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Composites Communications 6 (2017) 1719

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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
ITMO University, St. Petersburg 197101, Russian Federation
Institute of Chemistry of Komi SC UB RAS, Syktyvkar 167982, Russian Federation
Boreskov Institute of Catalysis SB RAS, Novosibirsk, 630090, Russian Federation
National Research Tomsk Polytechnic University, Tomsk 634050, Russian Federation


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

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

3. Results and discussion 30 VS

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

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
Benzene adsorption (mg/g)

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

Appendix A. Supplementary material

Supplementary data associated with this article can be found in the
40 online version at

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This work was supported by the President of Russia Scholarship (2000) 339346.
Program (grant 2456.2016.1). The authors are also grateful to the RAS
and FASO (project 0303-2016-0014). The experimental calculations