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FTIR Spectroscopy for Carbon Family Study
Vasilica Ţucureanu, Alina Matei & Andrei Marius Avram
To cite this article: Vasilica Ţucureanu, Alina Matei & Andrei Marius Avram (2016) FTIR
Spectroscopy for Carbon Family Study, Critical Reviews in Analytical Chemistry, 46:6, 502-520,
DOI: 10.1080/10408347.2016.1157013
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FTIR Spectroscopy for Carbon Family Study
Vasilica Ţucureanu, Alina Matei, and Andrei Marius Avram
National Institute for Research and Development in Microtechnologies, IMT Bucharest, Bucharest, Romania
ABSTRACT
Fourier transform Infrared (FTIR) spectroscopy is a versatile technique for the characterization of materials
belonging to the carbon family. Based on the interaction of the IR radiation with matter this technique
may be used for the identification and characterization of chemical structures. Most important features of
this method are: non-destructive, real-time measurement and relatively easy to use. Carbon basis for all
living systems has found numerous industrial applications from carbon coatings (i.e. amorphous and
nanocrystalline carbon films: diamond-like carbon (DLC) films) to nanostructured materials (fullerenes,
nanotubes, graphene) and carbon materials at nanoscale or carbon dots (CDots). In this paper, we present
the FTIR vibrational spectroscopy for the characterization of diamond, amorphous carbon, graphite,
graphene, carbon nanotubes (CNTs), fullerene and carbon quantum dots (CQDs), without claiming to
cover entire field.
KEYWORDS
Carbon nanotube (CNT);
carbon quantum dot (CQD);
diamond; diamond-like
carbon (DLC); Fourier
transform Infrared (FTIR)
spectroscopy; fullerene;
graphene; graphite
Introduction to FTIR spectroscopy
The infrared (IR) spectroscopy was the first structural spectro-
scopic technique and is an analytical method used to character-
ize the bonding structure of atoms based on the interaction of
the IR radiation with matter, and measures the frequencies of
the radiation at which the substance absorbs and lead to the
production of vibrations in molecules. IR spectroscopy pro-
vides a fast technique of identification and characterization of
chemical structures to obtain information from biological to
composite materials, from liquids to gases samples (Son et al.,
2001; Vaghri et al., 2012).
The vibrational spectroscopy history begins with the first IR
spectrum, obtained by Coblentz (in 1905), and achievement of
first IR spectrometer (in 1930s). FTIR spectrometry combines
an old tool, the interferometer (developed by Albert Michelson
in 1877) with an older mathematical principle, the Fourier
transform to convert the output from an interferometer (inter-
ferogram) to a spectrum and a new approach, computerization.
But the complexity of calculations stopped the development of
FTIR spectrometry until 1969 when the first commercial FTIR
spectrometer with a dedicated minicomputer was developed.
Now, using the computer, an interferogram is transformed
instantaneously into a spectrum and a modern software algo-
rithm allows the use of FTIR spectroscopy as a tool for qualita-
tive and quantitative analysis (Tanase, 1995; Ryczkowski, 2001;
Murali Krishna et al., 2013). Generally, a FTIR spectrum is a
graphical representation of the transmittance, in percent (T%)
or absorption, in units (A) versus IR frequency in terms of
wavenumber (cm¡1). In an IR spectrum the absorption bands
are characterized by a wavenumber at which absorption occurs
(corresponding to chemical bonds) and the intensity of absorp-
tion (proportional to the amount of substance from sample).
The IR spectrum can be divided into three spectral areas,
named in relation to the visible range: (1) near infrared (NIR),
near the visible region, may excite overtone or higher harmonic
vibrations – range: »13000–4000 cm¡1 (»770–2500 nm, 0.77–
2.5 mm), (2) mid infrared (MIR) excites mainly fundamental
vibrations—range: 4000–400 cm¡1 (2500–25000 nm, 2.5–25
mm) and (3) far infrared (FIR) excites lattice vibrations and
below 300 cm¡1 it can be used for rotational spectroscopy—
range: 400–10 cm¡1 (25000–1000000 nm, 25–1000 mm). Many
IR studies use the MIR region (including in our paper), but the
NIR and FIR regions can also provide important information
(Derrick et al., 1999; Reichenbacher et al., 2012; Singh et al.,
2012; Murali Krishna et al., 2013).
FTIR spectrometry is a non-destructive and real-time mea-
surement analytical method, enabling the identification of
unknown materials (quantitative determination) and their con-
centration (qualitative determination) from organic and inor-
ganic substances, from solid, liquid or gas samples. In some
molecules during vibration there is a change of the electric
dipole moment (selection rule). In this case, we speak of IR
active substances and the absorption of the radiation corre-
sponds to a change of the dipole moment. For IR inactive sub-
stances the electric dipole moment is zero, no matter how long
the bond is in the molecule (IR-active: polar bonds, asymmetri-
cal molecules. IR inactive: non-polar bond, symmetrical mole-
cule) (Stuart et al., 2004; Reichenb€acher et al., 2012; Singh et al.,
2012; Murali Krishna et al., 2013). In IR spectrometry each
chemical bond has a specific vibration frequency corresponding
to an energy level. E D hn D hc/λ and ṽ D 1/λ D n/c (where: h
D Planck’s constant, n D frequency, c D speed of light, λ D
wavelength and ṽ D wavenumber). The IR absorption appears
when radiant energy corresponds to energy of a molecular
CONTACT Vasilica Ţucureanu vasilica.tucureanu@imt.ro, vasilica.schiopu@gmail.com National Institute for Research and Development in Microtechnologies,
IMT Bucharest, 126A Erou Iancu Nicolae Str., code 077190 Bucharest, Romania
© 2016 Taylor & Francis Group, LLC
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY
2016, VOL. 46, NO. 6, 502–520
http://dx.doi.org/10.1080/10408347.2016.1157013
http://dx.doi.org/10.1080/10408347.2016.1157013
vibration. The vibrational mode of a molecule can involve a
variation in inter-atomic bond length (stretching, n) or bond
angle between two bonds (bending or deformation, d) (Stuart
et al., 2004; Reichenbacher et al., 2012; Singh et al., 2012). In
Table 1, the vibration modes that may appear in a molecule are
presented. The vibration mode may occur at: ṽ (symmetrical
stretching)be observed at about 1600–1450 cm¡1 (Li et
al., 2010; Zhang et al., 2012; Mewada et al., 2013; Wu et al.,
2013; Hao et al., 2015). In Table 8, some possible aassign-
ments for CQDs may be seen.
Table 7. (Continued ).
Wavenumber [cm–1] Probable assignment Characteristic vibration mode for: Ref.
et al., 1991; Menon et al.,
1996
586 d (>C=C=C=CC=C) C20, tadpole isomer Zamani et al., 2014
545–525 e1
’ or a1
”or a2
’ or a2
” or e2
” C70 Bethune et al., 1991; Iglesias-
Groth et al., 2011; Meilunas
et al., 1991; Menon et al.,
1996
544 d ( >CC=C) C20, tadpole/bowl isomer, e2 Galli et al., 1998; Zamani et al.,
2014
490 d ( C–C) C60(OH)n Alves et al., 2006; Krishna et al.,
2010; Tianbao et al., 1999
486 d (>C=C=C=Cdecreases with
increasing pH, indicating gradual deprotonation
of ¡COOH.
Hao et al., 2015
1335 C–O–C indicating the existence of CQDs in a complex Zhang et al., 2012
1260–1250 C–O–C indicating the existence of CQDs in a complex Fan et al., 2015; Zhang et al., 2012
1200–1190 n (C–O) CQDs Li et al., 2010; Wang et al., 2014
1080–1010 n (C–O) ! CQDs, carboxylic (COOH) group Fan et al., 2015; Li et al., 2010; Wu et al., 2013
! GQD
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	Abstract
	Introduction to FTIR spectroscopy
	Introduction to carbon family
	Diamond characterized by FTIR spectroscopy
	Amorphous carbon characterized by FTIR spectroscopy
	Graphite characterized by FTIR spectroscopy
	Graphene characterized by FTIR spectroscopy
	CNT characterized by FTIR spectroscopy
	Fullerene characterized by FTIR spectroscopy
	Carbon quantum dots characterized by FTIR spectroscopy
	Conclusion
	Acknowledgments
	Referencescm¡1 spectral range, the water molecule with n D 3 and thus
having 2-stretching vibration at about 3450–3200 cm¡1 (nas(O-
H)), 1640–1630 cm¡1 (ns(H��H)) and 1 scissors bending vibra-
tion 2130–2110 cm¡1 (dsr.(H-O-H)) (Raki et al., 2003; www1.
lsbu.ac.uk, 2015).
The IR spectra are very complicated as a consequence of:
frequencies of absorbed radiation being unique for each mole-
cule, bond strengths, atoms number, condition of the material
(the state, interference/contamination, concentration, tempera-
ture, etc), multiplicity of bending and stretching vibration
mode.
Introduction to carbon family
Carbon (C), the sixth element of the periodic table, is one of the
fascinating materials for both researchers and engineers. It may
be found almost everywhere from in the sun, to the atmos-
pheres of some planets, from living organisms to oil. Practi-
cally, on Earth, carbon is the building block of all living
systems, while for industry it is the most important material,
being used in many applications essential to a society in contin-
uous development. In the late years, various applications have
been developed for carbon coatings (i.e. amorphous and nano-
crystalline carbon films: DLC films) to nanostructured materi-
als (fullerenes, nanotubes, graphene) and carbon materials at
nanoscale or CDots. Carbon, a wonderful atom, forms a great
variety of crystalline and disordered structures due to it’s four
valence electrons ([He]2s22sp2) which may hybridize in many
ways. The hybridizations forms may be sp3, sp2 and sp, allow-
ing carbon to form linear chains, planar sheets and tetrahedral
structures. The most common chemical bonds in amorphous
and nanocrystalline carbon are sp3 and sp2 hybridizations. Up
to 1985, amorphous carbon, graphite (3D, sp2) and diamond
(3D, sp3) were the most known allotropic forms existing freely
in nature. Fullerene or the three allotropes form of carbon were
discovered in 1985 by R.E. Smalley, and with them research
into carbon family has experienced a real boom, culminating
with in the results in 1991 and 2004 when the first data on the
new materials known as CNTs and graphene respectively was
presented. Now-a-days researchers see the graphene (2D, sp2)
as the building block for several allotropic forms of carbon:
graphite (3D, sp2) may be seen as a stacked version of gra-
phene, CNTs (one dimensioanl (1D), sp2) as a rolled version of
graphene and fullerene (0D, sp2) as a wrapped version of gra-
phene. Based on their properties, the materials from the carbon
family are fascinating from the perspective of fundamental sci-
ence and technology. The importance of these materials has
been recognized with two awards: Nobel prizes in 1996 (for
Chemistry) and 2010 (for Physics) (Abrahamsson et al., 2007;
Chu et al., 2006; Marcinauskas et al., 2007; Mitroova et al.,
2010; Reche, 2004; Robertson, 2002; Sarkar, et al., 2013; Yadav
et al., 2008).
In this review, we will present the application of the FTIR
spectroscopy to the characterization of different types of carbon
materials, but without claiming that we can cover the entire
field. Vibrational properties are essential to the understanding
the carbon family properties (i.e. optical properties via pho-
non–photon scattering).
Diamond characterized by FTIR spectroscopy
The diamond is the most desired gemstone in the world, but it
also has many industrial applications. Diamond has a 3D dia-
mond cubic structure, formed exclusively by carbon atoms
where each atom has four nearest neighbors arranged in a tetra-
hedron reflecting the sp3 hybrid state of the C��C covalent
bonds (Marnnz et al., 1993; Singla et al., 2011). Diamonds are
elementally carbon formed from pure carbon, but during the
growth of natural or synthetic diamonds some chemical impu-
rities can be incorporated which may influence the properties
and color of diamond. Among impurities nitrogen, hydrogen
and boron are most important. The diamonds can be classified
in diamond type I: Ia—often natural, with aggregated nitrogen
and hydrogen (this type of diamond with no hydrogen is a rar-
ity), IaA—aggregated N pair, IaB—aggregated 4N and lattice
vacancy, Ib—often synthetic, with isolated nitrogen and dia-
mond type II – often synthetic, without nitrogen: IIa—without
nitrogen or boron, but sometimes with very low concentration
of hydrogen, IIb—with boron) (Fritsch, et al., 2007; Breeding et
al., 2009, Bruker, 2013; 2014).
The FTIR spectroscopy may be used to distinguish between
a natural diamond and a fake. IR vibration mode assignments
of natural, synthetic and fake diamond are summarized in
Table 2. The diamond FTIR spectrum may be divided into
Table 1. Vibration types in FTIR spectrometry.
Vibration type and symbols Ref
1 Stretching n symmetrical ns – – Stretch in-phase ns Singh et al., 2012; Stuart et al., 2004;
2 Stretching n asymmetric nas – – Stretch out-of-phase nas Singh et al., 2012; Stuart et al., 2004;
3 Bending or deformation d symmetrical ds scissoring sr or ə Deformation in plane b Singh et al., 2012; Stuart et al., 2004;
4 Bending or deformation d asymmetric das rocking r Deformation in plane b Singh et al., 2012; Stuart et al., 2004;
5 Bending or deformation d symmetrical ds wagging w Deformation out of plane g Singh et al., 2012; Stuart et al., 2004;
6 Bending or deformation d asymmetric das twisting t Deformation out of plane g Singh et al., 2012; Stuart et al., 2004
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 503
http://www1.lsbu.ac.uk
http://www1.lsbu.ac.uk
three regions: three-phonon region (4000–2600 cm¡1) for
intrinsic diamond and B or H in diamond, two-phonon region
(2600–1500 cm¡1) for diamond and B in diamond and one-
phonon region (1500–400 cm¡1) for N or B impurity in dia-
mond. In the 4000–1500 cm¡1 area some peaks appear which
can be caused by the vibration of C��C bonds of the diamond
lattice. The spectrum for pure natural diamond is defined by
absorption bands in the spectral range 2700–1600 cm¡1
(centered at about 2500, 2380, 2030 and 1970 cm¡1) which are
due to carbon itself. The bands in the range 1500–1000 cm¡1
can be assigned to nitrogen from diamond type I. For aggre-
gated N impurities (type Ia) the FTIR spectra shows peaks at
about 1280 cm¡1 (IaA) and 1175 cm¡1 (IaB) and for isolated N
(type Ib) at 1345 cm¡1 and 1135 cm¡1. The diamond type II,
with un-aggregated nitrogen or with barely detectable nitrogen,
may contain various impurities or adsorbed gases (hydrogen,
Table 2. The possible assignments for natural, synthetic and fake diamond.
Wavenumber
[cm¡1]
Probable
assignment
Characteristic vibration
mode for:
Ref.
4000–2600 B or H in diamond (type II), three-phonon region Breeding et al., 2009; Bruker, 2013, 2014;
Fritsch, et al., 2007; Peretti et al., 2013
4000–1200 – ZrO2 fake diamond, No band in this range Bruker, 2014
4000–800 – YAG fake diamond, No band in this range Schiopu et al., 2012; Tucureanu et al., 2015
3470 – H in diamond IaA, Ib (yellow and orange
diamond)
Fritsch, et al., 2007
3400 n (O��H) Diamond powder Ji et al., 1998
3395–3340 n (N��H) H, N in diamond Ib Fritsch, et al., 2007
3270–3240 – H in diamond Ib Fritsch, et al., 2007
3235 – H in diamond IaB, H-rich diamond, (from grey to
violet diamond). It is never observed in low-N
diamonds.
Fritsch, et al., 2007
3210–3150 – H in diamond Ib Fritsch, et al., 2007
3110 ns (C��H) H in diamond IaA and Ib. (near-colorless, yellow,
orange, brown, green, chameleon diamond)
Bruker, 2014; Fritsch, et al., 2007; Marnnz et al.,
1993
3095 ns (C��H) Diamond synthesized Fritsch, et al., 2007
3085–2980 – H in diamond Ib Fritsch, et al., 2007
2970 – H in diamond Ib or Ib/aA or Ib/aAB and rich in N2
and H2
Fritsch, et al., 2007
2965–2850 – H in diamond Ib Fritsch, et al., 2007
2930 B abs in diamond Breeding et al., 2009
2800–2460 B in diamond (type II) Breeding et al., 2009; Bruker, 2013, 2014;
Peretti et al., 2013
2800 – B abs in diamond Breeding et al., 2009; Bruker, 2014
2790–2780 – H in diamond Ib Fritsch, et al., 2007
2757 – Diamond synthesized Fritsch, etal., 2007
2741 – H in diamond Ib Fritsch, et al., 2007
2600–1500 B in diamond (type II), two-phonon region Breeding et al., 2009; Bruker, 2013, 2014;
Fritsch, et al., 2007; Peretti et al., 2013
2500 – Pure diamond, natural Bruker, 2014
2460 – B in Diamond IIb Breeding et al., 2009; Marnnz et al., 1993
2400–1200 – SiC fake diamond Bruker, 2014; Nassau et al., 1997
2350 CO2 O in diamond I and II, CO2 Marnnz et al., 1993
2125–1700 n (CHO) O in diamond I and II, from carbonate
(��O��CHO) group
Marnnz et al., 1993
2030 – Pure diamond, natural Bruker, 2014
1970 – Pure diamond, natural Bruker, 2014
1750 n (CHO) Diamond powder Ji et al., 1998
1700–1300 n (CHO) O in diamond I and II, from carbonyl (>CHO)
group
Marnnz et al., 1993
1630 d (O��H) Diamond powder Ji et al., 1998
1500–400 N in diamond (type I), one-phonon region Breeding et al., 2009; Bruker, 2013, 2014;
Fritsch, et al., 2007; Peretti et al., 2013
1460–1380 d (C��H) H in diamond Ib Fritsch, et al., 2007
1390–1350 – N added to diamond Breeding et al., 2009; Bruker, 2014; Marnnz et
al., 1993
1345 – N in diamond (type Ib), synthetic diamond,
dissapear when N2 -related absorptions are
high or atypical
Fritsch, et al., 2007
1330 – N in diamond, when N2-related absorptions are
high or atypical
Fritsch, et al., 2007
1290 – B in diamond IIb Marnnz et al., 1993
1280 – N in diamond (type IaA) Breeding et al., 2009; Bruker, 2014
1170 – N in diamond (type IaB), synthetic diamond Breeding et al., 2009; Bruker, 2014
1135 – N in diamond (type Ib) Breeding et al., 2009; Bruker, 2014
790 n (Al��O) YAG fake diamond Schiopu et al., 2012; Tucureanu et al., 2015
735–725 n (Y��O) YAG fake diamond Schiopu et al., 2012; Tucureanu et al., 2015
695–675 n (Al��O) YAG fake diamond Schiopu et al., 2012; Tucureanu et al., 2015
570 n (Y��O) YAG fake diamond Schiopu et al., 2012; Tucureanu et al., 2015
490 n (Y��O) YAG fake diamond Schiopu et al., 2012; Tucureanu et al., 2015
504 V. ŢUCUREANU ET AL.
boron). Peaks from 3500–2600 cm¡1 can be attributed to
H��H stretch vibrational mode from hydrogen absorbed in
diamond. In the case of boron absorbed on diamond in the
spectrum, it is characterized by peaks about 2800–2460 cm¡1
attributed to boron (Fritsch, et al., 2007; Breeding et al., 2009;
Willems et al., 2011; Almax, 2013; Bruker, 2013; 2014; Peretti
et al., 2013). The presence of oxygen in the diamond structure
is confirmed by peaks ranging from 2400 cm¡1 to 1300 cm¡1
and may be assigned to carbonyl and carbonate groups and to
CO, CO2 molecules (Marnnz et al., 1993). The peak intensity is
determined by concentration of the impurity and the thickness
of the diamond (Breeding et al., 2009).
From the chemical point of view, a fake diamond is Zirconia
(ZrO2), synthetic Moissanite (SiC), Yttrium aluminum garnet
(YAG), etc. The zirconia spectrum shows no absorption band
in the range 4000–1200 cm¡1, synthetic Moissanite is charac-
terized by peaks in the range 2400–1200 cm¡1 with intensity
lower than in the case of a natural diamond and garnet spectra
present peaks at 800–400 cm¡1 that can be assigned to O��O
and Al–O vibration mode (Nassau et al., 1997; Bruker, 2014;
Tucureanu et al., 2015).
Amorphous carbon characterized by FTIR
spectroscopy
Amorphous carbon, although does not have a crystalline struc-
ture, it is known as a structural allotropic of carbon. In nature
the amorphous carbon is found in coal earth and soot, and may
contain microscopic crystals of graphite and sometimes of dia-
mond (Jariwala et al., 2009).
Generally, DLC synthetic film is a form of amorphous car-
bon, metastable, containing sp2-bonded clusters interconnected
by a random network of sp3-bonded atomic sites. In the carbon
network, even sp1 carbon atoms can appear. The properties of
DLC materials are determined by the sp3/sp2 ratio and the
hydrogen content. DLC films can be films with hydrogen (i.e.
hydrogenated alloys amorphous carbon (a-C:H) and tetrahe-
dral amorphous carbon hydrogen (ta-C:H) films) or without
hydrogen (i.e. amorphous carbon (a-C) films and tetrahedral
amorphous carbon (ta-C)) and with a high content of sp3
bonding (i.e. ta-C and ta-C:H films). The hydrogen stabilizes
the sp3 bonds of the diamond on the film surface. By creating a
stable film, DLC can have properties similar to diamond, for
example: wide band gap, chemical inertness and mechanical
hardness (Alba et al., 1999; Robertson, 2002; Chu et al., 2006;
Jariwala et al., 2009; Vaghri et al., 2012). The characteristic
spectra for a DLC film show bands in the range 3500–600
cm¡1 where peaks can be attributed to different sp (aromatic
rings), sp2 (aromatic rings and olefinic chains) and sp3 carbon
configuration and hydrogen neighbors, assign to C-H from
CH2 (sp
2 and sp3) and CH3 (sp
3) groups and from C H C (sp2)
from chains structure. In the FTIR spectrum, the C H C bonds
may be seen as peak at about 1580 cm¡1 assigned to aromatic
ring structures while the peak from 1620 cm¡1 can be attrib-
uted to olefinic group stretching vibrations. In addition, some
peaks can be associated with the coexistence of sp2 and sp3
hybridization in a DLC film, these peaks can be attributed to a
mixed sp2–sp3 C��C vibration mode and appear at 1250 cm¡1
and 1515 cm¡1. The bands from 3000–2800 cm¡1 corresponds
to C��H symmetric and asymmetric stretching vibration from
CH2 and the CH3 groups indicate a hydrogenated DLC film
and hydrogen is binding from a sp3-hybridized carbon. The
lack of these absorption bands indicates the films without
hydrogen or at very low concentration. Also, in the 1700–1300
cm¡1 range absorption bands may be observed and attributed
to bending vibration of H��H groups (Alba et al., 1999; Bonelli
et al., 2000; Chu et al., 2006; Jariwala et al., 2009; Marcinauskas
et al., 2007; Robertson et al., 1991; Roy et al., 2007; Son et al.,
2001; Vaghri et al., 2012; Yan et al., 2004).
By deuteration in the DLC film a conversion of the sp2 to sp3
sites and extraction of H or chemical erosion of the a-C:H can
appear due to the insertion of the D atoms into the C H C
bonds and formation of the stable molecules. In case of deuter-
ation, DLC film can show bands at around 2100 cm¡1 attrib-
uted to C��D stretching and a decrease in C��H peaks
absorbance (if D-atom passivation appears after the extraction
of H) or a shift of the C��H region due to change of hybridiza-
tion from sp2 to sp3 (Jariwala et al., 2009).
In case of oxygen contamination, the DLC spectrum shows
peaks for C��O and C H O bonds, the most relevant contami-
nation band appears at 1720 cm¡1 (Marcinauskas et al., 2007).
The oxy-hydrogenated film is characterized by a broad band
centered at 3400 cm¡1, vibration due to O��H bond (Roy et
al., 2007).
In case of nitrogen contamination, from compounds that
contain nitrogen, a peak appears at 2820 cm¡1 because of the
CH��CH3 group (Roy et al., 2007). In Table 3, possible assign-
ments are presented for DLC films.
Graphite characterized by FTIR spectroscopy
Graphite crystal lattice is shaped as a two-dimensional (2D)
structure consisting of parallel layers made up of hexagonal
rings of carbon atoms sp2 hybridized. From thermodynamic
point of view, graphite is the most stable form of carbon, at
atmospheric pressure. Diamond can be transformed into
graphite at temperatures above 1500�C. In the FTIR spectrum
of pristine graphite there are no significant peaks relevant to
any functional groups, but weak bands may appear, which can
be assigned to adsorbed water molecules. Also, in the case of
exfoliated graphite process some peaks may appear due to
intercalation into graphite of some reactants implied in the pro-
cess (i.e. sulfuric acid, nitric acid, formic acid) (Shengtaoa et al.,
2011; Chang et al., 2013; Dissanayake et al., 2014). In Table 4,
the possible aassignments for graphite samples are presented.
Graphene characterized by FTIR spectroscopy
Graphene is a crystal with a flat single-atomic-layer of graphite,
consisting of sp2 hybridization carbons which are found in the
2D hexagonal honeycomb lattice.In the FTIR spectrum of pris-
tine graphene there are no significant peaks that are relevant to
any functional groups (Sangermano et al., 2011; Singh et al.,
2012; Kumar et al., 2013; Obreja et al., 2013; Ramachandran et
al., 2013; Dissanayake et al., 2014; Zahed et al., 2015). In the
graphene technology, the graphite powder is used for graphene
oxide (GO) synthesis. GO is an oxygen-rich carbonaceous lay-
ered material used for the formation of graphene. GO is a
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 505
chemically functionalized material obtained by introducing
some groups (containing oxygen) between graphite layers. In
the GO the graphite structure is maintained, but increases the
interlayer distance. GO is composed by sp3-hybridized carbons
(with hydroxyl and ether/epoxy functional groups arranged on
the top and bottom of the surfaces) and sp2-hybridized carbons
(with carbonyl and carboxyl functional groups in the sheet and
on the edges). Between the GO layers hydrogen bonds may
Table 3. The possible assignments for diamond-like carbon (DLC) films.
Wavenumber [cm-1] Probable assignment Characteristic vibration mode for: Ref.
3400 n (O–H) DLC, oxy-hydrogenated film Roy et al., 2007
3085 nas (C–H) DLC, a-C–H, CH2 (olefinic) group, sp
2 Chu et al., 2006
3035 n (C–H) DLC, a-C–H, CH (aromatic) group, sp2 Chu et al., 2006
3010–2990 ns (C–H) General assignments, CH (olefinic) Chu et al., 2006; Roy et al., 2007;
DLC, a-C–H, CH (olefinic) group, sp2 Son et al., 2001
2960–2955 nas (C–H) General assignments, methyl (CH3)
group, sp3
Alba et al., 1999; Bonelli et al., 2000;
Chu et al., 2006;
DLC, a-C–H, CH3 group, sp
3 Marcinauskas et al., 2007; Roy et al.,
2007; Yan et al., 2004
2930–2920 nas (C–H) General assignments, methylene (CH2)
, sp3
Alba et al., 1999; Bonelli et al., 2000;
Chu et al., 2006;
DLC, a-C–H, CH2, sp
3 Marcinauskas et al., 2007; Roy et al.,
2007; Son et al., 2001
2885–2870 ns (C–H) General assignments, CH3, sp
3 Alba et al., 1999; Bonelli et al., 2000;
Chu et al., 2006; Roy et al., 2007;
Son et al., 2001; Vaghri et al., 2012
DLC, a-C–H, CH3, sp
3
2860–2850 ns (C–H) General assignments, CH2, sp
3 Alba et al., 1999; Bonelli et al.,
DLC, a-C–H, CH2, sp
3 2000; Chu et al., 2006; Marcinauskas
et al., 2007; Roy et al., 2007; Son
et al., 2001; Vaghri et al., 2012;
Yan et al., 2004
2820 n (C–H) DLC, a-C–H, contaminated with N,
>N–CH group, sp3
Roy et al., 2007
1720 n (C=O) DLC contaminated with oxygen Marcinauskas et al., 2007
1680–1640 n (C=C) General assignments, C=C isolated Chhabra et al., 2012
1640–1620 n (C=C) General assignments, C=C conjugated Chhabra et al., 2012
1640–1600 n (C=C) DLC, a-C–H, C=C (Olefinic), sp2 Chu et al., 2006; Jariwala et al., 2009;
Marcinauskas et al., 2007; Vaghri
et al., 2012
1600–1580 n (C=C) General assignments, C=C (Aromatic),
sp2
Chu et al., 2006
DLC, a-C–H, C=C (Aromatic), sp2
1550 n (C=C) DLC, C=C, sp2 Bonelli et al., 2000
1515 CC DLC, a-C–H, CC group, from sp2– sp3
mixe
Chu et al., 2006
1480–1460 d (C–H) DLC, a-C–H, CH3 group, sp
3 Chu et al., 2006
1450 d (C–H) DLC, CH2 group, both the olefinic sp
2
and of sp3
Vaghri et al., 2012
1430 d (C–H) DLC, a-C–H, CH (aromatic) group, sp2 Chu et al., 2006
1415 d (C–H) DLC, a-C–H, CH2 (olefinic) group, sp
2 Chu et al., 2006
1400–1370 d (C–H) DLC, a-C–H, (CH3)3 group, sp
3 Chu et al., 2006; Vaghri et al., 2012
1300–1245 n (CC) DLC, a-C–H, CC group, from sp2–sp3
mixe
Bonelli et al., 2000; Chu et al., 2006
1180 C–H, C–C or C–O DLC Marcinauskas et al., 2007;
1100 C–O–C DLC contaminated with oxygen Roy et al., 2007
914 C–H DLC, CH2 (olefinic) group, sp
2 Vaghri et al., 2012
710 – DLC, attributable to the graphite form Bonelli et al., 2000
Table 4. The possible assignments for graphite samples.
Wavenumber
[cm¡1]
Probable
assignment
Characteristic vibration
mode for:
Ref.
4000–400 – Graphite, no peaks for graphite structure Chang et al., 2013; Dissanayake et al., 2014; Shengtaoa et al., 2011
4000–3000 n (O��H) Graphite, hydroxyl (OH) groups from water molecule (H2O) Chang et al., 2013; Shengtaoa et al., 2011
1640–1600 n (O��;H) Graphite, OH groups from water molecule (H2O) Chang et al., 2013; Shengtaoa et al., 2011
1635 d (O��H) Formic acid (HCOOH) from graphite exfoliation Shengtaoa et al., 2011
1384 n (NO3
¡) Nitric acid (HNO3) from graphite exfoliation Shengtaoa et al., 2011
1235 n (C��O) HCOOH from graphite exfoliation Shengtaoa et al., 2011
1080 n (SO4
2¡) Sulfuric acid (H2SO4) from graphite exfoliation Shengtaoa et al., 2011
975 n (C–O) HCOOH from graphite exfoliation Shengtaoa et al., 2011
605 n (SO4
2¡) H2SO4 from graphite exfoliation Shengtaoa et al., 2011
506
506 V. ŢUCUREANU ET AL.
appear (Stankovich et al., 2006; Das et al., 2013; Obreja et al.,
2013; Dissanayake et al., 2014).
FTIR spectroscopy is used for the characterization of the
functional groups in GO samples. In the GO spectra the char-
acteristic peaks for CO bonds appear at about 1230–1215
cm¡1, 1120–1110 cm¡1 (from epoxy), 1415 cm¡1, 1160 cm¡1
(from carbonyl or carboxyl) and 1080–1040 cm¡1 (from alkoxy
or epoxy), indicating the original extended conjugated p-orbital
system of the natural graphite was destroyed and CO groups
are inserted into graphite carbon skeleton. The presence of car-
boxyl groups onto the surface of graphene sheets is confirmed
by stretching the vibration mode of the carbonyl group at
1740–1720 cm¡1. Increasing the oxidation degree the C H O
peak intensity increases along with the decreasing intensity of
other O��O peaks (from OH��OH or O��O–C bonds). The
hydroxyl (H��H) groups are defined by the stretching mode in
the 4000–3000 cm¡1 range and the bending mode from 1640
cm¡1 to 1620 cm¡1. The presence of the band centered at 3450
cm¡1 suggests the possibility of adsorbed water and at about
3600 cm¡1 a OH��OH bond from hydroxyl groups may
appear. Because of these functional groups the GO was found
to be hydrophilic. Generally, the hydroxyl band (1640–1620
cm¡1) is overlapped with in-plane vibrations of the skeletal C
H C band of hexagonal aromatic ring from the graphene sheet
or corresponding to the remaining sp2 character from the non
oxide graphitic network. The C H C aryl stretching vibration
may appear at 1420 cm¡1 (Chang et al., 2013; Obreja et al.,
2013; Seresht et al., 2013; Zhang et al., 2013; Dissanayake et al.,
2014; Dumeea et al., 2014; Zahed et al., 2015). Wavenumber
data and possible assignments of the bonding interactions in
graphene materials are presented in Table 5.
Generally, in the FTIR graphene materials spectrum the
interpretation of peaks appearing in ranges below 900 cm¡1 is
not attributed because of the structural complexity (Lee et al.,
2010). By chemical/heating reduction, GO are used to prepare
chemically modified graphene or reduced graphene oxide
(RGO). The main goal of the reduction process is to obtain gra-
phene with properties similar to the pristine graphene ones
obtained by the mechanical exfoliation method. By the reduc-
tion of GO to graphene/RGO, the functional groups (C H O,
O��O or H��H) peaks were reduced until an almost total dis-
appearance or are barely detectable, due to the deoxygenation.
The final RGO spectrum, for a complete GO reduction, is pos-
sible to be characterized by the appearance of a peak centered
in the range of 1585–1565 cm¡1 which can be attributed to the
aromatic C H C group from the graphene sheet. At tempera-
tures below 1100�C the cracking of aromatic C H C bands can
be observed. In the case of chemical reduction an increase of
peaks intensity, in the 2950–2850 cm¡1 region, peaks assigned
to H��H bonds stretching vibration is observed (Chen et al.,
2010; Chhabra et al., 2012; Gao, 2012; Aldosari et al., 2013; Das
et al., 2013; Obreja et al., 2013; Seresht et al., 2013; Dissanayake
et al., 2014).
We will finish this section with some examples of intro-
ducing other functional groups and FTIR study of this pro-
cess. The functionalization of the existing groups on GO/
RGO may be realized by chemical or physicalinteraction,
by covalent bonds or by p interaction between the already
existing groups and the new ones in order to add other
functional species to form GO/RGO derivatives. From the
chemical point of view GO has numerous reactive groups,
so it is possible to be functionalized with a great number of
reagents. It is also possible that an attack to more reactive
groups from GO may simultaneously appear. In addition to
new functional groups to GO the amidization (at COOH
group), esterification (at COOH or –OH group), silanization
(at –OH group), and others may occur (Liu et al., 2009;
Obreja et al., 2013).
GO is the basis for obtaining IGO (isocyanate graphene
oxide) which may be reduced to IRGO (isocyanate reduced gra-
phene oxide) and it is used to obtain different composite mate-
rials, i.e. IRGO-P3HT (3-hexyl tiophene) nanocomposite. By
treating GO with isocyanates, results the transformation of car-
boxyl and hydroxyl groups in to amides or carbamate esters. In
these spectra a slight shift can be seen for C H O stretching
vibration from about 1740–1715 cm¡1 (in the case of COO¡
from GO) until 1705–1700 cm¡1 and it can be attributed to C
H O from carbamate esters group of the surface hydroxyl in
IGO. Also, in the IGO and IRGO spectrum the peaks originat-
ing from either amides or carbamate esters can be see, which
can be assigned to amide groups, amide I for C H O stretching
vibration and amide II mostly from the H��H bending vibra-
tion and from the N��N stretching vibration. The absence of
any isocyanate characteristic bands in the region 2280–2260
cm¡1 suggests the existence of a chemical reaction and no
absorption of isocyanate on the GO surface (Stankovich et al.,
2006; Chang et al., 2013; Obreja et al., 2013).
Graphene—TPP composite may be obtained starting from
amine-functionalized prophyrin (TPP-NH2) and GO. In the
composite spectrum, the peak from about 1730 cm¡1 (assigned
to C H O bond from COOH in GO spectrum) disappears and
two bands appear, one at about 1640 cm¡1 (C H O) and
another at 1260 cm¡1 (CN) attributable to the vibration mode
of amide linkages group. These peaks confirm the binding of
TTP molecules with GO through covalent amide bonds (Liu
et al., 2009).
Fullerene-graphene hybrid material, may be obtained start-
ing from pyrrolidine fullerene (C60(OH)x) and GO, coupling
reaction occurs between OH groups from fullerene and the
COOH groups from GO. In the pyrrolidine-C60, the band
from 1750 cm¡1 can be assigned to the vibration mode of the
COOCH3 group, in the GO the peak from 1730 cm¡1 can be
assigned to the C H O vibration mode from COOH, and in the
hybrid material spectrum two peaks exist at 1725 cm¡1 and at
1636 cm¡1 respectively that confirm the coupling and they can
be assigned to the carboxyl group and to the amide carbonyl
stretching mode (Zhang et al., 2008; Liu et al., 2009).
Silanization of hydroxyl groups from GO may be performed
with 3-aminopropyltriethoxysilane (APTES). In the GO-
APTES FTIR spectra peaks that may be assigned to Si-O-Si,
H��H and H��H bonds may be observed confirming that the
GO was modified by APTES (da Silva et al., 2014).
R(GO)-PMMA(polymethylmethacrylate) composites having
a FTIR spectrum exhibit the characteristic peaks for PMMA
chains and R(GO) sheets and the most important peaks can be
seen at 3420, 2950–2850, 1730, 1620 and 1150 cm¡1 corre-
sponding to the H��H, H��H, C H O C H C and O��O–C
bonds. The difference between these spectra and a R(GO)
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 507
Table 5. The possible assignments for graphene materials.
Wavenumber [cm-1] Probable assignment Characteristic vibration mode for: Ref.
4000–400 – Graphene, no peaks for graphene structure Dissanayake et al., 2014
3600 n (O–H) GO, hydroxyl (OH) groups from C–OH group Obreja et al., 2013; Zahed et al., 2015
3450–3350 n (O–H) GO, OH groups from C–OH group or water
molecule
Aldosari, et al., 2013; Zahed et al., 2015
3370 n (N–H) GO-APTES, NH2 groups da Silva et al., 2014
3300–2500 n (O–H) General assignments, OH from carboxylic groups
(COOH)
Chhabra et al., 2012
3100–3000 n (=C–H) General assignments, CH sp2 from aromatic ring Chhabra et al., 2012
2960–2850 n (C–H) General assignments, for CH2 or CH3 groups Chen et al., 2010; Chhabra et al., 2012; Obreja
et al., 2013
2930 nas (C–H) ! GO, CH2 group Ban et al., 2012; Chen et al., 2010; da Silva
et al., 2014 ; Obreja et al., 2013; Shahriary
et al., 2014
! RGO, CH2 group
! IGO, CH2 group
! IRGO, CH2 group
! GO-APTES, CH2 group
2850 ns (C–H) ! GO, CH2 group Ban et al., 2012; Chen et al., 2010; Obreja et al.,
2013; Shahriary et al., 2014
! RGO, CH2 group
! IGO, CH2 group
! IRGO, CH2 group
2830–2690 n (C–H) General assignments, in aldehyde (-CH=O) Chhabra et al., 2012
2815 n (O–H) GO, OH group from dimeric -COOH Chhabra et al., 2012
2260–2210 n (C�N) General assignments, in nitrile (–C�N) Chhabra et al., 2012
2250 n (N=C=O) IGO, isocyanate (–N=C=O) Obreja et al., 2013
1815 n (C=O) IGO, carbamate (– NH–COO¡) group Obreja et al., 2013
1760–1690 n (C=O) General assignments, –COOH group Chhabra et al., 2012
1760–1665 n (C=O) General assignments, carbonyls group (C=O) Chhabra et al., 2012
1750–1735 n (C=O) General assignments, esters (–COO¡) group Chhabra et al., 2012
1750 n (C=O) Pyrrolidine-C60, –COOCH3 Marcinauskas et al., 2007
1745 n (C=O) GO, –COOH group Krausw, et al., 2001
1740–1720 n (C=O) General assignments, in aldehyde (–CH=O) Chhabra et al., 2012
1735 n (C=O) IGO, –NH–COO¡ group Obreja et al., 2013
1735–1725 n (C=O) GO, –COOH group Aldosari, et al., 2013; Basheer, 2013; Chang
et al., 2013; Chen et al., 2010; Liu et al.,
2009; Obreja et al., 2013; Stankovich et al.,
2006; Zhang et al., 2013;
1725 C 1636 n (C=O) Graphene-C60 hybrid, carboxyl groupCamide Liu et al., 2009; Zhang et al., 2008
1720–1715 n (C=O) General assignments, ketones (>C=O) group Chhabra et al., 2012; Dumeea et al., 2014
1710 n (C=O) GO, –COOH group Gao, 2012
1700–1600 n (C=O) General assignments, in amide I (–CO–NH–)
group
Chhabra et al., 2012
1680–1630 n (C=C) GO, aromatic ring Aldosari, et al., 2013; Ban et al.,
RGO, aromatic ring 2012; Chhabra et al., 2012; Shahriary et al.,
2014
1680 n (C=O) GO, ketones (>C=O) group Lee et al., 2010
1655 n (C=O) IRGO, amide I (–CO–NH–) group Obreja et al., 2013
1645 n (C=O) IGO, amide I (–CO–NH–) group Obreja et al., 2013; Stankovich et al., 2006
1640 n (C=O) Compozite graphene-TTP, amide I (–CO–NH–)
group
Liu et al., 2009
1635–1625 d (O–H) GO, hydroxyl (OH) group Obreja et al., 2013; Shahriary et al., 2014; Zahed
et al., 2015
1622 n (C=C) RGO, GO, aromatic ring Aldosari, et al., 2013; Chang et al., 2013; Chen
et al., 2010; Dissanayake et al., 2014; Obreja
et al., 2013; Stankovich et al., 2006; Zhang
et al., 2013
1620 d/b (H–O–H) GO, OH groups from water molecule Gao, 2012
1618 n (C=C) GO, aromatic ring Seresht et al., 2013
1580 n (C=C) G-TiO2 composite Basheer, 2013
1580–1530 n (N–H) General assignments, in amide II (-CO–NH–)
group
Bykkam et al., 2013; Gao, 2012; Obreja et al.,
2013
1575–1560 n (C=C) RGO, aromatic ring Obreja et al., 2013; Stankovich et al., 2006
1545–1530 n (CN) C d (CHN) IGO, amide II (–CO–NH–) group Bykkam et al., 2013; Chen et
IRGO, amide II (–CO–NH–) group al., 2010; Zahed et al., 2015
1415 n (C–O) GO, –COOH group Lee et al., 2010; Shahriary et al., 2014
1412–1405 d/b (O–H or C–OH) GO, OH group Kumar et al. 2013; Kuzmany et al., 2004
1385 n (C–O) GO, –COOH group Lee et al., 2010; Shahriary et al., 2014
1380–1365 d/b (O–H or GO, OH group from tertiay alcohol Basheer, 2013; Chang et al.,
C–OH) 2013; Gao, 2012
1350 n (C–O) GO Dou et al., 2014
(Continued on next page )
508 V. ŢUCUREANU ET AL.
spectrum refers to an increase in the intensity of the H��H and
C H C bands and a decrease in the intensity of the C H O
bands. In the case of R(GO)-AgNPs-PMMA composites, the
FTIR spectra show that H��H and C H C peaks are shifted, up
to 3440 and 1660 cm¡1, and the others are reduced in intensity
as compared to R(GO)-PMMA spectrum (Aldosari et al., 2013;Alsharaeh, 2013).
We will end these section with the graphene-TiO2 compos-
ite. A TiO2 FTIR spectrum is characterized by absorption bands
in the range 750–600 cm–1 that can be attributed to the Ti – O
vibrations mode and at about 3400 cm–1 and 1620 cm–1 that
may be assigned to absorbed water at TiO2 surface. In the com-
posite spectrum besides the Ti-O and water bands, a new band
appears at about 1580 cm–1 which may be attributed to the
skeletal vibrations of the graphene sheets. Also a peak can be
observed at about 1210 cm–1 which may be assigned to the Ti–
C��C vibrations mode. These peaks confirm the formation of
the composite (Schiopu et al., 2009; Basheer, 2013).
CNT characterized by FTIR spectroscopy
CNTs can be regarded as 1D cylinder of one (single-wall CNTs,
SWNT or SWCNT) or more layers of graphene (multi-wall
CNTs, MWNT or MWCNT) with hemispherical caps at both
ends and with open or closed ends. The cylinders are long, thin
and hollow tubes and the MWCNT may be viewed as concen-
tric SWCNT or “Russian dolls” SWCNT. In the tubes, the sp2
carbons are in a hexagonal lattice and each carbon atom is
linked to three equivalents nearest neighbors by covalent
bonds. The structure of the CNT is influenced by angles and
curvatures in which a graphene sheet can be rolled into a tube
(zig–zag, armchair and chiral forms). There are only a few IR
active modes of CNTs and it depends on the CNTs form
symmetry. The wavenumbers from FTIR spectrum of CNTs
are influenced by the nanotube diameter. The diameter can
vary between 0.4 to 2.0 nm (SWNT) and 5 to 1000 nm
(MWNT) and the lengths range varies from 1 nm to several
mm. MWCNT comprises several diameters and the result is
broad bands that are built up of several component bands. For
SWCNT, the broadness of the C H C band can be explained by
the polydispersity in the geometry of nanotubes. As a result of
the structure, the CNTs are chemically inert and hydrophobic
materials, and because of the van der Waals’ attraction causes a
significant agglomeration. These disadvantages limit their
applications and to regulate this issue the surface is functional-
ized to incorporate some elements into the CNT sidewalls or
non-covalent surface modification. In this situation, the surface
functionalization, incorporation of some elements into the
CNT sidewalls or non-covalent surface modification are also
used to improve solubility, dispersion, etc. (Mitroova et al.,
2010; Barrios et al., 2012).
The most used method to achieve covalent functionalization
of the CNTs refers to the oxidation process in acid solutions or
by thermal treatment. In a purification process of CNTs in acid
medium (i.e. HNO3CH2SO4) besides purity improvement a
partial or total oxidization of carbon might occur. In this pro-
cess different oxygenated acidic surface groups are introduced
onto the carbon surface, such as the carboxyl group
(��COOH), carboxylic anhydride ((C H O)2O) groups,
unbound or free hydroxyl (��OH) group of phenol, lactone
group (��C��C H O), carbonyl (>C H O), quinone type units
( D O), ether groups (��O��) or O��O��C, S��S bonds, etc.
(Dang et al., 2006; Yudianti et al., 2011; Barrios et al., 2012;
Mansor et al., 2012). Pristine CNTs does not show noteworthy
IR signals compared to the functionalized CNTs. The hexago-
nal structure on the pristine CNTs is confirmed by peaks at
Table 5. (Continued ).
Wavenumber [cm-1] Probable assignment Characteristic vibration mode for: Ref.
1330–1240 d (CN) General assignments, amide III (–CO–NH–) group Bykkam et al., 2013; Gao, 2012; Obreja et al.,
2013
1280 n (C–O) GO, epoxy (–C–O–C–) group Zahed et al., 2015;
1260 n (C�N) Compozit graphene-TTP, amide III (–CO–NH–)
group
Liu et al., 2009
1230 n (C–OH) GO, OH group Chang et al., 2013; Stankovich et al., 2006
1230–1215 nas (C–O–C) GO, epoxy (–C–O–C–) group Aldosari, et al., 2013; Chen et al., 2010; Dou
et al., 2014; Obreja et al., 2013
1220 n (O–H or Ar-OH) GO, OH group from phenolic Gao, 2012
1210 n (Ti–O–C) G-TiO2 composite Basheer, 2013
1160 n (C–O) GO, –COOH group Obreja et al., 2013
1150 n (C–O–C) GO, epoxy (–C–O–C–) group Dumeea et al., 2014;
1115 n (C–O) GO, epoxy (–C–O–C–) group Chen et al., 2010
1110 n (C–OH) GO, OH groups from alcohol Shahriary et al., 2014
1080 n (C–O) GO, carboxyl (–COOH) or alkoxy (–O–) group Ban et al., 2012; Dissanayake et al., 2014
1075 n (C–O–C) GO, epoxy (–C–O–C–) group Zhang et al., 2013
1065 n (C–C C C–O) GO, skeletal mode of C–C and C–O bonds Chang et al., 2013; Gao, 2012
1060–1040 n (C–O) GO, carboxyl (–COOH) or alkoxy (–O–) group Dissanayake et al., 2014; Seresht et al., 2013
1055 n (C–OH) GO, OH groups Stankovich et al., 2006
1050 n (C–O–C) GO, epoxy (–C–O–C–) group Lee et al., 2010
1040 n (C–O) GO, –COOH group Obreja et al., 2013
1030 n (Si-O–Si) GO-APTES da Silva et al., 2014
850 d (C–O–C) GO, epoxy (–C–O–C–) group Dou et al., 2014; Obreja et al., 2013
740 n (C=O) GO, –COOH group Shahriary et al., 2014
735 n (Ti – O) TiO2 Schiopu et al., 2009
700–500 n (Ti – O) G-TiO2 composite Basheer, 2013
610 n (Ti – O) TiO2 Schiopu et al., 2009
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 509
about 1580–1530 cm¡1 (originating from the sp2-hybridized
carbon) and at about 1200–1100 cm–1 (originating from the
CNTs disordered regions likely consisting of disordered sp3-
bonded carbon, also serving as nucleation sites for hydrogen)
which are assigned to CH C bond from the CNT skeletal vibra-
tion mode. It was observed that by using a strong oxidant, the
CNTs the ends were opening and carboxylic groups were intro-
duced at the open ends and at defect sites on the CNTs, but by
a thermal treatment above 600�C the carboxylic groups might
be decomposed. After a peaks intensity decrease (assigned to C
H C bond) a peak at about 1800–1700 cm¡1 appears, which
can be attributed to the C H O bond stretching vibration mode,
as a result of carbon oxidation. This peak may suggest the car-
boxylation on the CNTs surfaces and the peak intensity
increases with the number of carboxyl groups, thus confirming
CNT surface functionalization with obtaining a
COOH��COOH material. The 1300–1000 cm¡1 region may be
assigned to the O��O vibration mode of ester, ether, phenol or
carboxyl groups, but in this region it is difficult to clearly assign
the peaks because of the absorption bands overlap from many
oxygen-containing ones. The band at 1640–1630 cm¡1 may be
attributed to the C H C with C H O conjugation or the interac-
tion of the skeletal CNT and carboxyl or ketone groups. In the
FTIR spectrum of purified and functionalized CNTs, peaks in
the 3000–2800 cm¡1 range absorption bands may be seen that
are assigned to the asymmetric and symmetric stretching vibra-
tion of H��H bonds from a long alkyl chain. The appearance
of these bands in the FTIR spectrum reveals the stability of
CNTs in the aqueous medium (Kouklin et al., 2004; Dang et al.,
2006; Teng et al., 2008; Mitroova et al., 2010; Yudianti et al.,
2011; Barrios et al., 2012; Mansor et al., 2012).
Doping CNTs with nitrogen atoms (CNT��CNTs) is used
as an alternative to surface oxidation in order to increase the
reactivity of the CNTs CNT��CNTs are hydrophilic due to the
presence of nitrogen based groups (i.e. amines), but the IR
spectra is more complex (i.e. interferences from benzene ring
of the aniline). If in the FTIR spectrum new peaks at about
1375 cm¡1 and 1250 cm¡1 are observed, these peaks may be
attributed to N��N and CH��CH3 bonds from the intercalated
N atoms between the graphite layers of the nanotube walls, but
both bands were gradually suppressed via thermal treatment
and completely disappearing at 900�C. The presence of the
N��N peak confirms the N doping of CNTs. By using various
methods for doping with N leads to several possible bonding
configurations to CNT, –CN, –NO, –NHx, –OOH, N replaces a
C atom in the graphitic lattice, N in pyridinic or pyrrolic con-
figuration, etc. (Misra et al., 2006; Ewels et al., 2007; Liao et al.,
2011; Motchelaho, 2011; Barrios et al., 2012). In Table 6, possi-
ble assignmentsare presented for different bonding types
involving Nitrogen-doped CNTs and other materials based on
CNTs. By inserting different compounds, the surface function-
ality of CNTs may increase and new applications may be found.
As in case of graphene, the insertion of other functional groups
improves the properties and the reactivity of these types of
materials. CNTs-based magnetic composites used CNTs with
carboxyl (COOH) group and magnetite (Fe3O4). In the FTIR
spectra of the Fe3O4, a strong absorption band may be seen at
590–560 cm¡1 assigned to Fe–O and H��H bands (possible
from Fe–OH, Fe–OOH or water molecules), and for these
applications, in the COOH��COOH spectrum the principal
band is assigned to the COOH group (C H O, 1800–1700
cm¡1). Comparable with the COOH��COOH spectrum, for
COO��COO–FeO composites is observed the maintaining of
the peak ascribed to C H C bond, the Fe–O bond may appear.
Also, the reduced of the C H O peak intensity and a little shift
along with appearance of two other bands due to symmetric
and asymmetric stretching of C��C–O, at lower wavenumber
than in COOH��COOH spectrum may be observed. The Fe–O
and C H O peaks reveal the presence of the magnetite particles
on the CNT structure by bridging interactions (in a reaction of
COOH groups with the surface of Fe3O4) (Mitroova et al.,
2010; Marquez et al., 2011; Zhao et al., 2012; Baykal et al., 2013;
Atta et al., 2014).
Fullerene characterized by FTIR spectroscopy
The fullerene is a closed cage structure molecule exclusively
formed by carbon atoms (Cn, n>20 or n D 20C6x, where, x is
a positive integer number and n is an even number) with sp2-
hybridized and each carbon is bonded to three neighbors (by
van der Waals bonds) having 12 pentagons and a variable num-
ber of hexagons (number of hexagons D [C– 20]/2). The differ-
ent number of hexagons leads to the existence of differently
shaped molecules (sphere, ellipsoid, tube, etc.) and to different
sizes—less than 300 carbon atoms, or buckyballs (i.e. C60 fuller-
enes) or with more than 300 carbon atoms or giant fullerenes
(i.e. single-shelled or multi-shelled carbon structures, ball-and-
chain dimers, nano-onions, nano/mega-tubes). Fullerene mole-
cules are stable, but unlike other family members, they are not
totally non-reactive. Research is oriented to increase reactivity
by introducing active groups at the fullerenes surface or smaller
molecules can be trapped in the cage to yield new materials.
C20 fullerene (D3d symmetry), the smaller fullerenes, present in
2300–400 cm¡1 range some peaks that may be assigned to
C��C bending (at low wavenumber) and stretching vibration
(at high wavenumber) from different isomers (Galli et al., 1998;
Zhang et al., 2007; Yadav et al., 2008; Lin et al., 2009; Li et al.,
2013; Zamani et al., 2014;). In Table 7, possible assignments for
some types of fullerenes and theirs derivates are presented.
The most popular and the most symmetric molecules are the
spherical C60 fullerenes (or buckminsterfullerenes—first discov-
ered), with the most stable molecular structure composed of 60
carbon atoms, 12 pentagons and 20 hexagons, with an icosahe-
dral symmetry (Ih) where all the rings are fused and all the dou-
ble bonds are conjugated in a soccer-ball type arrangement. In
point of the chemical reactivity, C60 which is not “super aro-
matic”, acts as an alkenes deficient electron and readily reacts
with electron rich species. By the C60 surface modification new
groups may be insertion in an open (i.e. hydrogenation) or
closed structure (i.e. 3, 4, 5 or 6-membered rings). Theoretically
the C60 fullerene molecule has 3N-6 D 174 vibrational degrees
of freedom, but only 4 are IR-active with F1u/T1u symmetry
(Prato, 1997; Kuzmany et al., 2004; Yadav et al., 2008; Iglesias-
Groth et al., 2011). Ibrahim et al. calculated all theoretical
vibrational modes for C60 and C80 and their epoxides (Ibrahim
et al., 2005). In practice, C80 has only eight intense vibrational
modes and, due to the high symmetry of the molecules, pristine
C60 shows a very simple FTIR spectrum with only four
510 V. ŢUCUREANU ET AL.
Table 6. The possible assignments for CNT samples.
Wavenumber [cm-1] Probable assignment Characteristic vibration mode for: Ref.
3800–3700 n (O–H) CNT, OH groups from unbound or free hydroxyl
of phenol
Mansor et al., 2012
3600–3200 n (O–H) CNT, hydroxyl groups from intermolecular
hydrogen bonded OH:OH, adsorbed water or
surface carboxylic and phenolic groups
Barrios et al., 2012; Baykal et al., 2013;
Dubey et al., 2005; Liao et al., 2011;
Mansor et al., 2012; Teng et al., 2008;
Yudianti et al., 2011
3420 n (N–H) N–CNT, NH and/or NH2 Ewels et al., 2007
3000–2800 n (C–H) CNT, CH2 and CH3 alkyl chain Dang et al., 2006; Ewels et al., 2007; Kouklin
et al., 2004; Liao et al., 2011; Mansor
et al., 2012; Misra et al., 2006;
Motchelaho., 2011; Teng et al., 2008;
Yudianti et al., 2011
2400–2000 n (C�N) N–CNT Ewels et al., 2007 ; Liao et al., 2011
2200 n (C�N) N–CNT Ewels et al., 2007
2177 n (C�N) N–CNT Ewels et al., 2007
2079 n (C�N) N–CNT Ewels et al., 2007
1800–1700 n (C=O) CNT–COOH, carboxyl, lactone or ketone groups Barrios et al., 2012; Dang et al., 2006; Johan
et al., 2014; Liao et al., 2011; Mansor
et al., 2012; Mitroova et al., 2010; Teng
et al., 2008
1755 n (C=O) CNT–COOH, carboxyl (–COOH) group Yudianti et al., 2011
1736 n (C=O) N–CNT Misra et al., 2006; Motchelaho., 2011
1725 n (C=O) CNT–COOH, nonconjugated –COOH group Dubey et al., 2005; Kouklin et al., 2004
1724 n (C=O) CNT–COO–FeO composite Mitroova et al., 2010;
1685 n (C=O) CNT–COOH, –COOH group Barrios et al., 2012 ; Seo1 et al., 2006
1640 n (C=O) CNT–COOH, carbonyl (C=O) of quinone type Barrios et al., 2012 ; Yudianti et al., 2011
1640–1630 d (O–H) CNT, hydroxyl groups Mansor et al., 2012 ; Yudianti et al., 2011
1640–1590 n (C=N) N–CNT Ewels et al., 2007 ; Liao et al., 2011
1636 n (C=OCC=C) CNT–COOH, H bonded Baykal et al., 2013
1599 n (C=C) CNT Dubey et al., 2005
1596 n (C=N) N–CNT Ewels et al., 2007
1585–1530 n (C=C) CNT, backbone of carbon nanotubes Barrios et al., 2012; Dang et al., 2006;
Kouklin et al., 2004; Mahore et al., 2014;
Mansor et al., 2012; Mitroova et al., 2010;
Teng et al., 2008; Yudianti et al., 2011;
1578 nas (–COO
¡) CNT–COOH Liao et al., 2011
1570 n (C=C) CNT–COOH Baykal et al., 2013
CNT–COO–FeO composite
1560 n (C=C) CNT, carbon skeleton Seo1 et al., 2006
1535 n (–NO2) CNT, from using HNO3 in purification and
oxidation process or oxidation of N–CNT
Barrios et al., 2012
1460 das/g (C–H) CNT, CH2 or CH3 Teng et al., 2008
1445 n (C–N) N–CNT Barrios et al., 2012
1400 n (C–N) N–CNT Ewels et al., 2007
1395–1380 ds/b (C–H) CNT, CH2 or CH3 Liao et al., 2011
1370 n (N–CH3) N–CNT Barrios et al., 2012; Ewels et al., 2007; Misra
et al., 2006
1365 n (NO2) CNT Johan et al., 2014; Motchelaho., 2011
1350 n (C=C) CNT, carbon skeleton Dubey et al., 2005
1340 n (–NO2) Oxidation of N–CNT Barrios et al., 2012
1270 n (C–O) CNT, ester, ether, phenol or carboxyl groups. Teng et al., 2008
1270 n (C–N or C¡H) N–CNT Ewels et al., 2007 ; Liao et al., 2011
1250 n (C–N) N–CNT Barrios et al., 2012; Ewels et al., 2007; Misra
et al., 2006
1235–1130 n (C–N) N–CNT Ewels et al., 2007
1220 n (C–O) C d (O–H) CNT, C–O stretching and O–H bending vibrations Dubey et al., 2005, Liao et al., 2011,
Motchelaho., 2011
1200 n (C=C) CNT, backbone of carbon nanotubes Kouklin et al., 2004
1200–1000 n (C–O) CNT, phenols and lactones Barrios et al., 2012
1180 n (C–C–C) CNT–COOH Baykal et al., 2013
1160 n (C–O) CNT–COOH Johan et al., 2014
1120 n (C=C) CNT, backbone of carbon nanotubes Dang et al., 2006
1120 n (C–O) CNT–COOH, ester, ether, phenol or carboxyl
groups.
Teng et al., 2008
1120 n (C–N) N–CNT Ewels et al., 2007
1100–900 – N–CNT, N heterocyclic ring modes Liao et al., 2011
1090–1020 n (C–O) CNT–COOH, ester, ether, phenol or carboxyl
groups.
Teng et al., 2008
1026 n (Si–O) CNT grown on Si wafer Misra et al., 2006
1000–500 n (C=C) CNT, backbone of carbon nanotubes Yudianti et al., 2011
875 d∕g(C–H) CNT, isolated aromatic C–H Teng et al., 2008
860 n (S–O–C) Yudianti et al., 2011
(Continued on next page )
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 511
characteristic peaks at about 1428 cm¡1, 1182 cm¡1 associated
with a tangential motion of the carbon atoms, 576 cm¡1 and
527 cm¡1 from a primarily radial motion of the carbon atoms.
In the case of fullerene C60 nanotubes (FNTs) and fullerene
dimers, the FTIR spectra are the same as for the pristine C60,
confirming that the FNTs or dimers are composed of C60 mole-
cules. Polymerization has been observed only for C60 and C70
molecules. The appearance of any different absorption bands
appear, they may be related to the presence of solvents or to
impurities (Smith, 1993; Resmi et al., 2001; Ibrahim et al., 2005;
Ibrahim et al., 2008; Iglesias-Groth et al., 2011; Qu et al., 2011;
Katiyar et al., 2014).
Modifying the surface in order to add epoxides groups to
the fullerene cage, (fullerene epoxides, C60On, n � 2) leads
to a FTIR spectrum showing a shift to lower wavenumbers
of the main peaks and a new peak assigned to epoxy groups
(1140 cm¡1). Also, for fullerene dimers oxides (C120On) the
C60 characteristic peaks are kept, indicating that the fuller-
ene cages are intact in these dimers and new peaks appear
that may be assigned to various intra-cage vibrations due to
dimerisation and epoxy groups (Ibrahim et al., 2005; Resmi
et al., 2001).
The water-soluble fullerene derivatives or fullerene (C60(OH)n
n D 2–28) spectra are characterized by absorption bands that
may be assigned to O��O (possible from hydroxyl, ether or
hemiketal groups) and the C H C vibration mode and no
absorption bands as are observed for C60. A small peak around
1720 cm¡1 assigned to the C H O stretching vibration mode
from carboxylic acid group is possible to appear, which might
have been formed by further oxidation of a hydroxyl group asso-
ciated with C��C bond cleavage of the fullerene nucleus (Alves
et al., 2006; Indeglia et al., 2014; Kokubo, 2012; Krishna et al.,
2010; Tianbao et al., 1999).
In case of C60 surface modification, for the purpose of intro-
ducing the polar functional groups (using air plasma), the FTIR
spectra appear modified and new absorption bands that may be
assigned to H��H aromatic bonds are observed (Vijaya-
lakshmi1 et al., 2014).
In a FTIR spectrum of C60-HEMA (poly(2-hydroxyethyl
methacrylate)) absorption bands attributed to groups from
HEMA part (hydroxyl, ester, metil, metilen) may be seen, as
well as bands due to fullerene (motion of the carbon atoms),
and the band from 525 cm¡1 confirm the formation of C60-
HEMA (Katiyar et al., 2014).
The TiO2-C60 composite spectra may show peaks, attributed
to C60 vibrational slightly changed (the 1182 cm¡1 peak split in
1225 cm¡1 and 1159 cm¡1, 1428 cm¡1 peak gradually dimin-
ished), in the 900–400 cm¡1 region the C60 peaks or Ti-O peak
(a more large band) appears. Also, there is a new band at about
1620 cm¡1 attributed to water molecules adsorbed on Ti4C site
(Zhang et al., 2010; Katsumata et al., 2012).
During the formation of fullerenes, atoms, ions or clus-
ters can be trapped inside the cage, resulting in so-called
endohedral fullerenes (endohedral doping), i.e. M@Cn
where M is a metal atom (i.e. Na, Cs, Li, Sr, Sc, Y, La, Gd
in order to obtain mono-, di-, tri- or tetra-metallofuller-
enes) or M3N@Cn (trimetallic nitride template—TNT: Sc3N,
Y3N, Ho3N) encaged in a Cn fullerene (i.e. C60, C70, C84,
C96). In this paper, we dwelt only on two examples, the
endohedral fullerenes spectra are different from a type to
another. Sc3N@C80 presents a complex structure below
1550 cm¡1 and a non-split peak at 597 cm¡1. For a TNT
endohedeal gadofullerols (Gd3N@C80(OH)m(O)n) spectrum
absorption bands appear, assigned to C H C (around 1600
cm¡1) and peaks for some functional groups attached to
the carbon cage (H��H, O��O) (Krause et al., 2001; Wang,
2006).
After C60 fullerenes, C70 molecules are the most abundant
and stable fullerenes. As compared with C60, in C70 the symme-
try (D5h) is reduced and may have 204 vibrational modes, in
theory, but only 31 are IR-active bands. In these conditions, the
C70 seem to have a more complicated FTIR spectrum (Iglesias-
Groth et al., 2011). Perhaps in a sample different types of fuller-
enes coexist and in the IR spectrum characteristic absorption
band appear for all types (i.e. C60 and C70, peaks for C60 at
1430, 1186, 576, 527 cm¡1 and C70 at 1134, 960, 795, 674, 642
cm¡1) (Alves et al., 2006).
Carbon quantum dots characterized by FTIR
spectroscopy
CQDs are a new class of carbon nanostructures (with sizes
below 10 nm) that may be prepared from graphite, gra-
phene (GQD), GO, CNTs, nanodiamonds. CQDs FTIR
spectra depend on the raw material, manufacturing method
and reaction parameters, leading to different functional
groups (hydroxyl, carboxyl, carbonyl, epoxy, amine) that
Table 6. (Continued ).
Wavenumber [cm-1] Probable assignment Characteristic vibration mode for: Ref.
CNT, sulfonic acid groups from using H2SO4 in
purification and oxidation process
800 (C¡N) N–CNT Liao et al., 2011
770 n (C–S) CNT, sulfonic acid groups from using H2SO4 in
purification and oxidation process
Mansor et al., 2012
700–600 n (C–S) CNT, sulfonic acid groups from using H2SO4 in
purification and oxidation process
Mansor et al., 2012
630–620 n (Fe–O) CNT–COOH, Fe3O4 Wang et al., 2010
595–570 n (Fe–O) CNT–COO–FeO composite Baykal et al., 2013; Mitroova et al., 2010;
Wang et al., 2010
590–560 n (Fe–O) Fe3O4 Atta et al., 2014; Marquez et al., 2011; Zhao
et al., 2012
512 V. ŢUCUREANU ET AL.
Table 7. The possible assignments for fullerene.
Wavenumber [cm–1] Probable assignment Characteristic vibration mode for: Ref.
3450– n (O–H) ! C60(OH)n Alves et al., 2006; Indeglia
et al., 2014;
3300 ! C60-HEMA, hydroxyl group from HEMA Katiyar et al., 2014; Krishna
et al., 2010; Tianbao et al.,
1999; Wang, 2006
! Gd3N@C80(OH)m(O)n
3000–2800 n (C–H) ! C60, CH2 and CH3 from aliphatic hydrocarbon
impurities
Indeglia et al., 2014; Katiyar
et al., 2014; Smith, 1993
! C60-HEMA, CH2 and CH3 alkyl chain
! C60(OH)n
2210 n (CC) C20, propellane isomer, CC in tetrahedron Zamani et al., 2014
2000 e4g C20, ring Galli et al., 1998; Zamani et al.,
2014
1944 – C20, ring isomer, D10h symmetry Galli et al., 1998
1905 Ag(2) C80 Ibrahim et al., 2008
1900150 – C20, cage isomer, D3d symmetry, 50 IR active peaks Galli et al., 1998
1850–1750 – Oxidation of C60, cyclic anhydrides Indeglia et al., 2014; Katiyar
et al., 2014; Smith, 1993
1817 n (>C=C=C=CC=C) C20, tadpole isomer Zamani et al., 2014
1538 Ag(2) C80 Ibrahim et al., 2008
1530 e1
’ or a1
” or e2
” C70 Menon et al., 1996
1500 a2
” C70 Menon et al., 1996
1475–1460 e1
’ C70 Menon et al., 1996; Bethune
et al., 1991
1470–1430 d (C–OH) C60(OH)n Alves et al., 2006; Krishna et al.,
2010; Tianbao et al., 1999
1469–1390 (CC in pentagon) C20, bowl isomer Galli et al., 1998; Zamani et al.,
2014
1460 das/g (C–H) C60-HEMA, CH2 or CH3 Katiyar et al., 2014
1451 F1u(4) C120On dimer oxide, F1u(4) vibrational modes Resmi et al., 2001
1450 a2
’ or e2
” C70 Menonet al., 1996
1445 Ag(2) C60, the two totally symmetric Ag(2) modes Ibrahim et al., 2005
1440 a2
” C70 Menon et al., 1996
1430–1420 e1
’ C70 Bethune et al., 1991; Iglesias-
Groth et al., 2011; Menon
et al., 1996
1430–1410 F1u(4)/T1u ! C60, tangential motion of the carbon atoms Alves et al., 2006; Arie et al.,
2009; Bethune et al., 1991;
Iglesias-Groth et al., 2011;
Katiyar et al., 2014;
Katsumata et al., 2012;
Kuzmany et al., 2004;
Meilunas et al., 1991;
Menon et al., 1996; Qu
et al., 2011; Resmi et al.,
2001; Smith, 1993
! C60 and C70 coexist, C60
! C120On dimer oxide, F1u(4) vibrational modes
1415–1410 n(C=C) C60(OH)n Indeglia et al., 2014
1415–1405 e1
’ or e2
” C70 Bethune et al., 1991; Iglesias-
Groth et al., 2011; Menon
et al., 1996
1390–1380 d (C–OH) C60(OH)n Alves et al., 2006; Indeglia
et al., 2014; Krishna et al.,
2010; Tianbao et al., 1999
(Continued on next page )
CRITICAL REVIEWS IN ANALYTICAL CHEMISTRY 513
Table 7. (Continued ).
Wavenumber [cm–1] Probable assignment Characteristic vibration mode for: Ref.
1390 ds/b (C–H) C60-HEMA, CH2 or CH3 Katiyar et al., 2014
1384 F1u(4) C120On dimer oxide, F1u(4) vibrational modes Resmi et al., 2001
1370 Ag(2) C80 Ibrahim et al., 2008
1356 b2u C20 (D2h), theory – in the spectrum are 21 IR active
peaks for C20 with D2h symmetry
Zhang et al., 2007
1355 a1
” C70 Menon et al., 1996
1352 b3u C20 (D2h) Zhang et al., 2007
1345–1340 e1
’ or a2
” or e2
” C70 Menon et al., 1996
1342 d (>CCC=C=C=C