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covalently functionalized multiwalled carbon

Cite this: Phys. Chem. Chem. Phys.,
2016, 18, 12784 nanotubes: unraveling disorder in graphitic
materials†
Susana L. H. Rebelo,*a Alexandra Guedes,b Monika E. Szefczyk,‡a André M. Pereira,c
João P. Araújoc and Cristina Freirea

Raman spectroscopy is highly sensitive to the morphology and electronic structures of graphitic
materials, but a convenient interpretation model has been lacking for multiwalled carbon nanotubes
(MWCNTs), in particular for the discrimination of spectral changes induced by covalent functionalization.
The present work describes a systematic investigation of the Raman analysis of covalently functionalized
MWCNTs by diazonium chemistry and oxidation methodologies, with typically different mechanisms and
reaction sites. A multi-peak deconvolution system and spectral band assignment were proposed based
on the chemical and structural modifications identified by X-ray photoelectron spectroscopy,
thermogravimetry, X-ray diffraction, specific surface areas and the comparative analysis of the first
Received 28th October 2015, and second order regions of the Raman spectra. Diazonium functionalization takes place mainly in the
Accepted 5th April 2016 p-system of the external sidewall, while oxidation occurs on defects and leads to structure burning. This
DOI: 10.1039/c5cp06519d allowed us to distinguish between spectral features related to aromaticity disruptions within the
sidewalls and spectral features related to changes within the inner tubes. The model was validated
www.rsc.org/pccp extending the studies to the functionalization of MWCNTs by the Bingel reaction.

Introduction convenient understanding of the origin of structural disorder

related to Raman analysis and the underlying phenomena has
Raman spectroscopy is becoming a technique of increasing been hampering its full application.5,6
relevance for the characterization of carbon materials.1,2 Apart On carbon materials, there is a close association between
from being non-destructive, it is simple and rather sensitive not structural complexity and the complexity of their Raman spectra.7,8
only to the crystal structure (the long range order), but also to Carbon allotropes with a highly uniform structure, such as
structural changes occurring at the molecular level (the short diamond and graphite, have very simple Raman spectra.
range order). Therefore, Raman spectroscopy has high potential Graphite, with planar and perfectly aligned layer stacking,
to access chemical functionalization and give further insights shows two sharp features in the Raman spectra: the G band
into electron microscopy or X-ray diffraction (XRD)3 that can in the first order region at about 1580 cm1 and the 2D (or G 0 )
be quite insensitive or inconclusive towards morphological band, between 2600–2700 cm1, in the second order region.9
modifications at the molecular level.4 However, the lack of a The presence of irregularities in that structure results in a weak
D band at near 1350 cm1.10 Therefore, the D band is known as
a
REQUIMTE/LAQV, Departamento de Quı́mica e Bioquı́mica, Faculdade de Ciências, the disorder or the defect band and its intensity has been
Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal. considered directly proportional to the level of defects in the
E-mail: [email protected]; Fax: +351 22 0402 659
b
sample.
Instituto de Ciências da Terra, Pólo da FCUP and Departamento de Geociências,
Ambiente e Ordenamento do Território, Faculdade de Ciências,
The G band is ascribed to in-plane vibrations from E2g
Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto, Portugal modes and the D band to out-of-plane vibrations from A1g
c
IFIMUP and IN-Institute of Nanoscience and Nanotechnology, modes.11 The 2D band is the second order of the D band and is
Departamento de Fı́sica e Astronomia, Faculdade de Ciências, Universidade do Porto, referred to as its overtone. It results from a two-phonon lattice
Rua do Campo Alegre 687, 4169-007 Porto, Portugal
vibrational process, but unlike the D band, it is not activated by
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c5cp06519d
‡ Actual address: Department of Bioorganic Chemistry, Faculty of Chemistry,
the proximity to defects.
Wrocław University of Technology, Wybrzeże S. Wyspiańskiego 27, 50-370 Wrocław, Carbon nanotubes (CNTs) are graphitic carbon allotropes
Poland. with more complex structures. They have relevant properties

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for diverse applications,12 such as in optoelectronic devices to shapes, such as the curvature in carbon nanotubes or nano-
afford one-direction conduction;13 in the fabrication of structural fibers,23 the reduction of the graphitic crystal size going from
and functional composites to afford mechanical robustness; or in bulk to nanoscale materials (the presence of edge structures)24,25
catalyst preparation, owing to the well-defined structure and high or the presence of amorphous carbon.26,27
surface areas, which are advantageous to afford efficient and In the present work, we report a comparative Raman study of
reproducible catalytic processes.14 covalently functionalized MWCNTs through a reaction with
For all these goals, covalent functionalization is preferred in anilines, in the presence and absence of isopentyl nitrite28
order to establish strong or conductive connections. Furthermore, and through oxidation by liquid and gas phase procedures29
multiwalled carbon nanotubes (MWCNTs) have increasing appli- (Fig. 1). A deep spectral analysis and correlation with characteri-
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cations compared to single-walled carbon nanotubes (SWCNTs) zation by relevant techniques was aimed to obtain a general
due to their higher structural and electronic integrity upon model for identifying and understanding the Raman signatures
functionalization.15 of MWCNTs and find appropriate tools to evaluate structural
Further exploitation of Raman spectroscopy for improved changes upon molecular functionalization.
MWCNT characterization is very relevant, with a consequent
better understanding of their conductivity, robustness and
reactivity.16 Experimental section
Remarkably, the Raman spectra of SWCNTs and MWCNTs
are characteristically different. SWCNTs generally show similar Commercial MWCNTs were purchased from Nanocyl S.A.,
spectra to graphite, with intense G and 2D bands and a week D Ref. NC3100, with an average diameter of 9.5 nm, a length of
band, although showing a slight broadening effect.17 1.5 mm and carbon purity 495% C, according to the supplier.
On the other hand, the Raman spectra of MWCNTs, even of Functionalization of MWCNTs by diazonium chemistry,
highly graphitic quality, are similar to the spectra of chars and reaction with anilines, oxidation and the Bingel reaction were
carbon blacks, showing a very intense D band and a significant carried out by previously reported procedures14,28,29 and
broadening effect.18,19 summarized in the ESI.†
For SWCNTs the degree of covalent functionalization has The Raman spectra were measured directly on the materials
been efficiently quantified by the ratio of band intensity ID/IG.20 using a Labram Dilor–Jobin-Yvon–Spex spectrometer, with the
However, the covalent functionalization of MWCNTs does not monochromatic red light at 632.8 nm of the He–Ne laser as
generally result in obvious changes in the ID/IG ratio.5,21,22 the excitation source, at a power of 20 mW. Once the D band
In order to quantitatively evaluate the functionalization is a resonant mode and exhibits dispersive behavior, both
degree, it is important to identify the disorder arising from its position and shape can vary with different excitation laser
covalent functionalization, related to the transformation of sp2 frequencies. Therefore, the excitation laser frequency was
aromatic carbon into sp3 carbon, and distinguishing it from the maintained for all measurements.
other structural effects and deviations to the perfect graphite A density filter was used to avoid thermal decomposition of
structure. These include, non-uniform planar-layer stacking samples by the laser. The 100 objective lens of an Olympus

Fig. 1 Preparation of studied materials illustrating the main functional groups introduced: (a) in situ formation of diazonium salts (r = molar ratio
isopentyl nitrite/aniline);28 (b) direct reaction with anilines;28 (c) oxidation by liquid (HNO3) and gas phase (O2) methodologies.29 In the center is the SEM
image of original MWCNTs (scale bar = 500 nm).

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optical microscope was used to focus the laser beam on the Fig. 2 shows the Raman spectra of the resulting Dz_R[r]
sample and to collect the scattered radiation. A highly sensitive materials (green lines) in comparison to original MWCNTs (red
CCD camera was used to collect the Raman spectra. Each lines). For a better comparison, all the spectra are normalized
Raman spectrum presented in this study corresponds to the for the D band.
accumulation of 20 spectra recorded from 1000 to 3500 cm1 The spectral patterns are similar for the different materials,
over 30 s; five accumulated spectra were collected for each displaying two broad features in the first order region (1000–
sample to access the within-sample heterogeneity, at spectral 2000 cm1) with maxima at near 1325 and 1585 cm1, attributed
resolutions near 1 cm1. to the D and G bands, as well as, a broad and asymmetric
Adequate fits to the experimental data were obtained using feature in the second order spectra (2000–3500 cm1) at near
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a mixed Gaussian–Lorentzian curve-fitting procedure in a 2650 cm1.

Labspec program. The goodness of the fittings was indicated by It can be noticed that the relative heights of the D and G
w2 value o 1. The fitting was performed without fixing or limiting bands were maintained upon diazonium functionalization.
the range of any spectral parameter in the iteration procedure. This behavior was unexpected, as generally the chemical func-
Powder X-ray diffraction (XRD) patterns were registered in a tionalization has been associated with an increase of the D
Siemens D5000 diffractometer at room temperature, using mono- band intensity. However, comparing the green spectral lines
chromatized CuKa radiation as an incident beam (l = 1.5406 Å; (Dz_R[r] materials) and the red ones (MWCNT), it can be seen,
40 kV and 30 mA conditions) with automatic data acquisition. a systematic band broadening effect and higher valley lines
Data were collected twice for each sample over the 2y range of between the D and G bands, upon functionalization, concomi-
10–901, at 0.05 steps and 16 s counting time per step. tantly with a slight decrease in the 2D band intensity. For
X-ray photoelectron spectroscopy (XPS) analyses were per- Dz_R[r] materials the spectral changes observed are nearly of
formed in a VG Scientific ESCALAB 200A spectrometer using the same magnitude, independently of aniline and the ratio of
non-monochromatic Al Ka radiation (1486.6 eV). The measure- isopentyl nitrite towards aniline [r] used (Fig. 2a–d).
ment was carried out using pellets of the materials. Binding The insets of Fig. 2 collect characterization data for those
energies were calibrated relative to the C1s peak at 284.6 eV. materials, namely the total heteroatom percentages by X-ray
The raw XPS spectra were deconvoluted by curve fitting peak photoelectron spectroscopy (XPS) and the thermogravimetric
components using the software XPSPEAK 4.1 with no preliminary (TG) mass loss percentages in the range of 20–900 1C.28 The
smoothing. Symmetric Gaussian–Lorentzian product functions graphitic structures do not decompose under an inert atmosphere
were used to approximate the line shapes of the fitting components in the temperature range 20–900 1C, whereas most ruptures on
after a Shirley-type background subtraction. Atomic ratios were that structure due to chemical functionalization (functional
calculated from experimental intensity ratios and normalized groups and sp3 carbon) decompose in that temperature range
by atomic sensitivity factors. and can be quantified by TG.
The thermogravimetry (TG) measurements were obtained The XPS heteroatom atomic percentages are practically
in a STA 409 PC device from NETZSCH. All samples (typically constant for all Dz_R[r] materials (6–8%), as well as, the TG
5–7 mg) were heated under nitrogen flow (200 cm3 min1) to mass losses (9–11%), confirming the efficiency of functionali-
900 1C at a rate of 10 1C min1. zations on materials Dz_R[r] that are mostly independent of the
The textural characterization by Brunauer–Emmett–Teller R group and of the amount of isopentyl nitrite used. This is in
(BET) surface area was based on the N2 adsorption isotherms agreement with the observed Raman effects.
determined at 196 1C using a Quantachrome NOVA 4200e
apparatus. Direct reaction with anilines
In order to test different functionalization pathways and
mechanisms, the functionalization of MWCNTs by a direct
Results and discussion reaction with p-substituted anilines was performed in the
absence of isopentyl nitrite (Fig. 1b). This reaction pathway is
Diazonium functionalization efficient for anilines carrying electron-withdrawing groups and
Diazonium chemistry is one of the most efficient and used is ascribed to the intermediacy of dipolar species that attack the
methodologies for the covalent functionalization of carbon p-system of the nanotube, although being inefficient for other
materials (Fig. 1a). In the presence of a reductant, such as anilines.28
isopentyl nitrite, anilines convert to azo compounds, which The Raman spectra of the resulting materials An_R (Fig. 2a–d,
then decompose at moderate temperature releasing N2 and aryl blue lines) show different effects depending on the aniline used.
radicals. The radicals formed undergo a coupling reaction with The spectra of materials An_CO2Et and An_CO2H (Fig. 2a and b)
the p-system of the nanotube. are very similar to the spectra of MWCNTs, indicating inefficient
The functionalization of MWCNTs through diazonium reaction with carboxyanilines. On the other hand, materials
chemistry in the presence of different p-substituted anilines resulting from the direct reaction with anilines carrying electron-
NH2–Ph–R (R = CO2Et, CO2H, OH, I) and isopentyl nitrite withdrawing substituents, An_OH and An_I (Fig. 2c and d), show
afforded materials Dz_R[r], where r is the ratio of isopentyl Raman spectra with significant differences relatively to MWCNTs.
nitrite towards aniline, r = 0.5, 0.7, 1.2. Namely, material An_OH shows notorious modifications.

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Fig. 2 Raman spectra of materials prepared by the reaction with p-substituted anilines (NH2–Ph–R): (a) R = CO2Et; (b) R = CO2H; (c) R = OH;
(d) R = I. The graphs compare MWCNTs with materials prepared in the absence of isopentyl nitrite (An_R, green lines) and in the presence of isopentyl
nitrite (Dz_R[r], blue lines, r = molar ratio of isopentyl nitrite towards aniline) normalized for the D band. The insets collect other characterization data:
a
sum of heteroatom percentages by XPS; b TG mass losses percentages obtained in the interval 20–900 1C under nitrogen and a heating rate of
10 1C min1.28

The chemical and structural characterization data collected However, some drawbacks arise from the application of
in the insets of Fig. 2 for An_R materials confirm the achieve- these models to broad spectral patterns, as the ones of the
ment of the highest functionalization for material An_OH (19% present materials. These include the difficulty in distinguishing
by XPS and 27% by TG), high functionalization for material accurately the highly overlapping bands, as the G and D 0 bands,
An_I (9% by XPS and 16% by TG) and inefficient functionaliza- and the non-uniform width distribution of the deconvolution
tion for materials An_CO2Et and An_CO2H. bands. Consequently, the quantification and attribution of
structural variability has been impracticable. This is more
Spectral fitting and band assignment evident when analyzing small variations, as the ones generated
Comprehensively the above data show a relationship between upon covalent functionalization.
Raman spectra effects and functionalization. Therefore, in The deconvolution strategy exemplified in Fig. 3 considered
order to quantify the observed spectral broadening and find the full region between 1000–3500 cm1 of the Raman spectra
relations with the chemical functionalization degree, it was fitted in a single process.35 Each base spectral feature of the
necessary to develop an appropriate deconvolution model. spectra was fitted with a multi-peak system, being supported by
The analysis of disordered carbonaceous materials by Raman relevant literature data.
spectroscopy evolved in the last decade, namely including the The deconvolution processes used the band shift combinations
splitting of the base Raman features.30 A band at B1615 cm1 observed in the second order region to identify, more accurately,
has been introduced in the fittings as a shoulder of the G band, the position of first order bands. This procedure was particularly
like the D band, it was associated with disorder and was usually useful when identifying small features since they combine with the
called the D 0 or D2 band, while in other studies, the two compo- strong D band in the second order region.
nents used to fit the G band were designated as G and G+.31 The present deconvolution model (Fig. 3) considered in the
A four-peak model32 or more often the five-peak model ‘‘D band region’’ a central D band and two satellite bands
proposed by Sadezky et al.33 has become popular curve fittings designed Dl (standing for D left) and Dr (standing for D right),
for graphitized carbonaceous materials, including MWCNTs.34 at B1250 cm1 and B1400 cm1, respectively. Other Raman
The latter model consists of the use of two very broad bands, with studies of chars applied a similar system.32,36 At the left side of
minor modulations, at near 1200 and 1500 cm1, in addition the spectra, one or two side bands (S and Sr) were considered
to the D, G and D 0 bands.33 at B1200 cm1.

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Fig. 3 Fitting of a typical Raman spectrum of functionalized MWCNTs using the developed deconvolution methodology.

In the ‘‘G band region’’ the fitting considered two Lorentzian shapes and sizes and this multiplicity explains the broadening
bands, G and Gr (G right) at B1580 and B1610 cm1, respec- effect.18,30,38 On the other hand, the two families of bands
tively, and one Gaussian band Gl (G left) near 1500 cm1. relate to the base G and D bands that are ascribed to in-plane
The rupture of aromaticity upon chemical functionalization (E2g) and out-of-plane (A1g) vibrations, respectively.10
leads to the formation of smaller sp2 domains that are confined In the second-order region, in addition to the 2D band, other
by sp3 bonds and have dimension comparable to PAH’s molecules. bands were assigned and their positions match the composite
More extended covalent functionalization can also introduce values of first order bands with the main D band, namely, D + S
polyene-like structures. (DS), D + Dl (DDl), D + D (2D), D + Dr (DDr), D + Gl (DGl), DG
Raman studies of polycyclic aromatic hydrocarbons (PAH’s) and also band 2G. The composite band DG position matches
showed bands at near 1250 and/or 1400 cm1, with variations the wavenumber of D plus the average of the values of G and Gr
in the position and relative intensity depending on the molecular and the position of band 2G matches the sum of band positions
size and symmetry, as well as, one peak at around 1600 cm1.10,36 values, G plus Gr.
On the other hand, the Raman spectra of polyacetylene show two The present model provided a quantification of the band
features at 1200 and 1500 cm1.37 broadening and a more uniform distribution of the bandwidths
Thus, bands Dl, Dr and Gr in the present deconvolution in the fitted spectrum, relatively to previous models.33 The
model were assigned to the presence of low size aromatic goodness of the fit in the extended region 1000–3500 cm1
domains, analogous structures to PAH’s,10,36 while S and Gl was indicated by low w2 values being always r0.6. The
bands are ascribed to fingerprints of polyacetylene like deconvolution of the spectra of materials Dz_R[r] and An_R
structures.37 using this model is collected in the ESI† (Fig. S1–S4).
Furthermore, the Raman spectra of fullerenes show a base
feature at B1500 cm1, thus the Gl band can also have contri- Oxidation of MWCNTs
butions from tube-end vibrations. In the case of the highly In order to study the application of the above model on
functionalized material An_OH, the deconvolution required a mechanistically different functionalizations, it was extended
band Gv (G valley) at near 1480 cm1 in order to obtain an to MWCNTs prepared by oxidation reactions.
accurate fitting. Oxidations typically occur on defects and tips of the carbon
This model is in accordance with Castiglioni et al.10 that nanotubes and in order to study the corresponding Raman
pointed out the first order region of the Raman spectra of any effects, three materials were prepared using different oxidation
‘‘graphitic’’ carbon sp2 system as two families of bands. These methodologies (Fig. 1c). These include (i) liquid oxidation
two families of bands relate to the convolution of Raman by HNO3 (material Ox_h); (ii) liquid oxidation by HNO3
transitions from domains of similar type but having different with subsequent thermal treatment at 400 1C under an argon

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atmosphere (material Ox_ht) and (iii) gas phase oxidation with directly to the XPS and TG data collected, evidencing the presence
5% O2/N2 at 500 1C (material Ox_ot). of more complex structural changes upon oxidation.
Fig. 4 shows the Raman spectra of oxidized materials, in Material Ox_h shows the highest oxygen atomic percentages
comparison to original MWCNTs, normalized for the D band. by XPS (7.8%) in agreement with an extended oxygenation on
The application of the previous deconvolution model to the the material that is confirmed by the high TG mass loss (25%).
spectrum of material Ox_h (Fig. 4b) showed the increase of On the other hand, material Ox_ht shows lower oxygen content
minor modulations (the satellite bands of the base features D, (4.0%) and the lowest TG mass loss among oxidized materials
G and 2D) that gain relevance comparatively to their intensity (11%). On its turn, material Ox_ot shows the lowest oxygen
on the spectrum of original MWCNTs. In addition, the S band content (1.5%), close to the value of original MWCNTs (1%).
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observed at 1143.9 cm1 on the MWCNT’s spectrum (Fig. 4a) However, it shows the highest TG mass loss percentage (32%),
splits into two bands, S and Sr, at 1122.1 and 1186.2 cm1, which indicates a strong disruption on the graphitic structure.
respectively. Furthermore, the Brunauer–Emmett–Teller surface areas
Instead, the spectrum of material Ox_ht (Fig. 4c) shows a (SBET, insets of Fig. 4) increase for all oxidized materials with
deconvolution pattern similar to original MWCNTs, which at respect to MWCNTs ascribed to the opening of endcaps and the
first sight indicates almost no functionalization. creation of holes in the sidewalls during oxidation.29 However,
Regarding material Ox_ot (Fig. 4d), the Raman spectrum this occurs in a significantly larger extent for material Ox_ot.
also shows an increase of satellite bands with respect to the Characterization by XRD. In order to gain further insights
base features, confirming the functionalization. However, this into the characterization of oxidized materials39 and under-
material shows a higher intensity of the Gr band relative to the stand their Raman spectra, these materials were further studied
G band and of the 2D band, relative to all the other oxidized by X-ray diffraction (XRD).
materials. This probably indicates the presence of different All the XRD patterns collected in Fig. 5 show peaks at 2y angle
structural and spectral effects on materials Ox_h and Ox_ot. B261 and B431, which are the characteristic reflections of
The insets of Fig. 4 collect relevant characterization data carbon nanotubes from the (002) and [(100), (101)] diffraction
obtained for the oxidized materials in comparison with original planes, respectively.40,41 The first peak is related to the perio-
MWCNTs.29 Inversely to what was observed on materials Dz_R[r] dicity between the graphene layers and the second within the
and An_R, the Raman data of oxidized materials do not relate graphene layer (honeycomb lattice at a single graphene sheet).42

Fig. 4 Deconvolution pattern of original and oxidized MWCNTs. The characterization data in the inset include the surface oxygen atomic percentages
determined by XPS, the TG mass losses percentages obtained in the interval 20–900 1C under nitrogen and a heating rate of 10 1C min1 and the BET
surface area (SBET) based on N2 adsorption isotherms at 196 1C.29

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layer stacking. Thus, the morphology and microstructures of

material Ox_ht improve and justify the XRD results and the
similarity of its Raman spectra to MWCNTs. Moreover, the TG
mass loss is the lowest among oxidized materials (11%),
although superior to MWCNTs due to the presence of oxygen
groups probably localized in the borders of opened endcaps.
Regarding the O2 oxidation performed at 500 1C, the carbonyl
and carboxyl groups formed can also decompose at that tem-
perature, resulting in the low oxygen content and in a localized
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burning of the carbon structure, with the formation of opening

tips and holes in the sidewalls. During this oxidation, the small
O2 molecule can permeate easily within the tubes and react in
the most internal graphene layers. The resulting interlayer
disruption justifies the extensive mass loss observed on TG
(32%) and the XRD results regarding the decrease of the (002)
peak. However, the intensity of the [(100), (101)] peaks for
Fig. 5 X-ray diffraction patterns of original and oxidized MWCNTs. The
position of the (002) peak on MWCNTs is observed at 2y = 26.11 this material evidences the maintenance of regular in-plane
corresponding to an interlayer spacing d002 = 3.41 Å, typical of MWCNTs aromatic domains.
and does not change significantly for oxidized materials. The differences in HNO3 and O2 oxidations can be due to the
different oxidation mechanisms. HNO3 reacts mainly on sp3
defects, but also on the p-system of the nanotube. On the other
The intensity of XRD peaks has been associated with the hand, O2 undergoes mainly radical reactions in the p-system of
extension of the corresponding domains.39 For material Ox_h, MWCNTs.
the intensity of the (002) peak decreases significantly in Generally, reactions in the p-system are regulated by Clar’s
comparison to original MWCNTs, while peaks [(100), (101)] rule,43,44 that is by a decrease of reactivity decreasing the size of
almost disappear (Fig. 5). These observations evidence a loss the aromatic domains. Thus, a second functionalization should
of periodicity, both in the inlayer and interlayer dimensions, occur at a distance from the first one. This can explain the
due to the extensive functionalization by HNO3. presence of regular large size aromatic domains on material
On the other hand, material Ox_ht shows the highest Ox_ot identified by the XRD [(100), (101)] peak in relation to
intensity of the (002) and [(100), (101)] peaks, indicating the material Ox_h, for which the undifferentiated reaction on
presence of a higher extent of the corresponding domains with p-system and defects leads to lower regularity.
respect to all other materials, including original MWCNTs.
This is in accordance with an improved layer package and Evaluation of ‘‘disorder’’ in MWCNTs
aromaticity within layers after this treatment. Aiming to gain insights into the correlation between the bands
Material Ox_ot shows the shortest (002) peak, while the resulting from the present deconvolutions and material’s
[(100), (101)] peaks have median intensity, indicating a signifi- functionalization previously described, Fig. 6 correlates band
cant decrease in the interlayer regularity although maintaining percentages with TG mass losses (grey area), as a measure of
most of the in-plane regularity for this material. This also functionalization/graphitization.
relates to the Raman observations that indicate an increase in Fig. 6 shows the comparison between materials resulting
the structural complexity for this material, although in a different from the reaction with anilines in the absence and presence
way with respect to material Ox_h. of isopentyl nitrite, materials An_R and Dz_R[r] and between
All the three oxidized materials also show higher FWHM for oxidized materials.
the (002) peak relatively to original MWCNTs, probably due to a The behavior of the G and D bands is shown in Fig. 6a
higher number of similar domains after oxidation. (orange and blue marks, respectively). Both their relative areas
Rationalization of oxidized material structure. All the decrease with the increase of TG mass loss and consequently,
above-described characterizations confirm a high degree of both these bands relate to the original structure of MWCNTs
functionalization/oxygenation for material Ox_h. On the other and express the ‘‘order’’ of the original graphitic-type structure.
hand, material Ox_ht results from a thermic treatment on This behavior was expected for the G band, but not for the
material Ox_h, at 400 1C, under an inert atmosphere. Under D band, which was typically associated with the disorder of
these conditions occurs the decomposition of carboxylic acid carbon nanotubes and was expected to increase with the
groups formed during the nitric acid oxidation, with release of functionalization degree.
CO2, although maintaining hydroxyl and ketone groups.29 This In order to rationalize the above result, it is important to
justifies the reduction of XPS oxygen content from 7.8% (Ox_h) clarify the concept of ‘‘disorder’’ in these materials.
to 4% (Ox_ot). This decarboxylation process also leads to Different levels of ‘‘disorder’’. The presently used original
the reconstruction of the sp2 system,29 decreasing defects and MWCNTs have highly ‘‘graphitic’’ quality (indicated by the
amorphous carbon, with a consequent improvement in the TG mass loss under nitrogen of 2%), but their structure is

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Fig. 6 Relative areas of the Raman bands for the different materials in comparison to TG mass loss.

inherently more complex than perfect graphite (XRD 2y peak disorder and expresses variability with respect to the planar and
B431 is indicative of a less-uniform material)45 and their Raman perfectly aligned layer stacking on graphite.
spectra show an intense and broad D band (the most intense Starting from the uniform structure of graphite and evolving
in the spectra). The D band has been typically associated with to other graphitic carbon materials, different elements can

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introduce complexity on the structures, such as the curvature in permeation of HNO3 and O2 oxidants. This introduced disruption
SWCNTs or the curvature plus multilayer stacking in MWCNTs. (Ox_h and Ox_ot) or a better package (Ox_ht) in the internal
Although these structures are more complex relatively to graphite, layers.
it does not seem to be very appropriate to call them ‘‘disordered’’, In the second order region, the most notorious feature is the
since they have a well-defined and regular structure. It seems to relatively high 2D band for material Ox_ot (Fig. 4 and 6c).
be more appropriate to refer as variability/complexity. Typically, the 2D band has an inverse behavior to the
The curved layer in SWCNTs results in a broadening effect of graphitic crystal size in the interlayer dimension. Thus, Raman
the G band and the appearance of a weak D band. Symmetry spectroscopy is used to differentiate the number of stacked
breaking effects associated with the SWCNT curvature result in layers during the exfoliation of graphite to few layer graphene
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various force constants along the nanotube axis causing the (FLG) or to single layer graphene, using the relative intensity of
splitting of the G band.46 In fact, the curvature effect can be the G and 2D bands.11,47 Larger 2D bands relate to lower layer’s
considered analogous to the presence of limited-size aromatic number.
domains set aside, consequently, the corresponding in-plane The intense 2D band on material Ox_ot can be explained
and out-of-plane vibrations are activated. However for SWCNTs, by the diffusion of O2 molecules in the deep internal layers
where no inter-layer packing is present, these effects are relatively (smaller than HNO3). This disruption in stacking can have
small and chemical functionalization can be quantified by the an effect similar to exfoliation, increasing the 2D band
relative increase of the D band intensity. intensity.
On the other hand, MWCNTs can be considered as an First order vs. second order spectra. It is also interesting to
ensemble of concentric SWCNTs with increasing diameters. compare the cumulative area of the two regions of the spectra
As a result, the intensity of the D band increases significantly with TG mass losses. As can be seen in Fig. 6d, the cumulative
with the number of stacked layers, which for the present area from the first order region correlates with structural
materials is the most intense feature in the spectrum. Materials complexity for An_R and Dz_R[r] materials and correlates
resulting from carbonization of amorphous carbon or with less with sample ordering for oxidized materials. Consequently,
regular layer stacking, such as carbon nanofibers or carbon the inverse is observed for the area under the second order
onions also show large D bands. Thus, the D band expresses region.
the stacking variability and its intensity has been efficiently This can be explained considering that reactions with anilines
used to compare the structural complexity of different carbon occur exclusively in the external wall, consequently, the D band is
materials. nearly constant and the total area evidences the increase of the
In this context, the structural complexity of original MWCNTs satellite bands in the first order region. On the other hand,
should be distinguished from the structural modifications intro- oxidations occur also in the interlayers and materials Ox_h and
duced upon covalent functionalization, if we aim to accurately Ox_ot show a decrease of the D band and a concomitant increase
quantify and analyze the functionalization degree and corres- of the 2D band and consequently, a decrease in the first order
ponding structural effects. area relatively to the second order area.
Behavior and significance of the individual bands. Fig. 6a
showed the relation between the D and G bands resulting from Quantification of the functionalization degree
the present deconvolution model and the ordering, since their Two main reasons have been hampering the quantitative
relative percentages decreased for more functionalized materials. analysis of chemical functionalization in graphitic materials
On the other hand, the relative areas of the satellite bands Dl, Dr, that are structurally more complex than SWCNTs. These are the
Gl, Gr and S + Sr (Fig. 6b) relate to structural variability/complexity difficulty in the correct assignment of the Raman features
introduced upon chemical functionalization, since they show the resulting from chemical functionalization and the broad nature
same behavior as TG mass losses of the materials. This is related of the spectra, which difficult the accurate measure of indivi-
to aromaticity disruption and the formation of small aromatic dual bands. As can be seen in Fig. 6e, commonly used Raman
domains and possibly of polyene-like structures, also confirming band ratios are not appropriate to quantify the chemical
the previous assignment of these bands. functionalization degree (CFD) of the present materials. The
P P
In Fig. 6a, it can also be observed that the D band changes ratio D bands/ G bands is independent of functionalization
are quite smooth for the materials resulting from reactions with and the individual band ratio D/G does not point out functio-
anilines, but they significantly change for oxidized materials. nalization/graphitization for oxidized samples and does not
This can be explained since the reactions with diazonium salts give coherent information.
and anilines occur only in the external layer, consequently, the An accurate measure of the CFD (chemical functionalization
layer’s stacking slightly disrupt. On the other hand, for oxidized degree) was obtained by the ratio of bands assigned to limit-
materials, the decrease in the D band is more evident for sized sp2 domains (the satellite bands S, Sr, Dl, Dr, Gl, Gr)
materials Ox_h and Ox_ot, while material Ox_ht, the more towards bands assigned to graphitic-type domains (the D and G
ordered material, shows the highest D band percentage. This bands), which are associated with the initial graphitic-type
can be explained by oxidation not only in the external layer structure of MWCNTs: CFD = (S + Sr + Dl + Dr + Gv + Gl + Gr)/
of the nanotube but also in the internal layers allowed by the (D + G). Furthermore, the use of compositions of bands avoids
open tips and holes in the sidewalls (SBET, Fig. 4-insets) and statistical uncertainties of curve fitting of the individual bands

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P P
Fig. 7 Plot of the chemical functionalization degree (CFD) obtained by Raman spectroscopy [Raman CFD = rel. area (S, Sr, Dl, Dr, Gv, Gl, Gr)/ rel.
area (D, Gl)  100], in comparison with the functionalization degree determined by TG mass loss percentage and XPS heteroatom percentage.

(ESI,† Fig. S5), enhancing the quantification accuracy. In Fig. 7, The results indicate a highly reliable feature to comparatively
the CFD obtained in this way is compared with the characteri- quantify structural changes upon chemical functionalization of
zation data from other techniques. MWCNTs for different reaction types and mechanisms.

Fig. 8 (a) Reaction scheme of functionalization under Bingel conditions; (b) comparison of the Raman spectra of original MWCNTs with nanotubes
functionalized through the Bingel reaction (MWCNT_B) and by further reaction with cysteamine (MWCNT_SH), the inset shows the atomic percentages
of relevant elements and the total heteroatom percentages by XPS.

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Fig. 9 Curve-fitting for materials involved in Bingel functionalization: (a) MWCNTs; (b) MWCNT_B and (c) MWCNT_SH. (d) Comparison of the chemical
functionalization degree (CFD) and XPS heteroatom percentage for original and functionalized MWCNTs.

Validation of the methodology on Bingel functionalized the CFD obtained from the Raman spectra and the heteroatom
MWCNTs percentage obtained by XPS (Fig. 9d). These results provide
The Bingel reaction is one of the most efficient procedures for further confirmation of the validity and applicability of the
the chemical functionalization of graphitic materials, it is present methodology for the analysis of covalently functiona-
based on the cyclopropanation reaction performed through lized MWCNTs.
nucleophilic addition on the p-system (Fig. 8a).
The Raman spectra of original MWCNTs, Bingel functionalized
nanotubes (MWCNT_B) and the Bingel material after the amidation Conclusions
reaction of the malonyl ester groups with cysteamine (MWCNT_SH)
are shown in Fig. 8b. In the inset are collected the data obtained Original MWCNTs show an intense D band due to the non-
from XPS elemental analysis for these three materials. planar package of multi-layers, which is absent in SWCNTs.
Fig. 8b shows a broadening effect in the first order region Thus, the difficulty in evaluating chemical functionalization
of the spectra going from original MWCNTs to material in MWCNTs arises from the overlapping of both effects, not
MWCNT_B, with the increase of the baseline between the two occurring in SWCNTs.
base features. In contrast, there are no significant changes The relatively broad spectral features of original MWCNTs
going from material MWCNT_B to material MWCNT_SH. and functionalized materials were deconvoluted with three
The nanotubes submitted to the Bingel reaction suffer families of bands in the regions of the D, G and 2D bands. In
functionalization in the external wall with disruption of the the first order region of the spectra, the features were fitted
p-system, consequently, the satellite bands increase and conse- with a central and more intense band assigned to vibrations
quently the spectral broadening increases, while keeping the from graphitic-type domains (D or G). Furthermore, as a novelty
relative intensity of D and G bands, as observed above for of the present work, the corresponding satellite bands were
diazonium functionalization. assigned on their left and right sides (S, Sr, Dl, Dr, Gl, Gr).
On the other hand, the amidation reaction occurs in the These features were ascribed to small aromatic domains and to
malonyl ester functional groups and does not affect the nanotube polyene-like structures. One other novelty of the present work is
structure. Thus, the Raman spectra are quite similar for that in the second order region, the presence of composite
MWCNT_B and MWCNT_SH, despite the increase in the bands DS, DDl, 2D, DDr, DGl, DG and 2G also helped the
heteroatom percentage in these materials from 14.6% to 16.4%. assignment of the first order bands.
The curve-fitting obtained for the three materials evidences The application of this model allowed a coherent interpretation
the above observations (Fig. 9a–c), as well as, the comparison of of the Raman spectra of MWCNTs covalently functionalized

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through diazonium chemistry, direct reaction with anilines, multi-walled carbon nanotubes, Phys. Chem. Chem. Phys.,
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In material Ox_ot also occurs the increase of the 2D band. This naceous materials using Raman spectroscopy: a comparison
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12 J. M. Schnorr and T. M. Swager, Emerging application
The work was financed by FCT (Fundação para a Ciência e a of carbon nanotubes, Chem. Mater., 2011, 23, 646–657.
Tecnologia) and FEDER (Fundo Europeu de Desenvolvimento 13 M. E. Lipińska, S. L. H. Rebelo, M. F. R. Pereira, J. L.
Regional) through PT2020 for the research centre REQUIMTE/ Figueiredo and C. Freire, Photoactive Zn(II)porphyrinmulti-
LAQV (UID/QUI/50006/2013). S. L. H. Rebelo also thanks FCT walled carbon nanotubes nanohybrids through covalent
for the Post-Doctoral Grant SFRH/101281/2014. The XPS analyses beta-linkages, Mater. Chem. Phys., 2013, 143, 296–304.
were performed with collaboration of Centro de Materiais da 14 C. Fernandes, C. Pereira, A. Guedes, S. L. H. Rebelo and
Universidade do Porto (CEMUP, Porto, Portugal). C. Freire, Gold nanoparticles decorated on Bingel–thiol
functionalized multiwall carbon nanotubes as an efficient
and robust catalyst, Appl. Catal., A, 2014, 468, 150–158.
15 M. E. Lipińska, S. L. H. Rebelo and C. Freire, Iron(III)
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