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J.C. Guevara a, J.A. Wang a,*, L.F. Chen a, M.A. Valenzuela a, P. Salas b, A. Garcı́a-Ruiz c,
J.A. Toledo d, M.A. Cortes-Jácome d, C. Angeles-Chavez d, O. Novaro e
a
ESIQIE, Instituto Politécnico Nacional, Col. Zacatenco, Av. Politecnico s/n, 07738 México D. F., Mexico
b
Centro de Fı́sica Aplicada y Tecnologı́a Avanzada, Universidad Nacional Autónoma de México, Apartado Postal 1-1010, Querétaro 76000,
Mexico
c
UPIICSA, Instituto Politécnico Nacional, Te 950 Col. Granjas-México, 08400 México D.F., Mexico
d
Programa de Molecular Ingenierı́a, Instituto Mexicano del Petróleo, Eje Lázaro Cárdenas 152, 07730 México D. F., Mexico
e
Instituto de Fisica, Universidad Nacional Autónoma de México, A. P. 20-364, 01000 México D.F., Mexico
Article history: For the first time, simultaneous production of hydrogen and nanocarbon via catalytic
Received 13 October 2009 decomposition of methane over Ni-loaded mesoporous Ce-MCM-41 catalysts was investi-
Received in revised form gated. The catalytic performance of the Ni/Ce-MCM-41 catalysts is very stable and the
13 January 2010 reaction activity remained almost unchanged during 1400 min steam on time at temper-
Accepted 16 January 2010 atures 540, 560 and 580 C, respectively. The methane conversion level over these catalysts
Available online 19 February 2010 reached 60–75% with a 100% selectivity towards hydrogen. TEM observations revealed that
most of the Ni particles located on the tip of the carbon nanofibers/nanotubes in the used
Keywords: catalysts, keeping their exposed surface clean during the test and thus remaining active for
Hydrogen production continuous reaction without obvious deactivation. Two kinds of carbon materials,
Methane catalytic decomposition graphitic carbon (Cg) as major and amorphous carbon (CA) as minor were produced in the
Carbon nanotube reaction, as confirmed by XRD analysis and TEM observations. Carbon nanofibers/nano-
Ce-MCM-41 tubes had an average diameter of approximately 30–50 nm and tens micrometers in length,
Ni-based catalysts depending on the reaction temperature, reaction time and Ni particle diameter. Four types
of carbon nanofibers/nanotubes were detected and their formations greatly depend on the
reaction temperature, time on steam and degree of the interaction between the metallic Ni
and support. The respective mechanisms of the formation of nanocarbons were postulated
and discussed.
ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
95% of the hydrogen is produced from carbonaceous raw and nanocarbons (nanotubes and nanofibers). These catalysts
materials, primarily fossil in origin and the rest from alterna- exhibit high catalytic stability in comparison with the tradi-
tive resources as biomass and water [5]. There are a number of tional Ni/SiO2 catalysts. Several kinds of nanocarbons are
emerging and attractive approaches or processes for the formed and their formation mechanisms are discussed and
production of hydrogen, as the natural gas catalytic decom- postulated.
position, steam reforming, photocatalytic decomposition of
water and biomass gasification, etc. [5–12]. Hydrogen produced
by photocatalytic decomposition of water is very clean and it is 2. Experimental section
an economical approach. Unfortunately, it still remains at
laboratory stage because of some technical difficulties for 2.1. Synthesis of Ce-MCM-41 mesoporous materials
scale-up. Steam reforming of methane is highly endothermic
and produces a large amount of COx (CO2 and CO). Therefore, The cerium promoted mesoporous materials (noted as
additional steps are required to remove these COx by-products Ce-MCM-41) were prepared by the use CeCl3$7H2O as cerium
in order to meet the requirements in the fuel cell applications, precursor, tetraethyl ortosilicate (TEOS) as silicon precursor
which increases the operation cost. Economic analysis has and cetyltrimethylammonium bromide (CTABr) bromide as
shown that if the carbon produced in the reaction procedure synthetic templating agent. A typical preparation of the
can be utilized, it will be financially attractive. It is noted that sample with a molar relationship of Si/Ce ¼ 20 was described
both hydrogen and carbon nanotube materials can be simul- as follows. Two solutions were prepared, the first solution
taneously produced through a single technical approach of was prepared by 1.86 g of CeCl3$7H2O and 22.8 ml of TEOS
methane catalytic decomposition (MCD) that is regarded as diluted in 50 ml of water with agitation; the second solution
a fully green chemical process. By methane catalytic decom- was made by addition of 11.4 g of CTABr in 200 ml hot water
position, COx (CO and CO2)-free hydrogen can be obtained with (near 50 C) with stirring, followed by the addition of 145 ml of
a moderately endothermic process [13–19]. For hydrogen NH3$H2O (28 wt.%). Then the first solution was added, drop by
production, the MCD process is believed to be superior to steam drop, into the second solution to obtain a mixture. During the
reforming from economical points of view, and it is also addition, the mixture was vigorously agitated for near 2 h
superior to the photocatalytic decomposition of water from the until the gel was formed. The resulting gel was heated at
technical point of view [2,20]. Moreover, MCD is easy for 100 C by 24 h. The solid was washed with deionized water
scaling-up for the production of carbon nanotubes, and it is and dried for 24 h. Finally the sample was annealed at 600 C
used to obtain multiwalled nanotubes with high mechanical by 5 h in air with a flow rate of 60 ml/min. The heating rate
strength, differing from the route of arc-discharge evaporation was set at 1 C/min. The other two samples with Si/Ce molar
of graphite where single wall carbon nanotubes could be ratio 10 and 5 were synthesized with the similar method as
produced [20]. described above.
The catalysts used for methane catalytic decomposition
usually consist of transition metals and a support. SiO2 2.2. Preparation of Ni/Ce-MCM-41 catalysts
[17,21–23], MgO [22], Al2O3 [20,24,25], SiO2–Al2O3 [26], SiO2–
CeO2 [27], ZnAl2O4 [28] and MgAl2O4 [29], zeolite [5], carbon The nickel supported catalysts were prepared by incipient
[30–32] and hydrotalcite-like materials [33] are the most impregnation of the calcined supports with Ni(NO3)2 solu-
common support. The active phases are usually group VIII tion. The Ni loading of the catalysts was 30 wt.% and 50 wt.%,
transition metals Fe, Co and Ni, others like Cu and Pd are respectively. After impregnation, the Ni supported materials
used as promoters [5,16,25,33–37]. Among these, the were dried at 80 C for 10 h and then calcined at 400 C for 4 h.
intensely studied catalysts are Ni supported alumina and Ni Before the catalytic evaluation, the oxidized catalysts were
supported silica. reduced using 99.9% H2 at 500 C for 2 h to obtain metallic Ni
The main influence factors on MCD are the reaction particles on the catalyst surface. These catalysts are noted as
temperature, nature of the support, type and quantity of Ni/Ce-MCM-41-x, where x is Si/Ce molar ratio, x ¼ 5, 10
active metals. The activity and the lifetime of the Ni supported and 20.
catalysts depend significantly on the size of the metal particle
and are sensitive to the textural properties and pore geometry 2.3. N2-adsorption–desorption isotherms measurement
of the support [29]. It is known that the surfactant-assistant
technique in the materials synthesis may provide materials The specific surface area, pore volume and pore size distri-
with appropriate pore diameter, high surface areas and bution of the Ce-MCM-41 samples were measured in a Dig-
a better access to the active sites [38,39]. The application of isorb 2600 equipment by using low temperature N2
mesoporous materials as catalysts support for hydrogen physisorption isotherms. Before the N2 adsorption, the
production has not been reported yet. In addition, in samples calcined at 600 C were thermally treated at 400 C for
a preliminary investigation, we found that ceria doped silica 2 h. The surface area was determined according to the stan-
as catalyst support shows a rather stable catalytic activity in dard Brunaur–Emmett–Teller (BET) method in a relative
the methane decomposition reaction [27]. In the present work, pressure range of 0.04–0.2 and the total volume was evaluated
we report some new results of the synthesis, structural from the amount of adsorbed N2 at a relative pressure (P/P0) of
characterization and catalytic properties of a series of Ni/Ce- about 0.99. The pore diameter distributions were calculated
MCM-41 mesoporous catalysts synthesized by a surfactant- based on the desorption isotherms by the Barrett–Joyner–
assisted technique for simultaneous production of hydrogen Halenda (BJH) method.
international journal of hydrogen energy 35 (2010) 3509–3521 3511
Table 1 – Ni atom position of metallic Ni crystals (space Table 3 – C atom position of the amorphous cabon
group: Fm3m). material (space group: P63/mmc).
Atom x y z Atom x y z
2.5. Powder X-ray diffraction and Rietveld refinement The methane catalytic decomposition was carried out in
a microreactor system (Advanced Scientific Design-RXM-100)
The power X-ray diffraction data were collected at room with a stainless steel fixed bed reactor (10 mm i.d. and 500 mm
temperature in a Siemens D-5000 diffractometer with Cu Ka in length) at atmospheric pressure. The reaction temperatures
radiation and a secondary beam monochromator. The inten- varied from 500 C to 540 C and 580 C. The catalyst loading
sities were obtained in the 2q range between 20 and 60 with was ca. 50 mg. The feed steam was a mixture of high-purity
a step of 0.02 and a measuring time of 2.67 s at each point. methane diluted in argon (20 mol % of methane). The total
The crystalline structures were refined using FULLPROF98 flow of the reaction gases was 75 ml min1. The temperature
code with the Rietveld method [40,41]. The atomic positions increasing rate was controlled at 30 C min1. The inlet and
and their coordinates of each structure corresponding to outlet effluents were monitored by an on-line gas chromato-
metallic Ni and graphite carbon and amorphous carbon are graph (GC) analyzer with a PE-Molsieve capillary column,
reported in Tables 1–3. The goodness of the refinement fitting using a thermal conductivity detector (TCD) for hydrogen
the experimental patterns reported as an Rwp closed to 0.14 analysis and a flame ionization detector (FID) for methane
was reached. analysis.
Si/Ce - 5
Table 2 – C atom position of graphite carbon (space group:
P63/mmc).
0 2 4 6 8 10
Atom x y z 2θ
C1 0.0000 0.0000 0.2500
Fig. 1 – Low angle of X-ray diffraction patterns of the
C2 0.3333 0.6667 0.2500
calcined Ce-MCM-41 samples.
3512 international journal of hydrogen energy 35 (2010) 3509–3521
1000
Si/Ce - 20
800
Vol Adsorbed (cc/g)
600
400
dV/dlog(D) (cc/g)
200
Si/Ce -20
1000
0
Si/Ce - 10
800
Vol Adsorbed (cc/g)
400
Si/Ce - 5
200
1000
0 10 100 1000
Pore Diameter (Å)
Si/Ce - 5
800
Vol Adsorbed (cc/g)
400 reflections of the solid. The XRD patterns indicate that the
long-range order of mesoporous molecular sieves with
hexagonal framework was formed in the materials. These
200
XRD patterns are very similar to the pure Si-MCM-41 sample,
indicating that a small amount cerium incorporated into the
0
Si-MCM-41 framework does not strongly modify the structure
0,00 0,25 0,50 0,75 1,00
of Si-MCM-41. However, it is observed that as the cerium
RELATIVE PRESSURE (P/Po) content increases, intensities of the XRD peaks gradually
diminish, showing a reduction of the structural ordering. For
Fig. 2 – Loops of N2-adsorption–desportion isotherms of the
the sample containing high cerium content, e.g., Si/Ce ¼ 5, the
Ce-MCM-41 samples.
peaks related to (110) and (200) are rather low, which indicates
that the hexagonal lattice structure might partially collapse,
forming wormhole-like pore system in some degree.
3. Results
3.1.2. Textural properties
3.1. Ce-MCM-41 supports Based on the IUPAC classification, the loops of the N2
adsorption–desorption isotherms belong to type IV profiles
3.1.1. Crystalline structure (Fig. 2). The presence of framework-confined mesoporous is
Fig. 1 shows the XRD patterns of the calcined cerium-con- indicated by the adsorption step centered in the relative
taining solids. All the samples have three diffraction peaks, pressure P/Po region from 0.25 to 0.45. It is found that the
which respectively correspond to (100), (110) and (200) shape and sharpness of the loops vary with the cerium
100
90
80
70
Conversion (%)
60
50
40
Ni30%/Ce-MCM-41-5
30
20 Ni50%/Ce-MCM-41-5
10
0
0 200 400 600 800 1000 1200 1400
TIME (MIN)
100
90
80
70
Conversion (%)
60
50
40
30 Ni30%/Ce-MCM-41-10
20
Ni50%/Ce-MCM-41-10
10
0
0 200 400 600 800 1000 1200 1400
TIME (MIN)
100
90
80
Conversion (%)
70
60
50
40
30 Ni30%/Ce-MCM-41-20
20 Ni50%/Ce-MCM-41-20
10
0
0 200 400 60 0 800 1000 1200 1400
TIME (MIN)
content. For example, as the cerium content increases in the solid, forming some pores with diameter around 3.5 nm. In
materials, the sharpness of the loop in the second stage addition to this, some large pores (Dlp) with a wide pore
gradually decreases. The lines of the N2 adsorption– diameter distribution were formed in the range between 40
desorption isotherms are almost overlapped in the region and 100 nm for the sample Si/Ce ¼ 10 and between 20 and
between P/Po < 0.75, indicating that the adsorption and 100 nm for the sample with Si/Ce ¼ 5. The formation of these
desorption behaviors in the pores of the samples are very pores in the mesoporous and macroporous region can be
similar. explained by the formation of voids due to inter-nanoparticles
The pore diameter distributions of the samples calculated in contact.
from the desorption branch of the isotherm by using the BJH The surface area (SABET) decreases from 820 to 620 and
method and the corresponding data are shown in Fig. 3 and 444 m2/g as the Si/Ce molar ratio decreases from 20 to 10 and 5,
Table 4. In the sample Si/Ce ¼ 20, pore diameter was respectively. Among these samples, the solid with Si/Ce ¼ 5
concentrated around 2.7 nm. As the cerium content increased, has the largest lattice cell dimension and smallest surface
bimodal pore diameter distributions were observed: the main area and most pore wall thickness (s). These observations
peak corresponds to pores having a diameter (Dp) approxi- show that cerium incorporation strongly affects the textural
mately 2.7 nm and a small one relates to some pores with properties of the resultant materials. High cerium content not
larger diameter (Dmp) around 3.5 nm. The structural ordering only leads to diminution of the long-range order of the mes-
is reduced as more cerium ions are incorporated, thus some of ostructure and surface area, but also increases the population
the adjacent pores might collapse at high cerium content of the pores with large diameter.
3514 international journal of hydrogen energy 35 (2010) 3509–3521
80 Cg Ni
70 50 wt % Ni /Ce-MCM-41-20
60
Cg
50
x10 Counts
40 Ni
30
3
a 20 CA
Intensity (a. u.)
10
0
-10
-20
b 20 25 30 35 40 45 50 55
Two theta (degree)
Fig. 6 – A Rietveld refinement plot of the sample 50 wt%
Ni/Ce-MCM-41 after 1400 min of reaction at 580 8C.
c Experimental pattern is shown by symbols and the
calculated one by a continuous line. This sample contains
metallic Ni, graphite and quasi-amorphous carbon. Marks
show Ni (upper), graphite (media), and carbon in
20 30 40 50 a descendent order (lower). The quality of the refinements
Two Theta (degree) is shown by the difference between both patterns which
appears as the lowest continuous line. In this case,
Fig. 5 – XRD patterns of the 30 Ni wt%/Ce-MCM-41 catalysts
Rwp [ 0.14.
after 22 h of reaction. This sample contains metallic Ni,
graphite and amorphous carbon. Marks show Ni (upper),
graphite (media), and carbon in a descendent order (lower). mesostructured catalysts have a great potential for application
(a) Si/Ce [ 20; (b) Si/Ce [ 10; (c) Si/Ce [ 5. in the hydrogen production due to their high stability and good
catalytic activity.
It has been reported that the use of basic or redox
promoters decreases the formation of coke during the
3.2. Hydrogen production over Ni/Ce-MCM-41 catalysts reforming of methane with CeO2 through a mechanism of
Ce4þ/Ce3þ. This means that Ce species promote the adsorption
A series of the catalysts of Ni/Ce-MCM-41 with Ni loading of CO2 and the elimination of coke species formed on the
30 wt.% and 50 wt.%, were used for methane catalytic decom- surface of the catalyst [42]. Additionally, it has found that Ce
position. Reaction temperature has a significant influence on addition increases the thermal stability and affects the
the methane conversion. Over all the catalysts, CH4 conversion metallic particle size in several catalysts and reactions [43]. In
increased with increasing of the reaction temperature (not the case of the methane decomposition reaction, in our
shown). In order to study the catalytic stability of the catalysts, previous work, we have found that addition cerium may
the CH4 decomposition reaction was continuously carried out enhance the catalytic stability [27] We speculate that cerium
for 1400 min. Fig. 4 shows the methane conversion via reaction addition may promote the carbon remove from specific
time at 580 C over the different catalysts. During the 1400 min surface to remain active Ni clean and stabilize the Ni particle,
continuous reaction, the methane conversion over different these roles are quite important for obtaining the catalysts
catalysts varied between 67 and 74%, no obvious deactivation with long lifetime.
was observed, indicating that the catalytic activity of the
catalysts is very stable under experimental conditions. 3.3. Carbon nanotube (CNT) formation
Compared with Ni/SiO2 catalyst on which complete deactiva-
tion took place after 2 h of reaction [27], the catalytic stability of 3.3.1. XRD analysis
the Ni/Ce-MCM-41 catalysts is greatly enhanced by approxi- The Fig. 5 shows the XRD patterns of the catalysts after
mately 10 times. These results show that Ni-based Ce-MCM-41 1400 min of reaction. The XRD reflections at 2q ¼ 44.2 and
Table 5 – Lattice cell parameters of metallic Ni, graphite and amorphous carbon materials.
Cell parameter (nm) Cubic Ni Graphite C Amorphous C
Fig. 7 – (a). Nickel unit cell, space group P63/mmc (S. G. 194) (b). Graphite unit cell. All atoms are C and colors are just used to
distinguish the two different atom positions corresponding to the space group P63/mmc (S. G. 194). (c) Amorphous carbon
unit cell (only for simulation purposes). All atoms are C and colors are just used to distinguish the four different positions
corresponding to the space group P63/mmc (S. G. 194).
53.8 correspond to metallic Ni [JCPDS No. 04-850] with an Rietveld refinement plot of the used catalyst 50 wt.% Ni/Ce-
average particle size approximately 40 nm. The reflections at MCM-41 with a Si/Ce molar ratio 10. Ni nanoparticles,
2q ¼ 26.1 and 54.0 are assigned to graphitic carbon [ICSD No. graphitic and quasi-amorphous nanocarbons were formed in
01-0640]. While, a peak located at 42.9 is indicative of the the sample. Quantitative data of the crystalline structures of
formation of quasi-amorphous nanocarbons. metallic Ni, graphite and quasi-amorphous carbon materials
The crystalline structures of each phase in the catalysts determined from the Rietveld refinements are shown in
were refined with the Rietveld method. Fig. 6 shows a typical Table 5.
3516 international journal of hydrogen energy 35 (2010) 3509–3521
-1
structure, whose symmetry corresponds to the space group
1352.5 cm
-1
1585 cm
Fm3m (S. G. 225). The cell parameter a is between 0.35288 and
0.35398 nm. Each cell contains 4 Ni atoms and stacking of this
cell forms particles or cubic crystallites of around 40 nm in 50wt % Ni/Ce-MCM-41-20
average diameter. The perspective packing drawings of the
Intensity (a.u.)
structures of carbon arrangements are shown in Fig. 7b and c.
These graphite and quasi-amorphous carbons have different
50 wt %NI/Ce-MCM-41-10
structures and particle sizes. The graphite carbon contributed
to the formation of CNTs. As shown in Table 5, the lattice cell
parameters corresponding to graphite structure vary within
a small range: a, from 0.23903 nm up to 0.25191 nm, and c from 50wt% Ni/Ce-MCM-41-5
0.67900 nm up to 0.68699 nm. The primitive rhombohedral unit
cell used for modelling the graphite structure, whose hexag-
onal symmetry corresponds to the space group P63/mmc. Note
that the angle g is 120 and that a hexagonal prism consists of
three unit cells. Every cell contains 4 atoms of C (Z ¼ 4). Stacking 800 1000 1200 1400 1600 1800
of this cell forms polyhedral crystallite particles with shape Raman Shift (cm )
-1
Fig. 9 – TEM micrographs of the carbon nanotubes found in the catalytic evaluation of 50 wt% Ni/Ce-MCM-41-20 after
1400 min of reaction. Inset A in Fig. 9b shows Ni particles producing carbon nanotube of different external diameter.
after the reaction, the Ni particle shows a shape diamond or graphite at a relative low temperature, for example, 400 C,
pear-like. The sharp tail of the Ni particle inserts into the which is even lower than the Tamman temperature of pure Ni
carbon nanotube. It seems that the Ni particle becomes quasi- particle [46,47]. Thus, Ni3C formation provides the possibility of
liquid during the reaction. As we know that the melting point of Ni or/C atoms fluidity. It is proven that carbon atoms produced
metallic Ni is 1452 C and its Tamman temperature is around from CH4 decomposition over the Ni-based catalysts can form
Tm ¼ 726 C. It is possible for a Ni particle to be fluidity only at NixCy solid solution as intermediate due to carbon atoms
the temperature reaching its Tamman point. Therefore, dissolution into the bulk Ni; at such condition, C atoms are able
a question is naturally arisen: how can the Ni particle possess to move within the Ni particles and they are then released from
unusual fluidity at a reaction temperature far below the the NixCy solid solution to form graphitic structure in the
melting point, herein, 580 C? It is reported that for a used support–metal interface [45]. The Rietveld refinements of our
Ni/SiO2 catalyst, the C1s level of the XPS spectrum consists of used catalysts confirm that the largest lattice cell parameter of
one bond at 281.9 eV that is attributed to carbide feature (Ni3C) metallic Ni in our catalysts is a ¼ 0.35389 nm with a maximal
and another at 284.7 eV assigned to filament carbon [45]. It is volume (Vm) of a close-packed arrangement of approximately
evident that Ni3C has lattice unit like hexagonal Ni crystal and 0.044354 nm3. It seems to be an insufficient room for carbon
it is an inactive phase for methane decomposition. Ni3C is atom (C atom radii is 0.077 nm) locating in the octahedral voids
unstable with respect to metal Ni and graphitic carbon; it, of Ni crystal. However it is noteworthy that when C atoms
therefore, can be decomposed into a mixture of nickel and transfer within Ni crystals, the lattice constituents oscillating
3518 international journal of hydrogen energy 35 (2010) 3509–3521
Fig. 12 – Mechanism of the formation of carbon nanotube with closed end and embedded small Ni pieces.
4.2.2. Carbon nanotubes with open end 4.2.4. Nanocarbons with closed end without Ni particle
It was observed that some of the carbon nanotubes have an on the tip
open end. The shape of the open end is the same or very There are some carbon nanotubes having a closed end
similar as pear-shape of Ni particle (Fig. 9b). Therefore, the without Ni particle on the tip nor small pieces of Ni particles
open end is probably formed due to the Ni releasing from embedded inside them (Fig. 12, path B). It is believed that the
the carbon tube end in certain reasons, for example, formation of these kind carbon nanotubes follows a similar
mechanical disturbing. Formation mechanism of the carbon pathway as the ones encapsulating small pieces of Ni parti-
nanotubes with open end is assumed to be the same as cles. However, due to interaction between Ni particle and
those with carbon nanotube filled with Ni particles as support is different, the strong interaction between them
described above. makes Ni particle difficult to move, hence, some of metals are
strongly fixed in the support and the carbon tubes have to
4.2.3. Carbons nanotubes embedding small pieces of Ni grow towards the solid–gas interface. As for whether or not
particles the carbon nanotubes contain small pieces of Ni particle, it
Some of the carbon nanotubes were found to embed small might depend on the reaction temperature and degree of the
pieces of metallic Ni particles (Fig. 9c). It is assumed that interaction between Ni particle and support. Usually, higher
some of the Ni particles are strongly interacted with the reaction temperature favors the formation of carbon tubes
support and they are deeply anchored into the support and embedding small pieces of Ni; if the Ni particle is deeply
are difficult for motion. Methane decomposition reaction anchored into the support, only small part of the surface is
occurs on the exposed surface of such kind Ni particles to exposed to the reaction atmosphere, the interaction between
form NixCy metastable solid solution intermediate. As the Ni particle and support is rather strong, these metal particles
NixCy is continuously formed and accumulated, C atoms are are difficult to be cut off into small pieces and thus the formed
released due to decomposition of the metastable CxNiy carbon nanotubes do not embed any pieces of small Ni
intermediate in the other side of the exposed surface of the particle.
Ni particles, but not in the interface between the lower potion
of Ni particle and support as usual. In such case, the carbon
nanotubes are constructed in the surface of the Ni particle
towards gas–solid interface. As a result, the Ni particle is 5. Conclusions
fixed in the support but leaving carbon tube growing with
a closed end (Fig. 12, Path A). Ce-MCM-41 mesoporous materials with large surface area and
The tails of the quasi-liquid NixCy particles are easy to be ordered pore structure system could be synthesized through
split into several parts, some of which can be enclosed into a surfactant-assisted approach. In the methane decomposi-
tubes. Similar phenomenon was also observed in the Fe/Al2O3 tion reaction, the catalytic activity of the Ni/Ce-MCM-41x
catalysts [49]. In the methane catalytic decomposition, the (x ¼ Si/Ce molar ratio ¼ 20, 10, and 5) catalysts show high
formed Ni carbide in our Ni/Ce-MCM-41 catalysts may be catalytic stability. During the 1400 min of reaction, no obvious
decomposed into supersaturation of the Ni particle with catalytic deactivation was observed. Both nanocarbons with
carbon that results in the emergence of graphite nucleus and graphitic structure and quasi-amorphous carbon were formed
then layers on the Ni particles. These graphitic layers are in the evaluated catalysts. The carbon nanotubes have 30–
initially oriented in parallel to the particle surface, they are, 50 nm in diameters and hundred nanometers to tens
however, distorted and their orientation may change to form micrometers in length and all the carbon nanotubes consist of
a hollow structure. As the carbon nanotubes grow further, its multiple layer walls. Most of the metallic Ni particles are
part in contact with the particle becomes narrowed and the located at the tip of carbon nanotubes and their exposed
tail of the metal particle is pulled inside the carbon capsule, surface remain clean after 1400 min of reaction, which
forming a small piece of Ni particle encapsulated in the carbon explains the high catalytic stability of these catalysts. Several
tube with diameter the same as the inner diameter of the types of carbon nanotubes/nanofibiers were formed in the
carbon tube. tested catalysts. Their formation mechanisms greatly
3520 international journal of hydrogen energy 35 (2010) 3509–3521
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