Materials Letters 102​–​103 (2013) 83​–​86

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Materials Letters
journal homepage: ​www.elsevier.com/locate/matlet

Characterization of surface chemical modi​fi​ed carbon nano-particles

Simona Trostová a​​ , Ivan Stibor b​​ , Jana Karpí​š​ková b​​ , Zde​ň​ka Kolská c​​ , Václav ​Š​vor​č​ík a​​ ,​n
a​
Department of Solid State Engineering, Institute of Chemical Technology, 166 28 Prague 6, Czech Republic b​ ​Institute for Nanomaterials, Advanced Technologies and Innovation,

Technical University of Liberec, Czech Republic c​ ​Faculty of Science, J.E. Purkyn​ě ​University, Ústí nad Labem, Czech Republic
article info
​ eceived 1 February 2013 Accepted 25 March 2013 Available online 1 April 2013
Article history: R
Keywords: C ​ arbon nano-particles Surface chemical modi​fi​cation Surface characterization TEM FTIR XPS BET isotherm
0167-577X/$ - see front matter ​& ​2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.matlet.2013.03.119
abstract
The surface of carbon nano-particles (CNPs) was modi​fi​ed by the functionalization of aromatic amine type and of amide-amine type. Transmission electron
microscopy (TEM) was used for investigation of surface morphology of pristine and modi​fi​ed nano-particles. The chemical composition of CNPs was studied by
X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The total pore volume, surface area and pore size distribution were
also determined by measuring of Brunauer​–​Emmett​–​Teller (BET). FTIR and XPS equally con​fi​rmed the presence of amino groups linked to the CNPs. It is shown
that by the chemical modi​fi​cation the CNPs surface and pores within were grafted with nitrogen functional groups.
& ​2013 Elsevier B.V. All rights reserved.
1. Introduction
Nano-particles (NPs) create a new class of materials with special properties and they have become the subject of basic and applied research
leading to important technological applications in e.g. heterogeneous catalysis, medicine, nano-electronics, optical communication and gas
sensing. Their properties are closely linked to their size and structure at nano-and atomic scale. NPs possess large surface/volume ratio and a large
fraction of surface atoms that are under-coordinated in comparison with those in the bulk ​[1]​.
Carbon nano-particles (CNPs) are composed of about 97​–​99% of elemental carbon ​[2] ​in the form of nearly spherical particles with the diameters
from 10​–​100nm ​[3]​. In addition, CNPs contains other elements, which are mainly hydrogen and oxygen. Carbon spherical particles, also named
primary particles, are invariably fused into larger aggregates having size in the range of 200​– ​1000nm and further to micro-sized agglomerates
[2​,​3​]. The aggregates have a signi​fi​cant effect upon bulk properties, although the quasi-graphitic microstructure associated with the primary
particle size will in​fl​uence surface properties ​[4]​.
The surface properties of CNPs desirable for certain applica- tions are not always achieved by the manufacturing process alone. Surface properties
can be modi​fi​ed either by physical or chemical treatments ​[5]​. CNPs having a large speci​fi​c surface area, are
hydrophobic in nature and strong cohesive forces occur between individual particles ​[6]​. To avoid these undesirable effects and to improve the
dispersibility, stability and hydrophilicity of CNPs their surface chemistry has to be modi​fi​ed. Introducing of cationic groups, commonly
quaternized amino groups is one of the possible methods ​[7]​.
In this study, the functionalization of surface was used to activate CNPs. The surface properties of CNPs were characterized by transmission
electron microscopy (TEM), chemical composition by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy
(XPS). The surface area, the total pore volume and pore size distribution were also determined by measuring of Brunauer​–​Emmett​–​Teller (BET)
isotherm. One of the motivation for the present work was the idea that modi​fi​ed CNPs, with higher wettability and special surface morphology
may exhibit increased biocompatibility and be of interest for applica- tions in tissue engineering ​[8​,​9​].
2. Experimental
Materials and chemical modi​fi​cation​: The carbon nano-particles (CNPs, supplied by Unipetrol, a.s. CR, electrical resistivity 120 ​Ω ​cm, pour
density 115 g l​−​1​) were used in this study. The CNPs were modi​fi​ed in two ways: the functionalization of (i) aromatic amine type and (ii)
amide​–​amine type.
n​
Corresponding author.
(i) The ​fi​rst procedure of the CNPs modi​fi​cation, adapted from ​E-mail address: V
​ aclav.Svorcik@vscht.cz (V. ​Š​vor​č​ík).
that already described in ​[10] ​comprises two steps: 1st
nitration step (formation of ​–​C​–​NO​2 groups)
​ and 2nd amine function (​–​C​–​NH​2 FTIR spectra, taken on Bruker ISF 66/V spectrometer equipped
a Hyperion microscope with ATR (Ge) objective, were used to examine the
​ The second procedure of the CNPs modi​fi​cation, adapted from that
formation). (ii)
es of CNPs chemical structure (mixed with KBr powder). The results are
already described in ​[11] ​includes two following steps: 1st oxidation step
nted as FTIR differential spectra obtained by subtraction of absorbance of
(formation of ​–​COOH groups) and 2nd amide function formation.
ne sample from that of chemically modi​fi​ed one.
XPS was used to measure the concentration of O, C, N and Cl
Diagnostic techniques​: Various methods were used for determi-
in the surface layer of CNPs. Photoelectron spectra were measured with
nation of the properties of the CNPs. TEM images of nanoparticles in water were
ron Nanotechnology ESCAProbeP spectro- meter (error of 10%). The O (1s),
obtained on JEOL JEM-1010 (JEOL Ltd., Japan) instrument operated at 80 kV
, N (1s) and Cl (2p) peaks were analyzed ​[13]​.
[12]​.
 Properties of porous CNPs (total surface area, total pore volume um correspond to ​– ​CONH​
2 ​groups. The bands at 856 and 789 cm​−​1
and pore size distribution) of were determined using a Colter SA 3100 (Beckman
Colter) analyzer. The results were obtained by evaluation of the shape of BET pond to C​ ​ –​N groups. The FTIR results prove that nitrogen was chemically
isotherms of nitrogen absorption and desorption ​[14]​. d to the CNP​'​s surface in the second version of chemical modi​fi​cation.
Using XPS method the atomic concentration of elements in the
surface layer about 1 nm (8​–​10 atomic monolayers) thick are determined.
3. Results and discussion spectra of pristine and chemically modi​fi​ed samples are shown in ​Fig. 3​. The
ntrations of observed elements, determined from the relevant peaks, are
CNPs were chemically modi​fi​ed in two ways to prepare CNPs with arized in ​Table 1​. After chemical modi​fi​cation, however, nitrogen appeared
nitrogen functional groups grafted on their surface. The structure of CNPs, pristine e CNPs surface. The concentration of nitrogen depends on the chemical
(A) and chemically modi​fi​ed ones (B, C) is seen from TEM images shown in ​Fig. 1​. i​cation used. It was only 0.7 and
One can see that CNPs agregate and form chain structures. From the images it is .5at% for the ​fi​rst and second way of chemical modi​fi​cation respectively. Nitrogen
also possible to estimate the CNP sizes which vary from 30​–​60 nm. There are no 1s) peak is observed at the binding energy of 405 eV (​Fig. 3​). Chlorine on the
signi​fi​cant differences in the visible structure of CNPs before and after the chemical CNPs modi​fi​ed in the second way was also observed at 200 eV binding energy. The
modi​fi​cation. Chemical modi​fi​cation improves wettability of the CNPs surface and hlorine presence may be due to insuf​fi​cient conversion of​–​COCl group with
the increased wettability leads to easier preparation of CNPs suspension after NH​ (CH​ )​ NH​ .
2​ 2​ 6​ 2​
modi​fi​cation in water. Surface area, total pore volume and pore size distribution were
FTIR spectroscopy was used for the characterization of chemical etermined by analysis of BET nitrogen adsorption/desorption isotherms ​[15]
composition of CNPs. Relevant part of the differential FTIR spectra (absorbance of measured on pristine and chemically modi​fi​ed CNPs. The results are summarized in
chemically modi​fi​ed nanoparticles minus absor- bance of pristine ones) are shown Table 2​. Pristine CNPs has surface area of 1050 m​2 ​g​−​1 ​and total pore volume of
in ​Fig. 2​. The bands at 1590 and about 1180 cm​−​1 ​in the upper spectrum correspond .36 ml g​−​1​. Chemical modi​fi​cations lead to dramatic decrease of both these
to SO​4​−​2 ​groups. These groups are present from the sulfuric acid which was used in arameters. After functionalization of aromatic amine type the
preparation of the nitration mixture. The bands of nitrogen containing groups which ig. 1. ​TEM images of CNPs, pristine (A) and chemically modi​fi​ed CNPs by aromatic amine type
are expected to be linked to the CNP​'​s surface after the chemical modi​fi​cation –​NH​2 ​(B) and by amide​–​amine type C​–​CONH(CH​2​)​6​NH​2 ​(C).
cannot be determined in this case because they are shadowed by the sulfur
containing groups mentioned before. The bands at 1559 and 1505 cm​−​1 ​in the lower
S. Trostová et al. / Materials Letters 102​– ​103 (2013) 83​– ​86 ​84
 iformly. The changes in the pore size are more signi​fi​cant for amide​–a​ mine type
odi​fi​cation. In this case more functional groups are adsorbed on CNPs surface.
th XPS and FTIR measurements con​fi​rmed this result. Higher amount of grafted
rogen groups are observed after the amide​–​amine type modi​fi​cation. Due to the
re ​fi​lling, the adsorption capacity of material decreases dramatically. The
steresis between adsorption and desorption isotherms indicates that the pore
apes are cylindrical or ​“i​ nk-bottle​” ​ones for both pristine and chemically modi​fi​ed
NPs ​[15]​.
The present results show that the CNPs surface can be modi​fi​ed by
afting with amino groups, which in turn could mediate their
. 2. ​FTIR differential spectra of CNPs (absorbance of chemically modi​fi​ed CNPs by aromatic amine
e minus pristine one ​– ​the black one, the upper line, and modi​fi​ed by amide​–​amine type minus
tine one ​– ​the red one, the lower line). (For interpretation of the references to color in this ​fi​gure
end, the reader is referred to the web version of this article.)

chemical bonding onto activated polymers ​[8]​. The latter are expected to exhibit
increased biocompatibility and could be applied e.g. in tissue engineering.
C-pristine 87.6 12.4 ​– – ​C​–​NH​2 ​89 89 0.7 ​– C​
​ –​CONH(CH​2​)​6​NH​2 ​80.0 80.0 5.5 6.2

Table 2 ​Surface area, total pore volume and pore size distribution of pristine (C-pristine) and

chemically modi​fi​ed CNPs by aromatic amine type (C​–​NH​2​) and by amide​– amine
​ type

(C​–​CONH(CH​2​)​6​NH​2​).

C-pristine C​– ​NH​2 C​

​ – ​CONH(CH​2​)​6​NH​2

surface area is 521 m​2 ​g​−​1 ​and total pore volume is 1.03 ml g​−​1​. Functionalization of
2 ​ −​1​ −​1​
amide​–​amine type results in the surface area of 33 m​2 ​g​−​1 ​and total pore volume of Surface area (m​ g​ ) ​1050.45 520.92 33.14 ​Pore volume (ml g​ ) ​2.36 1.03 0.17
0.17 ml g​−​1​. Both types of functionalization lead to a signi​fi​cant decrease of Pore diameter range (nm) Pore volume (​μ ​l g​−​1​) ​o ​6 409.17 251.79 12.33 6​–​8
particular pore volumes regardless of their size. The decrease can be explained by 136.58 48.73 5.92 8​–​10 66.92 21.08 4.49 10​–​12 57.93 23.30 6.63 12​–​16 61.91
bonding of the chemical substances used for chemical modi​fi​cations to the CNPs 29.53 3.80 16​–​20 76.64 40.55 14.42 20​–​80 1172.25 447.88 113.73 ​> ​80 266.01
63.50 16.21
surface and ​fi​lling of CNPs pores. The results indicate that all pores were ​fi​lled
S. Trostová et al. / Materials Letters 102​– ​103 (2013) 83​– ​86 ​85

4. Conclusions
The CNPs were modi​fi​ed by grafting with nitrogen containing
groups and their properties were characterized by TEM, FTIR and XPS methods.
The properties of the modi​fi​ed CNPs depend on the functionalization type.
According to XPS analysis, almost no nitrogen was grafted after functionalization
of aromatic amine type. Functionalization of amide​–​amine type was more effective
and it results in grafting with nitrogen groups which is proved by both FTIR and
XPS analyses. Chemical modi​fi​cation increases CNPs hydrophilicity substantially.
Total surface area and pore volume of CNPs decrease after chemical modi​fi​cation
substantially due to the ​fi​lling of surface and pores by chemical substances applied.
The hysteresis between pristine and chemically modi​fi​ed CNPs show, that
cylindrical and ​“​ink-bottle​” ​pores are present.
Acknowledgments
materials designed for body implants. Biotechnol Adv 2011;29:739​–​67. ​[9] ​Kubova O, Svorcik V, Heitz
This work was supported by the GACR under project P108/12/
Fig. 3. ​XPS spectra of pristine CNPs (pristine C, blue one, the upper line) and chemically modi​fi​ed
CNPs by aromatic amine type (C​-​NH​2​, the black one, the middle
​ line) and modi​fi​ed by amide​–​amine
type (C-CONH(CH​2​)6NH​2​, the red one, the lower line). The C (1s), O (1s), N (1s) and Cl (2p) peaks are
present. (For interpretation of the references to color in this ​fi​gure legend, the reader is referred to the
web version of this article.)
Table 1 ​Atomic concentrations of C (1s), O (1s), N (1s) and Cl (2p) determined from XPS
measurements (error of 10%) of pristine (C-pristine) and chemically modi​fi​ed CNPs by aromatic amine
(C​–​NH​2​) and by amide-amine type (C​–​CONH(CH​2​)​6​NH​2​).
Samples Atomic concentrations of elements (at%)
Cl (2p) C (1s) O (1s) N (1s)
and project TUL SGS 5860.
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