Pergamon

Carbon Vol. 34, No. 10, pp. 1249%1257,1996

Copyright 0 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
OOOE-6223/96 $15.00 + 0.00
SOUW6223( 96)00074-7
Fe-CATALYZED CARBON NANOTUBE FORMATION
K. HERNADI,~ A. FONSECA,~** J. B.NAGY,~ D. BERNAERTS~ and A. A. LUCAY
Institute for Studies in Interface Sciences, Facultds Universitaires Notre-Dame de la Paix,
61 rue de Bruxelles, B-5000, Namur, Belgium
bEMAT, University of Antwerp (RUCA), Groenenborgerlaan 171, B-2020, Antwerp, Belgium
(Received 8 February 1996; accepted in revised form 14 May 1996)
Abstract-The catalytic production of carbon nanotubes was investigated using various iron catalysts.
Catalyst samples were made by different preparation methods in order to improve both the quality and
the quantity of as-prepared carbon nanotubes. The catalysts were tested in the decomposition of different
hydrocarbons in the temperature range 650-800C using either fixed bed flow or fluidized bed reactor.
The quality of the products was characterized by means of transmission electron microscopy. By using
Fe/silica, the highest activity ever observed in catalytic nanotube formation can be reached. Copyright 0
1996 Elsevier Science Ltd
Key Words-Carbon nanotubes, catalytic synthesis, Fe-catalyst, iron carbide.
1. INTRODUCTION
The recent discovery of fullerenes and hollow gra-
phitic tubules of nanometer dimension opened a new
chapter in carbon chemistry. Because of their esti-
mated chemical and physical properties [l-4], spec-
ulations about the possible applications of carbon
nanotubes have been published [S-7]. For the syn-
thesis of carbon nanotubes several methods have
been proposed. Although the arc-discharge method
has been developed for Cm synthesis, the growth of
fullerene tubes was observed on its cathode [8-121.
Other methods such as plasma decomposition of
hydrocarbons [ 13,141 and co-evaporating catalyst
during a carbon arc-discharge [ 15-171 improved the
technique of nanotube synthesis. Recently, Ivanov
et al. [ 18,191 optimized the catalytic synthesis
towards the production of turbostratic carbon nano-
tubes having fullerene-like diameters.
From the early 7Os, the catalytic role of iron and
other transition metals in the formation of filamen-
tous carbon has been widely investigated [20-2.51.
Although, in catalysis research, much attention was
paid to the prevention of deactivation of catalysts,
many papers dealt with the mechanism of carbon
filament formation too.
Already in the 7Os, the structure and morphology
of carbon microstructures formed over iron and
nickel foils in pyrolysis of hydrocarbons were studied
by Baird et al. [ 261. Boellaard et al. [ 271 also studied
the morphology of filamentous carbon formed by
carburization over supported Ni and Fe catalysts.
Baker et al. investigated the formation of filamentous
carbon in the decomposition of acetylene over Ni-Fe
surfaces, using various oxide additives [28]. In a
subsequent paper [29] they reported that Fe0 has
at least one order of magnitude higher activity in
*Author to whom correspondence should be addressed.
1249
filamentous carbon formation than Fe. They also
proved that Fe& is not active in filament formation.
Recently, the same authors established the effect of
CO on the decomposition of ethylene over an iron
catalyst [30]. Sacco et al. [31] presumed a growth
mechanism and they found that Fe& could act as
an active phase. Audier and Coulon suggested a
mechanism for the growth of carbon tubes in which
the bulk diffusion of the carbon through the metal
particles appeared as the rate-limiting step [32].
Alstrup also developed a new model explaining
carbon filament growth over supported transition
metal catalysts [33]. Very recently, Fonseca et al.
suggested a growth mechanism leading to carbon
tubules and tubule connections on a catalyst particle
at a molecular level [34].
Since many literature data suggested its high activ-
ity in filamentous carbon formation and Co/silica
has already been found to be effective in the synthesis
of nanotubes [l&19], we started to investigate the
catalytic effect of iron in carbon nanotube formation
by using pyrolytic decomposition of different
hydrocarbons.
2. EXPERIMENTAL
Carbon nanotubes were synthesized in the catalytic
decomposition of acetylene, ethylene and propy-
lene in the temperature range 650-800C over
supported Fe catalysts. Catalysts were made by
different methods (impregnation, ion-adsorption pre-
cipitation) and by using various supports. For the
preparation of the catalysts, basic iron acetate
(Fe(OH)(CH,COO),, ICN Pharmaceuticals, Inc.)
was used except for one sample where FeCI, (RPL,
UCB) was applied as precursor. The following materi-
als were used as catalyst support: graphite flakes
(natural, 99.5%; Johnson Matthey GmbH), silica
1250
Support
K. HERNADI et al.
Table 1. Formation of carbon deposit over different iron catalysts
Graphite Y ZSM-5 Silica Silica Silica Silica
Method impr. impr. impr. impr. ion-ads. ion-ads. (pH = 7) ion-ads. (FeCl,)
Carbon yield (%) 3.4 41.6 21.3 29.5 116.6 160.0 184.0
30 minutes of synthesis at 700C.
(SILICA GEL 60, Merck, particle size: 15-40 pm),
NaY (Union Carbide) and ZSM-5 (NESTE, Finland).
For the impregnation method, the amount of iron
acetate was set to 2.5 wt% metal/support. The concen-
tration of the initial solution was chosen five times
higher for the ion-adsorption precipitation method.
The Fe/graphite sample was treated at 1200C for 5
hours in Hz atmosphere. The other samples were
calcined at 450C for 4.5 hours. In the case of certain
samples prepared by ion-adsorption precipitation,
the pH of the solution was set to 7 before filtration.
A more detailed description of catalyst preparation
is given elsewhere [ 35,361.
Reactions were carried out-on a catalyst amount
of approx. 30 mg-in two different types of reactor:
fixed bed flow reactor and fluidized bed reactor. The
fixed bed flow reactor is composed of a quartz boat
containing the catalyst placed in an horizontal quartz
tube (14 mm in diameter), while the fluidized bed
reactor is constituted of a vertical quartz tube (6.4 mm
in diameter) containing a sintered glass in the middle
supporting the catalyst. In the latter reactor the gas
flow enters from the bottom and is adapted so as to
make the catalyst floating. The gas feeds applied
during the reactions were the following: 8 ml/min
acetylene (or other hydrocarbon) (Alphagas, 99.5%
purity) in nitrogen flow of 75 ml/min in the fixed bed
flow reactor, and the same amount of acetylene in
nitrogen flow of 30 ml/min in the fluidized bed
reactor.
For calculation of carbon yield (deposited carbon
during the reaction), the following formula was used:
carbon yield (%) = (m,,, - m,,,)/m,,, 100,
where meat is the initial amount of the catalyst (before
reaction) and mtot is the total weight of the product
after reaction.
The nature of the carbon deposit on the catalyst
surface was characterized by transmission electron
microscopy (Philips CM 20 and JEOL 200 CX,
200 kV). For the sample preparation a Rh-Cu grid
and the glue technique were used [36].
3. RESULTS AND DISCUSSION
3.1 Catalytic role of iron carbide
According to literature data [ 27,30,37739], trans-
ition metal carbide was considered to be responsible
for deposition of carbon and filament formation.
Because of the previous investigations just referred
to, unsupported Fe& and iron carbide produced on
the surface of different supports such as graphite
flakes and silica, were tested in the catalytic decompo-
sition of acetylene. For the preparation of iron car-
bide, several methods are suitable. Like the majority
of metals, iron reacts with carbon at high temper-
atures (below its melting point) in a reducing atmo-
sphere [40]. This observation was applied for the
preparation of catalyst Fe/graphite. Production of
carbides can also be carried out in the reduction of
oxides by carbon-containing gases. This method is
mainly used to obtain the carbides of iron, nickel
and cobalt [40]. A sample of Fe/silica was prepared
in this way.
Over unsupported Fe&, no carbon deposit was
observed either by weighing or by electron micro-
scopy. A Fe/graphite catalyst sample showed very
low activity; the carbon yield was found to be 3.4%.
According to the electron microscopic observations,
carbon nanotubes and fibers formed on the surface
as illustrated in Fig. 1. However, some regions contain
carbon fibers hollow in the middle, but their structure
is not well turbostratic, and their appearance is
tortuous as can be seen even on the low magnifica-
tion image. Mostly fibers and not turbostratic tubes
with different diameter can be seen on the image.
Both the quality of the nanotubes and the quantity
of the carbon yield (49.5%) were much higher in the
case of Fe/silica. Further investigations proved that
previous reduction of iron oxide is unnecessary (as
was supposed by Baker et al. [29]); acetylene is able
to reduce the catalyst to the required extent under
reaction conditions. On the probable analogy with
Co/silica [35], the most active catalyst is only
reduced to about 20%, so iron carbide alone cannot
be responsible for the activity. This is in accordance
with our results obtained over unsupported Fe&. To
sum up, it is sufficient to form well-dispersed iron
oxide on the surface of the support from which
catalytic centers active in carbon nanotube formation
can develop during the decomposition of acetylene.
3.2 Catalyst support andpreparation method
After developing the necessary pretreatment of the
catalyst, different supports and preparation methods
were used in order to find catalyst samples which are
more effective in carbon nanotube formation. It fol-
lows from the foregoing that graphite flakes did not
prove to be a good catalyst support so investigations
were continued with silica and different types of
zeolites. As different preparation methods, ion-
adsorption precipitation on silica gel, ion-exchange
on zeolites and impregnation on both supports (using
Fe acetate or FeCl, as starting material) were applied.
Fe-catalyzed carbon nanotube formation 1251
Fig. 1. Carbon nanostructures formed in the decomposition of acetylene at 700C over Fe/graphite catalyst.
Zeolite-supported samples prepared by ion-
exchange were found to be inactive in the formation
of carbon nanotubes, while the samples made by
impregnation showed higher activity. The Fe/Y cata-
lyst gave better results than Fe/ZSM-5 as it can be
seen from data summarized in Table 1. The quality
of carbon nanotubes formed over Fe/Y prepared by
impregnation is illustrated in Fig. 2. Using Fe/ZSM-5,
not only the decrease of the activity (about half that
of Fe/Y), but amorphous carbon and carbon fibers
were also observed. The structure of the zeolite
support may modify the effectiveness of the catalyst
500 nm
I I
particles and this can explain the differences observed
between Fe/Y and Fe/ZSM-5 samples.
Applying silica support led to even better results.
Although Fe/silica prepared by the impregnation
method showed some inhomogeneity in the quality
of carbon deposit (besides carbon nanotubes it also
contained some amorphous carbon and thick tubes
having diameters larger than 50 nm) and produced a
carbon yield of lower value (Table l), using the ion-
adsorption precipitation method the properties of the
catalysts improved remarkably. While the value of
the carbon yield increased above lOO%, the tubes
Fig. 2. Carbon nanotubes formed in the decomposition of acetylene at 700C over Fe/Y catalyst.
1252 K. HERNADI et al.
became homogeneous in diameter, and less amor-
phous carbon was observed. According to the electron
microscopic observations, every catalyst particle is
covered by carbon nanotubes of regular diameter.
The average value of the outer diameter is approxi-
mately lo-20 nm and that of the inner diameter is
5-8 nm. Carbon nanotubes produced on Fe/silica
(ion-adsorption precipitation) can be seen in Fig. 3.
As can be seen in high resolution images (Fig. 3(b)),
the structure of their inner wall is turbostratic [lS]
for several layers-up to approx. one half of the
tube wall-and that of the outer wall is mainly
amorphous carbon. According to these images,
thicker tubes also exist and their inner wall structure
is turbostratic, too. The macroscopic appearance of
this material can be described as follows: the product
has a spongy texture and it is very fluffy and light,
easy to charge electrostatically. The tubes stick to
glass surfaces very strongly. After simply removing
the catalyst bed, a fairly large amount (a few mgs) of
almost pure carbon nanotube could be collected by
scratching the bottom of the quartz boat. It can be
seen in Fig. 4, that it contains only a small amount
of silica support and is free of amorphous carbon
pieces. A catalyst sample which was neutralized
during preparation showed even higher activity, keep-
ing the same good quality described before and,
contrary to other iron catalysts, formation of spiral
nanotubes could be observed on its surface as
illustrated in Figs 5 and 6. The formation of coiled
nanotubes is clearly enhanced in the catalyst formed
using a pH = 9 initial solution (Fig. 5). The existence
of these helices has already been described
[ 18,34-361 using supported Co/silica samples.
Although Boehm [ 371 reported a frequent formation
of coiled nanotubes on iron, most of our Fe catalysts
Fig. 3. Carbon nanotubes formed in the decomposition of acetylene at 700C over Fe/silica (ion-adsorption precipitation)
catalyst. (a) Low magnification; (b) high resolution.
Fe-catalyzed carbon nanotube formation 1253
Fig. 4. Almost pure carbon nanotubes collected by scratching the bottom of quartz boat (reactor)
Fig. 5. Carbon nanotubes formed in the decomposition of acetylene at 700C over Fe/silica (ion-adsorption precipitation using
pH = 9 as initial solution, but the pH was close to 7 before filtration) catalyst.
produced carbon nanotubes which were not regularly
bent and thus no helices are present.
For the catalyst preparation, iron acetate was used
in order to obtain the oxide without any anionic
contamination after calcination. In spite of literature
data from chemical handbooks, it was not completely
soluble in any solvent so small crystals of the salt
could adhere to the outer surface of the support, and
can result in the formation of thicker tubes in some
regions. Though their amount is not too high we
tried to avoid this side-effect by using FeCl, as a
starting material. In the catalytic decomposition of
acetylene this sample showed the highest activity ever
observed in nanotube formation (see Table 1). Their
quality is even better and they are not crumbled at
all (the overall aspect being similar to that of Fig. 6).
The turbostratic structure of the wall is extended
through the tube diameter and much less amorphous
carbon was found on the outer surface of the nano-
tubes as is illustrated in Fig. 7. Almost no thicker
tubes and fibers were observed in this sample. From
this experiment, it can be established that Cl- has
1254 K. HERNADI et al.
Fig. 6. Carbon nanotubes formed in the decomposition of acetylene at 700C over Fe/silica (ion-adsorption precipitation and
neutralized before filtration) catalyst.
Fig. 7. High resolution image of a carbon nanotube formed
in the decomposition of acetylene at 700C over Fe/silica
prepared from FeCl, solution (ion-adsorption precipitation
and neutralized before filtration) catalyst.
no negative effect on either the activity of the catalyst
or the quality of carbon nanotubes.
3.3 Reaction time
The catalytic behavior of Fe/silica prepared by the
ion-exchange method was studied as a function of
reaction time. In Table 2 carbon yield data are sum-
marized. The amount of carbon deposit increases
with time. After a reaction time of 1 minute, the
macroscopic appearance of the sample did not indi-
Table 2. Carbon yield as a function of reaction time over
Fe/silica
Reaction time (min) 1 5 10 30
Carbon yield (%) 4.8 35.3 57.1 116.6
Iron acetate (ion-adsorption precipitation) at 700C
cate the presence of carbon nanotubes since it was
not black but gray. Nevertheless, electron microscopic
observation verified the formation of nanotubes even
after 1 minute but only a few particles are covered
by them. After 5 minutes all of the particles are
overlaid by the nanotubes. It is interesting to remark
that formation of amorphous carbon on the catalyst
surface could not be observed even after 30 minutes.
At longer reaction times (> 1 hour), deposition of
soot begins on the catalyst surface and on the outer
surface of the tubes.
3.4 DiSferent reactants
In order to cbmpare the reactivity of acetylene
with other hydrocarbons, catalytic decomposition of
methane, ethylene and propylene have been checked
at different reaction temperatures (Table 3). In the
decomposition of ethylene and propylene at 7OOC,
the carbon yield over Fe/silica (ion-adsorption precip-
itation) is much lower than in that of acetylene, and
the quality of carbon nanotubes was much poorer so
that the formation of amorphous carbon and thick
tubes became significant, and the nanotubes were
Table 3. Carbon yield as a function of reactant and reaction
temperature over Fe/silica
Carbon yield (%)
Reactant 700C 750C 800C
Acetylene 116.6
_ _
Ethylene 34.0 60.1
_
Propylene 32.8 38.8
Methane 0 0 *0
Iron acetate (ion-adsorption precipitation) 30 min
reaction.
Fe-catalyzed carbon nanotube formation 1255
crumbled, which showed that the organization of
the wall was not good. Increasing reaction temper-
ature favored the developing of well-turbostratic
structures and at the same time the amount of soot
diminished to a great extent. For example, the carbon
yield was found to be 60.1% at 750C in the reaction
of ethylene (Table 3). Carbon nanotubes formed in
the catalytic decomposition of ethylene are shown in
Fig. 8. Fe/silica was almost inactive in the decomposi-
tion of methane even at 800C. At this reaction
temperature no carbon deposit could be weighed, but
a very small amount of amorphous soot has been
observed by electron microscopy.
In addition to experiments carried out in the fixed
bed flow reactor, a fluidized bed reactor was also
applied in the production of carbon nanotubes over
Fe/silica catalyst. Following literature data [41], its
advantages in both material and heat transport
inspired us to try this reactor, too. For the sake of
comparison, the flow of acetylene and the linear gas
speed was set to the same values in both reactors. In
the decomposition of acetylene, the quality of carbon
nanotubes was investigated at different reaction times.
As a result of the identical experimental parameters,
values of carbon yields were about the same in both
reactors. The real difference was observed in the
quality of the product. In the fixed bed flow reactor,
formation of amorphous carbon begins at 1 hour and
increases at higher reaction times. Appearance of soot
on the tubes ensues somewhat earlier in the fluidized
bed. While in the first case the homogeneous decom-
position of acetylene [42] leads to deposition of soot
on the outer surface of the tubes, in the second case
additional amorphous carbon from the inner pores
of silica can be released, too, due to the mechanical
action in the gas flow [43]. This supposition is
confirmed by the observations of broken tubes in
the system which can be seen in Fig. 9. (However,
strong sonication can have a similar effect on the
samples [43].) In the same image, the presence of
amorphous carbon can also be observed which is
characteristic only for the fluidized bed reactor using
this catalyst. Since the diameter of the well-tur-
bostratic tubes depends mainly on the dispersion of
the catalyst, only their length can grow in time [ 341.
Thickening of the tubes results by soot deposition
only. This can be seen in the electron microscopic
images, too. Breaking the nanotubes (probably at
those places where the structure of their wall was not
well organized) and cutting up the silica support to
smaller pieces occurs in the fluidized bed reactor and
the latter phenomenon causes soot liberation from
the inside pores. It means that in the fluidized bed
reaction not only the homogeneous decomposition
of acetylene results in amorphous carbon deposits on
the product but their higher amount can be explained
by the soot originating from the silica support.
3.5 Fluidized bed reactor
4. CONCLUSIONS
Summarizing the result obtained in the catalytic
synthesis of carbon nanotubes over supported Fe
catalysts it can be stated that Fe/silica (ion-adsorption
precipitation) is able to produce nanotubes with high
activity and selectivity. For the possible use of carbon
nanotubes, their preparation in large quantity under
mild reaction conditions can be of decisive impor-
tance. According to the structure of the as-made
product, on the basis of their high surface area, it
.._^^_. )_
5o(l nm
Fig. 8. Carbon nanotubes formed in the decomposition of ethylene at 750C over Fe/silica catalyst.
1256
K. HERNADI et al.
Fig. 9. Broken nanotubes together with some amorphous carbon formed in the fluidized bed reactor
could be applied, for example, as catalyst support
[44] or as the stationary phase in chromatography.
As far as purification of carbon nanotubes is con-
cerned, despite the lower formation of carbon deposit
(Table 1) on Fe/zeolite Y (impregnation), when com-
pared to Fe/silica (ion-adsorption precipitation), the
isolation of nanotubes is easier when the support is
zeolite [36]. In fact, zeolite catalysts being soluble in
aqueous HF, the isolation of nanotubes with some
amorphous carbon from Co/zeolite Y has already
been reported with 76% yield [ 361. The same purifi-
cation procedure will be applied to the nanotubes
produced on Fe/zeolite Y (impregnation).
Acknowledgements-The authors acknowledge the Wallonia
Region and the Belgian National Fund for Scientific
Research (FNRS, Brussels) for financial support. K. Hernadi
is grateful for the fellowship W 015751 (Human Resources
Development Project, 3313 HU, Young Scientists Support
Program, OTKA). This text presents research results of the
Belgian Programme on Inter University Poles of Attraction
initiated by the Belgian State, Prime Ministers Office of
Science Policy Programming. The scientific responsibility is
assumed by the authors. Thanks are expressed for the good
photographs to D. Van Acker.
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