Composites Communications 6 (2017) 1719

Contents lists available at ScienceDirect

Composites Communications
journal homepage: www.elsevier.com/locate/coco

Synthesis and characterization of carbon/ceramic composite materials for MARK

environmental applications

Pavel V. Krivoshapkina,b, Ilya V. Mishakovc,d, Aleksey A. Vedyaginc,d, , Yuri I. Baumanc,
Elena F. Krivoshapkinaa,b
a
ITMO University, St. Petersburg 197101, Russian Federation
b
Institute of Chemistry of Komi SC UB RAS, Syktyvkar 167982, Russian Federation
c
Boreskov Institute of Catalysis SB RAS, Novosibirsk, 630090, Russian Federation
d
National Research Tomsk Polytechnic University, Tomsk 634050, Russian Federation

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

Keywords: Nanoparticles of nickel oxide on the surface of macroporous ceramic support were prepared by means of a sol-gel
Macroporous ceramics technique. In order to improve the adhesion with a surface of support and prevent the penetration of the catalyst
Sol-gel synthesis into inner pores, two approaches have been proposed which are deposition of viscous dispersion of Ni hydroxide
Ni catalyst on the ceramic surface and preliminary formation of polymer layer followed by deposition of NiO particles. It
CCVD
was shown that after the treatment in reductive atmosphere required for formation of metallic Ni catalyst both
Carbon nanobers
Carbon/ceramic composite
samples were successfully covered with uniform carbon layer via catalytic chemical vapor deposition (CCVD) of
ethylene. Thickness and dispersity of carbon layer were controllably varied by the process parameters. Resulted
carbon/ceramic composite materials demonstrated appropriate eciency in adsorption of benzene used as a
model toxic compound.

1. Introduction provide the controllable composition and dispersity of the particles

Nowadays, nanostructured carbon is a large-tonnage product widely
applied in dierent industrial elds [1]. Modication of functional
materials with carbon nanostructures is considered to be the most in-
tensively developed direction in a modern science since it provides
obtaining of new class of materials with improved or even unique
properties. The process can come through two routes. Firstly, ceramic
or polymer matrix might be lled with carbon additive (bulk mod-
ication) which leads to an increase of mechanical characteristics, ap-
pearance of electroconductivity and other signicant changes [2,3].
Secondly, it is a surface modication covering the surface of macro-
structured materials with a layer of nanostructured carbon [47]. This
type of composite materials attracts attention to be applied as sensors,
components of electronic devices or as membranes [8,9]. One of the
most commonly used approaches to form nanostructured carbon layers
on the surface of support is catalytic chemical vapor deposition (CCVD)
process. Dierent metals (Ni, Co, Fe, etc.) and its compositions, being
supported on the surface and reduced from corresponding oxides, act as
a catalyst for this process [46]. The oxides, in its turn, can be obtained
by thermal decomposition of precursors (metal salts, metalorganic
compounds, etc.). On the other hand, sol-gel synthesis is known to
[10].
In present work, stable sols of nickel hydroxide obtained by con-
trollable hydrolysis were converted into oxide form and then reduced to
metallic state. Usually, the researchers use dispersions with organic
solvents to obtain sol, or skip the stage of stable sol formation, and
nally gelatinous superne product is resulted [11,12]. The use of such
product for deposition on the support is restricted due to complicity of
attaching the Ni hydroxide to the surface caused by low adhesion.
Additionally, the distribution of Ni particles is not uniform in this case.
Thus, present research was aimed to solve the problem of even dis-
tribution and anchorage of Ni particles on the surface of macroporous
ceramics.
2. Material and methods
Macroporous cordierite ceramics was obtained from natural raw
materials as described elsewhere [13,14].
Hydrosol of nickel hydroxide was prepared as follows. The sample
of nickel tetra-aqueous acetate was dissolved in water. Resulted solu-
tion was heated up to boiling point, and then aqueous solution of so-
dium hydroxide (0.01 M) was added dropwise at constant stirring with

Corresponding author at: Boreskov Institute of Catalysis SB RAS, Novosibirsk 630090, Russian Federation.
E-mail addresses: chemicalpasha@mail.ru (P.V. Krivoshapkin), vedyagin@catalysis.ru (A.A. Vedyagin).

http://dx.doi.org/10.1016/j.coco.2017.08.001
Received 26 April 2017; Received in revised form 31 July 2017; Accepted 2 August 2017
Available online 08 August 2017
2452-2139/ 2017 Elsevier Ltd. All rights reserved.
P.V. Krivoshapkin et al. Composites Communications 6 (2017) 1719

magnetic stirrer. As a result, opalescent sol of nickel hydroxide was 12

obtained. Nickel hydroxide content in a nal system was 0.12%.

Two approaches were used to deposit the catalyst precursor on the 10
ceramics. Firstly, the macroporous support was covered with viscous sol

(VS) of nickel hydroxide. 5% aqueous solution of oxyethylcellulose was
added to the previously obtained dispersion of Ni hydroxide which
results in viscosity increase up to 1520 mPa s. Viscous sol was then
evenly supported on the surface of porous ceramics and dried at 80 C.
The procedure was repeated iteratively until the nickel loading reached
2 wt.% regarding to the ceramics. The second approach is connected
with preliminary deposition of polymer layer on the surface followed by
supporting of catalyst precursor (PS). Viscous solution of oxyethylcel-
lulose (20 mPa s) was supported on macroporous material and dried in
order to block pores by polymer. Then, an aqueous dispersion of nickel
hydroxide was deposited over polymer layer and dried at 80 C. Ni
loading was 2 wt.%.
The ceramic discs with supported layer(s) were calcined at 700 C.
According to dierential scanning calorimetry, this temperature pro-
vides complete elimination of polymer and formation of NiO nano-
particles.
Catalytic chemical vapor deposition of ethylene was used to form
nanostructured carbon layer on the ceramics. Ceramic disc with sup-
ported nickel oxide nanoparticles was placed inside stainless steel ow
reactor. The sample was heated up to 600 C in an argon atmosphere,
and then kept in hydrogen ow during 15 min in order to reduce NiO to
metallic Ni. The reactor was purged with argon before reaction mixture
(40 vol.% of ethylene in argon) was fed into reactor. As a result, for-
mation of carbon nanobers (CNF) on the ceramics surface has oc-
curred.
The kinetic measurement of the carbon product accumulation was
conducted in a ow quartz reactor equipped with McBain balances.
Prior to catalytic experiment the sample was subjected to in situ re-
duction in hydrogen stream at 600 C for 15 min. After reduction the
sample was brought to a contact with the reactant mixture containing
40 vol.% of ethylene in an argon. Total ow rate was 15 L/h. CCVD
process was carried out at 600 C for 15 min.
Studying the samples by scanning electron microscopy (SEM) was
provided using JEOL JSM6460 (Japan). Dierential scanning calori-
metry (DSC) including dynamic experiments was carried out with a
Shimadzu DSC-60 under a nitrogen atmosphere at the ow of 80 mL/
min-1. The determination of pore size distribution was performed by
mercury porosimetry on the AutoPore IV 9500 V1.07 apparatus. The
particle size distributions in colloidal solutions were measured by
means of dynamic light scattering (DLS) method on a Malvern Zetasizer
Nano ZS (Malvern Instruments) instrument.
Adsorption of benzene vapors was studied in static regime at a room
temperature. The weight of the sample was controlled in an equal
period of time.
Intensity (%)
8
6
4
2
0
0 20 40 60 80 100 120 140
Size (nm)
Fig. 1. Particle size distribution in Ni(OH)2 sol measured by means of DLS method.
images of ceramics with supported NiO particles prepared via VS and
PS routes are presented in Fig. S2 (Supplementary Materials).
The CCVD process of ethylene over metallic Ni particles results in
growth of carbon nanobers. In order to nd optimal conditions for the
process, kinetic studies were performed. Small pieces (23 cm) of
ceramics with supported NiO particles were used for this purpose. The
main weight gain (Fig. 2) was observed during rst 7 min of ethylene
decomposition. After 12th minute carbon yield reaches a plateau in-
dicating the deactivation of both samples.
Fig. 3 shows SEM images for the carbon/ceramic composites ob-
tained via VS and PS routes. Duration of CCVD process was 30 s. As
seen, regardless to the preparation route the carbon layer is uniform.
CNFs are characterized with narrow size distribution and average dia-
meter of 80 nm. The thickness of carbon layer in both cases was about
10 m. Fig. S3 (Supplementary materials) demonstrates ceramic surface
covered with CNF and texture of nanostructured carbon layer. It should
be noted that the longer duration of CCVD process, improving the
carbon yield, inevitably results in a crush of porous ceramic. SEM
images of ceramics and released carbon bers are shown in Fig. S4
(Supplementary materials). As follows from the images of the samples
obtained after 3 min of CCVD process, intensive growth of carbon na-
nobers has led to a breakage of porous ceramic. Resulted carbon bers
are characterized by wide size distribution (from 100 to 500 nm).
Sorption properties of the prepared carbon/ceramic composites
were studied using benzene as a model toxic organic compound [15].
As follows from Fig. 4, adsorption behavior of the composites is similar.
The maximum capacity towards benzene reached after 2.5 h corre-
sponds to 90 mg g-1. The main advantages of such systems are their
applicability for ow-through gas-phase systems and simplicity of its

3. Results and discussion 30 VS

PS
Controllable hydrolysis of nickel acetate leads to formation of na- 25
Carbon yield (g/gNi)

nosized particles of nickel hydroxide. As seen from Fig. 1, average

hydrodynamic radius of the particles in sol is 64.3 nm. The surface 20
potential +62.1 mV indicates that prepared dispersive system is char-
acterized with appropriate aggregative stability. Particle sizes remained 15
the same during overall experiment. The fraction of disperse phase in
sol was estimated to be 0.12 wt.%. 10
In accordance with SEM (see Fig. S1 in Supplementary materials)
and mercury porosimetry data, macroporous ceramics is characterized 5
with a monomodal pore distribution (average pore size of 10 m) and
open porosity of 30%. 0
The size of NiO particles resulted from thermal treatment of cera- 0 2 4 6 8 10 12 14 16
mics with supported polymer and Ni precursor is estimated to be Time (min)
80100 nm. Both VS and PS routes give uniform distribution of the
Fig. 2. Kinetic curves for carbon nanobers growth over nickel supported on ceramics.
particles solidly anchored to the surface of support. Corresponding SEM

18
P.V. Krivoshapkin et al. Composites Communications 6 (2017) 1719

Fig. 3. SEM images for cross cleavage of the carbon/ceramic

composite discs: (a) VS; (b) PS.

100 were carried out at Tomsk Polytechnic University within the framework
VS
Benzene adsorption (mg/g)

PS
of Tomsk Polytechnic University Competitiveness Enhancement
80 Program (grant VIU-TOVPM-316/2017).

Appendix A. Supplementary material

60
Supplementary data associated with this article can be found in the
40 online version at http://dx.doi.org/10.1016/j.coco.2017.08.001.

20
0 [2] B. Tyson, R. Abu Al-Rub, A. Yazdanbakhsh, Z. Grasley, Carbon nanotubes and
0 20 40 60 80 100 120 140
Time (min)
Fig. 4. Kinetics of benzene adsorption on the samples of carbon/ceramic composites.
regeneration by thermal desorption or by destruction of organic pol-
lutants adsorbed.
4. Conclusions
In present study sol-gel method was successfully applied to syn-
thesize nanoparticles of nickel hydroxide with average size of about
64 nm. The use of viscous sol and consecutive deposition of polymer
and catalysts precursor has allowed us to achieve uniform distribution
and strong anchorage with the surface of ceramics. Thermal treatment
at 700 C followed by reduction in hydrogen leads to appearance of
metallic Ni particles active in CCVD process with formation of nanos-
tructured carbon. The carbon/ceramic composites obtained via short
(less than 1 min) CCVD procedure are characterized with presence of
uniform and monomodal layer of carbon nanobers (average diameter
of 80 nm). Regardless to preparation route, these composites were
shown to adsorb benzene vapors in amount of 90 mg g-1.
Acknowledgements
This work was supported by the President of Russia Scholarship
Program (grant 2456.2016.1). The authors are also grateful to the RAS
and FASO (project 0303-2016-0014). The experimental calculations
References
[1] L. Feng, N. Xie, J. Zhong, Carbon nanobers and their composites: a review of
synthesizing, properties and applications, Materials 7 (2014) 39193945.
160 carbon nanobers for enhancing the mechanical properties of nanocomposite ce-
mentitious materials, J. Mater. Civil Eng. 23 (2011) 10281035.
[3] S. Bal, Experimental study of mechanical and electrical properties of carbon na-
nober/epoxy composites, Mater. Des. 31 (2010) 24062413.
[4] I. Berlanga, R. Mas-Ballest, F. Zamora, J. Gonzlez-Julin, M. Belmonte, Carbon
nanotubes growth on silicon nitride substrates, Mater. Lett. 65 (2011) 14791481.
[5] S. Mazumder, N. Sarkar, J.G. Park, I.J. Kim, A novel processing technique for CNTs
growth on Co-supported molecular sieve coated porous ceramics, Mater. Lett. 161
(2015) 212215.
[6] I.V. Krasnikova, I.V. Mishakov, A.A. Vedyagin, Y.I. Bauman, D.V. Korneev, Surface
modication of microbrous materials with nanostructured carbon, Mater. Chem.
Phys. 186 (2017) 220227.
[7] M. Felisberto, L. Tzounis, L. Sacco, M. Stamm, R. Candal, G.H. Rubiolo, S. Goyanes,
Carbon nanotubes grown on carbon ber yarns by a low temperature CVD method:
a signicant enhancement of the interfacial adhesion between carbon ber/epoxy
matrix hierarchical composites, Compos. Commun. 3 (2017) 3337.
[8] E. Llobet, Gas sensors using carbon nanomaterials: a review, Sens. Actuators B:
Chem. 179 (2013) 3245.
[9] C. Zhu, Y. Yu, L. Gu, K. Weichert, J. Maier, Electrospinning of highly electroactive
carbon-coated single-crystalline LiFePO4 nanowires, Angew. Chem. Int. Ed. 50
(2011) 62786282.
[10] The sol-gel handbook: Synthesis, characterization and applications, 3-volume set,
Eds.: D. Levy, M. Zayat, 2015.
[11] C. Lin, S.A. Al-Muhtaseb, J.A. Ritter, Thermal treatment of sol-gel derived nickel
oxide xerogels, J. Sol.-Gel Sci. Technol. 28 (2003) 133141.
[12] S.R. Nalage, M.A. Chougule, S. Sen, P.B. Joshi, V.B. Patil, Solgel synthesis of nickel
oxide thin lms and their characterization, Thin Solid Films 520 (2012) 48354840.
[13] E.F. Krivoshapkina, A.A. Vedyagin, P.V. Krivoshapkin, I.V. Desyatyh, Carbon
monoxide oxidation over microltration ceramic membranes, Pet. Chem. 55 (2015)
901908.
[14] E.F. Krivoshapkina, P.V. Krivoshapkin, A.A. Vedyagin, Synthesis of Al2O3-SiO2-MgO
ceramics with hierarchical porous structure, J. Adv. Ceram. 6 (2017) 1119.
[15] R. Snyder, Overview of the toxicology of benzene, J. Toxicol. Environ. Health A 61
(2000) 339346.

19