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Journal of Alloys and Compounds 749 (2018) 85e102

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Journal of Alloys and Compounds


journal homepage: http://www.elsevier.com/locate/jalcom

Optimization of supported bimetallic (Fe-Co/CaCO3) catalyst synthesis


parameters for carbon nanotubes growth using factorial experimental
design
M.T. Bankole a, e, I.A. Mohammed b, A.S. Abdulkareem b, e, J.O. Tijani a, e, *, S.S. Ochigbo e,
O.K. Abubakre d, A.S. Afolabi c
a
Chemistry Department, Federal University of Technology, PMB 65, Minna, Nigeria
b
Chemical Engineering Department, Federal University of Technology, PMB 65, Minna, Nigeria
c
Department of Chemical, Metallurgical and Materials Engineering, Botswana International University of Science and Technology (BIUST), Plot 10071,
Buseja Ward, Palapye, Botswana
d
Mechanical Engineering Department, Federal University of Technology, PMB. 65, Minna, Nigeria
e
Nanotechnology Group, Centre for Genetic Engineering and Biotechnology (CGEB), Federal University of Technology, PMB 65, Minna, Nigeria

a r t i c l e i n f o a b s t r a c t

Article history: The FeeCo bimetallic catalyst supported on CaCO3 was prepared by a wet impregnation method. The
Received 29 September 2017 interactive effects among the key synthesis parameters such as drying time, calcination temperature,
Received in revised form stirring speed, mass of CaCO3 support on the yield and quality properties of the catalyst were investi-
27 February 2018
gated using 24 Factorial design of experiment. Additionally, the catalyst obtained under the optimal
Accepted 12 March 2018
Available online 21 March 2018
conditions was used to prepare Multi-walled carbon nanotubes (MWCNT) via chemical vapour deposi-
tion (CVD) of acetylene gas in a tubular horizontal reactor. The quality of the prepared materials was
examined for their morphology, microstructure, elemental composition, surface chemical properties,
Keywords:
Optimization
thermal stability, surface area, and mineralogical phase by HRSEM, HRTEM, EDS, TGA, FTIR, BET and XRD.
Factorial design The results revealed that maximum catalyst yield of 99.6% obtained at the drying time of 12 h, calcination
Bimetallic (Fe-Co) catalyst temperature of 100  C, stirring speed of 1000 rpm and mass of CaCO3 support of 10 g favoured the for-
Calcium carbonate mation of MWCNT at 700  C and 60 min reaction time. The results of statistical analysis demonstrated a
Carbon nanotubes direct relationship and synergetic effect between stirring speed and mass of support and the two factors
exerted highest impact on the yield of catalyst than other parameters. Microscopy analysis revealed
successful dispersion of Fe and Co particles onto CaCO3 support while XRD patterns confirmed the
presence of highly active crystalline mixed oxide (CoFe2O4) as the dominant phase. The HRSEM/XRD
analysis displayed the formation of tubular networks of graphitic carbon materials with few traces of by-
products. The study established the absorption and not diffusion mechanism of Fe and Co onto CaCO3 in
the reaction sequence produced CoFe2O4 during the wet impregnation process employed for catalyst
preparation.
© 2018 Published by Elsevier B.V.

1. Introduction electrical conductivity [1,2]. Different synthetic methods namely;


arc discharge laser ablation [3], electrolysis, catalytic chemical
In the last couple of years, the number of publications and vapour deposition (CCVD), plasma-enhanced, thermal or catalytic
patents on carbon nanotubes (CNTs) and its technological appli- have been employed to synthesis CNTs [4]. While methods such as
cations have increased rapidly due to its exceptional properties arc discharge laser ablation, electrolysis have certain shortcomings,
such as high mechanical strength, capillary properties and catalytic chemical vapour deposition (CCVD) stands out as an ideal,
simple and versatile method of obtaining high quality and large
quantity CNTs at low temperature and pressure [1e3]. Additionally,
catalysts preparation especially with supports for carbon nano-
* Corresponding author. Chemistry Department, Federal University of Technol-
ogy, PMB 65, Minna, Nigeria. tubes production have attracted attention among researchers due
E-mail address: jimohtijani@futminna.edu.ng (J.O. Tijani). to the impact of support materials on the properties and activity of

https://doi.org/10.1016/j.jallcom.2018.03.150
0925-8388/© 2018 Published by Elsevier B.V.
86 M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102

the catalyst mixture [4]. Transition metals namely; Fe, Co, Ni, Mo addition, the mechanism of catalyst formation is still not clear and
and their combinations on support materials such as SiO2, Al2O3, require further investigations. To the best of our knowledge, there is
MgO, zeolite, CaCO3, TiO2, kaolin amongst others in form of catalyst paucity of information regarding the optimization of effects of
have been used to produce carbon nanotubes of different synthesis parameters on the yield and properties of Fe-Co/CaCO3
morphology and diameter size [5,6]. These supports were selected catalyst.
due to their high surface area, high thermal stability and low cost, The present study focuses on optimization of synthesis param-
ease of dispersion accompanied by electronic interactions and eters such as drying time, temperature, stirring speed, and mass of
migration of metallic particles. On the contrary, there is difficulty in CaCO3 on the yield and quality of bimetallic Fe-Co catalyst sup-
the removal of these supports from CNTs after synthesis due to ported on CaCO3 used for carbon nanotubes growth. More so, sta-
their insolubility in mineral acids such as HCl, HNO3 or H2SO4. It is tistical approach of DOE based on factorial design was employed in
noteworthy to mention that, Fe, Co and Ni are mostly preferred catalyst synthesis to establish the parameters with most significant
transition metals due to high solubility and diffusion of carbon onto effects on the quality of the Fe-Co/CaCO3 catalysts.
metallic component at higher temperatures which in turn
enhanced the yield of CNT. Additionally, Fe, Co and Ni particles 2. Materials and methods
produced most active and effective phase required for CNTs growth
compared to other transition metals [11]. 2.1. Materials
Several supported bimetallic catalysts have been produced
however Fe-Co/CaCO3 is superior in terms of preparation and effi- The chemicals such as calcium trioxocarbonate (IV), cobalt (II)
ciency relative to other types of metal-support formulations trioxonitrate (V) hexahydrate, and iron (III) trioxonitrate (V) non-
[7e12]. CaCO3 is preferable to other supports due to the following ahydrate used in this study were obtained from Sigma Aldrich.
uniqueness namely; non-porosity, abundance nature, readily Liquid nitrogen, acetylene, argon and nitrogen gases were pur-
available and favoured suppression of amorphous carbon during chased from British Oxygen Company/Brin's Oxygen Company
CNT growth [12]. However, there is disparity of opinion as regards (BOC Gases Plc, Lagos, Nigeria). All the chemicals used in this study
the exact quantity of active phase of Fe or Co that must formed the are of analytical grade with percentage purity in the range of
Fe-Co catalyst which directly determines the CNT yields and qual- 98e99.99%.
ity. Although, bimetallic catalysts such as Fe-Co supported on
CaCO3 produced high quality and yields of MWCNT than other 2.2. Fe-Co/CaCO3catalyst preparation
catalyst supported on different materials [13]. This is because
CaCO3 used during CNTs growth is cheap and ease to remove from Optimization was systematically done by varying the following
the as-synthesized MWCNT via mild acid treatment. The higher parameters; drying time, the drying temperature, stirring speed
CNTs yield from bimetallic Fe-Co catalyst supported on CaCO3 and mass of CaCO3 support. The wet impregnation method
relative to others was ascribed to stronger metal-support interac- described by Ref. [10] was strictly followed with little modifica-
tion, smaller particles size and less particles aggregation [14]. tions. In this study, 3.62 g and 2.47 g of nitrate salts of Iron and
In view of the aforementioned exceptional qualities of CaCO3 Cobalt compounds, Fe(NO3)3$9H2O and Co(NO3)2$6H2O respec-
relative to other supports, Magrez et al. [7] and Li et al. [13] tively were weighed and dissolved in 50 cm3 of distilled water
investigated the effects of variations in Fe and Co compositions of followed by the addition of 10 g of CaCO3 under continuous stirring
bimetallic Fe-Co catalyst supported on CaCO3 on CNTs growth and at 2000 rpm for 60 min. The resulting slurry was then allowed to
found Fe2Co as the catalytically active phase. Mhlanga and Coville dry at room temperature and later dried in an oven at 120  C for
[8], observed that bimetallic Fe-Co catalyst supported on CaCO3 12 h, cooled to room temperature, ground and finally screened
prepared by wet impregnation gave better yield of MWCNTs with through a 150 mm sieve. The final powder was then calcined at
near 100% selectivity and excellent reproducibility than deposition- 400  C for 16 h. The dried catalyst was ground to avoid agglomer-
precipitation and reverse micelle impregnation methods. In the ation. Levels of the factors varied for optimization of preparation
same vein, Mhlanga et al. [9] investigated the dependence of CNTs parameters were chosen by considering the operating limit,
yield and quality on the method of preparation of a similar catalyst referred to as lower and upper levels. The lower levels () indicate
and found the stoichiometric amount of Fe and Co salts favoured variable values that were considered as lower limits, and the high
excellent CNTs. Surprisingly, in most of these studies, catalyst levels (þ) indicate variable values that were considered as upper
preparation parameters involving the use of statistical design of limits as shown in Table 1. Levels of factors were chosen following
experiment that will show the interactive mechanism among the preliminary studies by Ref. [10]. After drying at 100/120  C, all
synthesis parameters was not explored. In view of the influence of sixteen samples prepared according to the 24 factorial design of
the synthesis parameters on the catalysts growth, the idea of an experiment were subsequently calcined at the same temperature of
experimental approach involving variation of one variable at a time’ 400  C for 16 h. The yields of bi-metallic catalysts prepared in this
while keeping others constant may therefore not guarantee the present study were calculated after drying (YieldDried), and after
desired local optimum [14]. Besides not achieving the required calcination (YieldCalcined) according to Equations (1) and (2).
optimum, this approach is time consuming and generate large
number of experiments. Thus, these number of experiments can be Mass of catalyst after Drying
reduced by applying design of experiment (DOE) either central YieldDried ð%Þ ¼  100% (1)
Initial mass of mixture
composite or full factorial [15,16]. Nevertheless, the statistical DOE
allows the screening and identification of factors that are important Mass of catalyst after calcination
for explaining process variation. It also provides the systematic YieldCalcined ð%Þ ¼  100% (2)
Mass after Drying
investigation of the process and the parameters that influence the
quality of final product, thereby showing the direction of Statistical analysis using Minitab ANOVA, and response opti-
improvement to enhance manufacturability, reliability and quality mization was conducted on the factorial experimental design and
of the product [14]. Despite several successes recorded in the field the single catalyst with the best yield from optimization of four
of catalyst development, there is limited information of the roles catalyst synthesis parameters was chosen for carbon nanotubes
played by the parameters that influence the growth process [14]. In production.
M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102 87

Table 1
Levels of factors considered in 24factorial of catalyst preparation.

Drying time (hr) Drying temp. ( C) Stirring speed (rpm) Mass of support (g)

Upper (þ) level 12 120 2000 10


Lower () level 8 100 1000 8

2.3. Production of carbon nanotubes primary axis while the derivative percentage weight loss with
respect to time is on the secondary axis.
Carbon nanotubes were synthesized by the decomposition of The TGA curves in Fig. 1 indicates that the CaCO3 decomposed in
acetylene in a CVD reactor. A known weight (0.5 g) of the Fe-Co a single step between 630  C and 850  C to form stable oxide (CaO)
catalyst on CaCO3 support was placed in the ceramic boat, which and CO2 gas. Additionally, percentage weight loss of 44.89% which
was inserted in the horizontal quartz tube of the CVD furnace and corresponds to the stoichiometry thermal decomposition of CaCO3
heating was done at 10  C/min. The heating commenced and argon shown in Equation (4) was observed. The weight loss may be
gas was flown over the catalyst at a flow rate of 30 mL/min to purge attributed to partial destruction of the intramolecular framework of
the system of air. Once the set temperature was attained (700  C), CaCO3 the temperature increase from 630  C to 850  C. resulting to
the argon flow was adjusted to the required flow rate (230 mL/min) the formation of CaO and 44% mass of CO2 gas (see supplementary
and acetylene gas was introduced at its required flow rate (190 mL/ information, Table S2). Using the single-step thermal decomposi-
min). The process was allowed to proceed until the reaction time tion curve of Fig. 1, the chemistry of CaCO3 thermal decomposition
(60 min) was reached after which the flow of acetylene was reaction can be explained as follows:
stopped. The furnace was allowed to cool to room temperature
under continuous flow of argon. The ceramic boat was then CaCO3 ðsÞ / CaOðsÞ þ CO2 ðgÞ (4)
removed and weighed to determine the quantity of CNTs produced. |fflfflfflfflfflffl{zfflfflfflfflfflffl} |fflfflfflffl{zfflfflfflffl} |fflfflfflffl{zfflfflfflffl}
MCaCO3 ¼ 100:1 g=mol MCaO ¼ 56:1 g=mol MCO2 ¼ 44 g=mol
Percentage of CNTs yield was determined using the relationship
provided by Yeoh et al. [17], and Taleshi [18], as presented in Based on stoichiometry of the decomposition of CaCO3 repre-
Equation (3); sented by Equation (4), the mass changes calculations also show %
weight loss of CaCO3 to be 44% (Equation (5)),
MTotal  MCatalyst
CNTs yield ð%Þ ¼  100 % (3)
MCatalyst MCO2 44
m ð%Þ ¼  100 ¼  100 ¼ 44 % (5)
MCaCO3 100:1
where MTotal is the total mass of the final catalyst and carbon
Furthermore, it can be seen that the decomposition of CaCO3
products after CVD reaction process and MCatalyst is the initial mass
occurred at a temperature lower than CVD reaction temperature of
of Fe-Co/CaCO3 catalyst.
about 700  C, which suggest that when CaCO3 is used as catalyst
support, the CNTs could grow over the two different supports
2.3.1. Purification of as-synthesized CNTs (CaCO3 and CaO). This implies that CNTs was either grown on Fe-
The purification of the as-synthesized CNTs was achieved via an Co/CaCO3 or Fe-Co/CaO which is responsible for the formation of
acid treatment of 30% HNO3 and H2SO4. This was done to remove CNTs with different diameter. Another implication of Equation (4)
residual Fe, Co, CaCO3, including amorphous carbon that serve as in the TGA analysis is that, acid treatment resulted to the removal
impurities introduced into the samples during the catalyst pro- of residual catalyst particles, CaCO3 and CaO from as-grown CNTs as
duction. About 1 g of as-synthesized CNT sample was washed in shown in Equation (6a)e(6d);
100 mL of 30% HNO3 and H2SO4 by continuous stirring for 1 h. The
mixture was then refluxed and washed with distilled water until a H2 SO4 ðaqÞ þ CaCO3 ðsÞ/CO2 ðgÞ þ CaSO4 ðsÞ þ H2 OðlÞ (6a)
pH of 7 was achieved. The mixture was later filtered out to obtain |fflfflfflfflfflffl{zfflfflfflfflfflffl}
the wet CNT residue which was dried mildly at 120  C for 12 h. Precipitates out

2.4. Characterization of samples H2 SO4 ðaqÞ þ CaCO3 ðsÞ/CO2 ðgÞ þ CaSO4 ðaqÞ þ H2 OðlÞ (6b)

Catalysts, as-synthesized and purified CNTs samples were H2 SO4 ðaqÞ þ CaCO3 ðsÞ/CaSO4 ðsÞ þ H2 CO3 ðaqÞ (6c)
characterized for their morphologies, microstructures, elemental |fflfflfflfflfflffl{zfflfflfflfflfflffl}
Precipitates
composition, crystallinity, specific surface areas, functional groups,
particles size by High Resolution Scanning Electron Microscope
(HRSEM), (High Resolution Transmission Electron Microscope H2 SO4 ðaqÞ þ CaOðsÞ/CaSO4 ðsÞ þ H2 OðaqÞ (6d)
(HRTEM), Energy-dispersive X-ray spectroscopy (EDX). (Thermal |fflfflfflfflfflffl{zfflfflfflfflfflffl}
Precipitates
gravimetry analysis (TGA 4000 model), X-ray diffraction (XRD),
6000 model), Brunauer-Emmet-Teller (BET) analysis (NOVA 4200e The insoluble CaSO4(s) (slightly soluble, Equation (6b)) pre-
model), Fourier Transform Infrared (FTIR) (Perkin-Elmer 4000 cipitates out of solution and is easily decanted away from top layer
model) and Zetasizer Nano-S series). with some light carbonaceous substances. The previous studies did
not provide step by step reaction mechanism shown in Equations
3. Results and discussion (1)e(6d).

The thermal profiles of the CaCO3 as a support material for CNTs 3.1. BET analysis of Fe-Co/CaCO3
growth at CVD reaction temperature of 700  C under N2 atmo-
sphere and heating rate of 10  C/min was investigated using TGA. The BET analysis shows that the specific surface area of the
Fig. 1 shows the percentage weight loss of the pure CaCO3 on the CaCO3 sample is 3.94 m2/g, which however slightly increased to
88 M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102

Fig. 1. TGA and DTG curves of CaCO3 obtained at 10  C/min heating rate.

3.8 m2/g when the metallic particles filled the pores of CaCO3. The 3.2. The yield of Fe-Co catalyst supported on CaCO3
surface area of 3.8 m2/g obtained in this study is however lower
than 13.2 m2/g reported by Chiwaye et al. [12] for CaCO3, the reason In order to investigate the effect of preparation parameters on
being that the CaCO3 used by Chiwaye and colleague was in the quality of the Fe-Co/CaCO3 catalyst, the following synthesis
nanoscale form while conventional CaCO3 was used in this study. parameters namely; drying temperature, stirring speed, drying
The decrease in the surface area of Fe-Co/CaCO3 compared to CaCO3 time, and mass of CaCO3 support were varied at lower and upper
may be attributed to the blockage of the pores of CaCO3 by the level and their influence on the yield of Fe-Co/CaCO3 catalyst was
metallic particles. Using the CaCO3 true density of 2.71 g/cm3, the observed. Fig. 2 shows the effect of temperature between 100 and
BET average particle size was estimated to be 0.583 mm by Equation 120  C on the performance of Fe-Co/CaCO3 catalyst. Growth tem-
(7) assuming spherical geometry of particles [19]; perature influence metal-support interaction and stability of the
support which in turn determine the activity of the catalytic metals
and its yield. In our case, we noticed no clear cut difference in the
6000
DBET ¼ (7) catalyst yield with respect to temperature increment and other
ðSBET  rÞ
applied conditions in Fig. 2. For instance, the catalyst yields initially
increases at 100  C and thereafter reduces at the same temperature
where DBET is the estimated BET-particle size, SBET is BET-specific
but different stirring speed, dying temperature and mass of sup-
surface area (m2/g), and r is true density of CaCO3 (g/cm3).
port. Similar trend was observed at 120  C. Comparatively, when
Despite the unrestricted mono-multilayer adsorption in phys-
the drying temperature was increased from 100 to 120  C, it was
isorption, the CaCO3 has low monolayer capacity of 0.873 cm3/g as
found that the yield of the catalyst decreased due to the loss or
calculated from Equation (8), depicting a characteristic of a non-
evaporation of more moisture. This however contradicts the find-
porous solid material [20].
ings of McCarty et al. [23] who opined that the interactions be-
tween support and active material at high temperature may
SBET  MV resulted to high catalyst yield. Besides, the pre-calcination process
Vm ¼ (8)
LAV  AN2 may promote an increase in crystallite sizes of catalyst particles due
to restructuring of the materials and by extension slightly increase
where Vm is monolayer capacity (cm3/g), SBET is BET-specific surface the catalyst yield [24]. Comparatively, the yield of the catalyst ob-
area (m2/g), MV is the molar volume of nitrogen gas (22.414 cm3) at tained at drying time of 12 h was slightly higher than the corre-
STP, LAV is Avogadro's number (6.022  1023). AN2 is the cross- sponding 10 h possibly due to enhanced metal-support interactions
sectional area of adsorbed nitrogen molecule (the probe mole- at a longer holding time leading to formation of high catalyst yield.
cule) representing the area occupied by a single adsorbed nitrogen It can be summarized that the deposited catalyst yield is directly
gas molecule (16.2 Å2). Previous BET analysis of CaCO3 powder proportional to the drying time and independent of drying tem-
revealed poor pore properties of CaCO3 toward the nitrogen probe perature. The observed trend suggests high catalytic conversion of
molecule than common porous materials such as activated clay or Fe-Co/CaCO3 particles to carbon nanotubes following acetylene
zeolite [21]. Consequently, the wet impregnation technique was decomposition as function of reaction time.
chosen to deposit ions of catalyst active components on the CaCO3 Stirring speed guarantees homogeneous mixing and dispersion
support because it allows proper control of distribution of the of the metal particles on the surface of support materials during
metallic particles and high dispersions are possible; and works best catalyst preparation process. Fig. 3 shows the yield-dependence of
if ion/solid interactions are involved [22].
M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102 89

Fig. 2. Effect of drying temperature on catalyst yield at (a) 8 h, and (b) 12 h drying time.

Fig. 3. Effect of stirring speed on catalyst yield at (a) 8 g, and (b) 10 g CaCO3 support.

Fe-Co/CaCO3 catalysts as a function of variation of stirring speed. Fig. 4 shows the variation of drying time on catalyst yield from 8
According to Fig. 3, there is a direct linear relationship between to 12 h at constant temperature.
the catalyst yield and stirring speed only at 1000 rpm while no Studies have shown that the rate of drying of active catalyst
specific trend was observed at stirring speed of 2000 rpm. This components impregnated on the CaCO3 support may be affected by
means that lower stirring speed of 1000 rpm favours high catalyst two factors such as adsorption of solutes on the support and pre-
yield than at 2000 rpm. This suggests that the adsorption of cipitation (diffusion) of unabsorbed solute from the entrapped
metallic particles during impregnation was faster than moisture liquid in the solid pores during the drying process [27]. Again,
diffusion noticed during stirring at 1000 rpm than 2000 rpm. The drying time determines the transportation and adsorption mech-
stirring speed of 1000 rpm caused excellent dispersion of metal salt anism, and subsequently influence the distribution of final catalyst
solutions onto the CaCO3 support resulting in improved chemically obtained. Accordingly, in Fig. 4, it was noticed that the yield of
bound that are not easily removed during the mild drying treat- catalyst is directly proportional to the drying time, which suggest
ment [25]. Conversely, Aliyu et al. [26], found that increase in ease of decomposition of acetylene gas over Fe-Co/CaCO3 particles
stirring speed from 1200 to 2400 rpm favoured high yield of cata- to produce carbon nanotubes. The observed trend can be explained
lyst due to filtration and deposition of the active metal phase onto in terms of high rate of evaporation and transfer rate between the
the support. At stirring speed of 2000 rpm, the collision of the metallic particles and the support resulting to formation of mixed
metallic and support particles with wall of the container was rapid oxides, bond breakage and consequently loss of CO2. Other possible
however splash and loss of active phase of the catalysts become reason may be linked to the blockage of the agglomerated solutes
obvious. Also in Fig. 3, it was noticed that the yield of catalyst on the surface sites, thereby suppressing the transportation rate
samples generally decreased with increase in stirring speed after and by and large affecting the equilibrium between the adsorption
calcination. This decrease in yield irrespective of the stirring speed and transport mechanism during drying. Nevertheless, it was
after calcination process may be ascribed to loss of adsorbed difficult to explain the reaction mechanism observed at the
moisture and decrease in inter and intra molecular attractive forces following applied conditions of (100  C, 2000 rpm, 8 g) and (120  C,
as evident in the formation of mixed oxides such as Fe2O3 and CoO 1000 rpm, 8 g) probably due to the interactive and over bearing
observed in the XRD result shown in Fig. 12. influence of the other three parameters on the catalyst yield.
90 M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102

Fig. 4. Effect of drying time on catalyst yield at (a) 100  C, and (b) 120  C temperature.

Fig. 5 reveals the effect of mass of support (CaCO3) on catalyst powder in water followed by stirring, drying and calcination in the
yield at constant stirring speed. furnace caused some physico-chemical changes. In the present
When the mass of CaCO3 increased from 8 to 10 g, the adsorp- study, two schemes were proposed for possible chemical reactions
tion rate was fast due to increase in the binding site for impreg- involved in the catalyst formation. The first scheme demonstrated
nation than diffusion rate during drying process [28]. The variation parallel reactions between iron and cobalt nitrates resulting to
in the yield did not follow a specific trend, implying the existence of formation of an anhydrous salt due to the removal of hygroscopic
equilibrium between the solute adsorption and liquid diffusion. water (or water of crystallization). Secondly, there was a conversion
Generally, the chemistry of Fe-Co/CaCO3 synthesis reactions that of the nitrates into corresponding oxides as shown in Equations (9)
occurred during the catalyst preparation involved an and (10) [25].
impregnation-oxide formation process that comprises impregna-
tion, drying and oxide formation steps. While all nitrate salts are FeðNO3 Þ3 :9H2 O þ water/FeðNO3 Þ3 þ [9H2 O þ [water
soluble in water, calcium carbonate powder is almost insoluble. |fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl}
Drying removes excess water
Hence, the CaCO3 support did not undergo chemical reaction(s)
with other components in the catalyst mixture. This is because the (9a)
thermally decomposition temperature of 400  C employed for post-
calcination is far below CaCO3 decomposition temperature of CoðNO3 Þ2 :6H2 O þ water/CoðNO3 Þ2 þ [6H2 O þ [water
650  C as earlier presented in Fig. 1. However, particle size attrition |fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl}
was observed on its surface due to collision during stirring and Drying removes excess water

mechanical grinding. (9b)


Furthermore, there have been conflicting reports on whether or
not reactions occur between CaCO3 and the iron and cobalt metals 2FeðNO3 Þ3 /Fe2 O3 þ 6NO2 þ 1:5O2 (10a)
in the catalyst mixture during heat treatment [7,12,13,29]. None- |fflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflffl}
theless, the dissolution and mixing of the metallic salts Calcination removes nitrates
(Fe(NO3)3$9H2O, Co (NO3)2$6H2O salts) and the support (CaCO3)

Fig. 5. Effect of mass of support on catalyst yield at (a) 1000 rpm, (b) 2000 rpm stirring speed.
M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102 91

after calcination process suggest both tip and base-growth mech-


3CoðNO3 Þ2 /Co3 O4 þ 6NO2 þ O2 (10b) anism for the catalyst, an indication of strong and weak interactions
|fflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflffl} [8,9].
Calcination removes nitrates
For the purpose of optimization process, the responses obtained
It should be mentioned that the calcination process was on the effects of synthesis parameters on the yield and qualities of
responsible for the given off O2 and NO2 and subsequently catalyst were used in carrying out a factorial design analysis. This
contributed to the conversion of the anhydrous nitrates into oxides, involved an analysis of variance (ANOVA) to generate empirical
which in turn increases surface area. The iron and cobalt exist in the models for main and combined effects in post-calcination yields.
as-prepared catalyst as binary metal oxides (Fe2O3 and Co3O4). The The factorial design of experiment and its analysis was carried out
second scheme involves a chemical reaction between the two in Minitab statistical analysis software. The concept of p-
anhydrous salts, resulting in the formation of a ternary metal oxide, values < alpha-value of 0.05 were used to identify factors that have
cobalt ferrite (CoFe2O4) during calcination. The formation of a significant effect on catalyst yield. The overall evaluation of the
mixed oxide (CoFe2O4) is in agreement with the XRD results shown statistical factorial analysis revealed that stirring speed, and its
in Fig. 12. The conversion of iron and cobalt nitrate into cobalt iron interaction with mass of support were significant and positive in
oxide was accelerated by the thermal treatment at 400  C under air catalyst preparation. This is in agreement with the findings of
for 16 h. Very importantly, the second scheme was more likely to Haber et al. [22] and [27]. Morbidelli et al. [24] demonstrated that
occur and the overall reaction including impregnation, drying and two mechanism governing the catalyst distribution and yield are:
calcination steps is represented in equation (11). adsorption of metal particles onto the catalyst support at impreg-
nation and the transport (or diffusion) during calcination. However,
CoðNO3 Þ2 :6H2 O þ 2FeðNO3 Þ3 :9H2 O/CoFe2 O4 þ 8NO2 þ 2O2 the statistical analysis under the influence of stirring speed
þ 24H2 O revealed that the final yield of catalyst was governed by adsorption
mechanism and not transports type that occurred during impreg-
(11)
nation stage. It can be concluded that there was an existence of
The ternary (or multi-metal) oxide, containing more than one synergy between the stirring speed (p-value, 0.061) and mass of
type of metal cation, is characterized by superior properties as support (p-value, 0.076) given rise to a significant effect with an
compared to the binary systems [25]. Therefore, the proposed re- alpha-value of 0.10 (corresponding to 90% confidence level). The
action mechanism shows that the final catalyst composite is either effects of drying time, drying temperature, and mass of support on
a mixture of CoFe2O4 or (Fe2O3, Co3O4, CoFe2O4) evenly distributed the catalyst yield can also be seen in the Normal plot in Fig. 6. But,
on the surface of CaCO3 matrix. This is contrary to the outcome of the factorial design failed to uncover the statistical significance of
Chiwaye et al. [12], who established the growth of Ca2FeCoO5 on other factors because the sample size was probably too small. A
the surface of CaCO3 prior to heating. The difference in catalyst confidence level of 90% shows that at constant catalyst dosage,
preparation steps could be responsible for the different phases stirring speed and mass of support exhibited synergetic effects on
noticed in the both studies. catalyst yield.
Besides the formation of mixed oxides, there may be reduction The regression model in Equation (16) was generated using the
of the catalyst oxides during the CNT growth in CVD to metallic Fe general linear model in Minitab ANOVA;
and Co by the hydrogen from acetylene gas as evidence in the
HRSEM/EDS results shown in Fig. 8. This reduction phenomenon is Yieldð%Þ ¼ 23:49 þ 1:81312A  0:234125B þ 0:0182250C
normally responsible for the catalyst activation [12]. The catalytic þ 8:85125D  0:00051562AC þ 0:000290875BC
reduction follows the chemical reactions presented in Equations
 0:00568125CD
(12)e(14);
(16)
Fe2 O3 þ H2 /2FeO þ H2 O; FeO þ H2 /Fe þ H2 O (12)
where A ¼ time (hr), B ¼ temperature (oC), C ¼ stirring speed (rpm),
and D ¼ mass of support (g). The other factors such as temperature
Co3 O4 þ H2 /3CoO þ H2 O; CoO þ H2 /Co þ H2 O (13)
and drying time that were statistically non-significant in ANOVA
were observed to exert influence on the catalyst yield as revealed
CoFe2 O4 þ H2 /CoO þ 2FeO þ H2 O; (14a) by the surface plots of effects of these factors and their interactions
shown in Fig. 7.
CoO þ FeO þ 2H2 /Co þ Fe þ 2H2 O (14b) The numerical optimization of Equation (16) for the yield
otherwise called response optimization was conducted under the
This is contrary to the findings of Surowiec et al. [29] who
following optimal conditions: 8 h drying time, 100  C drying tem-
established in the temperature programmed reduction (TPR) that
perature, high stirring speed, and 10 g mass of support; having
complete reduction of FeO to the metallic Fe hardly occur in the
desirability of 1.000. Under these conditions, the maximum catalyst
CVD reaction temperatures of 700  C to 750  C (see equation (15)).
yield was 88.61%. The catalyst sample with optimum yield at the
stated optimum conditions was used in the production of CNTs via
3Fe2 O3 þ H2 /2Fe3 O4 þ H2 O; Fe3 O4 þ H2 / 3FeO þ H2 O
the CVD method.
(15)
Additionally, Chiwaye et al. [12], earlier noticed that reduction of 3.3. Characterization of Fe-Co/CaCO3 catalyst
Ca2FeCoO5 when equal ratio of Fe and Co salt were mixed in the
presence of hydrogen gas produced a mixture of Fe2Co, Co and not The morphology and elemental composition of the as-prepared
Fe alone. Fe-Co/CaCO3 catalyst obtained under the optimum conditions of
Therefore, the correct and balanced chemical reaction schemes stirring speed, mass of support, drying time and temperature was
involved in the Fe-Co/CaCO3 catalyst can be investigated further by examined using high resolution scanning electron microscopy
XRD analysis of the catalyst and as-synthesized CNTs. Additionally, (HRSEM) coupled with Energy-dispersive X-ray spectroscopy
the formation of various oxides due to metal-support interactions (EDS). The micrographs and the EDS spectrum are presented in
92 M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102

Fig. 6. Normal plot showing stirring speed and its interaction with mass of support as significant at a ¼ 0.10.

Fig. 7. Bi-factor yield-control of the catalysts at low/high settings of two other factors held constant at: (a.) 8 h, 1000 rpm, (b.) 12 h, 2000 rpm, (c.) 100  C, 1000 rpm, (d.) 120  C,
2000 rpm, (e.) 1000 rpm, 8 g mass of CaCO3, (f.) 2000 rpm, 10 g mass of CaCO3.
M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102 93

Figs. 8 and 9. found that the Fe-Co/CaCO3 catalyst has a specific surface area
The HRSEM image at low and high magnification revealed the almost equal to that of the support material. The BET specific sur-
presence of spherical, clustered solid catalyst material incorporated face area of catalyst was found to be 3.8 m2/g while the pure CaCO3
onto the support material. The level of agglomeration noticed in the used as support possessed BET specific surface area of 3.9 m2/g.
HRSEM images could be linked to the calcination process employed There was no significant change in surface area because no thermal
during sample preparation. At higher magnification of 49.63 KX decomposition of the major catalyst component occurred instead
(Fig. 8b), micropores can be identified in the catalyst, a property CaCO3 decomposed at the treatment temperature of 400  C. The
indicating that there was proper dispersion of Fe and Co nano- dispersion of Fe and Co nanoparticles in the support matrix could
particles on the CaCO3 support material with minute spaces within be responsible for the slight decrease in surface area. Also, the
the composite, which suggest a tip growth mechanism. The CaCO3 catalyst has specific pore volume of about 0.002 cm3/g, and pore
matrix sites were uniformly occupied by the oxides of Fe and Co radius of between 0.184 and 1.4 nm. The measured pores are lattice-
that were formed during calcination of the catalyst sample. This fringe patterns in the catalyst sample, demonstrated that the
observation was further confirmed by BET surface area results nanoparticles are highly crystalline in nature.
showing the micro porous radius in the order of (0.184e1.4 nm), Dynamic Light Scattering (DLS) technique was used to obtain
which are not characteristics pores of the catalyst components but the sizes of the as-synthesized catalysts in terms of particle diam-
lattice-fringe patterns in the catalyst sample [28]. The sizes of the eter, assuming spherical particle geometry. The samples particle
Fe-Co nanoparticles could influence the diameter of CNTs. In the sizes ranges between 163.2 and 775.7 nm (average of 409.7 nm)
present study, a high resolution SEM image of the catalyst pre- (Fig. S10(a), see supplementary information). The estimated BET
sented in Fig. 8 shows that the Fe-Co nanoparticles that were average particle size for pure CaCO3 support material was earlier
dispersed on the CaCO3 support material are sufficiently less than calculated to be 583 nm. After drying at 100e120  C, the catalyst
50 nm in size. The dispersion of the Fe-Co nanoparticles on the mixture particle sizes become smaller than that of the CaCO3
CaCO3 is also supported by the accompanying EDS spectrum support material; this was an evidence of conversion of the
showing that Fe, Co, Ca, C and O as the dominant element present in amorphous support material into a crystalline form. Another
the sample. The EDS spectrum qualitatively confirmed the chemical possible reason could be that the growth of CaCO3 crystals was
components of the Fe-Co/CaCO3 catalyst. The results also showed suppressed by the Fe and Co loaded onto the CaCO3 [31]. Again,
that the nitrates of Fe and Co salts have been converted to their some of the dried catalyst particles are larger than particles of
respective metallic oxides during calcination process. The per- CaCO3 with the biggest reaching about 775.7 nm due to agglom-
centage elemental compositions of the original catalyst mixture eration of particles. Drying was necessary to fix the metal catalysts
revealed that all particles contained both Fe and Co in the ratio of onto the CaCO3 support matrix however it was noticed that high
1:1 mass % as used in catalyst preparation. Fig. 9 also showed high temperature calcination does not cause a significant crystal defor-
oxygen content which could be as a result of iron and cobalt oxides mation, instead the drying of catalysts promoted the formation of
formation (CoFe2O4, Fe2O3 and Co3O4) during calcination process. agglomeration and sintering of catalyst particles. When such
Another important qualitative analysis from the EDS spectrum of catalyst is introduced into the reactor, only the outer surface of the
Fig. 9 is the use of standard line energy values at corresponding large agglomerates is exposed to the reaction gas hence the catalyst
wavelengths, and the result of each element (see supplementary efficiency will be strongly limited. To address this problem in the
information, Table S3). The elements such as carbon and oxygen present study, mechanical grinding of catalyst samples was
have low-energy (0.277 and 0.525 keV) Ka lines. Because oxygen is employed after calcination to prevent the catalyst particles from
possibly in the mixed oxides form of the following elements; Ca, Fe clustering. After calcinations at 400  C for 16e20 h, followed by
and Co, while the heavy elements can be found on the low-energy grinding of the dried catalyst, the particle sizes of the catalyst
(<0.8 keV) Ka lines [30]. It can be inferred that CaCO3 support and samples determined and found to be in the range of 97.4e110 nm as
Fe-Co oxides are present in the final catalyst sample. The occur- shown in Fig. S10b.
rence of the low-energy representations of the heavy elements Fig. S10 (a) and (b) (see supplementary information) showed
follow the order C<Ca<O<Fe<Co as seen in Fig. 8. Thus, the pres- that catalyst particles reduced after calcination because the dried
ence of CaCO3 and CoFe2O4 were speculated based on the relative catalysts were ground after calcination. Hence, the DLS size analysis
closeness of these elements in line energies around the usual po- showed that smaller particle sizes of the catalysts with narrow size
sition of oxygen in the spectrum. distribution were obtained after calcination, and the surface areas
Surface area analysis was carried out on the Fe-Co/CaCO3 cata- of catalyst particles have increased. It is important to reduce the
lyst obtained at the optimum conditions using BET method. It was particle size of the catalyst so as to obtain a high yield of CNTs [4].

Fig. 8. HRSEM image (a) low magnification (b) high magnification showing nanoparticles of Fe and Co dispersed on CaCO3 support.
94 M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102

Fig. 9. The EDS elemental compositions of Fe-Co/CaCO3 catalyst sample.

Thermogravimetric analysis (TGA) was used to investigate the has been driven off. The most probable reaction during the TGA
thermal profiles of the catalyst substance within temperature range heat treatment is the formation of Ca2FeCoO5. The initial mass
of the CVD reaction. In CVD method, the catalysts for CNT pro- losses prior to 380  C on the TG curve are due to the elimination of
duction are usually exposed to high reaction temperature of about volatile products and of the crystal water of the metal nitrates. The
700  C or above and the result is presented in Fig. 10. The samples slope between 380 and 550  C is attributable to formation of
showed variation in percent weight loss at different temperatures, Ca2FeCoO5 by oxidative decomposition of iron and cobalt nitrates
which means that the samples have different heat content. The mixture with elimination of O2 and NO2 [12,30]. Above 550  C, the
variation in TGA profile could be due to the different CaCO3 com- samples mass remained constant because CaCO3 has not decom-
positions used in preparation and moisture content of the samples. posed at that temperature. This scheme also proposes that the
Results as presented in Fig. 10 indicate that there were four regimes CaCO3 reacts with iron and cobalt liberating CO2 in the process. The
of weight losses in the TGA curve; at 45  C, 50e180  C, 180e380  C, reaction during TGA thermal analysis, where the Fe-Co/CaCO3
and 380e550  C. At approximately 45  C in all samples, weight loss catalyst was exposed to further heat treatment, are different from
can be attributed to loss of absorbed moisture. Upon heating, water those in the heat treatment calcinations of catalyst preparation that
of crystallization in the trioxonitrate (V) salts causes these salts to occurred around 400  C. Rather than CoFe2O4, the formation of
crack and dissolve. The salts only decomposed after all the water Ca2FeCoO5 is most likely during TGA. In order to investigate the

Fig. 10. TGA graph of Fe-Co/CaCO3 catalysts from 24 factorial design of experiment, obtained at 10  C/min in N2 environment.
M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102 95

effect of the CaCO3 support on thermal behaviour of the supported


catalyst, a comparison between their TGA curves was made (see Kl
SizeScherrer ¼ (17)
Fig. 11). ðFWHMÞ  CosðqÞ
As presented in Fig. 11, it was noticed that the Fe-Co/CaCO3ca-
talyst had an improved residual weight % at 850  C higher than that where FWHM is the full width at half maximum of a peak in the
of the support material (pure CaCO3) probably due to the iron and XRD pattern (in radians), K is shape factor called Scherrer constant
cobalt metals loaded onto the catalyst. Weight loss also occurred at with value between 0.2 and 2.0, l is the X-ray wavelength of
temperatures of 150  C, 550  C and 810  C. The loss in mass that 0.154 nm used in the X-ray diffraction, and q was evaluated from
occurred at 150  C was attributed to loss of absorbed moisture. the 2q values of the XRD pattern.
Again, the weight loss at 550  C was attributed to the formation of The average mean crystallite size was 61.92 nm, which showed
Ca2FeCoO5 [12]. This loss was due to CO2 evolution when CaCO3 that the catalyst particle is at nano level and a characteristic feature
reacted with the iron oxide and cobalt oxide. The third slope at of highly crystalline material. The different sizes of metals in the
810  C represents the decomposition of CaCO3 to CaO and CO2. The catalyst alloy are responsible for diameter distributions of nano-
weight losses were compared as summarized (See supplementary tubes [24]. The average crystallite size is 10 times greater than the
information, Table S4). value of 6.25 nm reported by Ref. [8]. The differences in the particle
A wide-angle X-ray diffraction (XRD) technique was used to size may be linked method employed for catalyst preparation,
identify phases that are present in the catalyst sample, its texture while [8] used a reverse micelle impregnation method, this study
analysis and crystallite size measurement. The phases identified in utilized only impregnation method. Mhalanga and Coville [8],
the XRD analysis of the Fe-Co/CaCO3 catalyst at room temperature found that no CNTs were formed due to the small size nature of the
are shown in Fig. 12. catalyst particles. Whereas in this study, high yield of CNTs were
The XRD peaks in Fig. 12 showed that the occurrence of a sharp obtained, which implies that the crystal sizes of the catalyst particle
and intense diffraction peak at 2q of ` e 36 with a corresponding are large (see supplementary information, Fig. S14) and hence
reflection plane (311), which has been reported connotes CoFe2O4 determine the yield of the carbon nanotubes [32].
[30]. While a short and less intense diffraction peak at 2q of 29e30 In addition to the HRSEM/EDS analysis, the catalyst particles
corresponds to CaCO3 peak [28]. The low and high intense peaks microstructures were equally examined using high resolution
observed at 2 thetha value of 30e40 are assigned to mixed oxides transmission electron microscopy (HRTEM). In the same vein, the
active phase such as Fe2O3, CoO including CaCO3 and CoFe2O4 corresponding selected area electron diffraction (SAED) pattern
respectively. The presence of Fe2O3 and CoO may be attributed to was collected for possible determination of different phases pre-
decomposition of their respective salts during the calcination sent in the sample. Fig. 16 reveals the presence of highly crystalline
process. The presence of active phases closely agrees with the metallic particles dispersed onto the whitish CaCO3 support matrix.
findings of Chiwaye et al. [12], who also identified CaCO3 and The presence of a crystalline phase in the HRTEM may be attributed
CoFe2O4 as the main phases in the Fe-Co/CaCO3 catalyst and suggest to the possible formation of CoFe2O4 in the final catalyst shown in
the crystalline nature of the catalyst. The crystallite sizes of the Fig. 13. The wet impregnation method used in catalyst preparation
catalyst calculated according to the Debye-Scherrer Equation (17) is proved to be effective in the dispersion of the metallic nano-
in the range of 26.81e121.65 nm [19]. particles onto the support matrix. This was enhanced by stirring of
the slurry mixture prior to heat treatment. Although, there were
some isolated zones where metal particles and CaCO3 support are

Fig. 11. Comparing Thermal behaviour of catalyst with that of the CaCO3 support.
96 M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102

Fig. 12. XRD pattern of Fe-Co/CaCO3 catalyst.

not in properly mixed (Fig. 13), excellently dispersion of crystals of solid, and the combined presence of Co, Fe and O at the line energy
the metal particles on the support matrix are illustrated in Fig. 14 position was a strong evidence of possible formation of a ternary
(a) and (b). The regions of metal particles are the active part or oxide (CoFe2O4) as shown in Fig. 15. The Cu detected in the sample
sites of the catalyst on which CNTs would grow, while the support- originated from the holey copper grid used during the HRTEM
dominated regions (white bulk regions) may be referred to as the analysis of the sample. The corresponding SAED pattern from the
inactive sites. catalyst HRTEM analysis is presented in Fig. 16.
It was however, difficult to determine the exact size and lattice The corresponding d-spacing calculated from the reciprocal
structures of the crystals of active components and that of the lattice spacings (1/d) in the SAED are as follows: 2.0, 3.2, 3.7, 4.5, 5.8,
CaCO3 support from the HRTEM images. The active sites identified 6.0, 6.5, 7.3, 9.0 nm1. In order to identify phases that correspond to
in Fig. 14 (b) showed that crystals of catalyst active components are spinel crystal structure, the lattice constant, a, was calculated using
in the order of 1 nm. Furthermore, the presence of lattice fringes in Equation (18),
the HRTEM micrographs further confirms the crystalline nature of
the as-synthesized catalyst. The HRTEM/EDS in Fig. 15 shows
similar qualitative elemental microanalysis to that obtained by qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 ffi
HRSEM/EDS. But, the HRTEM/EDS shows presence of Cu which a ¼ dhkl h2 þ k2 þ l2 (18)
represents the Cu grid used as sample holder in HRTEM analysis.
The EDS qualitatively confirms CaCO3 as part of the catalyst Equivalent 2q peak position was obtained from Equation (19),
where l ¼ 0.154 nm.

Fig. 13. HRTEM images of the catalyst showing a clear view of coloured metal ions; (light brown Fe3þ, dark/black Co2þ) and white CaCO3 bulk with modified crystal morphologies.
(For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102 97

Fig. 14. (a) Iron, Cobalt on CaCO3 matrix (evidence of good dispersal),and (b) active sites having regular arrangement of metal nanoparticles on the support.

Fig. 15. TEM/EDS of the Fe-Co/CaCO3 catalyst.

CoFe2O4. Other reflections are also present but some of these are
due to CaCO3 crystal structure. The hexagonal (trigonal) calcium
l ¼ 2dhkl sin qhkl (19)
carbonate crystal structure has lattice parameters/constants of
The calculations revealed that the sharpest ring in the SAED a ¼ 0.49896 nm, and c ¼ 1.7061 nm. Equation (20) gives the Bragg's
(Fig. 16) corresponds to plane (311) which may be due to CoFe2O4 relationship for this crystal system;
that occurred at 2q peak position of 33 , which is an evidence of
good crystallinity of the Fe-Co/CaCO3 nanoparticles. In the XRD  
1 4 h2 þ hk þ k2 l2
pattern presented in Fig. 12, this reflection occurred at 36 , the 2
¼ 2
þ 2 (20)
d 3 a c
discrepancy suggests a slight shift due to stress during the HRTEM/
SAED collection. However, the SAED result is closely agree with According to equation (20), the following reflections plane in
literature reports that have attributed the strongest peak around the SAED; (104), (110), (100), (101), (012), (006), (112), (114), (102)
35-36 to CoFe2O4 [29]. Again, the earlier presented XRD peak of and (011) can be due to CaCO3. Notably, the third ring formed from
CaCO3 (2q ¼ 29 ) which showed the intense diffraction peaks reflection of spinel (311) plane can be attributed also to (112) and
indicated the relative abundance of CaCO3 support in the catalyst (006) planes of the hexagonal CaCO3 lattice structure [12,30].
solid. This does not mean that CaCO3 is more crystalline than the Generally, the properties of the as-synthesized catalyst showed
98 M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102

the chemical equations, formation of the insoluble calcium sul-


phate (CaSO4) can be identified as a disadvantage of H2SO4 purifi-
cation when CaCO3 is used as catalyst support. But, this was
carefully handled in the present study. The insoluble CaSO4(s)
precipitates out of solution and was easily decanted away from top
layer together with some light carbonaceous substances. The yield
of 92.29% C in the purified MWCNTs represent its purity, which is
directly proportional to the stoichiometric amount of transition
metals (Fe and Co) loaded on the CaCO3 supported under the
applied conditions. This implied that the bimetallic (Fe-Co) catalyst
provided the nuclei for CNTs to grow and as such responsible for the
high yield and diameter of the carbonaceous materials. This means
that the catalyst yield of 88.61% under the applied synthesis con-
ditions transformed to 92.29% carbon yield, an indication of ease of
diffusion of acetylene gas onto the stoichiometry amount of Fe-Co
supported on CaCO3. The carbon yield obtained in this study is
Fig. 16. SAED of the Fe-Co/CaCO3 catalyst showing sharpest rings of CoFe2O4 (311) and 5.5 manifold greater that reported by Yang et al. [33], who utilized
CaCO3 (104). Nitrogen-doped porous graphitic carbons (NPGCs) supported on
CaCO3 to synthesize graphitic CNTs. The differences in the carbon
yield may be ascribed to reaction conditions applied during the
that the bimetallic (Fe-Co) was well-dispersed on the CaCO3 sup- synthesis. In this study, acetylene gas was used as a carbon source
port with thus make it suitable for CNTs production. The HRTEM which decomposed at temperature and reaction time of 700  C for
and HRSEM images of the carbon nanotubes are presented in Fig. 17 60 min however Yang and co-workers, utilized melamine-
(a, b) and (c) respectively. formaldehyde resin as a carbon source, which takes longer time
The HRTEM images (Fig. 17 a, b) show that multi-walled carbon to decompose and as such responsible for its low yield. Addition-
nanotubes (MWCNTs) were produced, and the MWCNTs have an ally, the CNTs yield obtained in this study is 9 times higher than the
average diameter of ~25 nm. It can be also observed from the amount reported by Escobar et al. [34], who demonstrated the
HRTEM micrographs that metal particle from the catalyst were synthesis of CNTs involving decomposition of benzene on the
encapsulated in the tip of the MWCNTs, suggesting the occurrence bimetallic Fe-Co catalyst supported on MCM-48 Silica at 650  C
of a tip-growth mechanism [30]. The HRSEM image in Fig. 17 (c) under nitrogen flow for 1 h. The differences in the carbon yield may
showed the formation of homogeneously and densely distributed be due to the nature of support material, reduction of metal particle
MWCNTs with little level agglomeration. More so, the BET-specific melting point, enhanced carbon solubility as well as successful
surface area of the as-synthesized MWCNTs is 270.06 m2/g, which dispersion of metallic clusters during CNTs growth [8,9,35]. The
is comparable with the values reported in the literature [25]. The percentage of the CNTs yield obtained from bimetallic Fe-Co cata-
elemental composition of the as-synthesized MWCNTs (see sup- lyst on different supports using different carbon sources previously
plementary information, Table S5) and it was found that the major reported in the literature in comparative with the present study are
element is carbon. While other elements such as Ca, Fe and Co given in Table 2.
originated from the support material (CaCO3) and the catalyst According to Table 2, it is obvious that several workers have
particle (Fe, Co). Table S5 (see supplementary information) also established different yield of CNTs as a function of applied experi-
shows that the acid purification treatment was responsible for the ment conditions. Additionally, it was noticed that the yield of CNTs
increase in the carbon content and decrease in the amount of other produced using acetylene gas was higher than other carbon sources
elements, which act as impurities. More effective purification due to its ease of decomposition at low temperature forming rad-
methods would be necessary to achieve complete removal of other icals and ions, thus aid easy formation of MWCNTs. While methane
elements. gas and other source of carbon favoured the formation of SWCNT
The H2SO4 acid treatment removed the residual CaCO3 and CaO and well aligned DWCNTs of different length and diameter. Table 4
catalyst from as-grown CNTs according to Equation 6 (a-d). From further revealed that the yield of CNTs depends largely on the type

Fig. 17. (a), (b)HRTEM and (c) HRSEM images of MWCNTs produced on Fe-Co/CaCO3.
M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102 99

Table 2
Comparison of the CNTs yield results of the previous and present study.

Catalyst Applied reaction conditions of CNTs growth CNTs yield (%) References

Fe-Co/zeolite-Y Mass of catalyst (50 g), reaction temperature (800  C), deposition time (2 h), argon flow rate (40 kPa), carbon source 95% SWCNTS [36]
(ethanol)
Fe-Co/ Argon flow rate (500 sccm), carbon source (CH4 þ H2), temperature (750e870  C), deposition time (10e60 min) The yield was not [37]
mesoporous determined
silica
Fe-Co/zeolite Mass of catalyst (700 mg), Reaction temperature (900  C), reaction time (30 min), argon flow rate (250 mL/min), >80% DWCNTs [38]
10 mL/min flow of acetylene gas as carbon source
Fe-Co/MgO Mass of catalyst (0.6 mg), Reaction temperature (900  C), reaction time (30 min), nitrogen flow rate (not specified), CNTs yield not [39]
1000 sccm flow rate of methane gas determined
Fe-Co/CaCO3 Mass of catalyst (0.5 or 1 g), Reaction temperature (700  C), reaction time (60 min min), 300 mL/min nitrogen flow Yield was not [40]
rate and 30 mL/min acetylene/ethyne flow rate calculated
Fe-Co/CaCO3 Mass of catalyst (50 mg), Reaction temperature (720  C), reaction time (30 min min), 70 l/h nitrogen flow rate and 30 MWCNTs [41]
10 mL/min acetylene flow rate
Fe-Co/CaCO3 Mass of catalyst (50 mg), Reaction temperature (600e850  C), reaction time (60 min), ethylene/hydrogen/nitrogen 89 MWCNTs [42]
mixture (50:1:450)
Fe-Co/USY Zeolite Pyrolysis temperature (700e850  C), carbon source (ethanol), argon flow rate (100 sccm), reaction time (120 min) 40 SWCNTs [43]
powder
Fe-Co/CaCO3 Mass of catalyst (0.5 g), temperature (700  C), the argon flow rate (230 mL/min), and acetylene gas flow rate 92.3 MWCNTs Present
(190 mL/min), reaction time (60 min) study

of the catalyst support, source of carbon, temperature, deposition diameter distribution is more suitable for industrial mechanical
time and argon flow rate. Some conclusions can be drawn that the reinforcement and polymer-composite applications. The value of
yield and quality of CNTs did not only depend on metal-support external diameter (25 nm) falls within the range (20e30 nm) re-
interaction alone but also on the source of carbon and its flow ported by Mhlanga et al. [9], for MWCNTs despite performing the
rate. Thus, suggest the existence of a linearly relationship between experiment under different set of standard conditions. On the other
the carbon yield and acetylene flow rate. The flow rate of acetylene hand, the average outer diameter (25 nm) reported in this study is
gas used in this study is 19 and 3 times higher than the flow rate smaller compared to average external diameters of 57.5 nm ob-
used by Yu et al. [5], and See and Haris [44], who obtained 30% and tained by Bahgat and co-workers who synthesized MWCNTs from
89% CNTs yield respectively. Furthermore, the high yield and bimetallic Fe-Co/CaCO3 catalyst pyrolysed in horizontal tubular
quality of CNTs in this study may be due to the formation of alloy reactor at 800  C for 40 min. The differences may be ascribed to the
phase and existence of synergetic effect between the Fe and Co different applied synthesis conditions. The SAED pattern suggests
catalyst. that the crystals arrangements in the as-synthesized MWCNTs are
The outer diameter-distribution of CNTs is important in their polycrystalline in nature as revealed by the presence of several
consideration for different applications. The outer diameter- bright spots and the rings. These concentric and bright rings
distribution of MWCNTs produced in this study is presented in correspond to the individual peaks observed in the XRD patterns.
Fig. 18 (a) and its corresponding selected area electron diffraction Fig. 19 shows XRD patterns of the unpurified and purified MWCNTs,
(SAED) pattern is shown in Fig. 18 (b). and accordingly similar diffraction peaks were observed in both
As shown in Fig. 18 (a), the average outer diameter of the carbon cases. A sharp and intense peak was clearly seen at 2 thetha value of
nanotubes was estimated to be 25 nm which is within the nano- 26.5 , which correspond to the crystal plane (002). Other peaks of
scale level. It has been established that MWCNTs with a narrow low intensities were noticed at 2 thetha value of 30.5 (110),

Fig. 18. (a) Diameter-distribution, and (b) the SAED pattern of MWCNTs.
100 M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102

Fig. 19. XRD patterns of purified and unpurified CNTs.

44.3 (100), 52.7 (220) and 61.8 (211). The two most dominant destroy the CNT structure (see supplementary information,
peaks at 2 thetha value of 26.5 and 44.3 are attributed to a highly Table S5). The TGA profile of the CNTs carried out under N2 envi-
graphitized CNTs, which have been widely observed by several ronment as presented in Fig. 20 shows a single-step degradation
authors [8e15]. Surprisingly, there was no observable peak for Fe, which is typical of a pure CNTs. It was also observed that the
Co or residual CaO in the as-synthesized CNTs. This could be nanotubes are thermally stable up to 600  C, where oxidation of
attributed to their nanometer size and high dispersion of metal carbon begins to occurs, which further suggest the suitability if the
particles on the surface of CaCO3. It could also be said that their prepared CNTs for high-temperature applications. Beyond 600  C,
concentrations were below the detection limits of XRD or that the only the remnant of metals particles (Fe-Co) and support materials
residual metallic and support particles were encapsulated within (CaO) still remain and were not completely removed despite the
the wall of the CNTs. In spite of this, the purification step did not acid purification treatment [30].

Fig. 20. TGA profile of the MWCNT.


M.T. Bankole et al. / Journal of Alloys and Compounds 749 (2018) 85e102 101

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