RSC Advances

PAPER

Towards a fine-tuning of surface chemistry in

aligned carbon nanotubes induced by nitrogen
Cite this: RSC Adv., 2016, 6, 13088
plasma discharge post-treatment: a combined
microscopic and spectroscopic study
Laith Hussein*

Received 22nd October 2015
Accepted 14th January 2016
DOI: 10.1039/c5ra22156k
www.rsc.org/advances
The modification of the surface chemistry of individual nanotubes inside vertically aligned carbon nanotube
(VACNT) arrays is a key challenge in developing successful active materials for many electronic, photonic and
catalytic applications. To this end, an efficient, clean, non-destructive and adjustable process for nitrogen
functionalization and doping of the VACNTs in a controlled manner is highly required. In this study, the
results of a systematic study using plasma discharge for this purpose by varying the N2/H2 gas volume
ratio, discharge exposure time, and the radio-frequency (r.f.) power are presented. This process resulted in
the generation of a few defects induced deliberately by the nitrogen radicals into the graphitic framework,
mainly as in; amine, amide, pyridinic, pyrrolic, graphitic-type nitrogen. The parameters of plasma
discharge were adjusted in a way that the densities and the relative ratios of nitrogen-containing
functional groups can be selectively controlled. Evidence for the induced structural and chemical bonding
changes, and the formation of different functional groups on the surface of the VACNTs are examined as
a function of nitrogen content, using proper combination of analytical methods of high-resolution
transmission electron microscopy (HRTEM), Raman, X-ray photoelectron (XPS) and Fourier transform
infrared (FTIR) spectroscopy. At the relatively low level of r.f. power and discharge nitrogen flow rate in
the feed, a preservation of the graphitic framework of the VACNTs has been demonstrated. The current
study, therefore, sets the stage for selective control of the densities and the relative ratios of different
nitrogen-containing acidic and basic surface functional groups on or within the nanotube framework
under defined process parameters without causing a dramatic loss of graphitic structures.

means of incorporating dopants, due to the quantum conne-

1. Introduction
Since the rst reported synthesis and observation of carbon-
based nano-tubular structure by Iijima in 1991,1 the sp2-
hybridized or graphitic nanocarbons (GNCs) have attracted
a great interest due to their unique structural perfection and
chemical inertness. These types of nanocarbons can form one-
and two-dimensional structures, i.e. carbon nanotubes (CNTs)
and graphene or carbon nanowalls, respectively.2 However, in
many instances, GNCs oen raise difficulties during the post-
processing, e.g. handling, purication, sorting, dispersing,
and mixing. Moreover, for some potential applications, there is
a need to tune the physical, chemical and electronic properties
of the GNCs based on the specic requirements.3
To this end, heteroatom doping or functionalization of CNTs
can considerably modify the electronic and optical properties by
Department of Chemistry, Eduard-Zintl-Institute of Inorganic and Physical Chemistry,
Technische Universität Darmstadt, Alarich-Weiss-Straße 12, 64287, Darmstadt,
Germany. E-mail: laith1997@gmail.com; hussein@ac.chemie.tu-darmstadt.de; Fax:
+49-6151-16-3470
ment effects and the curvature of the cylindrical surfaces of
nanotubes, which can be utilized in nano-electronics and
photonics.4 Selective controlling of the incorporation of defects
or foreign atoms results in tremendous technological implica-
tions, and still drives many experimental and theoretical
investigations focused on this topic.
It is commonly known that nitrogen doping (N-doping) of
CNTs creates electron donor states in the conduction band near
the Fermi level.5 Many recent research reports have demon-
strated that N-doping chemically activates the surface of CNTs,
changes their solubility, improves their electrical, thermal and
magnetic properties,6,7 and enhances electrocatalytic activity
with respect to the oxygen reduction reaction (ORR) in metal–air
batteries8 and fuel cells as well.9,10 Besides nitrogen-doped CNTs
(N-CNTs) have potential applications in the synthesis of three-
dimensional porous architectures,11 supercapacitor systems,12
in bio-sensing,13 as vapor or gas-sensing elements,14 in the
enhancement of lithium storage capability,15 as nano-
composites,16 or as eld emission sources.17 Owing to the
greater electron affinity of nitrogen in comparison with carbon,

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Paper
the direct substitution of carbons by nitrogen atoms in the
graphitic framework could facilitate the generation of n-type
materials.18 An overview of different possibilities that incorpo-
rate nitrogen atoms in CNTs is given in Fig. 1.
Doping as well as functionalization typically requires a rear-
rangement of neighboring carbon atoms in the GNC frame-
work.19 Generally, such an arrangement can induce different
kinds of defect creation (dangling bonds, substitutional, inter-
stitial, single and multiple vacancies) which are integral to the
modication of the properties of GNCs.
So far the majority of studies have concentrated on an in situ
doping of CNTs directly during their growth in the gas phase via
a chemical vapour deposition (CVD).20 Nevertheless, this tech-
nique brings some disadvantages, e.g. it results in apparently
uneven distribution of dopants, changes the nanotube
morphology towards a bamboo-like structure,21 and ultimately
gives potential rise to a to higher wall defect concentrations,
which renders the resulting CNTs mechanically weaker.6,22
In the most reported post-synthesis approach, a wet- or dry-
based synthesis process can be employed as an alternative route
to functionalization and doping. In both a wet-23 and vapor-
based process,24 the doping elements can be implemented
into already existing defect sites in graphitic framework, such as
pentagon–heptagon defects (Stone–Wales).25 This type of
process is oen performed in a solution and it requires rather
harsh conditions due to multiple bond-breaking events neces-
sary for the functionalization or introduction of the dopants. It
typically requires multistep reaction sequences, which are oen
hard to control with respect to the outcome of the doping
process.26 On the other side, intensive or long sonication
processes are required to disperse CNTs in organic solvents,
which could also cause a severe damage to the graphitic
framework of the CNTs and may even initiate cutting into
shorter tube fragments.27 Furthermore, the amount of
elemental doping has to be well-controlled in order to maintain
Fig. 1 Graphical representation of proposed general structures for the modified graphitic framework induced by nitrogen (a) and oxygen (b)
incorporations as well as surface functionalization, blue ball: nitrogen, red ball: oxygen. Note: in-plane nitrogen incorporation leads typically to
N-doping.
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RSC Advances
the characteristic properties of CNTs, e.g. electronic and
mechanical properties.28
Along this direction a modication of the CNT properties in
a “dry” process, e.g. the ball-milling of CNTs in reactive atmo-
spheres,29 has also recently been proposed. This technique, on
the other hand, has also some drawbacks such as the inho-
mogeneous distribution of doping elements along the nano-
tube. Other approaches apply high temperatures (over 1250


C),30 ion implantation31 or plasma discharge.32,33 With respect
to the latter, precursor gasses can be directly introduced into
the plasma chamber which allows incorporating oxygen,16,34
uorine35 or nitrogen13,32,33 in the graphitic framework of CNTs.
Typically, free radicals play a key role in such doping process.
Radio-frequency (r.f.) or microwave plasma discharge sources
have been applied for the formation of atomic, radical or other
unstable species.36 It is well known that the degree and type of
sidewall functionalization vs. graphitic framework incorpora-
tion depend upon the discharge parameters, such as the level of
applied power, gas compositions and exposure time.34,35 Addi-
tionally, r.f. plasma discharge has been demonstrated by many
studies to be the most efficient technique for incorporating
nitrogen atoms into the graphitic framework.37 Yet, an in-depth
study is still necessary to investigate the effect of discharge
parameters on the surface morphology of graphitic layer.
The main goal of this study is thus to ne-tune the surface
chemistry of the VACNTs. To this end, a systematic study has
been carried out using N2/H2 gas plasma discharge as an effi-
cient, clean, non-destructive and adjustable process for func-
tionalization and N-doping of the VACNTs. The selective control
of the densities and the relative ratios of different nitrogen-
containing functional groups are monitored using detailed
and combined microscopic and spectroscopic techniques. The
inuence of varying process parameters, such as r.f. power,
discharge exposure time and partial nitrogen ow rate in the
feed on the chemical bonding changes is additionally discussed
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and correlated to each type of nitrogen-containing functional
groups.
2. Experimental
2.1. Surface modication of the VACNTs by r.f. plasma
discharge
The VACNT arrays were synthesized using a catalyst driven,
water assisted thermal CVD, as described elsewhere.38 In short,
ethylene 100 sccm (standard cubic centimeters per minute) in
the presence of argon (600 sccm) was pyrolyzed at 850
C for 15
minutes. In a typical growth experiment, 400 sccm H2 and 200
ppm of H2O were applied.
The VACNT samples were subjected to a plasma discharge
treatment from the top side, using low-pressure parallel-plate
plasma system working at a capacitively coupled r.f. of 13.56
MHz, and with a power up to 200 W (FEMTO, Diener Electronic,
Ebhausen, Germany). The plasma discharge chamber was
evacuated to a base pressure less than 0.1 mbar and kept for few
minutes to reduce the effect of residual air on the sample. The
desired ow of high purity nitrogen and hydrogen to the system
was established through electronic mass ow controllers (MKS
Instruments), keeping the amount of total admitted gas at 20
sccm. The working pressure was allowed to increase and the r.f.
generator was switched aer achieving a constant working
pressure. The optimized power transfer to the plasma discharge
was maintained with the help of an automatic impedance
matching network. The incident power (Pi) and reected power
(Pr) were measured and the impedance was adjusted until the Pr
was very low (i.e. less than 0.02 W).
Aer the plasma reaction was terminated to quench any
reactive surface groups, rst argon, then air was fed into the
plasma chamber until the system returned to atmospheric
pressure. Subsequently, the chamber was opened. Unless
otherwise noted, all plasma discharges post-treatments are
summarized in Table 1.
2.2. Methods of analysis
Micro-Raman spectra were recorded for the pristine and as-
treated VACNTs in a backscattering mode using LabRam HR 800
micro-Raman spectrometer (Horiba Jobin Yvon, Bensheim,
Germany) equipped with an air-cooled, non-polarized green Ar+
laser (l ¼ 514.5 nm). The excitation line has its own interference
lter (to lter out the plasma emission) and a Raman notch lter
(for laser-light rejection). The measurements were performed
with a spectrometer grating of 1800 g mm1 and a confocal
microscope (long-working-distance objective, magnication
Table 1 Process parameters of plasma discharge at about 50
C
Experiment N2/H2 ow rate (sccm) Working pressure (mbar)
5N 05/15 0.70–0.76
10N 10/10 0.84–0.92
15N 15/05 1.10
20N 20/0 1.50–1.80
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50; numerical aperture (NA) 0.5; focused laser spot diameter
about. 2 mm). The laser power (20 mW) was attenuated on the
sample in the range of 2 mW to 20 mW by using neutral density
(ND) lters. Each Raman spectrum was collected between 200–
3500 cm1 with a peak position resolution of less than 1 cm1
and the spatial resolution of about 1 mm. D and G-band posi-
tions, their full width at half maximum (FWHM) and integrated
intensities were obtained by applying Lorentzian peak tting
using OriginPro (OriginLab, Northampton, MA, USA) for the
representative Raman spectra for each sample.
The morphology of the VACNT samples was examined using
a high-resolution transmission electron microscopy (TEM, FEI
CM 20 ST) operated at accelerating voltage of 200 kV. The
VACNT samples were dispersed in ethanol with assistance of
ultrasonication for few minutes and then one droplet of the
dispersion was transferred to a carbon-coated copper TEM grid
(PLANO, Wetzlar).
The elemental analysis and the chemical composition of the
as-treated VACNTs were carried out by using X-ray photoelec-
tron spectroscopy (XPS). The photoelectron spectra were
collected using a PHI VersaProbe 5000 spectrometer equipped
with monochromatic Al Ka source (hn ¼ 1486.6 eV) and using
the electron escape angle of 45
. The photoelectron survey
spectra were acquired with an analyzer pass energy of 93.9 eV in
the 0–1000 eV binding energy (BE) range to determine
elemental composition. The C(1s), O(1s) and (N1s) high-
resolution core level photoelectron spectra were collected
using a 23.5 eV pass energy with the energy resolution of the
spectrometer #0.7 eV measured by a reference experiment
using the full width at half-maximum intensity (FWHM) of the
Ag3d5/2 photoelectron line of a cleaned (carbon-free) Ag foil. The
base pressure in the measurement chamber was about 109
mbar and the diameter of the X-ray illuminated sample's area
was 200 mm. All the core-level BEs were referred to the Fermi
level of a cleaned Ag foil. The background under the high-
resolution photoelectron spectra was subtracted using a Shir-
ley-type function. The photoelectron peak positions and areas
were obtained by applying a weighted least-square tting of
a mixed Gaussian–Lorentzian product function to the experi-
mental data using XPSPEAK 4.1 soware, taking into account
a Doniach–Sunjic high BE tail for the C(1s) photoelectron line.39
During the deconvolution, all the tted peaks were self-
consistent and reproducible using 1.2 eV as a maximum limit
value of FWHM, allowing quantitative comparisons.
Fourier transform infrared (FTIR) spectra were recorded for
the as-treated VACNT samples with a Nicolet Magna 760 FT-IR
spectrometer operating in the attenuated total reectance
r.f. power (W) Post-treatment duration (min)
30 5, 60
30 60
30, 60 60
30 60
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Paper
(ATR) mode; 32 scans were taken with a resolution of 8 cm1.
The use of ATR-IR was in order to establish a straightforward
qualitative method for measuring CNT samples. Furthermore,
since the difference in refractive index between the carbon
sample and germanium (Ge) crystal is large (i.e. n ¼ 4.0)
compared to commonly used diamond or ZnSe crystal (n ¼
2.42), the ATR unit was equipped with the Ge which casts
a more shallow depth of beam penetration compared to
diamond.40
3. Results and discussion
3.1. Raman spectroscopy
Raman spectroscopic technique is a powerful tool to analyze
CNTs. In typical micro-Raman studies using a visible laser
source, the Raman-scattering bands mainly consist of two most
prominent characteristic modes. The rst mode is associated
with sp2-hybridized carbon, rst-order Raman, corresponding
to the aromatic stretching vibration in the graphitic planes (so-
called E2g mode or G-band), which is clearly observed at about
1582 cm1 and the second one is related to disorder mode (so-
called A1g breathing mode or D-band) at about 1350 cm1.41 The
Fig. 2 (a) Raman spectra of the as-treated VACNTs for the sample named 15N with a variation of the level of r.f. power at constant discharge
duration of 60 min, (b) the correlation between Raman-derived degree of disorder and graphitization degree, (c) the correlation between G-band
position and FWHM for D-band.
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RSC Advances
additional weaker band at 1610 cm1, referred to as D0 -band,
corresponds to a maximum in the phonon density of states and
normally exhibits a similar trend to that of the D-band.42 As is
well-known, the graphitic state of the carbon can only be
conrmed by the presence of the G mode.43
For an efficient nitrogen doping, the effect of variation in
plasma discharge parameters on the graphitization degree of
the as-treated VACNTs in comparison with the as-grown VACNT
microstructures will be correlated with the results obtained
from Raman spectroscopy.
Inuence of r.f. power level. It is quite obvious that the level
of r.f. power should be limited in order to avoid any possibility
of the excessive VACNT etching and deterioration. Indeed, the
Raman spectra (Fig. 2a) show that a loss of the CNT graphitic
structure mounts up with the increasing level of r.f. power. The
ratio between the integrated intensity of the D-band to that for
the G-band can be correlated with a number of defects existing
within the nanotube frameworks.34,35
The Raman-derived degree of disorder which can be ob-
tained from the integrated peak intensity ratio, ID/(ID + IG),
escalated from 0.42 for the pristine VACNTs to 0.47 and 0.56 for
30 and 60 W of employed r.f. power, respectively (Fig. 2b). In
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general, this indicates an increase of the degree of bond
disorder in the graphitic framework corresponding to a reduc-
tion in the size or number of planar coordinated sp2-hybridized
carbon centers.44 This is clearly supported by the emergence of
D0 -band (Fig. 2b), which becomes strongly Raman active with
the increasing r.f. power, and reects the presence of some
lattice defect inside the VACNT wall. On the other side, in the as-
treated VACNTs, the surface ordering of carbon atoms is an
indicative parameter for graphitization which is reected by the
FWHM of the G-band (WG),45 and it typically remains constant
upon plasma discharge. By contrast, there is a decrease of about
7.8 cm1 (Fig. 2c) for the FWHM of the D-band (WD) for the
VACNT sample treated at 60 W r.f. power compared to one
treated at 30 W under other similar plasma discharge condi-
tions.42 This may be indicative of the fact that at low r.f. power,
one can only remove some impurities, e.g. amorphous carbons
from the VACNTs due to a moderate plasma discharge, which is
unlike the relatively high r.f. power that could result in a severe
etching or damage to the graphitic framework. Additionally, the
WG/WD ratio of the treated samples at 30 W reveals similar to
that of the pristine VACNTs, which is shied by about 0.1 for the
Fig. 3 (a) Raman spectra of the as-treated VACNTs with variation of plasma discharge duration for the sample named 5N at the constant r.f.
power of 30 W, (b) the correlation between Raman-derived degree of disorder and graphitization degree, (c) the correlation between G-band
position and FWHM for D-band.
13092 | RSC Adv., 2016, 6, 13088–13100
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sample treated at 60 W. The latter represents rather a decrease
in the graphitization degree compared to the pristine VACNTs.
This could be understood, by increasing the incorporation of
nitrogen in the graphitic framework of the VACNTs, which
would be expected from an increase in the number of generated
free radicals.17,46 Still, downshis of about 7.0 to 4.5 cm1 of the
G-band positions are found (Fig. 2c) for the samples treated at
30 and 60 W, respectively, which are apparently uncorrelated to
the r.f. power employed. Nevertheless, those could be under-
stood in a way that at 30 W, plasma discharge treatment
generates a limited number of defect sites and a possible N-
doping can be generated. Nonetheless, the size or number of
sp2-hybridized carbon centers is still kept, which can easily be
correlated with a broadening of the D-band (i.e. high WD). This
is in contrast with the post-treatment at the r.f. power of 60 W,
i.e. reducing of sp2-hybridized carbon centers with an increase
in the amount of bond disorder and defects.
In summary, the result under 30 W r.f. power conrms that
the moderate plasma discharge processes rather promote
limited structural defects and lead to acceptable N-doping
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Paper
concentrations, without substantially affecting the size of
graphitic domains in the as-treated VACNTs.
Inuence of plasma discharge exposure time. In order to
investigate the effect of plasma discharge duration, the r.f. power
was kept at the optimum value of 30 W. Fig. 3a presents the
normalized Raman spectra of the as-treated VACNTs and clearly
shows the emergence of D0 -band, which becomes strongly
Raman active (Fig. 3a) by increasing the plasma discharge
exposure time. In addition, a detailed peak analysis in Fig. 3b
reects that the ID/(ID + IG) value shis from 0.42 for the pristine
VACNTs to 0.44 and to 0.43 for 5 and 60 minutes, respectively.
This again indicates an increase in bond disorder in the
nanotube framework, which manifests itself in a decrease in the
size or number of sp2-hybridized carbon centers. Nevertheless,
a strong decrease in the rst ve minutes of plasma discharge
treatment again might be due to the initial removal of some
amounts of amorphous carbon being present in the pristine
VACNTs. Aer that, the nitrogen doping effect commences and
leads to an increase in N-doping content. This interpretation is
supported with the fact that WD increases by about 11.4 cm1
upon plasma discharge for 5 minutes, compared to the pristine
Fig. 4 (a) Raman spectra of the as-treated VACNTs with a variation of discharge N2/H2 flow rate at the constant r.f. power of 30 W and discharge
duration of 60 min, (b) the correlation between Raman-derived degree of disorder and graphitization degree, (c) the correlation between G-band
position and FWHM for D-band.
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RSC Advances
VACNTs (Fig. 3c). The WG/WD ratio, however, decreases only by
about 0.02 for plasma discharge treatment of 60 minutes, but it
shis signicantly by about 0.1 that is a vefold increase for the
VACNT sample treated only for 5 minutes. The latter case
represents an apparent increase in graphitization degree
compared with the pristine VACNTs, unlike to the sample
treated for 60 minutes due to an efficient incorporating of
nitrogen atoms into nanotube frameworks, as will be discussed
in XPS analysis section. A signicant downshi of about 8.5
cm1 was also obtained for the G-band positions in the samples
treated for 60 minutes (Fig. 3c). This can be attributed to the
existence of more bond disorder or defects which provides
indirect evidence suggesting an increase of N-doping content
and can be conrmed by the narrowing of D-band (low WD).
Inuence of discharge N2 ow rate. In order to investigate
the effect of discharge nitrogen ow rate and detect possible
inuences on the amount of nitrogen functionalization during
plasma discharge post-treatment, the r.f. power and the
discharge duration were kept at optimum values of 30 W and 60
minutes, respectively. Moreover, Fig. 4a shows the normalized
Raman spectra of the as-treated VACNTs, which can be
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apparently correlated. The peak analysis in Fig. 4b, shows that
the ID/(ID + IG) value shis from 0.42 for the pristine VACNTs to
0.43, 0.44, 0.47, and 0.48 for 5N, 10N, 15N and 20N, respectively.
In general, this could reect an increase of the degree of bond
disorder in the as-treated VACNTs, correlating with a decrease
in the size or number of sp2-hybridized carbon centers and it is
supported by the emergence of D0 -band, which becomes
strongly Raman active with the increase of discharge nitrogen
ow rate in the feed (Fig. 4a). Additionally, the WG/WD ratio is
mainly constant for the 5N, 10N and 15N samples and similar to
that of the pristine VACNTs.
On the other hand, there is an upshi by about 0.08 for the
20N sample, which could reect a little decrease in graphitization
Fig. 5 HRTEM images of the as-treated VACNTs (15N sample) before
(a and b) and after (c and d) heat-treated at 550
C under air for 15
minutes.
Fig. 6 (a) X-ray photoelectron survey spectra of the as-treated VACNT samples, (b) the nitrogen to oxygen atomic ratio as estimated from the
high-resolution O(1s) and N(1s) spectral envelopes.
13094 | RSC Adv., 2016, 6, 13088–13100
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degree. This will be discussed later intensively in the XPS section.
In addition, Raman downshi up to 9 cm1 for the G-band
positions in all the as-treated VACNT samples (Fig. 4c) suggests
generation of defects or incorporation of nitrogen atoms within
the nanotube framework. Interestingly, the higher WD value (i.e.
a broadening of D-band) for 10N and 15N samples provides an
indirect evidence of the increasing number or size of the sp2-
hybridized carbon centers compared to other samples, which can
suggest an acceptable N-doping content without affecting the
graphitization degree signicantly.
Taken as a whole, the Raman spectroscopic investigations
suggest that the parameters of plasma discharge treatment have
been optimized by using discharge nitrogen ow rate between
10 to 15 sccm at 30 W for 60 minutes (see Table 1).
3.2. Surface morphological investigation
The electron microscopic measurements on the as-treated VACNTs
have been performed in order to verify the structural change and
the surface morphology of the as-treated nanotubes in comparison
with the previous result of the VACNTs on the pristine nanotubes.47
HRTEM images of an individual nanotube of the as-treated
VACNT before and aer thermal post-treatment at 550
C in an air
atmosphere (Fig. 5) clearly depict a decrease in non-conjugated
organic compounds. This can probably be ascribed to the partial
etching and gasication of amorphous carbons through plasma
discharge (Fig. 5a) and thermal post-treatment (Fig. 5b), respec-
tively. This is due to an apparent result of a moderate post-
treatment, and no further purication is required. Interestingly,
the presence of a little distortion in the linearity of the nanotube
structure along with a few corrugated fringes and round cap
morphologies on the as-treated nanotube clearly indicate the
incorporation of nitrogen atoms.48
3.3. XPS surface characterization
The changes in the elemental composition and chemical
bonding state of the carbon atoms induced by N-doping of the
graphitic framework were analyzed by XPS.
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The XPS survey spectra of the as-treated VACNTs (Fig. 6a)
demonstrate the presence of carbon, nitrogen and oxygen with
the BEs centered at about 284.7 eV, 400.0 eV and 532.0 eV for
C(1s), N(1s) and O(1s) core-level electrons, respectively.49 No
impurities in the samples have been detected. It is widely
recognized that the presence of oxygen-containing functional
groups accompanies the nitrogen functionalization. This is
either due to passivation of physical defects by oxygen during
ambient air exposure of the VACNT surfaces, or probably related
to the residual air in the plasma discharge chamber.50
As could be expected, the atomic surface concentrations of
nitrogen and oxygen increase in the as-treated VACNTs with the
increase of nitrogen ow rate in the feed during plasma
discharge functionalization, as seen in Fig. 6b and the inset
table. However, there is a slight increase of the N/O atomic ratio
at 10 sccm nitrogen ow rate, which can be considered as an
optimum condition for the efficient discharge process with high
content of nitrogen atomic radicals.
The high-resolution C(1s), N(1s) and O(1s) XPS spectral
envelopes of the as-treated VACNT as a function of different
nitrogen contents were plotted and tted into their compo-
nents. In general, the interpretation of XPS data is not
straightforward due to controversy in the literature.51 Yet,
Table 2 summarizes the most important documented XPS data
of characteristic BEs (in eV, 0.2) and their assignments for
various nitrogen and oxygen moieties in some carbon-based
materials. As the nitrogen content increases, the C(1s) XPS
spectral envelopes are becoming more asymmetric and slightly
broader towards higher BEs (Fig. 7a) which is a sign of nitrogen
incorporation into the graphitic lattice. The C(1s) XPS spectral
envelopes were tted into six main components; C1, C2, C3, C4,
C5 and C6. Fig. 7b presents the area percentages of tted peaks
as a function of nitrogen content. Thus, the most intense C(1s)
photoelectron line at about 284.5–284.7 eV, denoted as C1 in
Table 2, is assigned to the carbon bond with the sp2-hybridized
character as in graphite.24,49,52–54 As the nitrogen content is
raised to 12.39 at%, the peak area of the C1 component is
slightly increased, which is correlated with an increase of the
graphitic behavior observed in the as-treated VACNTs.
This result is consistent with the previous Raman spectros-
copy measurements, indicating that the graphitic framework of
the VACNTs is preserved for 15N sample in comparison with
20N sample. On the other side, there is a decrease in the peak
areas associated with C2 and C3 components, at about 285.2–
285.3 and 286.0–286.2 eV BEs. The C2 component is usually
attributed to the carbons in sp3-hybridization52–54 and/or sp2-
hybridized bonding of carbon with nitrogen moieties as in
pyridine,55 while C3 component refers either to sp3- and sp-
hybridized bonding of carbon connected to nitrogen,52,55 or to
oxygen moieties including ether or alcohol groups.24,49,52,54,56
Interestingly, the C4 component at about 287.1–287.5 eV shows
a very slight increase in the peak areas over the entire range of
nitrogen content attributed to carbonyl moieties, e.g. in ketone,
amide and lactam functional groups.24,49,52,54,56 In addition, the
peak areas of the C5 component at about 288.4–288.7 eV are
increased gradually and can correspond to either carbamide

Table 2 Set of characteristic BEs (in eV, 0.2) and their assignments in some reported carbon-based materials

Peak Binding energies (eV)

C(1s) C1 C2 C3 C4 C5 C6

284.1–284.7 285.0–285.7 285.9–286.9 287.0–288.0 288.4–288.8 289.1–290.4

C sp3 52–54 sp3 C–N C–*C]O O–C]O
sp C^N52,55 N–C]O N–C(N)]O N–O–C]O
C sp2 sp2 C]N C–OH epoxy O]C–O–C]O
Graphite24,49,52–54 Pyridine53 C*–O–C]O O–C–O O]C–N–C]O52 N–C(O)]O
C–O–C24,47,50,52,54 N–C–O24,49,52,54,56 O–C(O)]O52

O(1s) O1 O2 O3 O4 O5 O6

530.7–531.1 531.3–532.3 532.5–532.9 533.1–533.5 533.6–534.0 534.7–535.3

quinone24,51,57 C–C]O OH epoxy *C–C]O
*O–C(O*)]O
N–C]O C–C(O2)–O C–O O]C–O*–C]O C–O–NO*252
O–C]O* C–NO252 C–O–C N–C(O*)]O
N–C(N)]O O–C–C52,54,57 C–O*–NO2 52
O]C–N–C]O52

N(1s) N1 N2 N3 N4 N5

398.3–399.3 399.7–400.2 400.1–400.9 401.1–401.8 402.0–406.1

sp2 C–N amine sp3 C–N
pyrrolic substitutional (graphitic) pyridine-N-oxide
amide pyridone
pyrrolidone imide quaternary N51–53,60 NOx9,51–53,58–60
pyridinic-N22,51,52,58–60 urea N51,52,61 carbamate N51,52,58–60

This journal is © The Royal Society of Chemistry 2016 RSC Adv., 2016, 6, 13088–13100 | 13095
RSC Advances
Fig. 7 (a) High-resolution C(1s) photoelectron scans for the as-treated VACNTs and the fitted peaks, (b) the percentages of peak areas as
a function of discharge nitrogen content.
(urea) or imide functional groups.52 The increase of nitrogen
content at the expense of hydrogen intake in the plasma
discharge chamber makes all reactions take place under a rela-
tively low reducing atmosphere, i.e. N-doping of the VACNTs
occurs at more oxidative conditions as the nitrogen content is
augmented to about 23.35 at%, (Fig. 6a). This generates an
intense peak, denoted by C6 in Table 2, at 289.6 which is mainly
assigned to carbamate (urethate) functional groups,52 as will be
discussed later in the ATR-FTIR section. Further, resonance
shake-up satellite peak caused by p–p* transitions located
above 290.5 eV, refers to the presence of aromatic structures.10
This conrms that the optimized plasma discharge parameters
preserve to some extent the graphitization degree of the
VACNTs. Moreover, some aromatic nitrogen-containing struc-
tures could also give rise to this peak.
The O(1s) XPS spectral envelopes in Fig. 8a were tted into
six main components; O1, O2, O3, O4, O5 and O6, as denoted in
Table 2.
These may be related to different bonding constitutions of
carbon to oxygen moieties corresponding to quinine,24,51,57
carbonyl, e.g. in ketone, amide and carbamide,52 hydroxyl and/
or nitro (NO2),52 ether and/or epoxy,52,54,57 carboxyl and/or
carbamate,52 and nitrate (NO3) functional groups,52 respectively.
Fig. 8b presents the area percentages of tted peaks as
a function of nitrogen content. As the nitrogen content
13096 | RSC Adv., 2016, 6, 13088–13100
Paper
increases, the oxygen content associated with the O4 compo-
nent rises gradually. On the other side, there is an increase of
the peak areas as the nitrogen content approaches to about
12.39 at%, for both the O1 and O2 components at the expense of
the O5 and O3 components, respectively. This is due to the
chemical conversion of hydroxyl and carboxyl moieties to
quinine and amide/carbamide functional groups in the pres-
ence of more oxygen and nitrogen radicals (only 5 sccm H2).
Additionally, at the highest nitrogen content in this study (23.35
at%), the new component O6 was emerged at the higher BE of
about 535.0 eV, along with the increase of both O3 and O5
components. This is due to relatively strong oxidative condi-
tions, which results in a generation of more nitrogen oxides,
(e.g. NO2, NO3) and carbamate functional groups, respectively.
To gain a more detailed insight into the surface chemical
bonding states of nitrogen-containing functional groups, the
N(1s) XPS spectral envelopes as a function of nitrogen content
are plotted in Fig. 9a. Generally, the N1s photoelectron emis-
sion demonstrates a shi to higher BEs with the increase of
nitrogen content in the graphitic framework of the as-treated
VACNT samples. The N(1s) XPS spectral envelopes were tted
into ve main components; N1, N2, N3, N4 and N5. Fig. 9b
presents the area percentages of tted peaks as a function of
nitrogen content. The N(1s) XPS component at about 398.5–
399.1 eV, denoted by N1 in Table 2, is associated with pyridinic-
This journal is © The Royal Society of Chemistry 2016
Paper
Fig. 8 (a) High-resolution O(1s) photoelectron scans for the as-treated VACNTs and the fitted peaks, (b) the percentages of peak areas as
a function of discharge nitrogen content.
type nitrogen (Fig. 1), which occurs using exciting defects or at
the edge sites.22,51–53,58–60 The N2 component at about 399.4–
400.0 eV indicates to primarily the presence of amide or amine-
like nitrogen,51,52,61 whereas pyrrolic, carbamate or imide-like
nitrogen contributes to the N3 component with BEs centered
at about 400.2–400.9 eV.51,52,58–60 In addition, the N4 at about
401.1–401.8 eV is attributed to substitutional nitrogen (so-called
graphitic and/or quaternary nitrogen) as shown in Fig. 1.51,52,58–60
It is worth noting that only at high nitrogen content of about
23.35 at% (i.e. for 20N sample), can the weak N1s XPS compo-
nent at 402.8 eV be merged compared to other samples with the
lower nitrogen content. This component, referred to as N5 in
Table 2, can be associated with either pyridine-N-oxide or
different nitrogen oxide functional groups.9,51–53,58–60
Interestingly, from the relative atomic content in the inset
table of Fig. 6b, one can conclude that the augmented content of
graphitic (N4) and pyrrolic (N3) nitrogen in the as-treated
VACNTs is generally observed demonstrating the same trend
with increasing nitrogen content. Additionally, the increase of
the amount of pyrrolic-N (N3) obtained at 12.39 at% nitrogen
content exhibits a trend inversely correlated with that of
pyridinic-N (N1). This is supposed to be mainly due to a signif-
icant fraction of bond disorder within the nanotube framework
induced by an increase in nitrogen content. On the other side,
the amount of graphitic-N (N4) at 10.18 at% nitrogen content
shows a signicant increase at the expense of the dangling
This journal is © The Royal Society of Chemistry 2016
RSC Advances
bonds (N2) and the defects (mainly vacancies) created during
the plasma discharge. Besides, the rearrangement between the
neighboring carbon and incorporated nitrogen atoms in the
VACNTs creates a nitrogen mainly with sp3-hybridized
character.25
Taking also the results above obtained from the C(1s) XPS
study into consideration, one can conclude that they verify the
efficient incorporation of nitrogen atoms into the graphitic
framework.
3.4. Analysis of surface functionalization by ATR-FTIR
High-resolution XPS analyses have revealed the presence of
several types of nitrogen and oxygen moieties, such as those in
amines, amide, imines, as well as hydroxyl, ether, carboxyl,
carbonyl etc. However, the C(1s), N(1s) and O(1s) XPS spectral
envelopes cannot be fully resolved and could lead to misleading
and ambiguous results in terms of the calculated distribution of
functional groups. To overcome the limitations inherent in XPS
peak tting, the chemical characterization of the N-VACNTs has
to be strengthened further by an additional analytical method,
such as ATR-FTIR spectroscopy. This method can provide
molecular information that is complementary to the XPS data,
particularly regarding the organic functional groups. Fig. 10
illustrates the FTIR spectra of the pristine and as-treated-
VACNTs samples. The characteristic IR absorption bands that
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RSC Advances
Fig. 9 (a) High-resolution N(1s) photoelectron scans for the as-treated VACNTs and the fitted peaks, (b) the percentages of peak areas as
a function of discharge nitrogen content.
could be used in identifying various nitrogen and oxygen
moieties show broad spectra of the as-treated VACNT samples
that present signals with some spectral overlapping.
Nevertheless, the presence of amides can easily be detected
due to the presence of a relatively high-intensity spectral peak
around 1665 and 1560 cm1 corresponding to amides I and
Fig. 10 ATR-FTIR spectra of the as-treated VACNT samples compared
to the pristine VACNTs.
13098 | RSC Adv., 2016, 6, 13088–13100
Paper
amide II, respectively.62 Moreover, the broad IR absorption
region of the spectrum, which extends from 1450 to 1600 cm1
for all the as-treated and pristine VACNTs samples, is
commensurate with the preservation of their graphitic
structure.
In general, it is possible to identify six distinct absorption
bands around 3250, 2910, 1665, 1560, 1450, 1165 and 760–860
cm1. These bands can be assigned to N–H stretching vibra-
tions in amines or amides, sp3-hybridized C–H stretching
vibrations, overlap stretching vibrations of C]O and C]N
moieties in amides I (e.g. carbamide) and imines, respectively,
overlap stretching vibrations C]C/C]N stretching vibrations
in aromatic systems and N–H bending vibrations in amines,
sp3-hybridized C–H bending vibrations in alkanes (i.e. amor-
phous carbon), overlap stretching vibrations of C–N and C–O
moieties, and out-of-plane bending vibrations of both N–H and
aromatic ring C–H.62,63 It is worth noting that in the 20N
sample, a broad absorption band centered at 1710 cm1 has
been observed to give rise to overlap stretching vibrations of
both C]O and N–O moieties. Taking into consideration the
above results obtained from the XPS study, these overlap
vibrations indicate clearly the presence of carbamate formed
and nitrogen oxide functional groups, respectively. The
formation of carbamates normally occurs by reaction of
isocyanates with alcohols. Finally, the presence of N–O moie-
ties is also evidenced by the emergence of weak band
This journal is © The Royal Society of Chemistry 2016
Paper
absorption around 1370 cm1, which is mainly attributed to
the nitrate functional groups.62
4. Conclusions
This work investigates an efficient, clean, non-destructive and
adjustable process of modifying the surface chemistry of the
VACNTs by functionalization and doping in a controlled manner.
A systematic study has been performed by means of r.f. plasma
discharge with varying process parameters, e.g., N2/H2 gas
volume ratio in the feed, r.f. power and discharge exposure time.
The r.f. power was intentionally kept in the low range in order to
minimize the possible deterioration of the graphitic framework.
A combined spectroscopic and microscopic investigation
was carried out to evaluate the structural disorder of the as-
treated VACNTs as a function of nitrogen ow rate. The C(1s)
XPS results demonstrate that as nitrogen content increases up
to 12.39 at%, i.e. in the presence of both nitrogen and hydrogen
in the feed inside the plasma discharge chamber, the pure sp2-
hybridized carbons in the VACNTs increase. This occurred
along with the formation of sp3-hybridized carbons as well as
some of C–N and C–O moieties that become more Raman active
and reected by the emergence of D0 -band. At the high nitrogen
ow rate and absence of hydrogen in the feed, a formation of
carbamate, nitrogen oxide and pyridinic oxide on the surface of
the VACNTs were conrmed by XPS and ATR-FTIR analysis as
well. Interestingly, the textural characteristics using HRTEM
investigation indicated some corrugated fringes and round cap
morphologies on the as-treated nanotube with a signicant
decrease in non-conjugated organic compounds (i.e. amor-
phous carbon).
Moreover, the detailed XPS analysis revealed that the density
of some functional groups with acidic properties, mainly
pyrrolic and graphitic-type N, escalates as the nitrogen content
in the as-treated VACNTs increases, along with the undeliberate
augmentation of the acidic oxygen-containing functional
groups. The decrease in the densities of the pyridinic and
amine-type nitrogen-containing functional groups cannot be
explained as a simple creation of edges terminated by nitrogen
atoms, but rather as a rearrangement of the neighboring carbon
atoms that can take place within the nanotube framework. On
the contrary, under low nitrogen content, i.e. at reducing
atmosphere, the density of nitrogen-containing functional
groups with basic properties, mainly amine and pyridinic-type
N, increases.
Last but not least, the present work contends to lay the
groundwork for selective control of the densities and the rela-
tive ratios of different acidic and basic surface functional
groups on the surface of the as-treated VACNTs or within the
nanotube framework. The active N-CNTs are highly demanded
in different potential applications, e.g. in gas adsorption, ter-
ahertz time-domain spectroscopy, gas sensing and catalysis.
Acknowledgements
The LOEWE-Research Cluster “Sensors towards Terahertz STT”
has funded this work through the state of Hesse. The scientic
This journal is © The Royal Society of Chemistry 2016
RSC Advances
support from Prof. Jörg J. Schneider at TU Darmstadt by
allowing use his lab infrastructure is highly acknowledged. The
author thanks Dr Jörg Engstler for performing the TEM
measurements. The author is also grateful to Mr Deepu Babu,
Mr Sandeep Yadav and Dr Gennady Cherkashinin at TU
Darmstadt for their assistance in synthesizing the pristine
VACNT samples as well as Raman and XPS measurements,
respectively. Special thanks go to Prof. Christian Hess at TU
Darmstadt for fruitful discussions.
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