Inorganic Chemistry Communications 138 (2022) 109276

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Inorganic Chemistry Communications

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

Surface functionalization of carbon nanotubes via plasma discharge:

A review
Hamideh Hosseini *, Mohammad Ghaffarzadeh *
Chemistry and Chemical Engineering Research Center of Iran (CCERCI), PO Box 14335-186, Teheran, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: The use of carbon nanotubes in a wide range of academic and industrial fields has received considerable
Carbon nanotubes attention due to their uniqueness in structures and properties. Despite these advantages, there are still some
Surface modification significant challenges and drawbacks such as insolubility which can have negative impacts on the application
Non-thermal plasma
process. The introduction of functional groups on the surface of carbon nanotube can overcome this obstacle.
Atmospheric pressure
Plasma treatment
Plasma functionalization can be a preferred method in comparison to other ones as a quick and relatively non-
Functional group destructive, as well as environmentally-friendly method for the surface functionalization of carbon nanotubes.
This review presents a brief introduction to the types, properties, and functionalization methods of carbon
nanotubes for a better understanding. The focus of this review is on the modification of carbon nanotubes
through different types of plasma functionalization methods, notably plasmas that operate at an ambient tem­
perature and atmospheric pressure, to improve their properties. It also investigates the results obtained from
analytical methods for plasma treated carbon nanotubes.

1. Introduction
1.1. Carbon nanotubes (CNTs)
Carbon nanotubes are one of the crystalline allotropes of carbon.
Indeed, carbon nanotubes can be thought of as thin sheets of graphene
(graphite monolayer) that are tubular with open or closed ends. In other
words, the arrangement of wall carbon atoms in the cylindrical structure
of the carbon nanotube is the arrangement of the same regular carbon
hexagon rings found in graphite [1]. Carbon nanotubes were reported by
Sumio Iijima with an observation of multiwalled carbon nanotubes
(MWCNTs). They have structures with a diameter of 4–30 nm and a
length of about 1 µm, in carbon soot obtained in an arc-discharge
method in 1991 while single walled carbon nanotubes (SWCNTs) were
first identified in 1993 [2–4]. On the other hand, SWCNTs were syn­
thesized by Dresselhaus et al. at about the same time [5]. The discovery
of CNTs was the beginning of a new evolution in the world of science and
technology in the synthesis of nanostructure from carbon. Tremendous
interest in these carbon materials is growing in both academia and
industry.
1.2. CNT classification
Carbon nanotubes are classified into the following two types based
on the wall structure. These include Single-walled carbon nanotubes
(SWNTs) and Multi-walled carbon nanotubes (MWNTs). As their name
suggests, SWCNT consists of a single layer of graphene with a diameter
of less than 10 nm and MWCNT is made of multi-layered (2–10 layers)
graphene with diameters over 100 nm. Their length may vary from
several nanometers to even millimeters [6–7]. Many differences be­
tween these two classes of carbon nanotubes are mentioned in the lit­
eratures. For instance, catalysts are applied in the synthesis of SWCNTs

Abbreviations: APPJ, Atmospheric pressure plasma jet; APDBD, Air–atmospheric pressure dielectric barrier discharge; APGD-s, Atmospheric pressure glow
discharge stamp; A-f-CNTs, Air-functionalized carbon nanotubes; F-f-CNTs, Fluorine-functionalized carbon nanotubes; N-f-CNTs, Nitrogen-functionalized carbon
nanotubes; O-f-CNTs, Oxygen-functionalized carbon nanotubes; CNTs, Carbon nanotubes; CNTF, Carbon nanotubes film; DBD, Dielectric barrier discharge; F-
MWCNTs, Functionalized multiwalled carbon nanotubes; FGNPs, Functionalized graphene nanoplates; LTP, Low temperature plasma; MWCNTs, Multiwalled carbon
nanotubes; MWCNTs-g-mAN, MWCNTs grafted with acrylicnitrile; Pf-MWCNTs, Plasma-functionalized multiwall carbon nanotubes; PMMA, Poly (methyl methac­
rylate); PVA, Poly (vinyl alcohol); RF, Radio-frequency; RF-DBD, Radio frequency dielectric barrier discharge; RTIL, Room-temperature ionic liquid; SWCNTs, Single
walled carbon nanotubes; SEM, Scanning electron microscope; VACNTs, Vertically aligned carbon nanotube arrays; XPS, Xray photoelectron spectroscopy.
* Corresponding authors.
E-mail addresses: h.hosseini1173@yahoo.com (H. Hosseini), mghaffarzadeh@ccerci.ac.ir (M. Ghaffarzadeh).

https://doi.org/10.1016/j.inoche.2022.109276
Received 11 October 2021; Received in revised form 16 January 2022; Accepted 3 February 2022
Available online 7 February 2022
1387-7003/© 2022 Elsevier B.V. All rights reserved.
H. Hosseini and M. Ghaffarzadeh
whereas there is no catalyst in MWCNTs synthesis. Also, bulk synthesis
in MWCNTs is easier than in SWCNTs and the purity of MWCNTs
compared to SWCNTs purity is higher [8–10]. On the other hand,
depending on rolling up of the graphene sheet in a single-wall carbon
nanotube, another classification can be considered for SWCNTs which
includes zigzag, armchair, and chiral arrangements [11]. The electrical
properties of CNTs result from rolling up direction of graphene sheets so
that the electrical properties of armchair arrangement are similar to
metals. Researches on multi-walled carbon nanotubes have introduced
two types of MWCNTs. The parchment in which the graphene sheet is
rolled around itself as a rolled newspaper and the second model called
the Russian Doll in which the arrangement of the graphite sheets is in the
form of concentric cylinders concentric cylinders [12]. Other carbon
nanotubes with their unique structures and applications mentioned in
some articles and papers include graphenated CNTs [13–14], extreme
CNTs [15–17], torus [18–19], nanobud [17], peapod [20–21], and cup-
stacked CNTs [22–23] Fig. 1.
1.3. CNT properties
Due to the special geometric structure of CNTs, carbon nanotubes
have various properties such as electrical, mechanical, thermal, optical,
and chemical that have led to numerous applications in different in­
dustries. These properties of CNTs have been discussed in the literature
in detail. Some properties of CNTs presented in Table 1 [24–36].
2. CNT functionalization
2.1. Introduction
In order to modify the properties of carbon nanotubes, functionali­
zation strategies of CNTs have been applied [37]. For example, the hy­
drophobic surfaces of carbon nanotubes and their tendency to bundling/
aggregation have restricted their solubility in aqueous media. The lack
of solubility of CNTs in aqueous solutions can significantly affect CNT’s
performance in some applications such as the biological and medical
ones [38]. In terms of interactions between CNTs and active groups,
there are two main categories for the functionalization of CNTs include
covalent and non-covalent functionalization [37].
2.1.1. Covalent functionalization
Covalent functionalization occurs through the formation of covalent
bonds between the wall of CNT and the chemical moiety [39]. func­
tionalization of CNTs has been reported with various chemical groups
such as carboxylic groups [40], amide group [41], phenyl group [42],
Fig. 1. The classification of carbon nanotubes.
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Inorganic Chemistry Communications 138 (2022) 109276
Table 1
The properties of carbon nanotubes.
The properties of The results obtained from SWCNTs and MWCNTs related to the
CNTs properties
Electrical CNTs may behave electrically either as a metal or a
semiconductor depending on their chirality and their diameter.
In SWCNTs, nanotubes with the armchair arrangement are
metallic. Zigzag and chiral arrangements of nanotubes can be
either semiconducting or metallic. In MWCNTs, conductivity is
quite complex.
Mechanical The consideration of the strength of sp2 C-C bonds, tensile
strength, and elastic modulus of CNTs showed that carbon
nanotubes are the strongest and stiffest materials ever
discovered by mankind. Tensile strength of CNTs (~100–200
GPa) compared with that of high tensile steel (1.3 GPa) was
very high and Young’s modulus of CNTs was more than four
times greater than that of high tensile steel.
Thermal The unique structure and the small size of CNTs lead to their
thermal properties. In SWCNTs, thermal conductivity at room
temperature was 3500 Wm− 1K− 1 whilst in MWCNTs at room
temperature it ranged from 400 to 3000 W/mK, depending on
the type and the size of CNTs. So, carbon nanotubes can be
considered as good thermal conductors.
Optical SWCNTs exhibit more marvelous optical properties than
MWCNTs because of their size and their monolayer feature.
SWCNTs have the ability of optical absorption in the near-
infrared (NIR) range and the emission in the range of
800–2000 nm.
Chemical Based on the research findings, CNTs with smaller diameters
can have increased reactivity. Besides, if a comparison is made
between CNTs and other carbon allotropes, CNTs are usually
more chemically inert than others.
alkyl moiety [43], thiol groups [44], and other groups to improve CNT
mechanical properties [45], thermal resistance [46] and other ones. In
this type of functionalization, there is a change in the hybridization of
carbon atoms in CNTs from sp2 to sp3 and interaction is attained without
preserving CNT structure [47]. To date, numerous literatures in this field
have been published [48–49].
2.1.2. Non-covalent functionalization
In non-covalent functionalization, unlike the covalent method, the
intermolecular interaction between the walls of carbon nanotube and a
chemical group takes place through van Der Waals or π-π stacking [39]
with preserving the graphene structure of CNT. Also, the hybridization
of carbon is sp2 in this case [47]. Surfactants [50–51], amphiphilic
polymers [52–53], and biomolecules [54–55] wrapped or adsorbed onto
CNTs are used as functional groups in non-covalent functionalization.
H. Hosseini and M. Ghaffarzadeh
2.2. Methods of CNT functionalization
Some methods are used to functionalize carbon nanotubes such as
click chemistry, electrochemical, defect, and plasma discharge.
2.2.1. Click chemistry
Click chemistry is an elegant method of CNT functionalization for the
introduction of molecules onto the surface of carbon nanotubes [56–58].
In order to prepare nanotube-based materials, the Huisgen 1,3-dipolar
cycloaddtion catalyzed by Cu(I) was applied. Campidelli et al.
employed a 4-ethynylbenzene derivative for SWCNTs functionalization
and then reacted it with phthalocyanine molecules using the Huisgen
1,3-dipolar cycloaddition [58]. Other chemical moieties such as gold
nanoparticle-N3, amino-acid-N3, polystyrene-N3, phthalocyamine-N3,
β-cyclodextrin-N3, and PU-N3 functionalized CNTs are attached to car­
bon nanotubes via click coupling [59].
2.2.2. Electrochemical functionalization
Electrochemical functionalization is a selective, clean, and nonde­
structive chemical method for the functionalization of CNTs [60–61].
This method can be conducted with immersing a CNT electrode in a
solution that contains a suitable reagent in a constant potential or cur­
rent [61]. Niu et al. reported electrochemical functionalization of
SWNTs in room-temperature ionic liquid (RTIL) conditions [60]. The
electrochemical method is appropriate for modifying individual
SWCNTs and also entangled SWCNTs networks [61].
2.2.3. Defect functionalization
One of the methods of functionalization of carbon nanotubes is
defect functionalization. This functionalization is based on an oxidation
process accomplished in a liquid phase by immersing CNTs in strong
oxidant reagents such as KMnO4, H2SO4, HNO3, and H2O2 or in a gas
phase by oxidant gases such as ozone. Oxygenated functional groups
generated can be a carboxylic acid, ketone, alcohol, and ester [62].
These carboxylic groups can react with other functional groups and
bond with them. For instance, the reaction of the oxidized carbon
nanotubes containing the carboxylic groups which are mainly at the
ends of the nanotube and defect sites with thionyl chloride and their
conversion into CNTs with the more activated group were performed
and subsequently functionalized with amines or alcohols [63]. The use
of amidated carbon nanotubes as helpful precursors can be effective for
additional functionalization or interaction with biologically active spe­
cies like DNA, proteins, enzymes, and antibodies [39].
2.2.4. Plasma functionalization
The use of plasma is another suitable method to introduce the wide
range of functional groups onto SWCNTs and MWCNTs, in particular,
atmospheric pressure plasmas (APP) which are applied for the func­
tionalization of aligned nanotubes [72]. This functionalization method
is also used for the modifications of the MWCNT electrodonor properties
[64]. The functionalization of carbon nanotubes using various plasmas is
given in Section 3 in detail.
3. CNT functionalization via plasma
The plasma method is a promising method for the functionalization
of CNTs that has attracted attention in recent years. Plasma function­
alization has a short processing time and is a flexible and non­
contaminated method. The possibility of producing high contents for
scaling-up in commercial applications is another advantage of plasma
functionalization [64]. Recently, many efforts have been directed to
modifying CNTs using the plasma discharge method, which is discussed
below. Indeed, plasma is described as an environment full of energetic
species such as charged species (electrons and ions), excited molecules,
and neutrals (atoms and radicals). Based on the internal temperature of
electrons, plasma can be classified into high and low temperature
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Inorganic Chemistry Communications 138 (2022) 109276
plasma (LTP). Also, LTP can be thermodynamically divided into two
categories which include thermal and nonthermal plasma. All compo­
nents in thermal (hot) plasma are in thermodynamic equilibrium
whereas there is no thermodynamic equilibrium between the compo­
nents in non-thermal (cold) plasma and electron temperatures are much
higher than the gas temperatures in this type of plasma [65–66]. Cold
atmospheric plasmas are more popular among non-thermal plasmas.
Glow discharge, corona discharge, dielectric barrier discharge (DBD),
and atmospheric pressure plasma jet (APPJ) are a number of cold at­
mospheric plasmas that have been mentioned in various articles and are
used in diverse fields. In the present review, the functionalization of
CNTs using different plasmas is characterized. The effects of some
plasma processing parameters such as plasma application power, plasma
application time, type of the used gases, and plasma gas flow rate on the
functionalization of carbon nanotubes are investigated.
3.1. Dielectric barrier discharge (DBD)
Dielectric barrier discharges (DBDs), also called silent discharges,
can be made in several configurations with an insulating (dielectric)
material with the responsibility of a self-pulsing plasma operation be­
tween the electrodes Fig. 2 [67].
Dielectric barrier discharge as one of the various types of plasma
which operates under an atmospheric-pressure condition is applied for
plasma surface modification of carbon-based materials. By adjusting
plasma parameters such as application power, dielectric thickness,
process duration, the gases used during plasma processing, and etc,
different chemical functionalities can be created on the surface of CNTs
[67,72].
3.1.1. Nitrogen containing functional groups
Abdel-Fattah et al. studied the influences of Ar-N2 (60–100%)
mixture plasma on the efficiency of nitrogen functionalization of CNTs
by means of radio frequency dielectric barrier discharge (RF-DBD) [68].
In this plasma process, nitrogen functional groups such as pyridinic-N
(C–
– N), pyrrolic-N (C–N), and pyridinic oxide (O–C– – N) were
formed on the plasma treated MWCNTs outer surface and were
confirmed by The Xray photoelectron spectroscopy (XPS). On the other
hand, the change in the type of plasma gas and the gas composition ratio
has no effect on the tubular shape of the MWCNTs during the plasma
functionalization. Pourfayaz et al. Carried out the nitrogen functionali­
zation on MWCNTs outer surface with helium (He) plasma treatment
followed by ammonia DBD plasma to prepare PMMA based nano­
composites [69]. FTIR spectrum and Raman spectroscopy results indi­
cated that amine and amide functional groups on the surface of the
carbon nanotubes occurred during this process. In this study, the largest
quantity of the functional groups was obtained in the applied frequency
of 2.6 kHz and the voltage of 9 kV at the ammonia adsorption temper­
ature of 200 ◦ C for 6 min. It is concluded that the functionalized nano­
tubes (F-MWCNTs) have better electrical properties compared to
pristine and acid-treated MWCNTs. Khodadadei et al. reported amine
functionalization of MWCNTs by exposing the MWCNTs to helium at­
mosphere and then introducing NH3 under dielectric barrier discharge
(DBD) conditions Fig. 3 [70]. The structure of CNTs was preserved
during the functionalization and was attached to amin groups on
MWCNTs. In this study, the uniform dispersion of NH2-MWCNTs in
aqueous solutions is due to the presence of amine groups in MWCNTs.
NH2 functional groups on the surface of MWCNTs account for the
biocompatibility improvement of MWCNTs and also they create a suit­
able immobilizations of biomolecule for MWCNTs.
Rastian et al. conducted surface-functionalization of MWCNTs in a
DBD plasma reactor for amination and carboxylation on the MWCNTs
surfaces Fig. 4 [71]. In order to functionalize multi-walled carbon
nanotubes by amin groups, the activation of MWCNTs was performed by
helium (He) plasma at atmospheric pressure. Then the resulting CNTs
were exposed to NH3 while the production of the carboxylated MWCNTs
H. Hosseini and M. Ghaffarzadeh Inorganic Chemistry Communications 138 (2022) 109276

Fig. 2. Some planar configurations of DBDs containing (a) volume DBD (symmetric), (b) surface DBD (symmetric), (c) coplanar discharge, taken from ref. [67].

Fig. 3. Helium plasma and consequent ammonia DBD plasma for the production of amino-functionalized MWCNT, taken from ref. [70].

was done by humid air plasma and afterwards octadecylamine was used
for further amidation of carboxyl groups on the MWCNTs surfaces. The
results obtained from the spectroscopic analysis Fourier-Transform
Infrared Spectroscopy and X-ray Photoelectron Spectroscopy
confirmed the successful surface-functionalization of MWCNTs and
enzyme immobilization.

3.1.2. Oxygen containing functional groups

Okpalugo et al. examined the functionalization of CNTs in the air-
DBD system [72]. it is stated that air–atmospheric pressure dielectric
barrier discharge (APDBD) functionalization of CNTs is more convenient
and rapid (less than 5 s) than the chemical methods used for the func­
tionalization of carbon nanotubes. XPS analysis for atmospheric DBD
treated MWCNT revealed that the sp3C–C fractions as well as the C–O,
C–– O and /or COO– fractions increased while the sp2C– – C fraction
decreased Fig. 5.
In another study, APDBD was applied for both functionalization of
MWCNTs and to remove surface impurities [73]. In the obtained anal­
ysis from XPS, the atomic concentration of oxygen incorporation in DBD
functionalized MWCNT (28.2%) increased compared to the one in
pristine MWCNT (8.2%). The results of the Raman analysis showed that
there is no remarkable change in the radial breathing mode peaks
following DBD treatment. So, no damage happened in the structure of
the CNT during the plasma functionalization. Roy et al. accomplished
further modification of the acid treated carbon nanotubes by DBD
treatment in an ammonia atmosphere [74]. It was reported that there
Fig. 4. MWCNT-NH2, MWCNT-COOH, MWCNT-CONHR, taken from ref. [71].
were oxygen and nitrogen containing functional groups in C K edge, N K

4
H. Hosseini and M. Ghaffarzadeh
Fig. 5. The XPS spectra of MWCNT (a) before and (b) after DBD treatment (20 cycles), taken from ref. [72].
edge, and O K edge Near edge x-ray absorption fine structure (NEXAFS)
spectra of the MWNTs. Three types of local nitrogen π* bonding con­
figurations were identified in the energy region 398–403 eV in the N K
edge spectra attributing pyridinelike (N1), NO (N2), and graphitelike
(N3) structures. The presence of carbonyl (C– – O), π* (CO), and ether
C–O–C, σ*(CO) functionalities was confirmed in the O K edge. It is
stated that the π*(CO) resonances vanished and the σ*(CO) resonances
were still present upon heating in a vacuum to 900 ◦ C. Based on the
results from the C K edge spectrum, no remarkable change was observed
in the π* feature of this spectrum. Thus, CNTs tabular structure was
fundamentally preserved following the thermal decomposition of func­
tionalities on the CNT. Naseh et al. functionalized multiwall carbon
nanotubes (MWCNTs) using two methods containing a chemical treat­
ment using nitric acid and the plasma treatment which was done by DBD
plasma under air atmosphere [75]. The presence of C– – O and COOH on
carbon nanotubes was confirmed by data obtained from FTIR. Although
the plasma treatment generated less acidic groups compared to the
treatment by nitric acid, the functionalization using the treatment of
plasma was reported to be less destructive than using the treatment of
HNO3. In another study of plasma functionalization of carbon nanotubes
in dry air, the influences of some plasma parameters were investigated.
It was observed that the adjustment of DBD power and treatment time
were effective in the extent of functional groups on CNTs which were
mainly carbonyl and ether [76]. In this process, the optimum time
mentioned was 5 min. For maximum functionalization of CNTs, the
applied voltage and frequency were 9.0 kV and 2.5 kHz, respectively.
Pourfayaz et al. applied dielectric barrier discharge (DBD) plasma for
the functionalization of multi-walled carbon nanotube in the presence of
a mixture of carbon dioxide and a diluent gas at room temperature and
atmospheric pressure which led to the attachment of oxygen containing
functional groups on the surface of MWCNTs [77]. The range of the
plasma voltage was 5–9 kV with the constant frequency of 2.6 kHz in the
range of 5–60 s. It has been reported that maximum functionalization on
the surface of MWCNTs was caused by He, with the content of 60%,
among He, Ar, and N2 as diluent gases used in this treatment. In other
words, He gas can increase the plasma reactivity in the plasma treat­
ment. In the quantitative analysis by TPD, it was found that larger
number of functional groups were produced in higher voltages and the
maximum functional groups formed on the nanotube surface occurred at
20 s exposure time. Brković et al. prepared functionalized multi-walled
carbon nanotube (FMWCNTs) as well as functionalized graphene
nanoplates (FGNPs) in air under DBD conditions [78]. The presence of
oxygen containing groups such as the carbonyl and the carboxylic
groups for MWCNTs treated by DBD was confirmed by FTIR results. The
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Inorganic Chemistry Communications 138 (2022) 109276
maximum content of the surface functionalization MWCNTs was at the
delivered discharge energy of 720 Jmg− 1. The lower number of the
functionalized groups was achieved with further exposure to plasma.
Besides, no considerable structural changes were observed for carbon
nanotube during the plasma treatment through the results of SEM
analysis. Krushnamurty et al. applied both helium/air plasma treat­
ments with a DBD reactor and chemical treatments for the introduction
of oxygenated species onto multiwalled carbon nanotubes [79]. Analysis
methods such as temperature programmed decomposition (TPD),
Raman spectroscopy, elemental analysis, and BET surface area analysis
were used for the evaluation of changes in surface functionalities of
MWCNTs. Elemental analysis in combination with Temperature pro­
grammed decomposition studies revealed that the quantities of acidic
groups produced during air plasma treatment on the surface of MWCNTs
were more than those of the conventional chemical method. Also,
Raman spectroscopy studies showed that the degree of disorder for
MWCNTs was more in chemical functionalization compared to plasma
ones. Khodadadi et al. carried out oxygen functionalization of multi-
walled carbon nanotubes in the H2O-saturated atmosphere at 70˚C and
atmospheric pressure under DBD conditions [80]. The results obtained
showed that oxygen-containing functional groups such as carbonyl,
hydroxyl, and carboxylic groups were produced during plasma treat­
ment. Plasma application time to obtain the maximum amount of the
oxygenated functional groups on MWCNTs was 4 min. In the next step,
NiO-NPs were applied to attach to the MWCNTs by an electrodeposition
technique. Ultimately, GOx was immobilized on the surface of NiO/F-
CNTs. The fabricated electrode was employed for the detection of
glucose in experiments Fig. 6.
In another study, after electrodeposition of polyaniline on the
vertically aligned carbon nanotube arrays (VACNTs) and chem­
ical–mechanical polishing (CMP) step, the functionalization of the
fabricated CNTs was conducted through DBD plasma in the presence of
the water–vapor-saturated air atmosphere at 70 ◦ C and atmospheric
pressure [81]. The plasma functionalization resulted in the formation of
carboxylic acid groups on the surface of VACNTs/PANI electrode. Af­
terwards, the immobilization of GOx by (1-(3-dimethylamino-propyl)-3-
ethylcarbodiimide hydrochloride (EDC)) and hydroxysulfo-
succinimidesodium salt (sulfo-NHS) on the electrode was used for the
fabrication of point-of-care biosensor for the determination of glucose in
human blood plasma.
3.2. Glow discharge
Glow discharge is a plasma generated by applying a potential
H. Hosseini and M. Ghaffarzadeh
Fig. 6. The procedure of GOx/NiO/F-CNTs/GC electrode fabrication, taken from ref. [80].
difference between two electrodes in a cell filled with a gas at low
pressure. Free electrons and positively charged ions are obtained from
the ionization of the atoms of the discharge gas due to the potential
difference. The positive ions are accelerated towards the cathode
whereas the electrons are accelerated away from the cathode and arrive
in the plasma. Collisions of electrons with the gas particles lead to the
creation of such processes as excitation, ionization, dissociation, etc. The
excitation collisions and the radiative decay to lower levels can produce
the characteristic light of the ‘glow’ discharge. On the other hand, the
ionization collisions create ion–electron pairs such that the generation of
a self-sustaining plasma in the glow discharge is a result of this ion­
–electron multiplication process [82]. Some configurations of the glow
discharge are shown in Fig. 7.
Glow discharge is also used as a successful alternative method for the
generation of a wide variety of chemical species to modify nanotubes.
Functionalization of SWNTs with atomic hydrogen was implemented
using a glow discharge by Khare et al. [82]. Infrared band at 2924 cm2
which is assigned to the C–H stretching mode can be attributed to
atomic hydrogen functionalization by the plasma. Also, the UV–VIS-NIR
data indicated that a decrease in the ultraviolet absorption in plasma
treated CNTs was due to the loss of some conjugated C–C π bonds. In
another study, in order to further confirm the functionalization results
with atomic hydrogen in the previous work, the functionalized SWNT
was done with D atoms by deuterium gas in the microwave discharge
[83]. Two weak bands were observed in the region 2000–2250 cm− 1 in
FTIR spectra of SWNTs exposed to atomic D irradiation which belongs to
the C-D stretching mode. In addition, C-D bending vibrations appeared
in the region 1000–1300 cm− 1 in the functionalized SWNT. It is
Fig. 7. Two configurations of the DC Glow Discharge.
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Inorganic Chemistry Communications 138 (2022) 109276
concluded that the use of hydrogen atoms in a microwave discharge is a
helpful method to functionalize SWNTs. The application of ammonia
glow-discharge for the functionalization of single-walled carbon nano­
tubes was studied [84]. After 20 min of discharge, the presence of peaks
in regions corresponding to N–H stretching and bending of primary and
secondary amines, C– – N type bonds, and/or C– – C were evident in FTIR
Spectroscopy. Moreover, C–H bands were observed in FTIR spectra.
The researchers stated that the intensities of C-H bands increased
dramatically after 40 min of exposure because the reaction between
reactive H atoms and the SWNTs surface occurs preferentially at longer
times of plasma exposure. For the confirmation of the incorporation of
nitrogen functional groups on the SWNT, X-ray Photoelectron Spec­
troscopy was used and it demonstrated that the content of C, N, and O
for the NH3 plasma-exposed sample was 81.5% C, 6.6 % N, and 11.9% O,
respectively, whilst these values for the control sample were 88.1%,
0.4%, and 11.5%. Later, in other investigation, Khare et al presented
single-wall carbon nanotubes functionalized using nitrogen glow
discharge [85]. The finding indicated that the distance between the
discharge source and the sample is a key factor in the functionalization
of SWCNTs. At the longest distance (7 cm), no functionalization for
SWCNTs was found whilst a variety of nitrogen and oxygen products
were detected at 2.5 cm. According to the results from the FTIR analysis,
the obtained spectra of FTIR for the functionalized CNTs by an N2
discharge at 2.5 cm was very much similar to FTIR spectra in their
previous study in which NH3 was used as the source gas. In addition to
products detected for the longer distances, the presence of C– – N prod­
–
ucts was reported at the shortest distance (1 cm). Vohrer et al. used glow
discharge plasma to produce oxygen functionalities on CNT sheets as
H. Hosseini and M. Ghaffarzadeh
well as on CNT powders to improve their limiting properties [86]. The
presence of functional groups such as C–O, C– – O, and O–C– – O groups
were evident after the plasma oxidation from the obtained results. In
addition to the production of the maximum oxygen content by pure
oxygen in the plasma process, it has been expressed that the application
of pure oxygen plasma can cause a disruption in the structure of CNT. In
order to attain a more efficient and favorable hydrophilization, nitrogen
plasma was applied. However, the plasma treatment and consequent
hydrophilization led to the modification of some properties in CNTs like
the enhancement of the solubility, the reduction of the contact angles,
and the improvement of cell adhesion and proliferation. Hong et al.
presented super-hydrophobic carbon nanotubes which were achieved by
CF4 glow discharge plasma treatment on the surface of CNT powder at
low pressure [87]. It was observed that C–F, C–F2, and C–F3 groups
were created on the plasma-treated CNT powders. Both surface rough­
ness and fluorine coating were factors that played a constructive role in
the super-hydrophobicity of the CNT. Abbas et al. employed low-
pressure radio-frequency) rf) glow discharge to functionalize vertically
aligned carbon nanotubes by pure nitrogen plasma at room temperature
[88]. The majority of N atoms were incorporated in the graphitelike
structure and the small extent of atoms was introduced in pyridinelike
and cyanic structures. Based on the findings, highly active nitrogen
related defect sites were suitable for the adsorption of oxygen. So, ox­
ygen functionalities significantly increased in the CNx NT sample after
nitrogen plasma treatment based on the results of near-edge x-ray-ab­
sorption fine structure (NEXAFS) and XPS. Zschoerper et al. applied
glow-discharge plasmas with mixtures of Ar, O2, H2O, and H2 as the
process gas to attach oxygen functionalities on the CNT-sheets (bucky
papers) [89]. In this study, the effect of the plasma parameters such as
treatment time, process pressure, and gas composition on the composi­
tion of the produced oxygen functional groups like alcohol-, keto-/
aldehyde-, and carboxyl-groups was investigated. After plasma treat­
ment, derivatization reactions using fluorine-containing agents were
carried out in order to identify between groups featuring nearby binding
energies. Hordy et al. performed plasma functionalization on the surface
of CNTs using a helium glow discharge stamp (APGD-s) in ambient air
[90]. The dependencies of the plasma exposure time and source-to-
sample distance on the amount of oxygen grafted to the surface of the
CNTs were examined by XPS analysis. In the first 1 min of treatment, a
considerable concentration of oxygen was observed but the XPS spectra
were plateaus after that time in both 0.15 and 1 cm sample plasma
distances. Moreover, The highest level of functionalization was reported
to be approximately 5.7 at.% in XPS-derived surface atomic oxygen
concentration as a function of source-to-sample distance while the
functionalization level decreased when the distance was between 4 and
8 cm.
Fig. 8. Two kinds of RF plasma discharge include (a) Capacitively and (b) Inductively coupled discharge systems, taken from ref. [91a].
7
Inorganic Chemistry Communications 138 (2022) 109276
3.3. Radio frequency (RF)
In radio frequency discharge, plasma is generated either by inductive
or capacitive coupling energy in the frequency range 1KHz-103 MHz
which operates with an AC power source. Indeed, the Capacitively
Coupled Discharge (CCD) and Inductively Coupled Discharge (ICD) are
two kinds of RF plasma discharge based on the coupling mechanism
Fig. 8. More information about RF plasma discharge can be found in ref.
91a.
RF plasma is another efficient method for surface modification of
CNTs in which functional groups or polymer chains are bonded to the
surface of nanotubes. The attachment of fluorine groups on the surface
of CNTs was done at room temperature with the CF4 gas pressure in
radiofrequency plasma source by Valentini et al. [91]. The formation of
C–F covalent bond was confirmed by IR spectrum. It was proposed that
the use of F-SWNTs can be the chance for further chemical interactions.
For this purpose, fluoronanotubes reacted directly with aliphatic amines
at room temperature to form N–H bond. In this reaction, the elimina­
tion of HF and the formation of amino-sidewall functionalization of
SWNTs occurred. The application of amino-functionalized F-SWNTs as
reactive monomers was suggested for the production of thermosettings-
SWNTs polymer materials at room temperature. Felten et al. developed
Radio-frequency plasma functionalization of carbon nanotubes using
three various plasma gases such as O2 for grafting hydroxyl, carboxyl,
and carbonyl groups; NH3 for amines, nitriles, and amide groups; and
CF4 for fluorine species [92]. In this study, several parameters were
perused for plasma treatment gases mentioned above. It was found that
oxygen obtained on the CNTs was up to 21 at. % in distinguished con­
ditions. In case of short treatment time, and/or low plasma power, and/
or high pressure, the higher grafted hydroxyl groups were detected in
the after-glow discharge position while larger time and higher pressure
for the relative occurrence of the carboxylic groups and shorter time and
lower pressure for carbonyl groups as species with the highest abun­
dance were considered. In ammonia plasma treatment, up to 22 at. % of
nitrogen can be obtained on the surface of the carbon nanotubes using
low plasma power (15 W) and long treatment time (1500 s) in the
afterglow discharge region. Fluorine relative occurrence inside the glow
discharge and the after-glow discharge region were respectively up to
22.5 and 27 at. % in tetrafluoromethane plasma treatments. Depending
on the reaction conditions for CF4 plasma treatments, either polymeri­
zation of a fluoropolymer on CNTs or semi-ionic and covalent C–F
bonds were observed. Utegulov et al carried out the functionalization of
CNTs using isotropic plasma treatment by rf discharge in different
conditions [93]. By applying the plasma powers of 10 and 100 W and
using the essential components of the air under small base pressure of 30
mTorr which was present in the plasma reactor, the extent of oxygenated
H. Hosseini and M. Ghaffarzadeh
functionalities that mainly consisted of carbonyls, hydroxides, and
carboxyl groups enhanced with increasing plasma power. By intro­
ducing the NH3⋅H2O monomer into the reactor for a total pressure of 200
mTorr and rf power of 30 W, the high amount of C–NH2 and C–OH
functional groups was detected. The use of organic silicon compound,
hexamethyldisiloxans, as a plasma monomer with the same processing
parameters mentioned in the previous case led to the generation of the
polymer film on CNTs. The formation of the Si–CH3 functional groups
was confirmed in plasma treatment of the SWNT with HMDSO. It was
argued that the functionalization of SWNTs by plasma monomers like
ammonia and HMDSO in isotropic plasma treatment yielded n- and p-
type semiconducting nanotubes. In another investigation, the nanotubes
were exposed to a MW-generator as well as a RF-generated oxygen
plasma to functionalize the CNTs [94]. By measuring the water contact
angle, the quantity of functionalization surface was investigated. Up to
68% of wettability was improved in carbon nanofiber (CNF) treated by
MW-plasma. Also, an increase in wettability was observed at a plasma
power of 180 W with a treatment time of 6 min in plasma treatment with
a RF-generator. A 10 times increase was observed in the extent of oxygen
containing functional groups produced at the surface by a MW-
generated oxygen plasma. Felten et al. functionalized MWCNTs via an
oxygen RF-plasma and then covered the tubes with gold nanoclusters
deposited by thermal evaporation [95]. XPS analyses were applied to
appraise the chemical concentration and the chemical changes at the
MWCNT surface and the results showed that the relative concentration
of oxygen was approximately 10% in the oxygen plasma treatment. The
presence of hydroxyl, carbonyl (or ether), and carboxyl (or ester) groups
as oxygen functional groups grafted at MWCNTs were confirmed by XPS.
With plasma treatment, the dispersion of the cluster on the surface of
CNTs and the cluster size distribution of the particles appeared to be
more uniform than on CNTs not exposed to plasma Fig. 9. It was sug­
gested that nucleation centres of gold on the plasma treated CNTs can
arise in the vicinity of oxygenated defects produced during the plasma
process.
In another work, in order to attach Ag, Ni or Au atoms on the
MWCNT, the combination of RF-cold plasma treatment and thermal
evaporation in a vacuum was utilized [96]. Depending on the type of gas
used which can be styrene, O2, Ar, NH3 or CF4 for the treatment of the
MWCNT surface, the successful implementation for binding polystyrene,
oxygen, amine and fluorine groups was performed by RF plasma treat­
ments. In the next step, metal thermal evaporation took place on plasma
modified MWCNTs. It can be concluded that active sites created at de­
fects on the MWCNT during the plasma treatment can be used to control
the dispersion and even the growth of metal particles. Transmission
electron microscopy (TEM) analysis showed that the gas type used for
plasma treatment, the nature of the evaporated metal, the MWCNT
Fig. 9. TEM micrographs of (a) as-synthesized (b) oxygen RF-plasma treated MWCNTs covered with gold nanoclusters, taken from ref. [95].
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Inorganic Chemistry Communications 138 (2022) 109276
curvature, and the evaporation time can affect the dispersion and the
size of the metal particles on the MWCNT surface. To examine
morphology, microstructure, composition, and electrode performance in
plasma treatments of screen-printed carbon nanotube (CNT) films, Hou
et al. applied four plasma gases including Ar, O2, SF6, and CHF3 with
three gas-feeding methods including single component, multiple com­
ponents, and sequential method [97]. The elemental analysis of the
plasma treatments of CNT film (CNTF) using Ar, O2, O2/Ar, and SF6
indicated that the introduction of oxygen in all four treatments and
fluorine in the last one can be the evidence for the effects of function­
alization and/or coating during the plasma treatments. The most
effective results for ionization and field emission applications were ob­
tained by O2/Ar and mixtures of Ar + CHF3 + SF6 gas, respectively, in
the process of plasma treatments of CNT films. The functionalization of
the CNT surface was conducted by CF4 rf-plasma treatment to incorpo­
rate fluorine at the surface of MWCNT [98]. Based on the results re­
ported, the formation of C–F bonds (semi-ionic and covalent) occurred
during plasma treatment. The semi-ionic/covalent ratio and the atomic
concentration of fluorine depended on the plasma treatment time. As a
consequence, the active sites formed by the plasma treatment at the
CNT-surface were appropriate for grafting with a metal. Yoo et al.
modified multiwall carbon nanotubes using RF oxygen plasma. They
also studied the effect of the treatment of plasma on the ammonia
sensing performance characteristics of MWCNT/PANI films [99]. Oxy­
gen functionalities like the C–– O and COO groups were produced in the
plasma process. The presence of oxygen at the surface of plasma-treated
nanotubes showed a significant increase in ammonia sensitivity. Be­
sides, defects generated on the surfaces of carbon nanotubes during the
oxygen plasma treatment were suitable sites for the attachment of the
PANI. A linear response of about 0.19% per ppm NH3 was obtained for
concentrations in the range of 0 to 100 ppm in pf-MWCNT/PANI films.
NH3 plasma treatment of CNTs for amino functionalization of CNT
surfaces was reported by Yook et al. [100]. Several nitrogen containing
species, amino, imine, nitrile, amide, etc., which were formed at
different plasma powers during the plasma treatment were detected. The
degree of the amino groups increased at high powers of plasma. Based
on optical emission spectroscopy (OES) results, the occurrence of a
degradation on the CNT surface was serious at high RF power. There­
fore, low plasma voltages should be used to maintain the initial prop­
erties of nanocarbons during this plasma process.
Chen et al. employed the functionalized CNTs which were produced
through the plasma and amination process to react with epoxy resin to
generate CNT/epoxy composite [101]. The plasma treatment was car­
ried out by argon gas at an RF power of 50 W for 5 min to generate many
radicals on the MWCNTs resulted from breaking the C– – C sp2 bonding of
the nanotubes. Then the acrylicnitrile monomer (AN) was introduced
H. Hosseini and M. Ghaffarzadeh Inorganic Chemistry Communications 138 (2022) 109276

into the plasma reactor to graft on the surface of the MWCNTs. In the
next step, the amination MWCNTs-g-AN was performed by a hydroxyl­
amine solution and thereupon the reaction between the MWCNTs-g-
mAN and epoxy resin led to the formation of MWCNTs-g-mAN/epoxy
nanocomposites Fig. 10. In this study, the improvement of the CNTs’
dispersion ability in the epoxy resin was observed in the functionalized
CNTs. Also, the presence of the MWCNTs-g-mAN in nanocomposits
increased the electric conductivity of the polymer matrix.
Using CF4 plasma etching method, the production of short and
unzipped SCWNTs was studied [102]. By chemical microanalysis, it was
found that fluorine atoms were grafted to the formed carbon nano­
stripes. Hussain et al. obtained oxygen functionalized multi-walled
carbon nanotubes (MWCNTs) using H2O plasma treatment [103]. By
changing RF power and water pressure as the important parameters of
the water plasma, the content of oxygen functional groups such as
Fig. 11. A possible mechanism for the surface functionalization of CNT by
carboxyl, hydroxyl and carbonyl attached on the surface of CNTs was radio frequency air and oxygen plasma, taken from ref. [106].
examined. After plasma treatment, the relative oxygen level on CNT
surfaces enhanced with plasma power while high water pressures
to all graphitic materials, CO plasma treatments were carried out for the
affected negatively on the oxygen extent because of protecting the sur­
surface functionalization of nanoscaled carbon materials without the
faces of the nanotubes from plasma etching by a layer of condensed
degradation of the structure which was confirmed through Raman and
water. Moreover, a shift in the frequencies of the D and G bands was
scanning tunneling microscopy analyses [107]. According to the results
observed in Raman analysis, which was related to an enhancement in
reported, the surface O/C ratio using the O2 and CO plasma treatments
the number of defects and a reduction in the diameter of the nanotubes
were 0.11 and 0.69, respectively. In addition, the dispersion properties
after plasma functionalization. In another research, carbon nanotubes
of the treated specimens improved effectively after CO plasma treat­
were treated in an Ar/O2/C2H6 capacitively coupled RF plasma
ment. Hussain et al. performed radio frequency nitrogen plasma treat­
discharge to graft with poly (vinyl alcohol) for the production of well
ment of vertically-aligned multi-wall carbon nanotubes with the purpose
dispersed (PVA)/CNT nanocomposites [104]. Using XPS analysis, an
of introducing nitrogen containing groups to MWCNTs at the edges and
increase in the surface oxygen concentration from 2.5 to 21 at.% was
the basal planes of the MWCNTs with preserving their vertical align­
gained for the functionalized CNTs during the plasma treatment. A 54%
ment. [108]. The use of plasma pressures in the range of 150–260 Pa
increase in tensile strength and a 60% increase in modulus over the neat
resulted in the introduction of pyrrolic nitrogen, whereas the introduc­
PVA was observed in 0.75 wt-% functionalized- CNT nanocomposite.
tion of pyridinic functionalities happened at low plasma pressures (10
Zhao et al. used radio-frequency Ar/O2 plasma to modify vertically-
Pa). The results obtained from Raman spectroscopy indicated that
aligned carbon nanotube forests [105]. The quantitative analysis of
increasing the concentration of nitrogen enhanced the structural disor­
XPS showed that the quantity of sp2-hybridized C– – C bond decreased
der. It was reported the increase in specific capacitance of MWCNTs,
while the values of C O and O C– O functional groups on the surface
– – –
which was considerably observed in the plasma-treated nanotubes, was
of CNT forests considerably increased after the plasma treatment. By
due to an enhancement in the structural disorder and introduction of
decreasing plasma power from 100 W to 50 W and keeping other pa­
pyridinic and pyrrolic groups. In another research, the application of O2-
rameters unchanged, only small change was observed in the surface
fed low-pressure plasmas to prepare homogeneous functionalized
composition of the plasma-treated CNT forest. Hence, plasma of 50 W
MWCNTs was examined by Trulli et al. [109]. By increasing some
can be considered reasonable and sufficient to attach oxygenated func­
plasma parameters such as the treatment time and working pressure
tional groups on the surface of CNTs. The findings of Raman were in
during plasma processing more oxygen groups were incorporated on the
good agreement with the results from the XPS analysis indicating that
CNTs. Instead, an increase in RF power had a negative effect on the
there was no change in the CNT structure and the chemical composition
efficiency of the treatment. As a result, plasma-functionalized CNTs
for the interior nanotubes after functionalization. Scaffaro et al. syn­
represented a good dispersion and stability in aqueous solutions
thesized carbon nanotubes (CNT)/polyamide 6 composites by adding
compared to conventional methods. Steffen et al. proposed capacitive
air-plasma (A-f-CNT) and oxygen-plasma (O-f-CNT) modified CNTs to
coupled plasma radio frequency (RF) of Ar/O2 and Ar/O2/N2 at plasma
polyamide 6 [106]. During radio frequency air and oxygen plasma
powers of 40 W and 20 W in order to oxidize and insert nitrogen groups
treatment, the formation of carbonyl and carboxyl groups on the surface
in CNTs for the synthesis of epoxy nanocomposites [110]. Based on XPS
of CNTs was observed Fig. 11. In particular, the highest concentration of
results, an increase in the atomic concentration of oxygen inserted in
carboxylic carbons was achieved by oxygen plasma. Based on FTIR,
CNTs and the creation of more defects on the CNTs’ surface occurred at
Raman and XPS analysis, it was reported that the modification of the
40 W power whereas the formation of some C-N bonds as well as the
nanotubes by oxygen plasma was more impressive compared to air
insertion of oxygen containing functional groups on the surface of the
plasma. As a result, a remarkable increase in elastic modulus and the
CNTs were observed at 20 W power after plasma treatment. Also, the
impact strength in the composites obtained by O-f-CNTs was observed.
highest increase in the atomic oxygen extent on the surface of CNTs in
Unlike O2 plasma treatment, which caused a high degree of damage
the binary Ar/O2 gas mixture and the intriguing synergy for plasma-

Fig. 10. The schematic procedure of the fabrication of MWCNTs-g-mAN/epoxy nanocomposites, taken from ref. [101].

9
H. Hosseini and M. Ghaffarzadeh
treated CNTs in the ternary Ar/O2/N2 gas mixture were revealed. The
plasma functionalized carbon nanotubes in reaction with epoxy pro­
duced the nanocomposites such that the performance of the properties
of the epoxy matrix nanocomposite in the CNTs treated at 20 W was
better in comparison to the ones functionalized at 40 W because of C–N
bonds in CNTs. Another study presented a simple method to function­
alize CNTs through preparing a solid mixture of maleic anhydride as a
source of functional groups and CNT and then by exposing it to RF
plasma [111]. The influence of plasma treatment time on the atomic
percentage of O–C– – O bonds was effective in RF-plasma treated CNTs.
It means that this percentage increased by 43% relative to the untreated
CNT by increasing plasma application time. By means of the TEM im­
ages, the preservation of the CNT structure was observed after mixing
and/or plasma treating.
3.4. Atmospheric pressure plasma jets (APPJs)
One of the non-thermal atmospheric pressure plasmas is the atmo­
spheric pressure plasma jet (APPJ). To date, diverse APPJ designs have
been reported in the literature. Excited voltage such as direct current
(DC), alternative current (AC), microwave (MW), and radio frequency
(RF) can be applied in this plasma. Helium or argon as feed gas mixed
with air or oxygen is used in APPJ. Jõgi et al. produced the cold atmo­
spheric pressure plasma jet by AC power source in argon flow through
the 0.5-mm diameter quartz tubes with two configurations as shown in
Fig. 12 [120 a].
Among the plasma methods for surface functionalization, APPJ was
proposed as a facile and efficient method for modification of CNT sur­
faces [120]. Kolacyak et al. reported a fast plasma oxidative method for
the surface functionalization of multi-walled carbon nanotubes through
non-equilibrium atmospheric pressure plasma jet process [112]. XPS
results demonstrated that 6.9 at.% of total oxygen was grafted on the
Fig. 12. Two configurations of cold atmospheric pressure plasma jet (CAPI), taken from ref. [120a].
10
Inorganic Chemistry Communications 138 (2022) 109276
surface of CNTs after oxygen plasma treatment which mainly led to the
production of hydroxyl and carboxyl functional groups on MWCNTs.
The tubular structure of MWCNTs was effectually preserved when CNTs
were injected as a spray into the atmospheric pressure plasma which was
characterized by SEM analysis and Raman spectroscopy. The conse­
quence of another investigation in plasma jet system with an arc-like
discharge using nitrogen as carrier gas showed that the degree of func­
tionalization on the surface of MWCNTs, which depended on the type of
the used solvent for the spray injection of MWCNTs, was more effective
with ethanol than with other solvents [113]. In other words, the con­
centration of oxygen and nitrogen atoms on the surfaces of MWCNTs
after plasma treatment was reported to be 8.4 and 0.7 at.%, respectively.
It was stated that radical intermediates on the carbon skeleton were
produced during radical reactions resulting from the injection of nano­
tubes into the reaction chamber. Besides, after the plasma treatment, it
was possible for the surface functionalization to be conducted by the
remaining radicals. Malik et al. functionalized MWCNT sheets through a
helium/oxygen atmospheric pressure plasma jet to ameliorate their
properties in CNT-Polyvinyl Alcohol (PVA) Composites [114]. At two
various plasma powers and two different plasma exposure times, plasma
generated oxygenated functional groups such as carboxyl, hydroxyl, and
carbonyl groups on the sheet surface which was confirmed by data ob­
tained from Raman Spectroscopy, X-Ray Photoelectron Spectroscopy
and Fourier Transform Infrared Spectroscopy. The conclusion from the
plasma functionalization of CNT sheets was that mechanical properties
improved in plasma treated sheets in comparison to pristine sheet
composites in PVA matrix. Kolacyak et al. employed two concepts of
feeding MWCNTs, namely, dry and wet feeding, into the reactive plasma
zone under plasma jet conditions using oxygen and nitrogen gases for
the atmospheric pressure plasma functionalization of MWCNTs [115].
The formation of oxygenated groups and tiny quantities of nitrogen
containing functionalities on the surface of MWCNTs were identified in
H. Hosseini and M. Ghaffarzadeh
two concepts by XPS and contact angle studies. The feeding of the CNTs
into the plasma tube was direct in the dry feeding concept whereas in the
wet feeding concept, after dispersing the nanotubes in distilled water,
they were sprayed into the reaction chamber. By examining the multi-
walled tubular structure of the CNTs, it was found that the deteriora­
tion and the preservation of the MWCNT structure occurred in dry and
wet feeding, respectively. Abuzairi et al. performed the surface func­
tionalization of CNT by an atmospheric pressure plasma jet to generate
the functionalized carbon nanotube dot-array used as a precursor of
biomolecules of the bio-chip sensor [116]. Two-step plasma treatments
were considered for CNT functionalization, which included the pre-
treatment and the post-treatment. Ar discharge with − 500 V dc
biasing in pre-treatment step and a mixture of argon and ammonia
without bias in post-treatment step were applied to obtain amino-
functionalized CNT dot-array. The two-stage plasma treatment had
important roles in the implementation of surface functionalization by
the APPJ Fig. 13.
In another study, the maskless functionalization of carbon nanotubes
in an array form was accomplished by the treatment of nanotubes in an
ultrafine atmospheric pressure plasma jet by a helium and ammonia gas
mixture for amino group (–NH2) functionalization or by a helium and
oxygen gas mixture for carboxyl group (–COOH) functionalization
[117]. By means of optical Emission Spectroscopy, it was verified that
NH and OH radicals as essential radicals in the surface functionalization
of nanotubes were formed in the plasma treatments. The obtained re­
sults of chemical derivatization with the fluorescent dye revealed that
there was no interference between functional groups of amino and
carboxyl groups in the plasma functionalized CNT dot-array. Liu et al.
functionalized the MWCNT films in the atmospheric pressure plasma jet
by using the mixed gas of helium/oxygen to react with epoxy in order to
examine some properties of the CNT/epoxy [118]. After APPJ treat­
ment, XPS results showed the presence of oxygen functional groups such
as the C–O, C– – O and O–C– – O groups on the CNT film surfaces. As
plasma application time was extended, the agglomeration size signifi­
cantly decreased and the dispersion performance of the CNT films
improved due to more polar functional groups on the film. Increasing
the percentage of C-O group from 1.0% up to 9.2% after plasma treat­
ment led to the modification of the polarity of the surface and meliorate
the adhesion between the surface of CNT and epoxy, augmenting the
resin infusion and strengthening CNT film/resin interface bonding. In
another investigation, the CNT film was symmetrically modified by at­
mospheric pressure helium/oxygen plasma jet to build up CNT film/
epoxy composites with supreme tensile toughness, high gage factor and
Fig. 13. The process steps of the surface functionalized CNT by the atmo­
spheric pressure plasma jet, taken from ref. [116].
11
Inorganic Chemistry Communications 138 (2022) 109276
relatively stable electrical resistance and tensile stress for some appli­
cations. For instance, these composites can be applied in aerospace field
and some smart systems. [119]. The results illustrated that the com­
posites possessed a good resin infiltration and strong CNT epoxy
bonding because of the formation of the homogeneously oxygenated
groups including hydroxyl, carbonyl, and carboxyl groups on CNTs.
The fabrication of vertically-aligned carbon nanotube was conducted
by thermal chemical vapor deposition (TCVD) method and CNT-sprayed
films, and then was modified by atmospheric pressure plasma jet system
using nitrogen gas [120]. The presence of oxygen containing functional
groups such as hydroxyl and carboxyl groups, and nitrogen-induced
functionalities such as amine, pyrrolic, and pyridinic nitrogen compo­
nents were clearly observed after the plasma functionalization. Indeed,
APPJ treatment modified the surface of CNTs by changing their nature
from hydrophobic to hydrophilic through the formation of hydrophilic
functional groups on CNTs.
Table 2 compares some plasma factors, which can serve as important
parameters such as plasma gases, plasma pressure, plasma application
time, plasma application power, and the type of the created surfaced
groups for the selection of appropriate method to functionalize CNTs via
plasma. It should be noted that the functionalization of CNT via plasma
methods is not limited to those described above. In addition to the
aforementioned plasma methods that are widely used for the surface
functionalization of CNTs, there are other methods such as microwave
plasma that are applied for this purpose. Also, researchers should bear in
mind that the combination of these plasma parameters, depending on
the type of plasma in every plasma method and their precise control,
leads to the optimal functionalization of carbon nanotubes.
Table 3 summarizes the advantages of using different plasma
methods for the surface functionalization of CNTs. Indeed, structural
changes in CNTs that may be created during the functionalization pro­
cess are one of the important challenges for the researchers in this field.
The preservation of the CNT’s morphology has been mainly confirmed
and reported in plasma methods. Also, the mentioned applications of
plasma-functionalized nanotubes can assist researchers in selecting the
suitable plasma method.
4. Conclusion
The effects of plasma treatment on the surface functionalization of
CNTs have demonstrated that this method can successfully create
different active chemical groups on the surface of CNTs to change their
surface properties. Various plasma methods are employed for the
modification of CNTs in which active species produced interact with the
surface of nanotubes. This review focused on the surface functionali­
zation of carbon nanotubes through plasma methods such as dielectric
barrier discharge, glow discharge, radio frequency, and atmospheric
pressure plasma jet. In summary, depending on the type of plasma used
and the control of plasma parameters such as plasma treatment gases,
plasma gas flow rate, plasma treatment power, plasma application time
and other ones, the type and the content of functional groups incorpo­
rated on CNTs surface can be optimized.
The plasma treatment using dielectric barrier discharge as a soft
method for the introduction of reactive nitrogen and oxygen species on
nanotubes has been performed by plasma gases such as N2, NH3, air,
CO2, and water vapor saturated. In nitrogen-containing plasmas, amine,
amide, pyridinic-N, pyrrolic-N, and pyridinic oxide groups have been
generated on CNTs due to the introduction of nitrogen bearing groups
and/or nitrogen doping. Also, carbonyl, hydroxyl, and carboxylic groups
as oxygenated functionalities on the surface of CNTs were identified in
oxygen containing plasmas. These functional groups on CNTs by
creating a hydrophilic surface can improve the dispersion of CNT in
aqueous solutions.
Most studies for the functionalization of nanotubes by using plasma
have concentrated on the nitrogen- and oxygen-functionalized carbon
nanotubes. In researches conducted by nitrogen glow discharge, in
H. Hosseini and M. Ghaffarzadeh Inorganic Chemistry Communications 138 (2022) 109276

Table 2
The comparison of plasma parameters in various plasma methods for the surface functionalization of CNT.
Plasma Plasma parameters Ref.
method
Surface functionalization Plasma gas Plasma pressure Plasma time Plasma power

DBD •mainly carboxyl and hydroxyl groups Air periods of 10, 20, 4W [78]
There was an increase of the carboxyl and hydroxyl content from 0 to 30 and 40 min.
30 min while after that a faster decrease of the content of former was
observed.
• pyridinic-N (C–
–N) Ar-N2 500 Pa 6 min a RF power of 60 [68]
• pyrrolic-N (C-N) (60–100%) W
• pyridinic-N-Oxide (O-C– –N)
The percentage of three nitrogen functional groups depends on the
percentage of N2 in Ar-N2 mixture plasma.
The extent of nitrogen atoms on the MWCNTs reaches 13.37–14.43%
Glow • The oxygen addition depends on the exposure time and source-to- Air atmospheric 5 min 20 W of [90]
discharge sample distance. 5.5 at.% after 1 min and up to distances as far away as pressure continuous RF
8 cm power
1
• An increment in the functional groups like alcohol or carboxylic O2 2.0 × 10− mbar 10 s or 10 min 10 W [86]
groups
Longer treatment times lead to higher contents of oxygen.
• Products containing C≡N, N-H, and HNH at the shortest distance (1 N2 300–550 mTorr periods of 5, 15, 100 W [85]
cm) 30, and 45 min
Surface functionalization depends on the distance between the
discharge source and the sample.
1
An increase in the fluorine groups like C-F, C-F2, and CF3 groups CF4 2.5 × 10− Torr 20 min 20 W [87]
RF • The formation of oxygenated groups like –COOH and -OH Air 2, 5, 10 min 70,100, 120 W [106]
Oxygen plasma is more effective than air plasma and the concentration O2
of carboxylic carbons is maximum in oxygen plasma.
• The introduction of pyrrolic nitrogen at middle to high plasma N2 in the range of 120 s in the range of [108]
pressures (150–260 Pa) 10–260 Pa 10–140 W
• The introduction of pyridinic functionalities at low plasma pressures
(10 Pa)
• Other nitrogen functionalities such as pyridinic-N-oxide and
quaternary nitrogen
Nitrogen functionalities depend on the plasma conditions.
2
• The attachment of fluorine atoms to carbon nanostripes CF4 10− Torr 8 min and 1 min 4 W and 15 W [102]
Increasing the RF power leads to the creation of shortened plasma
treated carbon nanotubes.
APPJ • C––O, C-O, and O-C– –O groups He/O2 atmospheric 0.1, 0.2 and 0.3 s 150 W [118]
An increase of the percentage of C-O group from 1.0% up to 9.2% pressure
• functional groups such as hydroxyl and carboxyl groups N2 atmospheric from 1 to 30 s [120]
• amine groups, pyrrolic-N, and pyridinic-N pressure

Table 3
The advantages of various plasma methods for CNT functionalization. Oxygen, Nitrogen, and Fluorine functionalized carbon nanotube are indicated as N-, O-, and F-f-
CNT.
Plasma Advantages of CNT functionalization in plasma methods Ref.
method
Structural changes in CNTs Application of f-CNTs

DBD No significant damage has been reported in the CNT •N-f-CNT in the preparation of PMMA based nanocomposites From[68] to [81]
structure • N-f-CNT for glucose biosensor development
• N-f-CNT for the creation of a compatible interface for C. rugosa lipase
immobilization
• O-f-CNT in the preparation of C-epoxy composites
Glow No significant damage has been reported in the CNT • F-f-CNTs in the creation of super-hydrophobic CNTcushions From[82] to [90]
discharge structure
RF No significant damage has been reported in the CNT • F-f-CNT in the preparation From [91] to
structure of thermosettings-SWNTs polymer materials [111]
• O-f-CNT for the creation of gold coverage on CNT
• f-CNT in the preparation of CNT composites
• O-f-CNT in the preparation of nylon 6-based nanohybrids
• N- and O-f-CNT in the preparation of epoxy nanocomposites
APPJ Mostly no damage has been reported in the CNT •O-f-CNT in the preparation of CNT-Polyvinyl Alcohol (PVA) composites From [112] to
structure • N-f-CNT in the development of bio-chip sensors [120]
• O-f-CNT in the preparation of MWCNT film/epoxy composites

addition to other functional nitrogen-containing groups, the presence of
C≡N species on nanotubes has been delineated by analysis data. The
fluorination of carbon nanotubes by tetrafluoromethane glow discharge
plasma creates fluorine chemical species on CNT’s surface. The super-
hydrophobic behaviour of carbon nanotubes results from fluorination
coating and surface roughness in plasma-treated CNTs.
The chemical functionalization by radio frequency plasma has been
carried out by a wide variety of plasma gases, e.g., O2, air, NH3, N2, CF4,
CHF3, SF6, and etc., either alone or in combination with other gases, in
order to attach oxygen, nitrogen, and fluorine-containing functionalities
on the surface of CNTs. There are some studies on carbon nanotube
composites with improved electrical conductivity properties that have
been attained by resin and plasma functionalized CNT. Furthermore, the
combination of RF plasma treatment with thermal evaporation has been

12
H. Hosseini and M. Ghaffarzadeh
used for the attachment of metal atoms on the surface of CNTs. In this
process, factors such as the type of plasma gas, the evaporated metal
nature, the curvature of CNT, and the time of evaporation are effective
in the dispersion and size of the metal particles on CNT.
Although the surface functionalization of carbon nanotubes by at­
mospheric pressure plasma jets is still limited in the literature compared
to other non-thermal plasmas, the APPJ method can be employed as a
facile and efficient one to modify carbon nanotubes. The new methods of
plasma jet can functionalize CNT dot-array with different functional
groups selectively and masklessly.
Thus, plasma functionalization as a successful alternative method for
the surface modification of carbon nanotubes can improve the limiting
properties of CNTs to increase their application in diverse fields.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
We would like to thank the research committee of Chemistry and
Chemical Engineering Research Center of Iran for supporting this
review.
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Hamideh Hosseini is a Ph.D. candidate in the Department of
Organic Chemistry at Chemistry & Chemical Engineering
Research Center of Iran (CCERCI). She received her M.Sc. de­
gree in organic chemistry from the Kharazmi University, Teh­
ran, Iran, in 2008. Her research interests lie in the field of
performing chemical reactions and processes using plasma,
notably atmospheric plasmas. Her Ph.D. research focuses on the
synthesis of chemical compounds through atmospheric-
pressure plasma.
Mohammad Ghaffarzadeh is an associate professor in the
Department of Organic Chemistry, at Chemistry & Chemical
Engineering Research Center of Iran (CCERCI). He received his
M.Sc. and Ph.D. in organic chemistry from Sharif University of
Technology, Tehran, Iran in 1997 and 2002, respectively. He is
directing several industrial projects. His current research in­
terests include plasma-induced reactions and plasma applica­
tions in the industry.