, b, c) and MWCNT-(OSO3 H)n doped-PANI nanotubes (d, e, f) [121].
[103,134]), cationic (like cetyltrimethyl ammonium bro-
mide (CTAB) [131]) and nonionic (like poly(ethylene glycol)
mono-p-nonyl phenyl ether, O␲-10, polyvinyl alcohol
[135,136]) surfactants have been used for the micelle/CNT
hybrid template directed synthesis of CNT/PANI with coax-
ial nanostructures. Cationic and nonionic surfactants are
generally removed and not incorporated into the CNT/PANI
structure. The situation is different with anionic surfac-
tants that are incorporated into the composite as a dopant
of PANI chains. The type of surfactant was found to
affect greatly the surface morphologies of the resulting
SWCNT/PANI composite but not the molecular structure
of the corresponding conducting polymers [137]. With
CTAB, ribbonlike networks of SWCNT/PANI composites
were formed after reaction while the O␲-10 resulted in
wirelike structure (Fig. 16a and b).
The ribbonlike structure was ascribed to the formation
of lamellar mesostructures between cetyltrimethylammo-
nium (CTA) cations and oxidizing anions of APS (Fig. 17).
The thin SWCNT can be located within the layer spaces
of lamellar mesostructures (CTA)2 S2 O8 and, thus, ribbon-
like networks of CNT/PANI are formed after reaction.
However, compared with SWCNT, (CTA)2 S2 O8 mesostruc-
tures cannot affect the micelle/CNT hybrid template
strategy, due to the larger diameter of MWCNT [18].
Generally, pristine carbon nanotubes (MWCNT or
SWCNT) with hydrophobic nanotube surface are used. A
significant study has been devoted to the fabrication of
DBSA doped PANI-grafted MWCNT nanocomposite with
solubility and stability in organic solvents (such as THF)
using aminobenzoyl functionalized MWCNT as base CNT
[103].
2.2.4. Inverse emulsion pathways
The synthesis of CNT/PANI composites using water in
oil system has been mentioned as one of the methods
serving to prepare CNT/PANI composites. Different varia-
tions of the protocols can be found in the literature. These
variations have likely an effect on the morphology of the
CNT/PANI composite. One representative method, desig-
nated as ‘inverse microemulsion polymerization’ [138,139]
is illustrated in Fig. 18.
It involves the formation of small drops (a few nanome-
ters) of water trapped within assemblies of surfactant
molecule (like sodium dodecybenzenesulfonate (SDBS)
and dispersed in a continuous phase (like hexane or
toluene). With an ionic surfactant containing a single
hydrocarbon chain (which is the case of SDBS), microemul-
sions are only formed if a co-surfactant (example: a
medium size aliphatic alcohol such as butanol) is also
present. After the addition of pristine CNT, some of SDBS
micelles are adsorbed onto their outer surface. Once aniline
hydrochloride is added into the inverse microemulsion,
they would reside in the SDBS micelles. When APS is added
to the reaction system, some of the aniline hydrochlo-
ride resided in the adsorbed micelles polymerized initially.
This led to adhesion of the PANI particles to the surface of
CNT. When aniline hydrochloride encapsulated in adsorbed
micelles had been oxidized, the residual aniline hydrochlo-
ride would be expected to diffuse toward the surface of
the CNT and be further oxidized. The resulting CNT/PANI
core–shell nanowires are stabilized by the SDBS, the surfac-
tant being removed after precipitation with acetone. TEM
image for the MWCNT/PANI composite clearly shows the
spherical PANI nanoparticles (80–100 nm) onto the surface
of the MWCNT (Fig. 19). High resolution transmission elec-
tron microscopy (HRTEM) allows to clearly distinguish the
PANI shell and the MWCNT core (inset Fig. 19).
Kim et al. have proposed an alternative protocol
based on the use of carboxyl acid functionalized MWCNT,
c-MWCNT, rather than pristine CNT [74]. c-MWCNT
were dispersed in cyclohexane containing DBSA with
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 719

Fig. 13. Preparation of MWCNT/SPAN water soluble composite by (a) sulfonation of a MWCNT/Cl− doped PANI [124] and (b) ex-situ polymerization [86].

ultrasonication. Then, aniline and a solution of APS
dissolved in water were successively added to the dis-
persion. The postulated mechanism for the synthesis of
c-MWCNT/PANI is illustrated in Fig. 20.
One key aspect of the mechanism is the stronger
affinity of c-MWCNT with water than with hydrocarbon.
Consequently, c-MWCNT are supposed to be transferred
into water in the inverse micelle. At the interface of
the water and oil, polymerization of aniline was initi-
ated through oxidation by APS. Finally, the PANI doped
with DBSA propagates by radical coupling in the water
medium and is adsorbed on the surface of c-MWCNT. It
must be noted that while the aniline concentration was
0.1 M, the concentration of DBSA was varied from 0.01 M
to 1 M, which gives different pH conditions. It is impor-
tant to realize that the initial pH of the medium will
determine the distribution of aniline between organic sol-
vent and water. This must have an impact on the final
nanostructure morphology. At pH > 5, the neutral form of
aniline with a limited miscibility with water dominates
and the monomer will be mainly present in the organic
phase.
720 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748

Fig. 14. Patterned assembly of single-walled carbon nanotubes on silicon allows the creation of patterned CNT/PANI composites. AFM images of (a) CNT
coated silicon, (b) CNT/PANI coated silicon before and (c) after peeling off adhesive tape (adapted from ref. [126,127]).

Fig. 15. Schematic diagram of micelle/CNT hybrid template-directed synthesis of CNT-based coaxial nanowires [137]. It is noted that TEM observations
showed that SDS molecules do not adsorb perpendicular to the surface of CNT but form half-cylinders oriented perpendicular to the tube axis, helices or
double helices depending on the symmetry and the diameter of CNT [294].
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
Fig. 16. (a) SWCNT/PANI composites without coaxial nanostructures by using CTAB for micellar molecules; (b) SWCNT/PANI composites with coaxial
nanostructures by using O␲-10 for micellar molecules [137].
TEM images of the dispersed particles obtained after
different reaction times showed that the deposition layer
became thicker as the reaction time increased (Fig. 21).
It can be concluded that the capping of c-MWCNT result-
ing from adsorption of PANI molecules was not an irregular
aggregation between PANI particles and c-MWCNT. It
was assumed that PANI molecules form highly ordered
structures on c-MWCNT which was confirmed by X-ray
diffraction results.
2.2.5. Interfacial polymerization
Static (without stirring) and dynamic (with stirring)
interfacial polymerization (IP) is typically performed in an
aqueous/organic biphasic system with aniline dissolved
in an organic solvent and the oxidant, generally APS,
dissolved in an aqueous acid solution [140,141]. PANI
nanofibers was the preferred morphology obtained by
IP [142,143,144,145]. Two reasons were considered to
explain the formation of nanofibers by IP (1) the reduced
local dielectric constant of water at the organic/water
interface which would favor the formation of phenazine
nucleates at the interface [146,147]; (2) the organic phase
removes a part of aniline from the aqueous phase, thus cre-
ating the conditions typical of a dilution technique which
is known to promote the stacking of nucleates over their
Fig. 17. Lamellar mesostructural (CTA)2 S2 O8 precipitate containing pyr-
role [295] monomers. The same organization was speculated for aniline.
In a more recent study [296], the formation of PANI with 2D-nanoclip like
morphology was explained by the lamellar packing of a folded twin-tailed
model for (CTA)2 S2 O8 complex.
721
random agglomeration [142]. Static IP can be performed in
presence of CNT dispersed in the organic phase [148]. As
polymerization was occurring at the interface, protonated
PANI homopolymer and PANI-g-MWCNT diffuse into the
top aqueous phase (Fig. 22).
Vaidya et al. [149] reported the use of anionic sur-
factant namely SDBS and SDS, to facilitate the combined
processing between ES-PANI and SWCNT. A phase inver-
sion phenomenon occurred from aqueous to organic phase
when SDBS or SDS were added to a Cl− doped PANI
or SWCNT/PANI composite prepared by IP (Fig. 23a). It
was proposed that the hydrophobic interactions between
surfactant tails with SWCNT and the strong interactions
between PANI–surfactant headgroups are very much likely
to be responsible for stabilizing this three phase system in
the organic solvent (Fig. 23b).
Salvatierra et al. [150] prepared CNT/PANI nanocom-
posites self-standing films by dynamic IP in which both
the synthesis and processing of the nanocomposites are
performed together in a single step (Fig. 24).
The CNT/ES film formed at the water-toluene inter-
face immediately after stopping the stirring, which was
explained by the interface stabilization by solid CNT/PANI
composites, like in Pickering emulsions [151].
2.2.6. Plasma polymerization
PANI was formed on MWCNT [152,153] and SWCNT
[154] by using plasma induced polymerization technique.
This technique includes two steps: (a) the activation of
the c-CNT surface by using N2 plasma and (b) the plasma
induced polymerization of aniline monomer.
2.2.7. Ex situ polymerization
The ex situ method is a solution processing method
which generally consists in mixing PANI (ES or EB) and
CNT solutions or dispersions together. Good solvents for EB,
such as NMP, dimethylformamide or N,N -dimethyl propy-
lene urea (DMPU) will be the preferred solvent for the
preparation of EB–CNT composites [155].
722 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
Fig. 18. Synthetic scheme of MWCNT/PANI core-shell nanowires using inverse microemulsion [138].
Ex situ water processing of ES–CNT composites has
also been reported [88,156–158]. In this case, the use of
CNT functionalized with hydrophilic groups, like carboxylic
acid groups [84,96,156,158], and/or hydrophilic PANI, like
sulfonated [156,159] or boric acid [160] self-doped PANI,
improve the water dispersibility of such systems. When
PANI is externally doped, the nanoscale structure of PANI
(such as nanofibers) was found to be an important con-
dition for the preparation of stable aqueous colloids of ES
[88,161].
Uniform CNT/PANI nanocomposites can be prepared
by simply mixing a positively charged PANI nanofibers
aqueous colloid and a negatively charged c-CNT aqueous
Fig. 19. TEM and HRTEM images of MWCNT/PANI composite obtained by
the inverse microemulsion polymerization pathway [138,139].
dispersion [88,162], or a surfactant-aided dispersion of
CNT [161]. FTIR and Raman spectroscopy results revealed a
strong electrostatic interaction between the C N+ species
of the PANI nanofibers and the COO− species of the
CNT [88,96]. The ␰ potentials of the oxidized MWCNT
and PANI aqueous colloids were found to be −12.54 mV
and 31.35 mV, respectively, confirming that the oxidized
MWCNT take some negative charges whereas PANI takes
some positive charges.
Hu et al. [163] created MWCNT/PANI/PSS multilayer
film. First, the solubility and processability of the CNT
were improved by wrapping them in poly(sodium 4-
styrenesulfonate) (PSS) via noncovalent supramolecular
approach [164]. Then, the negatively charged PSS wrapped
MWCNT is doped with cationic PANI via a layer by layer
assembly. It was found that PSS wrapped MWCNT can
effectively dope PANI and shift its electroactivity to a neu-
tral environment.
The use of p-hydroxybenzene sulfonic acid (PHBSA) as
a bifunctional dopant was supposed to act as a bridge
between PANI chains and c-MWCNT, hydroxyl groups of
PHBSA interacting through hydrogen bonds with COOH
groups of c-MWCNT and sulfonate groups interacting with
C N+ groups of PANI through ionic bonds [158].
An interesting alternative was reported by Zhao et al.
[165], poly(aminobenzene sulfonic acid) being covalently
attached to SWCNT to form water soluble graft copolymers
with a water solubility of about 5 mg/ml (Fig. 13b).
Composites of MWCNT in a dinonylnaphthalene disul-
fonic acid (DNNDSA)-doped PANI thermoreversible gel
were prepared from a formic acid medium [166]. Well-
dispersed MWCNT, wrapped by DNNDSA-PANI through the
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 723

Fig. 20. Schematic representation of the synthesis of c-MWCNT/PANI composite in inversed micelle [74].

Fig. 21. TEM images of PANI composite doped with 0.2 M DBSA in which 5 wt% c-MWCNT was applied, at different reaction times [74].

Fig. 22. Static interfacial polymerization of aniline; top aqueous 1 M HCl layer with APS; bottom chloroform layer with aniline and aminobenzoyl function-
alized MWCNT, NH2 -MWCNT; photographs of reaction vials as function of reaction time. The product in aqueous phase consists of PANI/PANI-g-MWCNT
mixture. The black residue at the bottom of organic phase was identified as the unreacted NH2 -MWCNT [148].
724 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748

Fig. 23. (a) Phase inversion phenomenon in steps from A- PANI as prepared, B- intermediate state and C- organic dispersion, (b) Hypothetical model for
interactions between PANI-surfactant -SWCNT using SDBS or SDS [149].

Fig. 24. Schematic representation of the synthesis and deposition of CNT/PANI films [150].

␲–␲, CH–␲ and acid–base interactions, formed a fibrillar
network structure (Fig. 25).
Abalyaeva et al. [167] compared the morphology of
MWCNT/PANI prepared by chemical synthesis and electro-
chemical polymerization. A sponge and uniform coating
was observed for the sample prepared by chemical syn-
thesis while the composite synthesized electrochemically
present clearly nanotubes separated from the polymer
(Fig. 26).
The nanotubes were inserted in the bulk polymer form-
ing a conducting network in the polymer and the greatest
part of MWCNT was not coated with the polymer.
2.2.8. Preparation of micrometric CNT/PANI fibers
Wet-spinning [168–172], electrospinning [173–175] or
melt spinning [176] were used to prepare conductive
CNT/PANI fibers with high tenacity. The key points for wet
spinning methods are to prepare solutions of appropri-
ate viscosity (2000–3000 cP) and stability to allow enough
time for spinning prior to gelation. PANI fibers are gener-
ally produced from EB or leucoemeraldine base forms of
PANI [177]. Fibers are then rendered conductive by doping
using an aqueous acid comprised of small anions (such as
methane sulfonic acid [170]). As a representative example,
CNT were integrated in PANI fibers from a feed solu-
tion containing 10% (w/w) PANI (EB or leucoemeraldine
base) and 2% (w/w) CNT in DMPU, a solvent which gives
more delayed gelation for EB solution than NMP [171]. An
alternative method consists in doping of PANI in solution,
which results in more homogenous doping. The production
of 2-acrylamido-2-methyl-1-propanesulfonic acid AMPSA-
doped PANI fibers containing CNT using dichloroacetic acid
as a dispersant for CNT and ES PANI [168,169]. Using this
approach, the conductivity of the composite containing 10%
(w/w) SWCNT was more than 25 times higher than that
obtained with neat PANI [168]. The morphology of PANI
and CNT/PANI fibers was compared [170]. A fully dense
structure was observed for the pure PANI fiber while the

Fig. 25. TEM micrograph of the DNNDSA doped MWCNT/PANI composite with (a) 1% MWCNT and (b) 3% MWCNT [166].
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 725

Fig. 26. Micrographies illustrating the morphology of the MWCNT/PANI composites prepared by (a) chemical synthesis and (b) electrochemical synthesis
[167].

PANI fiber containing CNT displays fracture marks on its
cross-section (Fig. 27), and there is also evidence of some
porosity in these fibers.
Therefore, electrochemical properties of the PANI fibers
as an electrode material and using an ionic liquid (ethyl-
methyl bis (trifluoromethane sulfonyl) amide) as an
electrolyte are improved by the incorporation of CNT.
Dynamic light scattering provides important information
about the distributions of diameters and lengths of CNT
bundles. It is especially used to determine particle sizes.
Badaire et al. [124] have found that a bimodal distribu-
tion of CNT exists in DMPU whereas the addition of PANI

Fig. 27. Scanning electron micrographs of cross-section of (a) PANI and (b) CNT/PANI fibres at low and high magnification [170].
726 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
leads to a decrease of the hydrodynamic radius and also to
a monomodal particle size distribution.
Till date, few studies report the fabrication of CNT/PANI
fibers using the electrospinning technique. One drawback
of this method is that it often needs to blend PANI with
an insulating polymer to prepare the nanofiber structure.
Kang et al. [173] reported the fabrication of well-oriented
SWCNT in water soluble PANI and poly(vinyl alcohol) using
electrospinning technique. However, the conductivity of
composite nanofibers was not greatly enhanced due to the
low conductivity of the water soluble PANI. The nanofi-
brous membranes of PANI-poly(ethylene oxide) loaded
with SWCNT that were prepared in non-aqueous solvent,
showed nearly four orders of magnitude increase of elec-
trical conductivity (1.2 S cm−1 ) at 11.9 wt% SWCNT [174].
The preparation of CNT/PANI fibers by melt spinning
was described for the first time by Soroudi et al. [176]. ES
PANI and MWCNT have been blended with polypropylene
and blends have been melt spun to fibers by extrusion. The
drawback of this method is that the fiber extrusion process
leaded to inhomogeneous fibers with a rough surface as
well as a large filament diameter variation.
3. CNT/PANI ternary composites
3.1. CNT/PANI incorporating noble metal nanoparticles
CNT/PANI composites incorporating noble metal
nanoparticles (NPs) such as Au, Ag, Pt, Pd, Rh, Ru and their
alloys have shown very attractive applications in many
fields, especially in heterogeneous catalysis, fuel cells and
chemo/biosensors (see applications section) [80,178–185].
The metal NPs were deposited on CNT before, simultane-
ously or after PANI deposition to give CNT/M/PANI, CNT/M,
PANI and CNT/PANI/M ternary composites, respectively.
The strategies used to prepare such structures can be
classified according to the method for NPs deposition
into four categories: electrochemical deposition, chemical
reduction deposition, dispersion of noble metal NPs on
functionalized CNT and physical methods. A high disper-
sion and small particle size of noble metal NPs on CNT are
generally desired for the aimed applications and also for
cost reasons. The particle sizes of noble metal NPs in the
representative CNT/PANI nanohybrids are summarized in
Table 1.
3.1.1. Electrochemical deposition
In this method, the noble metal NPs nanohybrids are
obtained via electrochemical reduction of noble metal
complexes, such as tetrachloroauric acid, chloroplatinic
acid, dipotassium tetrachloroplatinate(2-) on CNT [186]
or CNT/PANI [178,180] modified electrodes. CNT and
CNT/PANI composite films typically do not react with the
noble metal salts but act as molecular conducting wire and
supports for the deposition of noble metal NPs.
The main advantage of the electrochemical deposition
method is that the particle size and surface coverage of
noble metals NPs can be tuned with potential, deposi-
tion time, and metal salt concentration [186]. However,
it is a challenge to synthesize noble metal NPs with high
dispersion and small particle size on CNT or CNT/PANI
Fig. 28. SEM and TEM (as inset) micrographs of the MWCNT/PANI/Pt
ternary composite (ratio of PANI/MWCNT: 0.54) [182].
by electrochemical deposition method due to the con-
tradiction between a larger driving force (more negative
deposition potential) for critical nuclei formation and an
inhibitive mechanism for deterring crystal growth (less
deposition charge or smaller current density).
As a representative example, MWCNT-grafted PANI
were decorated by Au NPs through a two-step sequential
electrochemical procedure. In the first step, MWCNT-g-
PANI film was electrodeposited onto the working electrode
(Au) using cyclic voltammetry. In the second step, Au NPs
were incorporated into MWCNT-g-PANI film by electro-
chemical reduction of HAuCl4 . A two-step electrochemical
process was also reported by Zhu et al. using a 4-
carboxylicbenzene modified MWCNT prepared via in situ
generation of the diazonium (Fig. 3). MWCNT/PANI films
decorated with Au nanoparticles exhibit good electrocat-
alytic activity toward ascorbic acid oxidation [185]. The
electrocatalytic activity was shown by an enhanced peak
current and a negative shift of oxidation overpotential of
0.41 V.
3.1.2. Chemical reduction
In the chemical reduction process, as opposed to elec-
trochemical reduction process, a chemical species whose
redox potential is suitably lower than that of the metal
species being reduced provides the driving force for the
reaction.
Xu et al. [182] fabricated first MWCNT/PANI by in situ
chemical oxidation polymerization. Then, Pt NPs were
deposited on the MWCNT/PANI composites by a chemical
reduction method using NaBH4 and H2 PtCl6 . As it can be
seen in Fig. 28, a uniform distribution of Pt NPs has been
obtained.
Lee et al. [187] used the same reducing agent to deposit
Pt and Ru binary catalysts on MWCNT/PANI from H2 PtCl6
and RuCl3 precursors. The Pt and Ru dispersions are homo-
geneous on MWCNT/PANI whereas the binary catalyst
supported on bare MWCNT displayed a Pt rich core and
a Ru rich shell nanostructure.
The polyol method is one of the most popular chemical
method for the synthesis of nanoparticles of metals and
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 727

Table 1
Characteristics of noble metal NPs in CNT/PANI ternary composites.

Noble metal Particle size (nm) Deposition method of NPs Type of ternary composite Reference

Pt 20–40 nm Electrochemical deposition CNT/PANI/M [178,179]

Pt 4.8–8.4 nm Chemical reduction CNT/PANI/M [182]
Pt 2–4 nm Chemical reduction (polyol process) CNT/PANI/M [181]
Pt – Chemical reduction (polyol process) CNT/M/PANI [298]
Pt–Ni 0.2–1 ␮m Electrochemical deposition CNT/PANI/M [180]
Pt–Ru 2–4 nm Chemical reduction CNT/PANI/M [187]
Pd 10–20 nm Chemical reduction (polyol process) CNT/PANI/M [189]
Pd–Fe – Physical method (␥ irradiation) CNT/SPAN/M [192]
Au 5–8 nm Electrochemical deposition CNT/PANI/M [78]
Au ∼20 nm Chemical reduction CNT/M/PANI [183]
Au ∼3 nm Chemical reduction CNT/M/PANI [184]
Au – Au NPs/chitosan dispersiona CNT/PANI/M [241]
Ag 2–4 nm Chemical reduction (hydrazine) CNT/M/PANI [254]
Ag 5 nm Spontaneous reduction on c-CNT CNT/M/PANI [299]
Pt–Ru 7 nm Electrochemical deposition CNT/PANI/M [300]

– not available.
a
The positively charged Au/chitosan dispersion is adsorbed onto the negatively charged c-MWCNT/PANI.

alloys [183,188]. Conventional polyol process takes long
reaction times but with improvements in the method of
heating, i.e. using microwave, the reaction time has come
down to minutes. In a typical polyol process, inorganic salt
is reduced by the polyol at a high temperature (near boil-
ing temperature). The polyol used is generally ethylene
glycol which serves as both solvent and reducing agent.
Sapurina et al. [189] deposited Pt, Pd, and Rh – on the sur-
face of CNT/PANI from solutions of the corresponding acid
or salts – H2 PtCl6 , Pd(NO3 )2 , and Rh(NO3 )3 – in ethylene
glycol–water mixture (80 vol.%) by the microwave-assisted
polyol method.
He et al. [181] reported the preparation of SWCNT/PANI
composites loaded with highly dispersed Pt nanoparticles
with particle sizes ranging from 2 to 4 nm. The Pt col-
loids were prepared in presence of aniline and CNT using
ethanol as reducing agent and H2 PtCl6 as metal precursor.
The induction period until sufficient Pt atoms have accu-
mulated as nucleation sites was shortened through heating
and increasing the pH of the solution. Pt nanoparticles were
anchored onto the surface of PANI because at the end of
the PANI molecule the free electron pair of N complexes
the space orbital of Pt, as confirmed by the N(1s) peak at
398.23 eV in the X-ray photoelectron spectroscopy spec-
trum of the composite. At the other end of the molecule,
the phenyl rings interact with CNT through ␲–␲ bond-
ing.
Ingeniously, a one pot synthesis of MWCNT/PANI,
Au nanocomposite has been established [183,184] when
HAuCl4 is mixed with aniline in a MWCNT aqueous dis-
persion, the reduction of HAuCl4 and the oxidation of
aniline occur simultaneously, leading to the formation of
Au NPs and PANI adsorbed at the surface of MWCNT. These
nanocomposites were used as sensors to ammonia gas (see
Section 5).
There are scarce examples of CNT/PANI incorporating
metal NPs using the dispersion of noble metal NPs on
functionalized CNT. Surface functionalization of CNT is
generally carried out to introduce binding sites for anchor-
ing metal NPs. PANI grafted to MWCNT was found to
introduce such binding sites for the loading of gold NPs
through electrostatic interactions between Au NPs and
PANI. These MWCNT/PANI/Au nanocomposites were pre-
pared by directly adding a gold colloid aqueous solution to
the solution of MWCNT/PANI [80].
3.1.3. Physical methods
Physical methods including sputtering deposition, ion
and electron beam irradiation and evaporation deposition,
have been widely used to depose noble metal NPs on the
surface of CNT [190,191]. Compared with the chemical
method, these methods have the advantages of homoge-
neous reduction and nucleation which lead to small and
monodispersed noble metal NPs. As a representative exam-
ple, a suspension of MWCNT–SPAN in ethylene glycol, also
containing Fe ions, Pd ions, or a mixture of Fe and Pd ions
was exposed to ␥ irradiation. ␥ irradiation induced the
reduction of metal ions to obtain metal NPs within a short
irradiation time (60 s) [192].
3.2. CNT/PANI incorporating metal oxides
Metal oxides (MOs) such as Fe3 O4 , TiO2 , MnO2 , NiO
and RuO2 have been incorporated to CNT/PANI compos-
ites as a thin layer on CNT, nanoparticles or nanoflakes
[188,193–196]. These ternary composites have shown
attractive applications in many fields. Specifically, Fe3 O4
(in the crystalline form of hematite) is of great impor-
tance for its good magnetic properties, nanosized-MnO2
and RuO2 were used for redox supercapacitor elec-
trodes, NiO in biosensor devices and TiO2 as dielectric
filler.
MOs were deposited on CNT before, simultaneously
or after PANI deposition to give CNT/MO/PANI, CNT/MO,
PANI and CNT/PANI/MO ternary composites, respectively.
MOs and CNT deposited simultaneously on PANI modified
electrodes were identified as CNT, MO/PANI ternary com-
posites. The strategies used to prepare such structures are
summarized in Table 2, by specifying the size and shape of
MO and the method for their deposition.
CNT/PANI containing Fe3 O4 NPs are typically pre-
pared in two steps. First, deposition of Fe3 O4 (hematite
728 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748

Table 2
Characteristics of metal oxides, MOs in CNT/PANI ternary composites.

Metal oxide Shape of MOa Size (nm)b Deposition method of MOs Type of ternary composite Ref

Fe3 O4 NP 17.6 Coprecipitation of Fe2+ and Fe3+ CNT/MO/PANI [193]

Fe3 O4 NP 20 Coprecipitation of Fe2+ and Fe3+ CNT/MO/PANI [195]
Fe3 O4 NP 6 Thermal decomposition CNT/MO/PANI [194]
Fe3 O4 NP 20 Fe3 O4 NPs dispersion CNT/MO,PANI [222]
TiO2 NP 20 TiO2 NPs dispersion CNT/MO,PANI [188]
MnO2 IC – Thermal decomposition CNT/MO/PANI [297,301]
MnO2 NF 10–50 Chemical oxidation (KMnO4 ) CNT/PANI/MO [255]
MnO2 UL 1–2 Chemical oxidation (H2 O2 ) CNT/MO/PANI [198]
MnO2 UL 10 Thermal reduction of KMnO4 CNT/MO/PANI [256]
NiO NP 20 Dispersion of NiO NPs CNT,MO/PANI [196]
RuO2 NP 70–100 Electrochemical deposition CNT/PANI/MO [257]

–, not available.
a
NP nanoparticle, NF nanoflakes, IC inner cavity of CNT, UL uniform layer.
b
Diameter for NP, NF and film thickness for UL.

crystalline form)NPs on the CNT’s sidewalls is realized
by in situ co-precipitation of Fe2+ and Fe3+ [185,197] or
in situ thermal decomposition process [194]. Subsequently,
a PANI layer is deposited by the in situ polymerization
of aniline using FeCl3 [193] or APS [194,195] as oxidant
to give CNT/Fe3 O4 /PANI composite. To prevent the nano-
structure of MWCNT/Fe3 O4 NPs from being destroyed, no
kinds of acids were introduced and FeCl3 (rather than APS)
was used as the oxidant in the second step [193]. Other
authors used acid conditions and APS as oxidant for the
in situ polymerization step but did not report such obser-
vation. For the Fe2+ /Fe3+ coprecipitation method, CNT were
functionalized with negative carboxylic groups which have
affinity with positive ferrous and ferric ions. After the addi-
tion of NH3 ·H2 O aqueous solution, Fe3 O4 NPs formed on the
surface of CNT (Fig. 29).
Wang et al. [195] used these ternary structures to immo-
bilize trypsin (see other applications for details). Zhang
et al. [194] prepared small (6 nm) and monodispersed
Fe3 O4 NPs (Fig. 29) using the thermal decomposition of
a mixture of ferric hydroxide oxide and oleic acid in the
presence of 1-octadecene. The surface of fabricated Fe3 O4
NPs was coated by a thin layer of oleic acid, which has
hydrophobic characteristic. In order to overcome the dif-
ficulty of hydrophobic Fe3 O4 NPs dispersing into the HCl
solution, the authors ingeniously turned the surface of NPs
Fig. 29. HRTEM images of Fe3 O4 NPs on CNT prepared by in situ thermal
decomposition process [194].
hydrophilic using 11-aminoundecanoic acid tetramethy-
lammonium salt to remove the oleic acid from the surface
of Fe3 O4 NPs [193,195].
Phang et al. [188] prepared nanorods/tubes hexanoic
acid (HA) doped PANI containing TiO2 NPs and CNT by an
in situ polymerization in water. CNT and TiO2 NPs exist in
the center of Ani/HA micelles during polymerization. Dur-
ing polymerization reaction, Ani/HA micelle without TiO2
or CNT, act as a soft templates in the formation of nano-
structure; Conversely, TiO2 or CNT as nucleus, act as a hard
template since they are insoluble in the solution.
The case of CNT/PANI incorporating MnO2 is interest-
ing because different shapes of MnO2 have been reported,
namely filling the inner cavity of CNT, as a uniform and thin
layer on CNT or as nanoflakes (Fig. 30).
It is noted that poly(4-styrenesulfonic acid), was used to
disperse MWCNT in water as well as to attract the positive
Mn2+ ions through electrostatic interactions and, thereby,
function as the template for the formed MnO2 nanostruc-
tures on MWCNT [198].
3.3. CNT/PANI graphene
A hierarchical film with coaxial CNT/PANI nanocables
uniformly sandwiched between graphene (GN) sheets has
been fabricated by flow-directed assembly from a complex
dispersion of graphite oxide (GO) and CNT/PANI [199]. Mix-
ing the GO and CNT/PANI suspensions (pH = 2.6) resulted
in coagulation after several hours, owing to the acid char-
acter of doped PANI which restrains the ionization of
the carboxylic acid and phenolic hydroxyl groups on the
GO sheets. A stable suspension of GO and CNT/PANI was
obtained when the pH of the mixture was adjusted to
4.5 (after several cycles of washing-centrifugation). The
GO/CNT/PANI precursor film was obtained by filtration,
reduced to GN by gas-based hydrazine followed by reoxi-
dation and redoping of the reduced PANI (leucoemeraldine
base) to obtain GN/CNT/PANI film (Fig. 31).
A novel electrochemical biosensor based on horseradish
peroxidase (HRP) induced deposition of PANI on the
designed graphene-CNT-nafion/gold–platinum alloy
nanoparticles modified glassy carbon electrode was
described by Sheng et al. [200] (Fig. 32).
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 729

Fig. 30. TEM images of CNT/PANI incorporating (a) MnO2 filling the inner cavity of CNT [297], (b) a uniform MnO2 layer on CNT [198] and (c) MnO2
nanoflakes [255]. Note in (a) that the filled MWCNT have a dark contrast, suggesting that the filling of MnO2 in the inner cavity of MWCNT was efficient
and very homogeneous.

Fig. 31. Preparation of PANI (ES form)–CNT graphene sheet [199].

4. Properties the same temperature range in air and in nitrogen [201].

4.1. Thermal stability
Thermogravimetric analysis (TGA) is one of the most
used methods for testing the thermal stability of compos-
ites.
Normally, MWCNT are stable in air up to 650 ◦ C and
become completely decomposed above 750 ◦ C. The first
mass loss (putting aside the water) in ES decomposi-
tion is the dopant release which converts ES to EB. This
step is not dependent on the atmosphere and occurs in
After the dedoping step, a steady decrease in mass occurs
which reveals the decomposition of PANI [202]. In air, the
decomposition of PANI is complete at 700 ◦ C while, in nitro-
gen, PANI is converted into nitrogen-containing carbon
[159,201].
The thermal oxidative decomposition of PANI in
MWCNT/PANI increases with the increase in MWCNT con-
tent of the composites [138,203]. The increased thermal
stability of MWCNT/PANI over that of the pure PANI was
explained by (i) the long conjugate ␲–␲ bond formed
between PANI and MWCNT [125] or by the absorption

Fig. 32. Scheme diagram of the H2 O2 biosensor based on enzyme-catalyzed deposition of PANI on the designed modified electrode [200].
730 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748

by the activated carbon nanotube surface of free radi-

cals generated during polymer decomposition [138]. The
degradative pathway in air of ES–CNT composites is com-
plex due to the dopant loss that partially overlaps with the
degradation of the PANI backbone. This is the reason why
ES is usually dedoped to EB before TGA measurement to
simplify the interpretation of TGA data [81]. It is notewor-
thy that during chemical deprotonation, the contacts of the
MWCNT and coating with EB break due to volume contrac-
tion. This leads to materials with lower thermal stability
at high temperatures than MWCNT/EB obtained by ther-
mal aging as volume contraction does not happen during
thermal deprotonation at high temperature [204].

4.2. Electrical properties

The effect of the percentage of MWCNT on the con-

ductivity of CNT/PANI composites was studied by several
authors [73,205]. For low fractions of CNT, the conductivity
is principally determined by the PANI as it is the main com-
ponent. The conductivity of ES based composites generally
increases with CNT content [203,205,206]. For example,
the conductivity of MWCNT/PANI composites prepared by
in situ emulsion polymerization increases from 0.8 × 10−3
to 6.6 × 10−2 S cm−1 when CNT content increases between
0.2 and 10 wt%[133]. It was proposed that the addition of
low content of MWCNT as 0.1 wt% leads to a random dis-
tribution of the fillers in the PANI matrix whereas at higher Fig. 33. The conductivity of carbon nanotubes mixed (a) or coated (b) with
contents, the fillers could form a percolation network protonated PANI [104].
and so serve as a “conducting bridge” between PANI-ES
conducting domains [206]. The increase of conductivity
EB can mediate the electron transfer over short distances
observed in the presence of CNT may also be attributed to
between the CNT by a tunneling mechanism of conduction,
the dopant effect or charge transfer process from PANI to
similarly to the ES form. SWCNT/PANI nanocomposites
CNT [206]. The same authors demonstrated that the electric
have higher electrical conductivity and Seebock coeffi-
conductivities at room temperature of PANI-ES containing
cient as compared to pure PANI [211]. Recently, it was
0.1 wt% of MWCNT are about 50% higher than that of PANI
found that the electrical properties of CNT/PANI can be
without MWCNT while an increase of 70% was reached at
tuned by changing the nature of CNT template [212]. The
1 wt% MWCNT. In comparison, the introduction of 1 wt%
MWCNT based composites are less conducting as com-
SWCNT can improve the conductivity of the composite to
pared to the SWCNT-containing series. In addition, the
more than twice than that of the PANI [105].
unoxidized CNT yield higher conductivity as compared
Konyushenko et al. [104] compared the conductivity of
to oxidized CNT. Unoxidized SWCNT (6.6%)/PANI are the
PANI coated CNT with the conductivity of MWCNT/PANI
highest conducting hybrid (530 S cm−1 ) and are nearly 650
mixtures (Fig. 33).
times more conducting than pristine PANI. The positive
For MWCNT/ES mixtures, the maximum conductivity,
effect of CNT on the conductivity of PANI was also indi-
7.7 S cm−1 was obtained at a 70 wt% CNT while a value of
rectly deduced by fluorescence analysis. Chakraborty et al.
25.4 S cm−1 for ES coated MWCNT was reached at the same
[213] compared the photoluminescence (PL) intensity of
MWCNT content. The later value is much higher than the
PANI, MWCNT/PANI, c-MWCNT/PANI and MWCNT-NH2 -
conductivity in the order of 10−1 S cm−1 reported for simi-
PANI samples. The presence of MWCNT influences the PL
lar composites [207,208] and in the same range than other
intensity of the different samples. The maximum enhance-
reported results [125,209,210]. The differences between
ment of intensity was observed for c-MWCNT/PANI and
the CNT/PANI mixture and PANI coated CNT is more evi-
could be explained by an enhancement of the ␲ electron
dent in the case of PANI EB. The percolation behavior was
mobility in the composite. This fact favors the formation of
more remarkable with MWCNT/EB mixture which exhibits
singlet excitons, which decayed radioactively to the ground
a percolation threshold at 4 wt% MWCNT. In EB coated
state resulting in an increase of PL.
CNT, the direct electrical contact between CNT is prevented
by the surface coating with an insulating polymer. This
is why a percolation threshold was not distinguishable. 4.3. Mechanical properties
Yet, the conductivity continuously increases with increas-
ing content of CNT and reaches 19.6 S cm−1 , a value not far Mechanical properties of high molecular weight
from the maximum value for ES coated MWCNT. It is sug- MWCNT/PANI composite films were investigated
gested that, when the thickness of EB coating decreases, [155,214]. An improvement of mechanical properties
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
of PANI with added CNT was observed. Physical charac-
terizations of the composites by tensile testing, dynamic
thermal mechanical analysis, and atomic force microscopy
measurements indicate that PANI containing 1% car-
bon nanotubes present higher thermal and mechanical
properties than neat PANI. Besides, the shear stress of
MWCNT/PANI increase with an increase in applied DC
electric field strength [136]. CNT/PANI fibers prepared
by wet-spinning method show a 150% increase in tensile
stress and a 110% increase in Young’s modulus with the
addition of 2% CNT [177]. A reduction in modulus and
strength after acid doping of PANI fibers is obtained; it
is related to the introduction of charges on the polymer
chain and counter-ions [169].
5. Applications of CNT/PANI
CNT/PANI composites present great interest for vari-
ous applications due to their easy synthesis, processability
and the possibility to combine the properties of CNT
(high mechanical strength, high conductivity and large
surface area) and the properties of PANI (wide range of
conductivity available, exceptional case of doping by oxida-
tion/protonation with insertion of anion, . . .) with synergic
effects.
5.1. Non-enzymatic sensors
The CNT doped PANI binary and ternary composites
have been successfully used to the detection of several
chemical components.
Ammonia. MWCNT/PANI was prepared by in situ poly-
merization for ammonia gas sensor applications [215]. The
sensing mechanism is governed by the deprotonation of
PANI ES by ammonia gas molecules to PANI EB, leading to
an increase of the electrical resistance. The introduction of
polar groups on the surface of MWCNT by the oxyfluori-
nation method highly improved response in detecting NH3
gas owing to the more uniform and thinner coating of PANI.
A sensor with good repeatability used in detecting ammo-
nia gas was developed by Chang et al. [183]. Upon exposure
to 200 ppm of NH3 , SWCNT/PANI synthesized in a H2 SO4
aqueous solution exhibit a sensitivity of about 4.2, higher
than those of neat PANI and SWCNT [216]. One drawback of
PANI-based NH3 gas sensor is the poor selectivity toward
NH3 among various gases which could deprotonate PANI.
Anthrax. A sensor for the diagnosis of Anthrax was
achieved by covalent immobilization of Anthrax protective
antigen PA, onto the surface of the MWCNT surface of an
acyl chloride functionalized MWCNT/PANI electrode [217].
Ascorbic acid. A Cu NPs/c-MWCNT/PANI ternary com-
posite modified Au electrode displayed higher electro-
catalytic activity to ascorbic acid oxidation than the
MWCNT/PANI binary composite modified electrode [218].
This non-enzymatic sensor has a detection limit of 1 ␮M
and its response is linear for up to 600 ␮M ascorbic acid
concentration.
Bisphenol A. The MWCNT/PANI nanorods modified pen-
cil graphite electrode showed a linear dynamic range
for bisphenol A detection from 1 ␮M to 400 ␮M, with a
detection limit of 10 nM and a sensitivity c.a. 2.5 and 1.4
731
times higher than the electrode modified with only PANI
nanorods, and MWCNT, respectively [219].
Celecoxib. A sensor for the adsorptive reduction of cele-
coxib was fabricated by electrochemically grafting PANI
chains onto amino-functionalized MWCNT over the sur-
face of ITO electrodes [220]. A linear calibration plot was
obtained covering the concentration range from 10 pM to
1 ␮M with a detection limit (10 pM) much higher than elec-
trodes using hanging mercury drop and other detection
techniques such as spectrophotometry, chromatography
and fluorimetric methods.
DNA. Yang et al. [221] described the integration of PANI
and MWCNT in a Chitosan CS film for fabricating elec-
trochemical biosensor with improved sensitivity toward
DNA detection. The MWCNT/PANI/CS composites were
prepared by simply dispersing MWCNT/PANI in an aque-
ous CS solution, followed by deposition on a carbon paste
electrode (CPE) surface. DNA was then immobilized on
CPE to give DNA/PANI-MWCNT/CS/CPE. This biosensor is
applied to the sensitive detection of the DNA specific
sequences of the transgenic genes in the genetically mod-
ified crops, such as the phosphinothricin acetyltransferase
gene and the terminator of nopaline synthase gene. The
DNA sensor could be regenerated eight times without
losing its sensitivity. More recently, biotinylated probe
DNA was immobilized onto electrochemically prepared
PANI-n/Fe3 O4 − /MWCNT/ITO electrode using biotin–avidin
interaction. It was shown that this genosensor can be used
as a platform for bacterial infectious disease (Neisseria gon-
orrhoeae) detection at concentration as low as 1 × 10−19 M
[222,223].
Dopamine. Tremendous efforts have been made to
detect biogenic amines, especially dopamine which could
potentially be used for molecular diagnosis of schizophre-
nia, Huntington and Parkinson’s disease.
Zheng et al. [224,225] have found that single-stranded
DNA (ss-DNA) can disperse bundled carbon nanotubes
in aqueous solution, resulting in a helical wrapping of
SWCNT by ss-DNA (ss-DNA/SWCNT) [85]. The prepara-
tion of poly(anilineboronic acid)/ss-DNA/SWCNT biosensor
consists to modify first a gold electrode with a self-
assembled monolayer of 2-amino-ethanethiol so that
the ss-DNA/SWCNT could adsorb onto the electrode.
Poly(anilineboronic acid) was then electrodeposited onto
the modified Au electrode.
The complexation between dopamine and
poly(anilineboronic acid) is illustrated in Fig. 34.
The high binding affinity between dopamine and
boronic acid can affect the electrochemistry of PANI. Differ-
ential pulse voltammograms of the composite in phosphate
buffer solution PBS showed an anodic current decrease pro-
portional to the concentration of dopamine introduced into
the electrochemical cell [226] (Fig. 34). It was hypothesized
that the conversion of the boronic acid to the boronate ester
complex along the PANI backbone interrupted the intra- or
inter-chain tetrahedral boron–nitrogen interactions. This
decreased the self-doping and therefore the electrochemi-
cal activity of the polymer in neutral solutions.
Formaldehyde. MWCNT doped PANI films show a
higher response for hydrogen gas in comparison to pure
PANI [227]. Based on the electrochemical activity of
732 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
Fig. 34. (a) Reaction between dopamine and poly(anilineboronic acid) (b) Differential pulse voltammograms of the composite in PBS and upon addition of
different concentrations of dopamine. Potential scan rate: 100 mV s−1 ; pulse amplitude: 50 mV; pulse width: 50 s [226].
formaldehyde with Pt electrocatalysts, Pt/MWCNT/PANI
electrodes have been developed by Jin et al. [179]
toward formaldehyde sensing. A good linear response from
1 × 10−9 to 1 × 10−3 M was obtained with a detection limit
of 4.6 × 10−11 M.
Heavy metals. MWCNT/PANI modified electrodes were
prepared for the detection of heavy metals traces. It was
reported that MWCNT/PANI coated glassy GCE had a bet-
ter performance than the bare GCE in the anodic stripping
analysis of lead trace in a 0.1 M acetate buffer solution
[228].
Hydrogen peroxide. The determination of hydrogen per-
oxide (H2 O2 ) plays an important role in environmental,
pharmaceutical, clinical, and industrial research.
A non-enzymatic H2 O2 sensor [229] was prepared by
electrodeposition in a room temperature ionic liquid of a
SWCNT/PANI film on a Pt electrode. The resulting sensor
was used to measure H2 O2 more than 50 times in a 0.05 mM
H2 O2 solution at pH 7.0.
H2 O2 sensors were also prepared by deposition of c-
MWCNT and Au NPs on the surface of an Au electrode
modified with an electrodeposited PANI layer. The Au NPs
dispersed on the surface of c-MWCNT might provide a large
available surface and so an enhancement of the electrocat-
alytic activity for H2 O2 electro-oxidation. It was suggested
that the response to H2 O2 may be due to the partial oxi-
dation of CNT by H2 O2 via a charge transfer mechanism
between CNT and H2 O2 molecules.
l-Phenylalanine. Recently, an electrochemical sensor for
sensitive l-phenylalanine detection was fabricated by com-
bining ␤-cyclodextrin (␤ CD) incorporated MWCNT with
imprinted sol–gel films on an electrodeposited PANI layer
modified carbon electrode (CE) (Fig. 35).
The response mechanism of the imprinted sensor was
based on the inclusion interaction of ␤ CD and molecular
recognition of the molecularly imprinted polymer (MIP) for
l-phenylalanine. A linear range from 0.5 ␮M to 0.1 mM has
been reported with a detection limit of 1 nM and an excel-
lent selectivity, emphasized by the strong discrimination
between l-phenylalanine and d-phenylalanine [230].
Nitrite. A MWCNT/PANI modified gold electrode was
found to exhibit enhanced electrocatalytic behavior to the
reduction of nitrite [92] because this reduction was medi-
ated by the leucoemeraldine/emeraldine redox transition.
A linear range from 5 ␮M to 15 mM has been observed with
a detection limit of 1 ␮M.
The characteristics of the non-enzymatic sensors are
summarized in Table 3.
5.2. Enzymatic sensors
Conducting CNT/PANI composites have received signif-
icant interest for the construction of various electrochemi-
cal enzymatic sensors. The immobilization of enzyme to an
electrode surface without its bioactivity being sacrificed is
a crucial step for the design of biosensors [231]. CNT could
effectively increase the amount of immobilized enzyme.
CNT also promoted electron-transfer reactions at a lower
potential and acted as an electrocatalyst whereas the major
effect of PANI on the biosensor is to act as a support for the
enzyme immobilization.
Covalent and non-covalent immobilization strategies
for the immobilization of the enzyme will be successively
discussed.
5.2.1. Covalent immobilization
Covalent immobilization approach has been frequently
used to avoid the leakage of the enzyme.
Ascorbic acid. An ascorbate biosensor was fabricated by
covalent immobilization of ascorbate oxidase (AsOx) onto
a c-MWCNT/PANI [232] layer electrochemically deposited
on the surface of an Au electrode.
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 733

Fig. 35. Preparation process of the MIP/␤-CD-MWCNT/PANI/CE electrochemical sensors for l-Phenylalanine [230].

Choline. Choline is an essential nutrient required by the
body for healthy cell membrane. Using a layer-by-layer
approach, assembled functionalized MWCNT and PANI
multilayer films were successfully used as choline biosen-
sor.
The choline biosensor was elaborated [95] by alterna-
tive deposition of a MWCNT dispersion in ethanol and
electrodeposition of PANI on a GC electrode. The electrode
was first modified with five alternative layers of MWCNT
and PANI, followed by the electrodeposition of three lay-
ers of PANI and finally, immobilization of choline oxidase
onto the electrode surface by crosslinking the enzyme with
bovine serum albumin through glutaraldehyde (GA).
Cholesterol. A cholesterol biosensor was constructed by
covalently immobilizing cholesterol oxidase ChOx using N-
ethyl-N (3-dimethylaminopropylcarbodiimide) (EDC) as
the coupling agent and N-hydroxysuccinimide as the acti-
vator onto PANI/c-MWCNT/ITO electrode (Fig. 36).
The biochemical reaction shows that MWCNT/PANI
accepts electrons from the reduced ChOx due to electron
hopping through MWCNT that mediate electrons transfer
via the reduction of PANI [233].

Table 3
Characteristics of the non-enzymatic sensors.

Tested molecule Sensor assembly Synthesis method Detection Response Sensitivity Stability Ref
CNT/PANI limit (␮M) time (s) (␮A ␮M−1 cm−2 ) (days)

Ammonia gas MWCNT/PANI In-situ 1a 5 – – [215]

polymerization
MWCNT/PANI/Au In-situ 0.638a 1–10b – – [183]
polymerization
Anthrax Peptidec /c-MWCNT/PANI/GCE EP 1.41 × 10−3 – 500 6 (60%) [217]
Ascorbic acid CuNPs/c-MWCNT/PANI/Au EP 1 – 1.05 120 (50%) [218]
Bisphenol A MWCNT/PANI/modified PGE EP 0.01 – – [219]
Celecoxib MWCNT/PANI/ITO EP 10−5 – – – [220]
DNA DNA/PANI-MWCNT/CS/CPE EP 2.7 × 10−7 – – 10 (92%) [221]
Dopamine PABA/ss-DNA/SWCNT/Au EP 6 × 10−4 – – - [226]
Formaldehyde Pt/PANI/MWCNT/choline/WGE EP 6 × 10−5 2b – 30 (13%) [179]
Heavy metals c-MWCNT/PANI/GCE Ex-situ – – – – [228]
Hydrogen peroxide SWCNT/PANI/Pt EP 1.2 4 – 30 (100%) [229]
l-Phenylalanine MIP/␤ CD-MWCNT/PANI/CE EP 10−3 3 719.2 × 103 30 (92%) [230]
Nitrite MWCNT/PANI/Au EP 1 – 8(85%) [92]

–, not available.
a
In ppm.
b
In minutes.
c
Peptide: HKHAHNYRLPASGGKK.
734 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748

Fig. 36. Schematic illustration of biochemical reaction of ChOx/PANI-c-MWCNT/ITO bioelectrode [233].

Glucose. Most glucose biosensors are based on the oxi-
dation or reduction of enzymatically produced H2 O2 . A
matrix for the immobilization of glucose oxidase (GOD)
and the catalytic materials for electro-oxidation or reduc-
tion of H2 O2 are necessary to construct a glucose biosensor.
Prussian Blue (PB) is an excellent catalyst for H2 O2 reduc-
tion at low potentials. PANI-PB composite was prepared by
the spontaneous redox reaction between aniline and ferric
chloride–potassium ferricyanide [234]. PANI-PB/MWCNT
modified GC electrode was the prepared by the spinning
method from a dispersion of PANI-PB and MWCNT in
dimethylformamide. GOD solution was immobilized onto
the PANI-PB/MWCNT electrode surface using glutaralde-
hyde as a crosslinker. An amperometric glucose biosensor
was fabricated using PANI and chitosan (CS)-coupled CNT
(CS-CNT) [235] as the signal amplifiers and GOD as the
glucose detector on a gold electrode (Fig. 37).
CS-CNT were covalently bonded to the PANI-modified
gold electrode using GA as a bifunctional linker while GOD
was covalently bonded to the pendant hydroxyl groups of
CS using 1,4-carbonyldiimidazole as a coupling agent.
A Pt/MWCNT/PANI ternary composite on a glassy car-
bon electrode was prepared by electrodeposition of Pt
nanoparticles (NPs) onto the surface of MWCNT/PANI com-
posite prepared by in situ polymerization [236]. GOD was
immobilized on the surface of Pt/MWCNT/PANI modified
electrode via covalent interactions with GA and adsorption
effect with Pt NPs.
Glutathione. A glutathione biosensor was prepared by
a covalent immobilization of GSHOx (through NH2 groups
on the surface of the enzyme and the free COOH groups
of c-MWCNT) on the surface of AgNPs/c-MWCNT/PANI/Au
electrode [237]. The following electrochemical reactions
were suggested to occur during the response measure-
ments:
2glutathione + O2 → GSHOxglutathionedisulfide + H2 O2
H2 O2 → O2 + 2e− + 2H+
The glutathione biosensor was employed for measure-
ment of glutathione content in hemolyzated erythrocyte.
Hydrogen peroxide. A covalent immobilization of
cytochrome c onto nickel oxide NPs/c-MWCNT/PANI com-
posite electrodeposited on Au electrode was reported for
the determination of H2 O2 [196]. This sensor showed an
enhanced selectivity for H2 O2 in the presence of interfer-
ence by dopamine, ascorbic acid, l-cysteine and glucose.
Oxalate. An electrochemical oxalate biosensor was con-
structed by covalent immobilization of oxalate oxidase
(OxOx) on a c-MWCNT/PANI composite film electrode-
posited on Pt electrode. OxOx was immobilized on the

Fig. 37. Process of fabrication of the Au-g-PANI-c-(CS-CNT)-GOD [235].

 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
c-MWCNT/PANI surfaces through amide bonds created
between the free COOH groups of c-MWCNT/PANI films
and the NH2 groups of the enzyme surface, by using EDC
and N-hydroxy succinimide chemistry [238].
Pesticides. An electrochemical biosensor was prepared
for the determination of methyl parathion and chlorpyrifos.
Self-assembled monolayers of SWCNT wrapped by thiol
terminated single strand oligonucleotide on gold were used
for AChE enzyme immobilization using GA [239], in PANI
matrix (Fig. 38).
MP and CP inhibit the AChE-acetylcholine reaction by
the blocking of serine hydroxyl groups of AChE with cova-
lently bound phosphate group of the pesticide. The reaction
between AChE and acetylcholine generate pH changes in
their local environments through their byproduct acetic
acid, resulting in protonation of PANI and, consequently,
changes in the redox activity of the electrode.
Phenolic compounds. A biosensor for determination
of phenolic compounds was fabricated by immobilizing
covalently a laccase onto a NiNPs/MWCNT/PANI/Au elec-
trode. Cyclic voltammograms showed an increasing in both
reduction and oxidation current with the addition of gua-
iacol, which indicate the improved catalytic properties of
modified electrode to the reduction of guaiacol [240].
Sulfite. A sulfite biosensor based on AuNPs/chitosan onto
the c-MWCNT/PANI/Au electrode was developed by Rawal
et al. [241]. The following electrochemical reactions were
suggested to occur during the current response measure-
ments of the sulfite biosensor:
SOx
Sulfite + O2 + H2 O−→Sulfate + H2 O2
0.47 V
H2 O2 −→ 2H+ + O2 2e−
Au NPs CS
2e− −→ ⁄ Au electrode
c-MWCNT /PANI
Uric acid. Biosensors were constructed to determinate
the uric acid level in serum by immobilizing uricase. Deter-
mination of uric acid was performed by electrochemical
oxidation of enzymatically generated H2 O2 onto PANI/c-
MWCNT deposited on ITO-coated glass plate through
carbonamide linkage [242] or onto a CS network using GA
as a coupling agent, on a PB/c-MWCNT/PANI/Au modified
electrode [243].
Xanthine. Devi et al. [244] prepared a xanthine biosen-
sor by covalently immobilizing xanthine oxidase (XOD)
using EDC onto c-MWCNT/PANI/Pt electrodes. The electro-
chemical reactions involved in response measurement of
xanthine biosensor are given below.
XOD on Hybrid film
Xanthine + O2 + H2 O −→ Uric acid + H2 O2
0.4 V
H2 O2 −→2H+ + O2 2e−
c-MWCNT
2e− −→ ⁄PANI Pt electrode
The produced biosensor is applied to determine xanthine
in fish meat, which is an indicator of the fish freshness.
The characteristics of the covalent enzyme immobiliza-
tion sensors are summarized in Table 4.
735
5.2.2. Non-covalent immobilization
Non-covalent approaches have been also investigated
since the cross-linking agents used in covalent strategies
can frequently bond themselves to the active sites of the
enzymes, thus inhibiting its activity.
Glucose. A SPAN based interconnected network, SPAN-
NW, provided a unique environment for the immobiliza-
tion of GOD [245]. The SPAN-MWCNT-g-SPAN-NW/GOD
electrode showed direct electron transfer for GOD to the
electrode.
The characteristics of the non-covalent enzyme immo-
bilization sensors are summarized in Table 5.
Hydrogen peroxide. A new strategy reaction was adopted
to immobilize cytochrome c (cyt c) onto PANI grafted
MWCNT [246] PANI units were oxidized at an applied
potential of +0.8 V into the pernigraniline form to acquire
positive charges that effectively immobilize negatively
charged cyt c. MWCNT-g-PG-cyt c electrode exhibited
bioelectrocatalytic activity toward hydrogen peroxide.
The same approach using electrostatic interactions was
reported for the immobilization of the positively charged
horseradish peroxidase, HRP, onto negatively charged PANI
films doped with MWCNT [162].
Pesticides. Cesarino et al. [231] have developed
MWCNT/PANI films prepared by electropolymerization on
GC for the immobilization of AChE as enzyme on the
surface. The developed GC/MWCNT/PANI/AChE biosensor
allowed the determination of carbaryl by square wave
voltammetry. The AChE biosensor is based on the inhi-
bition of the activity of the enzyme by carbaryl. Such
inhibition was evaluated by the decrease in the oxidation
peak associated to the formation of dithio-bischoline from
the enzymatic reaction between AChE and acetylcholine
chloride. The MWCNT were found to improve the electro-
chemical response of the enzymatic product and acted as
an electrocatalyst. It is noteworthy that such biosensor do
not use any crosslinking agent as the three dimensional
structure allows the adsorption of the enzyme inside the
composite cavities and promotes the interactions between
carboxyl groups of the enzyme and amino groups present
in PANI.
Du et al. [247] proposed a PPy and PANI copolymer
doped with MWCNT. The electrochemically formed copoly-
mers were synthesized by electropolymerization of aniline
on a PPy/MWCNT modified electrode leading to a porous
and homogeneous morphology.
This structure provides an ideal size to entrap enzyme
molecules not only thanks to the high surface area but also
with the favorable microenvironment around the enzyme
molecules which permit a stabilization of their biological
activity and prevent them from leaking out of the interface.
Moreover, the method for preparation did not involve the
use of any cytotoxic agent. The obtained composite was
tested for screening of organophosphates (OPs) exposure.
5.3. Actuators
Actuators directly convert an electrical energy to a
mechanical energy. In a CNT/PANI actuator, PANI will
contribute to a high actuation strain and the CNT com-
ponent to a high modulus. CNT/PANI composites showed
 736
Table 4
Characteristics of the covalent enzyme immobilization sensors.

Tested Sensor assembly Synthesis method Immobilized Coupling agent Response Detection Sensitivity Linear range (␮M) Stabilitya Ref
molecule CNT/PANI enzyme time (s) limit (␮M) (␮A mM−1 cm−2 )

C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748

Choline ChOd{c- EP ChOd GA 3 0.3 – 1–2000 30 (80%) [95]
MWCNT/PANI}5 /{PANI}3 /GC
Cholesterol ChOx/PANI/c-MWCNT/ITO EPh ChOx EDC 10 – 68 × 105 1.3 × 10−3 –1.3 × 10−2 90 (95%) [233]
Xanthine XOD/c-MWCNT/PANI/Pt EP XOD EDC 4 0.6 – 0.6–58 200 (50%) [244]
Pesticidesb AChE/PANI/ssDNA-SWCNT/Au EP AChE GA – 10−18 – – 5 (86%) [239]
Glucose GOD/(CS-CNT)/PANI/Au Ex situ GOD CDI 8–10 0.1 × 10−3 21 10−3 –2 × 10−2 20 (87%) [235]
GOD/PANI-PB/c-MWCNT Spin method GOD GA, Nafion 15 0.01 × 10−3 15.36 10−3 to ∼10−1 30 (90%) [234]
GOD/Pt/MWCNT/PANI/GCE EP GOD GA 5 1.0 16.1c 3 × 10−6 –8.2 × 10−3 48 (90%) [236]
Uric acid Uricase/PBNPs/c- EP Uricase CS-GA 4 5 – 5 × 10−6 –8 × 10−2 210 (63%) [243]
MWCNT/PANI/Au
Ascorbic acid AsOx/c-MWCNT/PANI/Au EP AsOx GA 2 0.9 – 2–206 – [232]
Oxalate OxOx/c-MWCNT/PANI/Pt EP OxOx EDC, NHS 5 3 0.0113c 8.4–272 100 (50%) [238]
Glutathione AgNPs/c-MWCNT/PANI/Au Ex situ GSHOx Amide bondd 4 0.3 477c 0.3–3500 [237]
H2 O2 NiO/c-MWCNT/PANI/Au EP Cyt c Amide bondd – 0.2 3.3 × 103 3–700 60 (85%) [196]
Phenolic Ni NPs/c-MWCNT/PANI/Au EP Laccase Amide bondd 8 0.05 0.694 0.1–500 120 (85%) [240]
com-
pounds
Sulfite Au NPs/chitosan/c- EP Sulfite oxidase Amide bondd 3 0.5 – 0.75–400 90 (70%) [241]
MWCNT/PANI/Au

–, not available
a
Remained activity (in %) after a definite time in days at 4 ◦ C.
b
Parathion and chlorpyrifos.
c
In ␮A mM−1 .
d
Amide bonds formed by reaction between COOH groups of c-MWCNT and NH2 groups of enzyme.
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 737

Fig. 38. Schematic representation of biosensor fabrication and its functions. Step 1–SWCNT wrapping with thiol terminated ssDNA; Step 2–ssDNA
wrapped SWCNT self assembled on gold electrode; Step 3–controlled electrochemical polymerization of aniline on the Au/ssDNA–SWCNT layers; Step
4–immobilization of AChE enzyme by glutaraldehyde; Step 5–pesticide sensing mechanism of Au/ssDNA–SWCNT/PANI/AChE [239].

significantly higher actuation strain (0.2–0.5%) compared
with pure CNT (0.06%) [248]. The addition of CNT into
PANI fibers allowed significant improvements in their elec-
troactivity resulting in an enhancement of the actuation
performance. With the same goal, Spinks et al. [249] stud-
ied the coating of PPy fibers with CNT/PANI (EB) on and
observed an improvement of the electrical conductivity.
Co-spun fibers of a chitosan hydrogel and PANI exhibit
independent pH and electrochemical actuation responses,
while the addition of SWCNT improved the conductivity
and mechanical strength of the fibers.
5.4. Capacitors
The electrochemical capacitors, also called supercapac-
itors or ultracapacitors, possess much higher capacitance
(∼105 times) than those achievable with normal capaci-
tors and can operate at substantially higher specific power
than batteries due to the cyclic redox capability. The mech-
anism for charge storage in electrochemical capacitors is
based on the ion absorption of the electrical double layer at
the electrode and electrolyte interface for electrochemical
double layer capacitors or on fast and reversible redox reac-
tions of metal oxides transitions or of electrical conductive
polymers for pseudo-capacitors [250].
Since 2006, several binary [81,251–253] and ternary
CNT/PANI [198,199,254–257] composites have been pre-
pared for electrochemical capacitive energy storage
applications. The larger specific capacitance (SC) in these
composite films compared to the SC values found for pure
PANI films was generally related to the strong interaction
between PANI and CNT, as well as the doping effect of CNT
on PANI films. Furthermore, the addition of CNT to PANI
will preserve PANI from mechanical changes (shrinkage
and breaking) increasing the cyclic stability of the superca-
pacitor.
5.4.1. Binary composite capacitors
Gupta and Miura [258] were the first to propose
that SWCNT/PANI composites can be effectively used as
electrodes for the supercapacitors, the highest specific
capacitance (SC) value of 463 F g−1 was obtained for 27 wt%
CNT.
Zhou et al. [120] obtained SC values of 312 F g−1 for com-
posites with a SWCNT content of 8 wt%.
SWCNT present more excellent electronic properties
than MWCNT but SWCNT are more difficult to purify and
have a higher cost than MWCNT. Therefore, MWCNT are
more convenient for the wide applications in compos-
ite materials. In this optic, Dong et al. [251] reported SC
values up to 328 F g−1 for PANI with 25 wt% of MWCNT
obtained by a chemical oxidative polymerization process.
Later, Zhang et al. [259] have studied the effect of the addi-
tion of CNT on the supercapacitive behaviors of PANI films
prepared by in situ electrochemical polymerization of an
aniline solution containing different CNT contents by CV,
738 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748

charge–discharge tests, and AC impedance spectroscopy.

Higher specific capacitance, better power characteristics,
better cyclic stability, and so more promising properties

[231]
[247]

[246]
[162]

[245]
[302]
[200]
for supercapacitors were obtained for CNT/PANI film elec-
Ref

trodes in comparison to pure PANI film electrodes. The

presence of only 0.8 wt% MWCNT in PANI layers allow the
formation of a core–shell nanowires microstructure with a
Stabilitya

40 (88%)

30 (92%)
fiber diameter of about 100 nm and SC values of 500 F g−1 .
PANI electrodeposited on a vertically aligned CNT array
60
30

10

–
(CNTA) framework leaded to a CNTA/PANI composite
with superior capacitive performances, including high SC
0.5–1.5 × 103

(1030 F g−1 ), superior rate capability (95% capacity reten-

0–9 × 103
tion at 118 A g−1 ) and high stability (5.5% capacity loss after
Range of

9.9–49.6
(␮A mM−1 cm−2 ) linearity

0.5–102
86–104
0.2–19
(␮M)

5000 cycles) [260]. These characteristics are related to the

geometry of the composite electrode with a hierarchically
–

porous structure, i.e. a tube-covering-tube nanostructure.

The thickness of the PANI layer played a crucial role
Sensitivity

in determining the specific capacitance of the compos-

ites. A maximum SC of 560 F g−1 was achieved for a
194.9
156.7
32.2b

4.34b
529

MWCNT/PANI composites with 66 wt% PANI [260] while

–
–

sulfonated MWCNT modified PANI nanorods exhibited a

maximum SC of 515.2 F g−1 at the 76.4 wt% PANI [261,262].
limit (␮M)

Recently, the pseudocapacitive properties of the LB, ES

4.6 × 10−3
1.0 × 10−3
Detection

and PB forms of PANI in MWCNT/PANI composite elec-

0.17

0.11
300

trodes were studied [252]. LB/MWCNT and PB/MWCNT

0.2
86

powders were prepared by chemical reduction (using

phenyl hydrazine) and chemical oxidation (using APS
solution), respectively, without changing the morphology
Response

of PANI.MWCNT/PANI electrodes showed specific capaci-

time (s)

tances of 217 F g−1 , 328 F g−1 and 139 F g−1 at 5 mV s−1 for
2.9

12
–
–

5
–

the LB, ES and PB, respectively. EIS measurements were

Electrostatic interactions between negatively charged c-MWCNT/PANI and positively charged HRP.

made using a cavity-microelectrode. For PB/MWCNT, the

45◦ Warburg line is absent. This line is attributed to the
ion (SO4 2− ) diffusion in the PANI layer on the MWCNT sug-
Immobilized

gesting that the electrochemical reaction was limited to the

enzyme

surface layer of PANI in the PB/MWCNT composites. This

AChE
AChE

HRPc
Cyt c

GOD
HRP
HRP

explains the low SC value for PB.

It could be underlined that the construction of flexible
sheets of supercapacitors composed of PANI and MWCNT
has been also demonstrated [263,264].
Synthesis method
Characteristics of the non-covalent enzyme immobilization sensors.

5.4.2. Ternary composite capacitors

CNT/PANI

Conducting polymers suffer from cracks or breaking

Remained activity (in %) after a definite time in days at 4 ◦ C.
Ex situ

In situ

during cycling because of volumetric changes during the

ECD
ECD
EP
EP

EP

doping/dedoping process. CNT suffer from low specific

capacitance (5–200 F g−1 ) [265] while transition metal
oxides suffer from poor intrinsic electronic conductivity
and un-optimized morphology. The combination of CNT,
HRP/PANI/c-MWCNT/Au
Cyt c/MWCNT/PANI/ITO
AChE/MWCNT/PANI/GC

GOD/MWCNT-SPANI/Pt
HRP/MWCNT/PANI/GC

PANI and metal oxide in composite electrodes are believed

PANI/HRP/GE-CNT-

to alleviate the above drawbacks (disadvantages) inherent

PPy/MWCNT/GCE
Sensor assembly

to the individual (single) components.

Nafion/AuPt
AChE/PANI-

Representative examples for the preparation of ternary

CNT/PANI composites used for electrochemical energy
NPs/GC

storage applications are shown in Fig. 39.

Recently, a hierarchical film with coaxial CNT/PANI
nanocables uniformly sandwiched between GN sheets
In ␮A mM−1 .

showed high electrochemical capacitance (569 F g−1 ), good

–, not available.

rate capability and excellent electrochemical stability (4%

-Carbaryl
molecule

Pesticide

Glucose

capacity loss after 5000 cycles).

Tested
Table 5

H2 O2
H2 O2
H2 O2
H2 O2
-OPs

So far, the highest value of capacitance for CNT/PANI

composites is 1030 F g−1 [266] which is still far lower
a

c
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 739

PANI MnO2 nanoflakes

M M M
MWNT 1) PSS 1) Mn(CH3COO)2

MWNT

MWNT
W W W 330 F g-1 (0.5 M Na2SO4)
N 2) aniline, APS N 2) KMnO4 N
T T T

RuO2 parcles
M RuCl3 xH2O,
MWNT

1) aniline, HClO4, APS 0.01 M HCl,0.1 M KCl

W 441 F g-1 (1M H2SO4)
N 2) Cast of MWNT-PANI icath=5 mA cm-2
T slurry in NMP on Pt foil

Pt MWNT-PANI film

PANI
MnO2
M M Aniline, M
1) PSS
MWNT

MWNT

MWNT
APTS sodium salt
W W W 384 F g-1 (0.5M H2SO4 - 0.5M Na2SO4)
APS
N 2) MnSO4.H2O, H2O2 N N
T T T

PANI
MnO2
M M M
KMnO4 Aniline
MWNT

MWNT

MWNT

W W W 350 F g-1 (0.5M Na2SO4)

APS
N Citric acid N N
T T T

Ag Ag Ag Ag PANI
M M M
AgNO3 Aniline, APS
MWNT

MWNT

MWNT

Ag Ag
W W Ag
W Ag 205 F g-1 (1M H2SO4)

N Hydrazine Ag N Ag Ag N Ag

T Ag
T Ag Ag
T Ag

Fig. 39. Preparation of CNT/PANI ternary composites for electrochemical energy storage applications. The mass specific capacitance and electrolyte are
reported in each case.

than the value of 5000 F g−1 reported for the commercially
supercapacitors based on activated carbon.
5.5. Fuel cells
CNT/PANI composites have been used as efficient elec-
trocatalytic materials in fuel cell reactions. An enhanced
catalytic activity for formic acid [84], methanol [267] and
formaldehyde [268] electrooxidation with CNT/PANI hosts
compared to PANI hosts was reported. As example, a
PANI-grafted MWCNT modified glassy carbon electrode has
shown a 610 mV more positive current onset potential for
oxygen reduction and a 20-fold enhancement in ampero-
metric current [77].
Many studies use CNT/PANI (pristine [187,267,268] or
functionalized [84]) as support matrix for dispersing noble
metal catalyst nanoparticles. The authors explained the
higher dispersion of nanoparticles in CNT/PANI supports
by an increased porosity and an enhanced electrical con-
ductivity thanks to CNT.
Microbial fuel cells (MFCs) permit the direct conversion
of organic and inorganic matter to electricity using bacteria
as catalysts to the oxidation. To improve the power out-
put of MFCs, research has mainly focused on the cathode
modification and the optimization of bacteria inoculums
[93,269,270].
The anode is also an important actor of the MFC perfor-
mance and is often a limiting factor for a high power output.
Thus, Qiao et al. [271] evaluated a CNT/PANI composite as
an anode material for high-power MFCs. The electrocat-
alytic activity was improved by the cumulating advantages
of both components. CNT provide high surface area and
enhanced electronic conductivity capability leading to a
considerable increase of the electrochemical activity of the
anode reaction, and so a higher power output while PANI
supports the electron transfer through a continuous matrix.
740 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
5.6. Electronic devices
Ramamurthy et al. [272] fabricated metal semicon-
ductor devices composed of high molecular weight PANI
and various weight percentages of SWCNT using solution
processing. SWCNT/PANI composites present a conductiv-
ity and a current level which significantly increase with
SWCNT content in the composite. Current–voltage (I–V)
characteristics of these devices plotted on a log–log scale
showed two distinct power law regions with different
exponents. In the lower voltage range, the charge trans-
port mechanism is governed by Ohm’s law whereas in the
higher voltage range, the charge transport mechanism is
consistent with space charge limited (SCL) emission in the
presence of shallow traps. The critical voltage (Vc ), which
characterizes the onset of SCL conduction, was found to
decrease with increasing SWCNT concentration. The ohmic
characteristics obtained suggest that the SWCNT/PANI
composite is near its percolation threshold at a SWCNT
concentration of around 10 wt%. This fraction could be con-
sidered as an upper limit to the SWCNT concentration for
semiconductor application. These initial results indicate
that with further improvements in material consistency,
the SWCNT/PANI composite materials can be used to fab-
ricate organic electronic devices leading to many useful
applications in microelectronics.
A write-once read-many-times memory device com-
posed of two layers of electroactive polymers sandwiched
between an aluminum electrode and an ITO electrode was
fabricated by Li et al. [273] The electroactive polymer
bilayer consisted of a conjugated copolymer film of 9,9-
dihexylfluorene and Eu-complexed benzoate (P6FBEu) and
a composite film of soluble self-aligned CNT/PANI.
5.7. Electromagnetic waves absorption
MWCNT/PANI composites have found recently applica-
tions as microwaves absorber due to the combination of
their magnetic and dielectric properties. The electromag-
netic waves absorption requires specific materials with
tunable thickness and high conductivity, permittivity and
permeability parameters. Zhao et al. [159] investigated
the microwave permittivity of the MWCNT/PANI compos-
ites in the frequency range of 2–18 GHz. The real part (ε )
and imaginary part (ε ) of the complex permittivity are
small at low frequencies, which make it easy to match
the impedance of free-space in the design of microwave
absorbing materials. They measured a high dissipation fac-
tor tan ı (ε /ε ) at low frequencies suggesting that these
composites could easily find application as microwave
absorbent. Ting et al. [274] prepared MWCNT/PANI by
in situ polymerization and studied the microwave absorb-
ing properties of this composite in an epoxy resin in the
frequency range 2–40 GHz. The complex permittivity and
permeability of the materials were increased thanks to
the incorporation of PANI in the MWCNT-epoxy system.
The enhanced microwave absorption properties (below
−10 dB) which is mostly due to the increase of the dielectric
loss of the composite materials can be tuned by the PANI
content in the composite. The sample thickness allows
tuning the intensity and the position of the frequency
maximum reflexion loss. Yun et al. [275,276], which pre-
pared PANI-coated MWCNT by in situ polymerization,
controlled the thickness of the PANI coating thanks to the
oxyfluorination of the MWCNT surface. An oxyfluorina-
tion with a higher oxygen content led to more hydrophilic
groups on the MWCNT surfaces and so to a higher affinity
between PANI and MWCNT. This resulted in an improve-
ment of the uniformity of the PANI coating on the MWCNT
surfaces. The authors showed that this uniformity is essen-
tial for the shielding properties and that the sample with
the highest oxyfluorination level presents the highest real
and imaginary permittivities. These factors lead to higher
electromagnetic shielding properties. A mean reduction of
47 dB was measured in the 900–3000 MHz frequencies for
the composites prepared with the most oxidized MWCNT.
That is about 12 times higher than the composites prepared
without any oxidation of the MWCNT.
5.8. Depollution/extraction
MWCNT/PANI composites were promising candidates
for cost-effective water decontamination of heavy metal
or radionuclide due to (i) the high sorption capacity and
regeneration features of MWCNT and (ii) the magnetic
properties of PANI. In this optic, Sheng et al. [277] studied
the sequestration capacity of 64 Cu(II) onto MWCNT/PANI
composites prepared by a plasma induced grafting tech-
nique as a function of pH, ionic strength and natural
organic matter concentrations. The sorption of Cu (II) was
not affected by the ionic force whereas they observed an
increase of the sorption from 0% to 100% with increasing
pH from 3 to 7; the thermodynamic data revealed that
the sorption reaction is spontaneous and endothermic and
enhanced at higher temperature. The presence of natural
organic matter depends on the pH value. At low pH, the
coexistent natural organic matter enhanced Cu(II) sorp-
tion whereas at high pH (pH > 7.5), the opposite effect was
observed.
The organic [152] and heavy metal [153] pollution
cleanup in the nature was investigated by Shao et al.
MWCNT/PANI have shown a very high adsorption capacity
in the removal of aniline, phenol and Pb(II) from aqueous
solutions (waste water, . . .). Due to the magnetic property
of PANI, MWCNT/PANI composites can be separated and
recovered from solution by simple magnetic separation.
MWCNT/PANI have also found application as coating
for the fabrication of solid phase microextraction probes
for the extraction of chemical substances of organic sol-
vents. Khajeamiri [278] electrodeposited PANI coating and
MWCNT/PANI coating on platinum wire surface using
cyclic voltammetry technique and studied the capabil-
ity of these probes to extract palmitic and oleic acid
from chloroform. Gas chromatography-mass spectrometry
experiments showed that the amount of extracted acid was
increased about 6 and 12 times thanks to the incorporation
of MWCNT on the PANI coating of the probes. This increase
of the absorbing capability was justified by an increase of
the surface area due to the modification of the polymer
structure in presence of MWCNT.
CNT/PANI composites synthesized by chemical oxida-
tion were also used successfully for bromated reduction.
 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748 741

The electrochemical reduction of bromated occurred

while polyaniline transformed from emeraldine into leu-
coemeraldine in acid solution. The CNT/PANI electrodes
displayed high electrocatalytic activity as proved by the
very small reactive energy of bromate (10.98 kJ/mol)
[279].
SWCNT/PANI composites synthesized by in situ poly-
merization were used for electrode fabrication by Yan
et al. [280]. These electrodes showed a high electrosorption
capacity and an easy regeneration and recyclability. The
salt removal efficiency of these electrodes was improved
by 12% compared to that of the SWCNT electrodes.

5.9. Electrochromic devices

PANI is one of the most used coloring electrochromic

polymers thanks to its multicolor electrochromism in the
visible region. Its use for electrochromic device applica-
tions would be enlarged if higher optical contrast and
higher kinetics could be achieved. In order to increase
the electrochromic contrast, Xiong et al. [281] synthe-
sized hybrid materials composed of PANI grafted SWCNT
uniformly dispersed in a PSS/PANI matrix. The addition
of PSS allows having a water-processable polymer. It
was reported that the hybrid materials present a charge
transfer resistances of only 20% of those of PANI/PSS at
+1.5 and −1.5 V with only 0.8% of SWCNT. This enhance-
ment of the electron transport leads to an increase of the
electrochromic contrast from 0.34 for PANI to 0.47 for
SWCNT/PANI.
5.10. CNT/PANI with optical activity
It is well known that the addition of chiral acids trans-
forms EB into the corresponding ES, whose backbone then
adopts a chiral structure which is responsible for its opti-
cal activity. The fabrication of optically active CNT/PANI
conducting composites by chemistry [282–284] and elec-
trochemistry [284,285] methods has been reported. These
composites were aimed at developing conducting com-
posite membranes in chiral separation and novel chiral
electrodes for asymmetric electrosynthesis. The stere-
oselectivity of the chemically prepared composites was
preserved although somewhat reduced compared to that
of pure polymer, which was attributed to large amount of
CNT (10–50 wt%) [282]. The optical activity of electrode-
posited optically active composite films can be tuned by
the selection of either the electrode material or nanotube
content in the electrolyte. A very low content of nanotubes
in the electrolyte can increase the “enantiomeric purity”
of the composite films [94]. (S)-(+)-10-camphorsulfonic
acid (HCSA) doped MWCNT/PANI composite films showed
fibrous structures related to “free” PANI and dendritic
structures mediated by the presence of CNT (Fig. 40).
It was assumed that optical activity was due to free poly-
mer and polymer loosely adsorbed onto nanotube while
PANI strongly interacting with the nanotubes surface does
not contribute to the optical activity (Fig. 41) [283].
Fig. 40. Optical micrograph image of thin film of optically active HCSA
doped PANI/MWCNT composites [94].
5.11. Other applications
Wang et al. [195] immobilized trypsin on Fe3 O4 /carbon
nanotube coated with PANI to improve protein digestion.
The produced magnetic biomaterial can digest within 5 min
bovine serum albumin, myoglobin and lysozyme and the
digest fragments were observed in the MS spectra.
Schottky diodes fabricated [286] using high molecular
weight PANI and MWCNT composites can produce current
levels of significantly higher magnitude than pure PANI
devices.
Photovoltaic textile structure composed of PANI and
CNT materials has been investigated [287]. Their good flex-
ibility, make them suitable for a wide range of flexible
energy converter devices [288].
CNT/PANI composites have already found applications
as printable conductors for thermal imaging techniques
[289,290].
Karim et al. [291] prepared successfully dye-
sensitized solar cells with an efficiency of 3,15% by
using MWCNT/PANI composites as ionic liquid-based
electrolyte instead of the conventional iodine elec-
trolytes. MWCNT/PANI nanoparticles allow diminishing
the charge diffusion length and serve as the catalyst for
electrochemical reduction of I3 − .
« loose »
Nanotube
« free »
« strong
Fig. 41. Strong, loose, and free refer to polymer adsorption levels onto
nanotube surface [283].
742 C. Oueiny et al. / Progress in Polymer Science 39 (2014) 707–748
6. Conclusions and challenges
In this review, we have provided a general view about
the recent evolution in CNT/PANI nanocomposites field.
CNT/PANI binary composites are synthesized by both
chemical and electrochemical methods. Many papers in
the literature are focused on the chemical processing as
it is more versatile than the electrochemical route. When
chemical methods are used, the main challenge is still to
obtain processable CNT/ES composites. Several strategies
for overcoming these difficulties have been highlighted
in this review. Stable dispersions of CNT/ES composites
in organic medium (NMP, THF) can be prepared by post
doping method, inverse emulsion polymerization or ex
situ polymerization, as representative examples. Stable
water dispersions of CNT/ES can be obtained by sulfona-
tion of aromatic rings of a preformed CNT/PANI composite,
micelle–CNT hybrid template directed synthesis, inter-
facial polymerization, covalent functionalization of CNT
with a water soluble polymer or electrostatic interactions
between two oppositely charged ES and CNT aqueous
colloids (two latter methods are ex situ polymerization
routes).
From the literature review, it is evident that control of
CNT functionality is the key to improve dispersion of the
nanotubes in the liquid (aniline, solvent) and consequently
in the CNT/PANI composite. It also helps to direct the for-
mation of PANI chains at the surface of CNT instead of bulk
PANI by promoting ␲-stacking (with non-functionalized
CNT), electrostatic or covalent interactions between PANI
and CNT.
CNT/PANI ternary composites incorporating noble
metal nanoparticles and metal oxide have been used in a
large number of potential applications which have been
discussed in this review. It is underlined that CNT/PANI is
generally processed as a film on a metallic substrate in view
of the target applications. This is why the electrochemical
route is generally preferred over the chemical route. The
recent progress in CNT functionalization chemistry [292]
should help to improve the tuning of CNT/PANI interfacial
properties, and, more important, to better understand the
role of CNT/PANI interface in the macroscopic properties
of the composites. The heterogeneous nature of CNT also
constitutes a major drawback for the future development
of CNT/PANI composites. CNT materials produced by cur-
rent methods are composed of a multitude of subtypes that
differ in length, diameter, and chirality, along with different
amount of impurities (residual catalyst and non-nanotube
carbonaceous impurities) and structural defects. The recent
advances in the synthesis and purification of CNT [201,293],
will certainly give a better understanding of these mate-
rials and, consequently, will increase their usefulness in
such applications as sensors or capacitors. The control of
CNT characteristics in CNT/PANI composites is definitely
an important area of investigation in the future.
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