CNT Review

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Progress in Materials Science xxx (2005) xxxxxx

www.elsevier.com/locate/pmatsci
The catalyst in the CCVD of carbon

nanotubesa review
Anne-Claire Dupuis
Commissariat a` lEnergie Atomique, DRFMC, 17 rue des Martyrs, F-38054 Grenoble Cedex 9, France
Abstract
Since their discovery [Ijima, 1991, Nature, 354, 56], carbon nanotubes (CNTs) have been
widely studied due to their large potential applications. First produced in arc-discharge process or by laser-ablation, the CNTs grown by catalytic chemical vapor deposition (CCVD)
have been showing however a large expansion for the past decade. A fundamental question
remains after this 10-year experience: What is actually the role played by the catalyst in the
CCVD of CNTs? This review intends to synthesize the data published in the scientic literature on this topic in order to better understand the parameters governing the catalytic properties of the metal nanoparticles. In particular, we will discuss the inuence of the
composition of the catalyst material, of the morphology of the catalyst nanoparticles, of the
support, of the preparation method of the nanoparticles and of the reduction pretreatment.
2005 Elsevier Ltd. All rights reserved.
Contents
1.
2.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Preparation methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Solgel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Coreduction of precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3. Impregnation, incubation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4. Ion-exchangeprecipitation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
E-mail address: ac.dupuis@web.de

0079-6425/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pmatsci.2005.04.003
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A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx
3.
4.
5.
6.
2.5. Ion-adsorptionprecipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6. Reverse micelle method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.7. Thermal decomposition of carbonyl complexes . . . . . . . . . . . . . . . . . . . . .
2.8. Metalorganic chemical vapor deposition (MOCVD) . . . . . . . . . . . . . . . . . .
2.9. Physical deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Models of catalytic growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Catalysts used for CNT growth. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Parameters determining the catalytic properties . . . . . . . . . . . . . . . . . . . . . . . . .
5.1. Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.1. Experimental comparison of different catalysts . . . . . . . . . . . . . . .
5.1.2. Electronic structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.3. Carbon solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.4. Stabilization of the catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.5. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2. Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.1. Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.2. Crystallographic orientation . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.3. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3. Preparation method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.1. Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.2. Electronic structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.3. Other aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.4. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4. Support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4.1. Experimental comparison of different supports . . . . . . . . . . . . . . .
5.4.2. Formation of intercompounds . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4.3. Supportcatalyst interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4.4. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.5. Pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.5.1. Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.5.2. Role of pretreatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.5.3. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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1. Introduction
Carbon products in tubular form, called carbon laments, were rst observed
when electron microscopes came into wide use around 1950 [1]. In the early 90s, such
laments were observed with a diameter in the range order of the nanometer [2] and
have then been called carbon nanotubes (CNTs). These rst observed multi-walled
CNTs (MWNTs) were grown in an arc-discharge process. A transmission electron
microscope image of MWNT is shown in Fig. 1. Two years later, single-walled
carbon nanotubes (SWNTs) could be grown by laser-ablation. At the same time,
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Fig. 1. Transmission electron microscope image of a multi-walled carbon nanotube [11].
the catalytic chemical vapor deposition (CCVD) method was rst used to grow
CNTs.
Because of the peculiar electronic transport properties of the single-walled carbon
nanotubes (SWNTs) on the one hand [3,4] and the high conducting properties of the
multi-walled carbon nanotubes (MWNTs) on the other hand [5], CNTs arouse great
interest in the microelectronics community and hope for new functional electronic
devices [69]. The attraction and development of CCVD for growing CNTs by the
scientic community can be partly explained by the fact that it is very familiar with
CVD techniques. However, the ability to grow CNTs directly on a substrate at a desired position is a great challenge from a technological point of view. This control
over the CCVD growth of CNTs would permit the integration of the CNT growth
into fabrication processes of microelectronic circuits since the CCVD process requires moreover much lower temperatures than the arc-discharge and laser-ablation
processes. The CCVD methods thus seems to be more adapted for large-scale production at lower cost [10]. This explains why many research groups in the whole
world are working on the growth of CNTs by CCVD.
The CVD process on a supported catalyst consists of several steps. The rst is to
prepare metal nanoparticles on a substrate. The substrate is then placed in a furnace
and the nanoparticles are then generally submitted to a reduction treatment upon
heating under typically H2 or NH3. And nally, hydrocarbon gas or CO is let into
the furnace and carbon deposition occurs by catalytic decomposition of the hydrocarbon molecules on the metal nanoparticles by temperatures ranging roughly from
500 to 1200 C (Fig. 2).
A fundamental question remains, even if the CCVD of CNTs works properly:
What is actually the role played by the catalyst in the catalytic chemical vapor depo-
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Fig. 2. Schematic illustration of the CVD process.
sition of carbon nanotubes? One could simply answer, the rst role of the catalyst is
to decompose the hydrocarbon molecules. Surely it is. But its activity for hydrocarbon decomposition cannot be accounted for its ability of CNT formation [12,13]. In
many cases, hydrocarbon molecules will decompose without forming CNT, as has
been found for example by Sen et al. [14] who studied the decomposition by pyrolysis
of benzene and/or metallocene. One may easily concede that the role of the catalyst is
more complex than only hydrocarbon decomposition. But what happens exactly at
the catalyst during the growth process? Why are transition metals appropriate for
CNT growth? Why do dierent metals and combinations of them lead to sometimes
completely dierent results?
This review does not intend to answer fully all these questions, but to synthesize
what is known today about the catalyst in the growth of CNTs. Because of the very
large number of papers about carbon nanotubes, the review cannot be too exhaustive, but may help to explain how to better understand and thus control the parameters governing the catalytic properties of the metal nanoparticles. Since the
catalyst is one essential key in the CCVD process, improving it should improve
the quality of the obtained CNTs. In Section 2, we will see what are the principal
methods used to prepare catalyst nanoparticles. As will be discussed in Section 5,
there is certainly a correlation between the size of the nanoparticles and the diameter
of the resulting CNTs. The preparation method therefore must fulll strong requirements on the geometry of the nanoparticles. In Section 3, a synthesis is given of what
is known about CNT growth mechanisms. In Section 4, we review the results obtained on most of the catalysts used in the last decade for CNT growth. They are
principally based on iron, cobalt and nickel. We then try in Section 5 to discuss
the results found in the literature in order to determine what are the important
parameters of the catalyst on which the results of CNT growth depend.
2. Preparation methods
It has been found that transition metals such as iron, cobalt and nickel are catalysts for the growth of CNT. However, bulk iron as itself, for example, is not able to
catalyze the decomposition of methane to form carbon laments: it has to be rst
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dispersed [15]. In order to obtain nanotubes, one therefore has to nd methods to

prepare catalyst nanoparticles.
2.1. Solgel
In the heterogeneous solgel method, a porous precursor of the active component is
impregnated with the precursor of a textural promoter taken in the estimated amount
to have a given weight ratio between active component and textural promoter in the
end product. The role of the textural promoter is to stabilize the active component
structure and to prevent its sintering in the course of posttreatments [15]. One generally uses hard-to-reduce oxides (HRO) such as silica or alumina as textural promoters.
To get iron/silica nanocomposite particles, one can mix e.g. tetraethoxysilane
(precursor of textural promoter) with iron nitrate (precursor of the active component) aqueous solution and ethanol. The mixture is then gelated, dried to remove
the excess water and solvent and nally calcinated [16].
2.2. Coreduction of precursors
Nitrates of a catalyst and of a metal oxide support, e.g. Co- or Ni(NO3)2 6H2O
and Mg(NO3)2 6H2O, are mixed with an organic compounds like urea or citric acid
and water [1719]. Heating the mixture leads to reduction of the precursors to form
intimately mixed oxide particles.
2.3. Impregnation, incubation
The impregnation method consists in rst dissolving a catalyst precursor (e.g. ironoxalate [20]) and then contacting a support with this solution. In this method, the
whole precursor deposits onto or into (in case of a porous material) the substrate.
The solvent is then evaporated and the catalyst dried [21].
In a case of organic supports and molecules, one speaks about incubation [22], but
the method remains the same.
2.4. Ion-exchangeprecipitation
In this preparation method, a solution of a catalyst precursor (e.g. cobalt-acetate
[23] or cobalt-nitrate [20]) is also used and brought in contact with a zeolite support.
But in this case, the anion of the precursor is exchanged with an anion of the zeolite,
giving a new precursor molecule. Calcination allows the thermal decomposition of
the catalyst precursor and gives the catalyst element in an oxidized form.
2.5. Ion-adsorptionprecipitation
In the ion-adsorptionprecipitation method, the support is put in a catalyst precursor solution (e.g. Co(H3CCO2)2 4H2O [24]). An acidbase reaction takes place
at the surface of the support, leading to precipitation of the catalyst precursor (co-
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baltacetate in the example above). The reaction can be controlled by the pH of the
initial catalyst precursor solution. The sample is then calcinated to get only the catalyst element in an oxidized form.
2.6. Reverse micelle method
In the reverse micelle method, a cationic surfactant is dissolved, e.g. in toluene.
First metal salt is added to the solution and afterwards a reductor agent in order
to reduce the oxidized metal to its neutral form. It results in a colloidal dispersion
of metal nanoparticles [25]. The nanoparticles are then puried and the nal dispersion can be cast onto a substrate and dried at room temperature.
2.7. Thermal decomposition of carbonyl complexes
Metal can be synthesized in form of nanoclusters by thermal decomposition of its
carbonyl complex. The procedure consists in mixing the carbonyl complex in an ether
solution and adding protective agents to prevent the nanoparticles from aggregation
(e.g. octanoic acid [26]). The solution is then reuxed at a temperature allowing the
decomposition of the precursor (e.g. 286 C [27]). In [27], Cheung et al. reported
the obtention of nanocluster solutions with distinct and nearly monodisperse diameters of 3.2, 9 and 12.6 nm for three dierent protective agents used, respectively.
2.8. Metalorganic chemical vapor deposition (MOCVD)
A metalorganic precursor (e.g. iron pentacarbonyl [21]) is vaporized and carried
to the reactor zone by a carrier gas. Heating of the reactor zone allows the precursor
to decompose and to depose onto the substrate.
2.9. Physical deposition
Metal can be evaporated or sputtered to be deposited onto a substrate. The metal,
if deposited at room temperature, will generally be amorphous and form a more or
less smooth lm on the surface of the substrate. Upon annealing, the equilibrium
shape may be reached. To know this shape, the Youngs equation describing a contact between two phases A and B and the ambient atmosphere has to be considered:
cA cAB cB cos h
with c the corresponding interface energies, see Fig. 3. The physical deposition of B
on a substrate A is largely used for epitaxy of B on A when the following condition
yielding layer growth (h = 0) is fullled [28]:
cB cAB < cA
When Eq. (2) is not satised, B deposits on A in the form of islands (VolmerWeber
growth) as shown in I and II of Fig. 3.
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Fig. 3. Conditions on the surface energies of substrate (A), deposit (B) and interface AB in determining
the type of growth: island or VolmerWeber growth for I (non-wetting) and II (wetting) and layer-growth
for III.
The property of island growth is required for obtaining nanoparticles on a substrate by physical deposition. After deposition usually performed at room temperature, annealing allows the atoms to move and reach the energetical most favored
conguration. This method has been used to obtain nanoparticles of nickel, cobalt,
iron or alloys of them to grow CNT. It has been found that the size of the particles
(typically 10100 nm) directly depends on the thickness of the deposited material
[2932]. For breaking up the thin lm obtained after deposition, many authors reported the use of NH3 [29,3335] or H2 [36] during annealing. The surface energies
cA and cB used above are dened relative to the atmosphere gas and thus a change in
the gas can dramatically change the nal shape of B on A.
3. Models of catalytic growth

This review focuses on the catalytic growth of CNTs by CVD. The growth process
may be quite dierent in the CVD process compared with the arc discharge and
laser-ablation methods and we shall not discuss the possible dierences here. Because
of the analogy between CNTs grown by CVD on a supported catalyst and carbon
laments grown also by CVD on a supported catalyst, we will rst discuss the
growth model for carbon laments.
The carbon lament growth model generally adopted is based on the concepts of
the VLS (vaporliquidsolid) theory developed by Wagner and Ellis [37]. In this
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model, molecular decomposition and carbon solution are assumed to occur at one
side of the catalytic particle, which then becomes supersaturated [1]. Carbon diuses
from the side where it has been decomposed to another side where it is precipitated
from solution [38]. It is not clear at this point of the model which is the driving force
for carbon diusion within the catalytic particle. For many authors, this force originates from the temperature gradient created in the particle by exothermic decomposition of the hydrocarbon at the exposed front faces and endothermic deposition of
carbon at the rear faces, which are initially in contact with the support face [38,39].
Others ascribed the driving force to a concentration gradient [1,40]. However, because of a much lower surface energy of the basal planes of the graphite compared
with the prismatic planes, it is energetically favorable for the lament to precipitate
with the basal planes as the cylindrical planes [1]. The metalsupport interactions are
found to play a determinant role for the growth mechanism [38,41]. Weak interactions yield tip-growth mode whereas strong interactions lead to base-growth. Both
growth modes are schematically shown in Fig. 4.
This growth model for carbon laments has been widely used for carbon nanotubes. However, the specicity of the growth of nanotubes on nanoparticles with regard to the growth of carbon laments is their nanometer dimensions. The energetic
argument of the precipitation of carbon on its low-energy basal planes is for example
no longer valid since the curving of the graphite layers introduces an extra elastic
term into the free-energy equation of nucleation and growth, leading to a lower limit
of about 10 nm [1]. Other mechanisms are therefore necessary to explain the growth
of CNTs, whose diameter can be much smaller than this lower size limit [42]. In the
catalytic growth of CNTs, not the uid nature of the metal particle as in the VLS
model has to be considered but the chemical interactions between the transition metal 3d electrons and the p carbon electrons [43]. Nanoparticles exhibit a very high
Fig. 4. The two growth modes of lamentous carbon.
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surface energy per atom. The carbon in excess present during CVD process could
solve this energetic problem by assembling a graphene cap on the particle surface
with its edges strongly chemisorbed to the metal. Since the basal planes of graphite
has an extremely low surface energy, the total surface energy diminishes. This is the
Yarmulke mechanism proposed by Dai et al. [44]. The hemifullerene cap so formed
on the partially carbon-coated particle lifts o and additional carbon atoms are continuously added to the edge of the cap, forming a hollow tube with constant diameter
which grows away from the particle [45]. The driving force for the lifting process is
believed to originate from the free energy release due to relaxation of the strain built
up in the carbon cap around the spherical surface of the catalyst nanoparticle when
carbon fragments assemble to form a CNT [46,47].
Growth of SWNTs in the arc-discharge and laser-ablation methods has been already widely discussed from a theoretical point of view. Molecular dynamics and total
energy calculations revealed the basic atomic process by which single-shelled nanotubes can grow out of metal-carbide particles by the root growth mechanism [48]. In
contrast, almost no theoretical work could be found on the CCVD growth of CNTs
until the recent publication of Shibuta and Maruyama [49]. The authors performed
molecular dynamics simulation of SWNT growth by CCVD and showed that carbon
atoms are absorbed into the metal cluster until saturation to make a hexagonal network of carbon atoms inside the surface of the cluster. Further supply of carbon then
leads to a separation of the carbon network from the metal surface itself. Furthermore,
carbon atoms inside the supersaturated nickel cluster gradually lift up the carbon-shell.
This described process can be regarded as an initial stage of the growth process of
SWNT and at any rate conrms the Yarmulke mechanism proposed by Dai et al. [44].
A recent paper from Helveg et al. [50] deals with a high-resolution in situ transmission electron microscope observation of catalytic tip-growth of CNTs by decomposition of methane over a nickel-based catalyst. The nickel particles are observed rst
to elongate with simultaneous formation of graphene sheets with their basal planes oriented parallel to the nickel surface. A contraction follows, explained by the fact that the
increase in the nickel surface energy can no longer be compensated for by the energy
gained when binding the graphitic tube to the nickel surface. This study furthermore
reveals that monoatomic steps are present at the nickel surface and that a graphene
sheet terminates at each of these steps. Between a pair of such step edges, an additional
graphene layer grows as the nickel steps move towards the ends of the nickel cluster and
vanish, involving transport of carbon atoms towards and nickel atoms away from the
graphenenickel interface. Note that this proposed growth process, conrmed with
density-functional theory calculations performed by the authors, concerns a tip-growth
mechanism. It therefore is not really surprising that it clearly diers from the Yarmulke
mechanism presented above, valid for base-growth processes.
4. Catalysts used for CNT growth

Metals used to catalyze CNT formation are most often transition metals, in particular iron, cobalt and nickel. A very large number of papers can be found in the
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literature reporting CNT growth. We will cite a few of them in the following, according to the catalyst used, so that the reader can have a short and quick overview of the
general results obtained, especially as regards MWNTs and SWNTs.
Most of the papers available in the literature about growth of CNTs on ironbased catalysts report growth of MWNTs [1216,20,21,23,24,33,36,5162]. Many
groups also obtained SWNTs [10,22,27,45,6368]. Most of the reported results obtained with cobalt-based catalysts concern formation of MWNTs [20,23
25,34,56,57,6974], a few others SWNTs [68,7577]. Nickel-based catalysts generally
lead to MWNTs [20,3032,57,7888], seldom to SWNTs [47,76,77]. Mixtures of
transition metals are often observed to be more ecient for CNT production than
one metal alone. Iron-nickel alloys are found to produce MWNTs [8991], iron
cobalt alloys seem to produce rather SWNTs [9296] and Dai et al. obtained SWNTs
with a nickelcobalt alloy [44]. Other authors studied several alloy catalysts and
mainly obtained SWNTs [12,76,77,97,98]. Palladium seems to be an interesting metal
for connecting carbon nanotubes since the contact between this metal and metallic
CNTs is ohmic in nature [99]. The catalyst nanoparticle would therefore not disturb
the electronic transport properties of the nanotube by forming a Schottky barrier.
Nevertheless, palladium has been used a little as a catalyst for CNT formation, as
described in [100102]. These three papers report growth of MWNTs. Other metals
than iron, cobalt, nickel or palladium have been used as cocatalyst. These metals are
generally but not necessarily non-active catalysts alone but at any rate are used to
improve the performance of the classical catalysts when added to them in dierent
quantities. Molybdenum is the most important, added to iron [26,41,103111] or to
cobalt [29,112121]. Except for in [119], all these papers report formation of SWNTs
with ironmolybdenum or cobaltmolybdenum catalysts. Magnesiumnickel oxides
have been used as catalysts for MWNT growth [17,122,123] and magnesiumcobalt
oxides for SWNT growth [124,125,121].
5. Parameters determining the catalytic properties

The peculiar ability of transition metals such as iron, cobalt and nickel to catalyze
CNT formation is mostly linked to their catalytic activity for the decomposition of
carbon compounds, their ability to form carbides and the possibility for carbon to
diuse through and over the metals extremely rapidly ([126] and references therein).
Is this sucient to explain their performances in CNT growth? In this section, we
want to analyze the experimental results found in the literature in order to track
down the inuence of ve aspects of the catalyst nanoparticles on the results obtained by CNT growth, namely: their composition, their morphology, their preparation method, their support and their pretreatment.
5.1. Composition
As seen in Section 4, the three usual catalysts for CNT synthesis are iron, cobalt
and nickel, all of them 3d-metals. If they all catalyze CNT growth reaction, they do
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not yield exactly the same results. In this section, we will rst summarize some of the
results found in the literature where dierent catalysts were directly compared. We
will then discuss the inuence of the composition nature of the catalyst on three
important properties for the catalyst activity: electronic structure, carbon solubility
and stabilization of the catalyst material.
5.1.1. Experimental comparison of dierent catalysts
Klinke et al. tested iron-, cobalt- and nickel-based catalyst on silica for CNT
growth with acetylene. Iron produced the highest density of carbon structures at
any considered temperature between 580 and 1000 C [57]. Hernadi et al. tested ironand cobalt-based catalysts with dierent hydrocarbons on dierent supports and observed that iron/silica presents the highest activity in the decomposition of dierent
unsaturated compounds [56]. Kong et al. came to the same conclusion [97]. However, an improvement of the quality of the CNT was obtained on silica by using cobalt [56]. The observations of Fonseca et al. [24] summarize the aforementioned
results: iron is more active than cobalt but the quality of the resulting CNTs, in terms
of graphitization and structure, is less good with iron. Ivanov et al. also observed a
better graphitization on cobalt than on iron, but on nickel most of the laments were
amorphous [20]. They also tried with copper but found only amorphous carbon. The
large majority of groups working with nickel-based catalyst interestingly reports
growth of MWNTs, many of them with bamboo structure, or bers.
In [13], iron-based catalysts prepared by the solgel method with dierent iron
contents were tested. The authors found out that MWNTs were obtained with
acetylene for all tested catalysts but in dierent quantities and above all the type
of the carbonaceous products strongly depends on the iron quantity in the catalyst.
A catalyst with only 2.3 wt% iron exhibits MWNTs in only very small amounts.
Increasing the iron amount to 4.4 wt% increases the amount of CNTs observed.
For both catalysts, no bers or carbon encapsulation are observed. Conversely,
the catalyst with 8 wt% iron yields a large amount of amorphous carbon besides
CNT. This is even worse for the 28.5 wt% iron containing catalyst with which
coiled structures, carbon nanobers and carbon encapsulated particles were also
observed.
Mixtures of two metals as catalyst had already been observed to dramatically
change the catalyst performances for carbon lament growth ([38] and references
therein). The same is observed for CNT growth when two of the transition metals
iron, cobalt and nickel are mixed [76,127] or when another metal is added to one
of them [29,41,107,115,116,128]. Mixing of two or more metals yields improvement
of the catalyst performance in terms of quality of obtained product or of lowering of
reaction temperature. Platinum, palladium and chromium were e.g. added to a cobaltnickel catalyst in order to lower the growth temperature from 7001000 C to
500550 C (with dierent success rates) [127]. Harutyunyan et al. [107] found that
unreduced iron was active for CNT growth only from 900 C whereas it becomes active even at 680 C with addition of 20% molybdenum. Terbium, in combination
with iron, is shown to improve the uniformity and purity of the MWNTs obtained
by pyrolysis of xylene [128].
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5.1.2. Electronic structure

The rst action of the catalyst is to bond the hydrocarbon molecules at its surface.
The hydrocarbon, now in an adsorbate state, interacts with the catalyst by transferring an amount of its electron density to the catalyst. This electronic interaction between a donor adsorbate and an acceptor catalyst metal is schematically
illustrated in Fig. 5. Generally, simultaneous back-donation takes place, i.e. electron
transfer from the catalyst to the non-occupied, antibonding orbitals of the adsorbate
molecule. The electronic structure of the adsorbate is then changed in such a manner
that dissociation of the molecule can occur. The transition metals have non-lled d
shells and are for that reason able to interact with hydrocarbons and show catalytic
activity. More precisely, properties contributing to the ability to make and break
adsorbate bonds are: (i) the center of the d-bands, (ii) the degree of lling of the
d-bands and (iii) the coupling matrix element between the adsorbate states and the
metal d-states [129]. Therefore, the ability of a metal to catalyze dissociation of a
hydrocarbon molecule is intimely linked to its electronic structure. This can explain
why iron is found to be more ecient than nickel and cobalt by hydrocarbon decomposition [24,56,57,97]. Some papers also exemplify that an added component can
lower the activation energy for dissociation, and thus the growth temperature, by
changing the electronic structure of the catalyst [107,127]. Nevertheless, it is not clear
whether dierences in electronic structure between dierent catalyst materials can account for the observed dierences in the quality of MWNT in terms of graphitization. Copper, a non-transition metal with its 3d shell completely lled, was
Fig. 5. Schematic illustration of electronic interactions in chemisorption. A lled orbital on the adsorbate
overlaps with an empty one on the metal. For the sake of clarity, discrete levels of the metal are
represented rather than electron bands.
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observed to yield only amorphous carbon [20]. In addition, the growth model presented in Section 3 supposes formation of a carbon cap on the metal particle with
its edges strongly chemisorbed to the metal particle [44]. One may therefore speculate
that overlap of metal 3d empty orbitals with carbon valence orbitals plays not only a
role in the hydrocarbon dissociation process, but also an essential part in the initial
stage of the CNT growth process, since it allows chemisorption of the carbon cap
edges to the catalyst nanoparticle. Besides, Kim et al. studied the formation of carbon lament structures on coppernickel catalysts and found that the wetting behavior of the metal on graphite is extremely sensitive to the chemical nature of the
particles [130]. Kim et al. namely supposed that metals that readily wet graphite will
produce highly ordered carbon lament structures. As seen in Section 2.9, wetting
behavior depends on the relevant interfacial energies. Roughly, two materials will
wet if their interfacial energy is low, in other words, if they exhibit high interactions.
These interactions can originate e.g. from Van der Waals forces but also from overlap of orbitals (chemisorption). One sees that both aspects just discussed may combine. However, it should be further investigated if and how the unlled 3d-metal
orbitals have an eect on the growth process and thus on the graphitization of the
whole CNT.
5.1.3. Carbon solubility
The nite solubility for carbon of 3d-metals in certain temperature ranges [131]
may play an important part in the growth process, since, once the hydrocarbon molecules are broken, carbon atoms are believed to diuse into the catalyst particle,
leading to supersaturation of carbon in the metal, as explained in Section 3. This
process can eventually yield formation of carbides. The role of solubility of carbon
in the metal catalyst is subject to controversy in the literature. Kock et al. e.g.
claimed that high carbide contents are required before nucleation of carbon laments proceeds [132]. Fe3C has been detected during CNT growth process on iron
nanoparticles and it was suggested that it may be the real catalyst [13,15,133]. However, Herreyre et al. [134] studied the evolution of iron catalysts during disproportionation of CO. They indeed detected formation of Fe3C but identied this phase
as the only one present when the catalyst was entirely deactivated. They therefore
attributed this phase to the cause of catalyst poisoning. Yoshida et al. [135] and Arie
et al. [136] also identied the catalyst particle at the end of nanotubes to be Fe3C and
Ni3C, starting from an iron and nickel catalyst, respectively. Hernadi et al. moreover
tested Fe3C nanoparticles and could not observe any catalytic activity [55]. This last
result does not seem to us a paradox since the formation of a metal carbide probably
is an intermediate step in the whole growth process. In the VLS growth model,
hydrocarbon dissociates to lead to formation of a metal carbide. This dissociation
process requires a catalyst that is the metal. The next step of the growth process is
carbon diusion within the nanoparticle, followed by precipitation and CNT
growth. If the driving force for carbon diusion is a concentration gradient within
the nanoparticle, the composition of the nanoparticle cannot be homogeneous,
otherwise the catalyst would not be active anymore. This corresponds to the observations of catalyst poisoning mentioned above and reported in [134136]. Note that
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the yarmulke mechanism proposed for SWNT growth does not inevitably imply carbon diusion into the metal nanoparticle and thus carbide formation.
5.1.4. Stabilization of the catalyst
Whereas molybdenum alone is completely inactive for CNT growth and cobalt
alone is unselective (i.e. yields formation of both SWNTs and MWNTs and eventually other carbonaceous deposits), molybdenumcobalt alloys are found to be good
catalysts for SWNT formation [114]. Liao et al. [119] also studied the composition of
cobaltmolybdenum nanoparticles and its inuence on the carbon morphology.
They found that particles with 515 at.% cobalt tend to produce long CNTs, those
with 4045 at.% cobalt tend to produce short CNTs, and those with 8598 at.% cobalt tend to produce onionated morphology.
The functioning of cobaltmolybdenum catalysts for SWNT formation has been
quite well understood: cobalt is the real catalyst and molybdenum stabilizes Co2+
ions. Indeed, when cobalt is not interacting with molybdenum, it sinters in the reduced state and forms large metal aggregates, which generate defective MWNTs, laments and graphite nanobers. In the presence of molybdenum, Co2+ ions are
embedded in a molybdate-like environment. The cobalt ions, the actual catalysts,
are stabilized in that geometry since the so formed complex remains unchanged during the reduction step at high temperature. When CO is introduced into the reaction
chamber, the molybdate dissociates to form molybdenum carbide, thus liberating the
cobalt ions which can then catalyze SWNT formation because of the still small size
of the newly formed cobalt particles [114,116]. Liao et al. [119] moreover explained
the observed trends with dierent compositions of cobaltmolybdenum nanoparticles by directly relating the CO decomposition activity to the cobalt content. The cobalt content therefore determines which step between CO decomposition and carbon
diusion is rate-limiting and thus the type of carbon deposit. Note, however, that
Lan et al. succeeded in synthesizing bundles of SWNTs by disproportionation of
CO on pure cobalt catalysts [137]. This result shows how important is the role played
by the process conditions as a whole.
Not only molybdenum has been used as non-transition metal additive to a usual
transition metal catalyst (iron, cobalt, nickel) but also e.g. magnesium. The few
authors who studied magnesium- and cobalt- or nickel-based catalyst all reported
formation of a solid solution of type Ni(or Co)xMg1xO. The Ni2+ in the solid solution are found to be highly dispersed (hostdopant type) and thus dicult to reduce
completely (valence stabilization by MgO crystal-eld) to Ni0, which constitute the
active sites. Deep reduction of nickel is therefore inhibited in NixMg1xO and thus
the aggregation of the Ni0 to form large particles [17,122]. Flahaut et al. [125] used a
CoxMg1xO catalyst with small amount of cobalt and no reduction treatment before
growth and obtained SWNTs. They put forward kinetic arguments to explain their
results, assuming that the low cobalt content is favorable for SWNT growth as it is
equivalent to slow carbon decomposition rate.
Concerning the mixture of two catalysts, Pinheiro and Gadelle [138] performed a
thermodynamic study of the chemical state of a supported ironcobalt catalyst during CO disproportionation. They showed that the stability of the catalyst and thus
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the progress of the disproportionation reaction directly depends on the composition

of the catalyst alloy. The most stable alloy is found to be that with roughly 50 wt%
Co. More iron leads to formation of Fe3C or Fe3O4 and more cobalt to Co2C when
contacted with COCO2 mixtures.
5.1.5. Conclusion
The ability of a catalyst metal to dissociate hydrocarbon or CO molecules is
linked to its electronic structure. Overlap of non-lled 3d-orbitals with carbon orbitals can favor the dissociation process. It should be further investigated if interactions between metal 3d and carbon orbitals could also have an eect on the
further growth process.
The carbon solubility of the catalyst material might be an important factor since
carbon is believed to diuse through the catalyst nanoparticle during the growth process (see Section 3). From the experimental results, it seems obvious that Fe3C forms
during CNT growth on iron particles but its actual role in the catalysis process remains unclear.
Addition of other components to or mixture of transition metals generally exhibits better results in terms of catalytic activity and CNT quality. This can be explained
rst by changes in the electronic structure, which can e.g. yield a lower activation energy and thus a lower growth temperature. Second, catalysts composed of several
components can form either stable complexes or solid solutions which remain in
the form of small nanoparticles until the beginning of the growth process or stable
alloys, preventing then formation of species leading to a change of the catalytic
behavior. The stabilization of the catalyst in small-scale particles seems to be crucial
since large catalyst particles are found to be inactive for CNT growth. The relation
between CNT growth and size of the catalyst nanoparticle will be treated in the next
section.
5.2. Morphology
As mentioned in the introduction of Section 2, the catalyst is able to catalyze the
formation of CNTs only if it is in the form of particles. We want here to discuss the
eect of the size and crystallographic orientation of the nanoparticles on the growth
process.
5.2.1. Size
There is a consensus in the literature concerning the correlation between the size
of the catalyst nanoparticles and the CNT diameter. Indeed, many groups observed a
direct dependence of the two quantities [20,22,27,29,44,67,77,88,96]. When the nanoparticles are prepared in holes or pores, the diameter of the former is subjected to the
size of the latter and thus the resulting CNTs have a diameter roughly equal to the
diameter of hole or pore [52,71]. Nikolaev et al. stated that the particle size after
CNT growth is larger than the CNT diameter, suggesting that particles continue
to grow even after nucleating a tube [45]. The relevant size of the nanoparticles
for the resulting diameter of the CNTs is thus their size at the time of nucleation.
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Fig. 6. Transmission electron microscopy image of SWNTs produced by decomposition of CO on a

molybdenumcobalt catalyst. The size correlation between catalyst nanoparticle and CNT is clearly
shown. Reprinted with permission from [118]. Copyright (2002) American Institute of Physics.
Fig. 6 shows a transmission electron microscopy image obtained by Lan et al. [118]
who produced SWNTs by decomposition of CO at 700 C on an opal matrix embedded with molybdenumcobalt catalyst. The correlation between the size of the catalyst nanoparticle and the nanotube is here clearly seen.
Dai et al. noticed that larger particles always appear to be onionated and so are
inactive for catalysis of CNTs [44]. Formation of non-selective forms of carbon was
also observed by Perez-Cabero et al. with the ironsilica catalysts with higher iron
content [13]. They explained this result by the fact that the degree to which metallic
iron aggregates upon reduction into metallic particles depends on the iron content.
Thus catalysts with higher iron content exhibit larger metallic iron particles, leading
to other forms of carbon than nanotubes. Large particles therefore appear to be unable to catalyze CNT growth. What are the arguments found in the literature to explain this result?
First of all, since the catalyst particles used in CNT formation are of the nanometer range, there may be a size eect contributing to their catalytic properties. For a
particle size smaller than 5 nm, the number of atoms in low-coordinated positions is
greater than 10% of the total [139]. This may modicate the electron density of the
nanoparticle material or stabilize unusual faces or sites on the surface of the aggregates [140]. Both will change the surface electronic structure, what can in turn aect
the catalysis process, as discussed in Section 5.1.2. Furthermore, as seen in Section 3,
the Yarmulke mechanism is valid only for very small nanoparticles, which exhibit a
very high surface energy per atom. On the other hand, Hafner et al. supposed that
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supply-limited growth allows more time to anneal to the lowest-energy structure so

that smaller particles produce CNTs while larger particles are encapsulated [106].
This kinetic argument is closely akin to the one invoked by Flahaut et al. [125] to
explain formation of SWNTs with CoxMg1xO catalyst containing small amount
of Co (see Section 5.1.4).
5.2.2. Crystallographic orientation
Beyond the size of the catalyst nanoparticles, another morphologic parameter
might play a part in the catalytic growth process: the crystallographic orientation
of the supported nanoparticles. Audier et al. studied the crystallographic characteristics of the catalyst particles at the end of carbon laments (top-growth) [141]. Their
study yields a correlation between the particle orientation and the tube axis. More
recently, Ermakova et al. claimed that hydrocarbon decomposition on nickel occurs
on dierent edges of the nanoparticle due to anisotropy of nickel and that the lament axis is found to be parallel to the nickel (1 1 1) planes [15]. The theoretical work
of Shibuta et al. indicates strong interaction between the hexagonal carbon network
formed in the rst stage of the growth process and the structure of catalytic metal
atoms [49]. The crystal orientation may thus play a critical role in the determination
of chirality. Similarly, Vinciguerra et al. showed that the (1, 1, 0) plane of iron (bbc)
and the (1, 1, 1) planes of cobalt and nickel (fcc) have the appropriate symmetry and
distances to overlap with the lattice of graphene sheet [46]. It should be emphasized
that these considerations about the eect of crystallographic orientation of catalyst
nanoparticles on growth of CNTs make sense only if the nanoparticle remains solid
during the growth process.
5.2.3. Conclusion
The size of the catalyst nanoparticles seems to be the determining factor for the
diameter of the CNT grown on it. Beyond this size correlation, only small nanoparticles are able to catalyze formation of CNT. This can be explained on the one hand
by the fact that such very small nanoparticles can exhibit peculiar electronic properties (and thus catalytic properties as shown in Section 5.1.2) due to the unusual high
ratio surface atom/bulk atom. On the other hand with a growth mechanism implying
formation of a carbon cap on the nanoparticle surface to reduce its unusual high surface energy. Kinetic arguments are also invoked. Finally, the crystallographic orientation of the catalyst nanoparticle can be crucial for CNT growth.
5.3. Preparation method
As seen in Section 5.2, it is essential, in order to get CNTs of a given diameter, to
be rst able to produce nanoparticles with control over their sizes. The chosen method to get catalyst nanoparticles therefore has a rst inuence on the catalytic growth
process via the morphology of the obtained nanoparticles. Various preparation
methods of nanoparticles have been presented in Section 2 and as we shall see in
the following on the basis of few examples, they may yield dierent catalytic
properties.
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5.3.1. Morphology
5.3.1.1. Size. Li et al. [26] produced ironmolybdenum nanoparticles by thermal
decomposition of their carbonyl complexes in octyl ether solution under a nitrogen
atmosphere. They investigated the dependence of the particle size on the reactant
concentration, reaction time and molar ratio of metal carbonyl and protective
agents. By varying e.g. the reactant concentration and nature, the particle size
can decrease from 16 nm to about 4 nm, as shown in Fig. 7. In such a complex system, the size of the produced nanoparticles depends on many factors, including the
number of nuclei created, the total concentration of reactants and the eect of protective agents. All these factors inuence simultaneously the size of the obtained
products.
Vander Wal et al. compared the decomposition of a metal precursor (nitrate salt)
on a metal oxide surface with ferrouid, i.e. maghemite particles stabilized as a
water based suspension [142]. The morphology and size of the resulting nanotubes
or nanobers is much more uniform with the ferrouid. Keeping in mind that the
size of the nanotubes is directly dependent on the size of the catalyst particle, the
authors explained this result by considering that the morphology of the preformed
catalyst particle does not depend on the support. The size distribution of the particles will thus roughly remain the same on the support as in the solution. In contrast,
Fig. 7. Ironmolybdenum nanoparticles synthesized with dierent protective agents. A: 1 mmol of

octanoic acid. B: 2.5 mmol of octanoic acid. C: 1 mmol of octanoic acid and 1 mmol of bis(2ethylhexyl)amine. D: 1 mmol of bis(2-ethylhexyl)amine. E: 2.5 mmol of bis(2-ethylhexyl)amine. The scale
bars in all gures are 100 nm. Reprinted with permission from [26]. Copyright (2001) American Chemical
Society.
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the size of in situ prepared catalyst particles by decomposition of a precursor on a

support is determined by the physical structure of the support, in particular by its
void volume. Therefore, with in situ prepared catalyst particles, a further diculty
still remains, since the growth process implies high temperatures (5001200 C) and
therefore can yield sintering of the nanoparticles. Ago et al. [25] indeed obtained
well separated cobalt nanoparticles using the reverse micelle method. They found
a mean diameter of 4 nm for their nanoparticles. Nevertheless, the inner diameters
of the obtained MWNTs were ranging from 8 to 20 nm and the outer ones from 20
to 40 nm, suggesting that the as-prepared cobalt particles aggregate to form bigger
clusters.
5.3.1.2. Dispersion. Ivanov et al. noted a better dispersion of metal on SiO2 with precipitationion-exchange than with impregnation [20]. Cassel et al. [41] prepared iron
nanoparticles by impregnation of support materials in salt solutions. They compared
the use of Fe2(SO4)3 vs. Fe(NO3)3 on Al2O3 supports and claimed that catalysts obtained with Fe2(SO4)3 in aqueous solution was superior in the growth of SWNT.
They could probe the structures of catalyst materials and found dierent textural
properties between the Fe2(SO4)3 and Fe(NO3)3 derived catalysts, namely a larger
pore volume for the former. They explained this result rst by the strong interactions
existing in aqueous solution between sulfate ions and surface sites of alumina, which
allows the metal species to be uniformly dispersed and anchored on the alumina surface. And second, the decomposition of these highly dispersed and strongly anchored
sulfate species to Fe2O3 occurs at relative high temperature, leading to the generation
of the observed textural pores.
5.3.1.3. Trapping with porous support. These few examples illustrate the challenging
diculty associated with each preparation method to produce nanoparticles of small
enough size and well dispersed on the support surface in order to get CNTs with the
desired diameters. In the face of this diculty, a widely used way is to resort to porous supports. Hayashi et al., e.g. did not use zeolite as a template but to limit the size
and the structure of catalytic particles [64]. Fan et al. observed iron oxide nanoparticles to form with a narrow size distribution on porous silicon due to their strong
interaction with the support [54]. The idea is to trap the particles into the pores of
the substrate (e.g. zeolite, which is a highly porous material) and thus prevent them
agglomerating. This trapping by a zeolite support is schematically illustrated on Fig.
8 for both growth modes.
There are many ways to obtain porous supports. One possibility is to prepare
anodic aluminum oxide (AAO) by anodizing Al in various electrolyte solutions using
dc current [71]. By varying the anodizing conditions, one can control the density,
diameter and length of the pores of the substrate. One can also lithographically dene nanoholes [52]. The solgel method is based on the use of aerogel materials as
textural promoter, which exhibit high surface area and high porosity [109]. This
method ensures a highly homogeneous distribution of transition metal ions in the
gel. On this extremely porous support, the CNTs grow outward perpendicularly
and form an aligned CNT array [12,16,143].
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Fig. 8. Schematic image of growth of carbon nanotubes in which the catalyst nanoparticles (red balls) are
trapped into the pore of the zeolite support (brown base). Reprinted with permission from [64]. Copyright
(2003) American Chemical Society. (For interpretation of the references in color in this gure legend, the
reader is referred to the web version of this article.)
5.3.2. Electronic structure

Kukovecz et al. performed UVVIS measurements on cobalt, iron and nickel
incorporated into solgel SiO2TiO2 matrices [144]. They could show that the composition of the matrix and the calcination treatment have an eect on the detected
electronic transitions, i.e. on the valence shell electron structure of the bimetallic catalysts they tested. They moreover observed non-identiable bands which may result
from metalmetal electronic interactions. These interactions could be the explanation for dierent catalytic activity in producing CNTs between the dierent samples.
5.3.3. Other aspects
Besides the morphologic aspect, the preparation method of the nanoparticles may
play an important role in their catalytic properties. Hernadi et al. [23,55] found striking dierences in the properties of the catalyst depending on the preparation method.
So cobalt supported on Y prepared by ion exchange is found inactive for CNT formation whereas it exhibits high activity in the same growth conditions when prepared by impregnation [23]. Inversely, iron/silica is found to have better carbon
yield and to lead to more homogeneous CNT diameter distribution and less amorphous carbon when prepared by ion-adsorptionprecipitation compared to impregnation [55].
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Su et al. found out that a supercritical drying process is a crucial step in preparing
a catalyst by the solgel method [109]. They observed a weight gain varying from
roughly 5% to 200% as function of the drying process.
Wang and coauthors studied growth of CNTs with a nickel-iron catalyst prepared
whether by plasma of by conventional (chemical) way [91]. They observed the presence of encapsulated metal within the obtained CNTs when the catalyst had been
prepared by plasma and not otherwise.
Fonseca et al. studied the eect of the pH of the catalyst precursor solution on the
catalytic properties of the nanoparticles obtained by ion-adsorptionprecipitation
[24]. The authors reported quite dierent qualities of CNTs as function of the pH,
suggesting that the pH has an important inuence on the obtained nanoparticles
by the ion-adsorptionprecipitation method.
5.3.4. Conclusion
The preparation method of the catalyst nanoparticles is shown to have an inuence on their size and dispersion on the support surface and thus to their catalytic
properties. Porous supports are often used to get small nanoparticles with narrow
size distribution. The composition of the matrix into which the catalyst metal is
incorporated and the calcination treatment can have an eect on the electronic transition of the catalyst. Many authors observed dierent CNT growth results with the
same growth parameters and the same catalyst, but prepared by dierent ways. The
reported eects have not been understood yet. One can suppose that dierent preparation methods lead to dierent crystallographic orientations of the nanoparticles,
or that surface groups may form on the nanoparticle when prepared by a particular
method, yielding particular catalytic properties.
5.4. Support
Many of the publications cited in Section 4 reported results of CVD of CNTs on
non-supported catalysts. In these cases, the catalyst in the form of a powder is placed
in a quartz boat and then introduced into the reactor. In the case of supported catalysts, the interactions between the support and the catalyst nanoparticles have to be
taken into account. They might play an essential part in the whole growth process
since these interactions can alter all the other parameters treated in Section 5. Many
authors compared the results of CNT growth with the same catalyst but on dierent
supports. We shall in the following rst review some of these comparison results and
then try to elucidate the role of the support in the growth process.
5.4.1. Experimental comparison of dierent supports
In [55], dierent iron-based catalysts prepared by impregnation were tested. Iron
on graphite showed low activity and bad quality of CNT (bers) whereas iron on silica yielded the best results (Y and ZSM-5 were also tested). Su et al. observed better
results on Al2O3 than on SiO2 [109] and also a higher rate of SWNT with iron
molybdenum nanoparticles supported on an Al2O3 monolayer than with pure iron
nanoparticles [110]. Colomer et al. also got better results for catalyst nanoparticles
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supported on Al2O3 than on SiO2 [76]. Kukovecz et al. found nickel on alumina very
active (but not for CNT formation!) whereas nickel on silica is poorly active [12].
Willems et al. observed that cobaltmolybdenum exhibits better results on alumina
than on zeolite [96]. Kong et al. tested dierent catalysts on dierent substrates and
reported that CoO/alumina and NiOCoO/silica yield SWNTs whereas CoO/silica
and NiOCoO/alumina yield no SWNTs [97]. Vander Wal et al. tested copper, iron
and nickel on CaO, Al2O3, SiO2 and TiO2 and observed that nickel was most active
on TiO2, less active on SiO2 and Al2O3 and almost unreactive ib CaO. Copper was
found most active when supported on CaO and SiO2 and less on TiO2 and Al2O3.
Finally, CaO was the best support for iron and Al2O3 the worst.
These few results demonstrate that the couple catalyst/support has to be considered. The support has to be carefully chosen since, rst, intermediate indesirable
compounds can form and, second, the interactions between support and metal nanoparticles are found to be crucial for the catalytic properties of the latter.
5.4.2. Formation of intercompounds
The drawback posed by silicon substrates is the high propensity to interdiusion of
silicon and metal. Indeed, diusion of nickel catalyst into silicon substrate is observed
to occur at temperatures above 300 C [84]. Likewise, iron on silicon yields formation
of an iron silicide upon heating up to 850 C (temperature of CNT growth) [145]. The
problem can be circumvented by using a diusion barrier, generally SiO2 or TiN
[84,86,102]. Vajtai et al. stated that when deposited using a substrate voltage of
200 V, TiN is denser and more ecient as diusion barrier [102]. They could not
observe any chemical interaction between iron and TiN upon heating and obtained
much better results of CNT growth with TiN than with silicon. Use of silicon substrates for CNT growth can moreover lead to formation of SiC [102].
5.4.3. Supportcatalyst interactions
Interactions between a catalyst metal and its support can be physical or chemical.
A physical interaction is e.g. the size determination of a metal particle by its porous
support [142]. In contrast, chemical interactions involve charge transfer between the
support and the catalyst. This charge transfer can take place via dierent pathways,
e.g. via oxidation/reduction or acid/base (donor/acceptor) reactions. When the substrate is a metal oxide, oxidation/reduction reactions can occur by addition of neutral oxygen from the substrate to the metal particle. Acid/base interactions are linked
to the corresponding Lewis acid and base characters of the materials involved. In a
metal oxide substrate, surface anions act as Lewis base sites (electron pair donor)
and cations as Lewis acid sites (electron pair acceptor). Supportcatalyst interactions
can aect the electronic structure of the catalyst and have an eect on the dispersion
of the metal on the support.
5.4.3.1. Eect on electronic structure. Vander Wal et al. showed the importance of
electronic interactions between metal nanoparticle and support on the ability of
the metal to decompose adsorbate (hydrocarbons or CO in the case of CNT formation) [142]. Indeed, acquisition of negative charge by the metal catalyst from the sub-
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strate can enhance its catalytic activity by strengthening back-donation of electron

density into antibonding orbitals of the adsorbate. This electron sharing between catalyst and adsorbate suciently weakens the bonding within the adsorbate, resulting
in its dissociation. As seen above, the propensity to electron donation of a surface is
linked to its Lewis base character. The great catalytic activity of copper observed on
support media with strong Lewis base sites (CaO and SiO2) [142] exemplies this
phenomenon. Indeed, as mentioned in Section 5.1, the catalytic activity of a metal
is in a rst approximation inversely dependent on the lling of its d-band. Bulk copper should therefore be catalytically inactive since its d-shell is completely lled. Nevertheless, upon acquisition of partial negative charge from the support (that here acts
as a Lewis base), copper can donate negative charge to the adsorbate. In this view,
the catalyst particle acts as a conduit for transferring negative charge to the
adsorbate.
5.4.3.2. Eect on catalyst morphology. As shown in Eq. (1) of Section 2.9, the interactions between support surface and metal particle, expressed in terms of interface
energies, will determine the shape of the particle. Wright et al. compared the shape
of nickel nanoparticles on TiN and on MoSiO2 and found that nickel particles are
more spherical on MoSiO2 because of a weaker wetting on MoSiO2 than on TiN
[86]. Generally, one can assume that strong metalsupport interactions lead to a
good dispersion of the metal on the support surface. Many authors de facto ascribed
their better results obtained on Al2O3 compared to SiO2 to the stronger Lewis acidity
of the former support, yielding a better dispersion of the metal [109,76,41]. However,
too strong an interaction between catalyst and support yields strong wetting and prevents the formation of appropriately shaped catalyst particles for CNT growth [47].
Seidel et al. emphasized that the surface diusion rate of a specic atom on a substrate depends not only on the substrate nature but also on its roughness [47]. Delzeit
et al. also studied the role of the underlayer in the growth of CNTs [104]. They suggested that ion-beam sputtering of the underlayer increases its surface roughness,
thus providing more active nucleation sites. Surface roughness can therefore hinder
surface diusion of the catalyst and thus its coalescence into (too) large particles.
Interactions between metal particles and surface of course not only depend on the
support material but also on its surface orientation and on the metal as well. So
Hongo et al. observed a dependence of the SWNT yield with the face of their sapphire support whereas they could not obtain any SWNTs with silicon or SiO2
[65]. Su et al. obtained better results with ironmolybdenum nanoparticles on
Al2O3 than with pure iron ones, because the former more interact with the the
Al2O3 surface than the latter. One can moreover imagine that the support will also
have an impact on the crystallographic structure of nanoparticles, in particular on
their orientation, and thus inuence the morphology of the obtained nanotubes,
as seen in Section 5.2.
5.4.3.3. Eect during growth mechanism. The majority of authors working with nickel-based catalysts observed a tip-growth mechanism where the catalyst particle is detached from the support during CNT growth. This shows that nickel probably
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exhibits weak interactions with the most supports. This can have a bad inuence on
the quality of the nanotubes since bamboo structures are often observed with this
growth type.
As already mentioned in the previous section, many groups use porous supports
[13,53,54,100]. The porosity of the support may also have an eect on the CNT
growth itself, besides its function as particle trap. Indeed, CNTs were observed to
grow at a rate of about 50% faster on porous silicon than on plain silicon [54]. This
result might be explained by the porous structure of the support which makes it permeable to the ethylene molecules so that carbon feedstock reaches the catalyst at a
higher rate.
5.4.4. Conclusion
Interactions between catalyst and support are essential since they can aect the
electronic structure of the nanoparticles and their morphology and in turn their catalytic properties. Chemical interactions involve charge transfer between support and
catalyst. This charge transfer is roughly correlated to the Lewis base or acid character of the support. These catalyst-support interactions have to be strong to ensure
good dispersion of the catalyst on the support but not too strong since it then yields
strong wetting and will prevent formation of appropriately shaped catalyst particles
for CNT growth.
5.5. Pretreatment
The inuence of pretreatment of the catalyst nanoparticles on the following CNT
growth process has not been thoroughly studied until now. A few experimental data
can however be found in the literature. We will further discuss the role played by the
pretreatment.
5.5.1. Experimental results
Ago et al. observed that pretreatment with H2S gas straightens the MWNTs and
yields a wider range of outer diameter [25]. They wondered whether catalytic activity
of cobalt is reduced by sulfur, forming SCo. Ren et al. observed no CNT growth if
N2 is used instead of NH3, although the surface of the nickel layer after NH3 or N2
plasma etching seems to be essentially the same in terms of morphology [32]. They
further observed that when NH3 and C2H2 are introduced simultaneously, the obtained CNTs exhibit larger diameters, suggesting that the etching process and thus
the resulting particle size is dependent on the etching gas. Harutyunyan et al. tested
iron and ironmolybdenum nanoparticles for CNT growth with and without prereduction [107]. They claimed that both catalysts are active at 680 C in the reduced
state. In contrast, iron unreduced is found to be unactive at this temperature (becomes active only at 900 C) and ironmolybdenum unreduced is active at 680 C.
5.5.2. Role of pretreatment
5.5.2.1. Eect on electronic structure. Intuitively, one may think that pretreatment
will rst change the electronic state of the catalyst. Oxides are reduced to the metallic
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state which is a priori the actual catalyst. Nonetheless, Baker et al. found out that
FeO appears to be a much better catalyst than metallic iron for the formation of lamentary carbon and thus claimed that there was no reduction before to growth
[146]. Others, like Hernadi et al. [55], considered that reduction pretreatment of iron
oxide is not necessary since the hydrocarbon atmosphere is able to reduce the catalyst to the required extent under reaction conditions.
5.5.2.2. Eect on catalyst morphology. The second eect of pretreatment is on the
nanoparticle morphology. Heating the substrate allows atoms to diuse. The deposited particles then incur the risk of sintering and thus change their morphological
characteristics, such as their diameter and height. In the case of physical deposited
metal, an annealing step is essential to obtain nanoparticles. The right annealing time
must then be found in order to get nanoparticles of the right size: too small catalyst
clusters and isolated catalyst atoms poison the catalyst support surface and too large
particles are unable to catalyze CNT growth [47]. As mentioned in Section 2.9, the
atmosphere gas used by breaking up the lm may have a great inuence on the shape
of the obtained nanoparticles. Kanzow and Ding claimed that a hydrogen atmosphere generally leads to a much better wetting behavior. The contact angle of the
metal on the carbon substrate is shown to be strongly aected [39].
5.5.3. Conclusion
The pretreatment of the catalyst nanoparticles has the role of reducing the mostly
oxidized catalyst metal. For catalysts prepared by PVD, the pretreatment ensures
formation of nanoparticles and parameters such as type of gas, time and temperature
will then be essential to get nanoparticles with the right shape.
6. Conclusion
This review has shown the complexity of the role of the catalyst in the CCVD of
CNTs. We showed in Section 5.1 that mostly 3d-metals are used to catalyze formation of CNTs because of their ability to decompose hydrocarbons. However, they are
not all equivalent and, in particular, alloying them with each other or with other
non-transition metals dramatically changes (generally improves) their catalytic properties. For few cases discussed in Section 5.1, the role of the non-transition metal is
to disperse and to stabilize the catalyst metalso an eect on the geometric aspect.
On the other hand, eects of alloying two transition metals on e.g. the electronic
structure or the carbon solubility and diusion have still to be studied to explain
the observed improvement in the catalyst performances. Furthermore, overlap of
catalyst 3d-orbitals with carbon orbitals after hydrocarbon dissociation could be a
relevant parameter for the CNT growth process and should be investigated.
The link between the size of the catalyst nanoparticles and the diameter of the
CNTs and the consequently absolute necessity to prepare stable nanoparticles of
controlled size have been emphasized (Section 5.2). To meet this severe constraint
high-technological eorts have to be made. Though, other parameters concerning
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the catalyst morphology have an inuence on the growth process like the crystallographic orientation of the nanoparticles.
The preparation method of the catalyst particles also plays its part in the knotty
problem of the factors inuencing the catalytic properties of the metal nanoparticles.
Section 5.3 deals with this question and we show there that the choice of the preparation method determines the morphology of the obtained nanoparticles. We also
discussed the use of porous support to limit the size of the nanoparticles. But the
inuence of the preparation method is not limited to morphological eects and
can directly aect catalytic properties, even if this inuence has been little studied
and is not yet clear.
The problem is complex since, as pointed in Section 5.4, a given catalyst can yield
completely dierent results upon CCVD when supported on dierent materials. One
actually has to consider not the catalyst alone but the couple catalyst/support. The
interactions between catalyst and support are found to be essential. First, they partly
determine the morphology of the nanoparticles and, second, they also alter the electronic structure of the nanoparticles, thus altering their catalytic properties. These
interactions depend on both support and catalyst materials but also on their crystallographic orientations, on the surface roughness and porosity of the support.
Finally, pretreatment can be essential for activating the catalyst by reducing it to
its actual catalytic form (pure metal) or by forming nanoparticles in the case of catalysts prepared by PVD, as seen in Section 5.5.
One therefore realizes how challenging it is to control these numerous parameters
since they are all interdependent and have to be within the specic process window.
Moreover, we have considered here only parameters concerning the catalyst nanoparticles, which cannot alone explain whether CNTs will grow or not and how they
will grow. The catalytic process requires a hydrocarbon gas (or CO) coupled with a
supported catalyst in charge of its dissociation and the subsequent growth of the
CNT. Lee et al. compared dierent source gases with various catalysts and indicated
that the results of CNT growth depend on the gas used [147]. The couple catalyst/gas
or rather the trio support/catalyst/gas should be considered for a complete understanding of the growth process.
Other important factors inuence the kinetic and thermodynamic aspects of the
growth process, e.g. temperature, pressure, ow rate and reaction time. Many
authors explain their success in producing SWNTs by the very small size of their catalyst nanoparticles. However, the dierentiation between SWNT and MWNT
growth processes is not really clear and kinetic arguments are often invoked. Production of SWNTs is then explained by limitation of the carbon supply, which is believed to be the limiting growth step (and not carbon diusion through the
catalyst particle) [106].
Acknowledgements
We thank E. Rouvie`re, L. Jodin, M. Delaunay and R. Baptist for helping gather
relevant literature and for subsequent discussions, G. Maheut for her explanations
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concerning the chemical preparation methods and P. Gadelle and F. Triozon for
proofreading this document and helpful comments.
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Progress in Materials Science xxx (2005) xxxxxx

The catalyst in the CCVD of carbon

E-mail address: ac.dupuis@web.de

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

Fig. 1. Transmission electron microscope image of a multi-walled carbon nanotube [11].

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

Fig. 2. Schematic illustration of the CVD process.

dispersed [15]. In order to obtain nanotubes, one therefore has to nd methods to

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

3. Models of catalytic growth

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

Fig. 4. The two growth modes of lamentous carbon.

4. Catalysts used for CNT growth

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

5. Parameters determining the catalytic properties

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

5.1.2. Electronic structure

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

the progress of the disproportionation reaction directly depends on the composition

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

Fig. 6. Transmission electron microscopy image of SWNTs produced by decomposition of CO on a

supply-limited growth allows more time to anneal to the lowest-energy structure so

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

Fig. 7. Ironmolybdenum nanoparticles synthesized with dierent protective agents. A: 1 mmol of

the size of in situ prepared catalyst particles by decomposition of a precursor on a

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

5.3.2. Electronic structure

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

strate can enhance its catalytic activity by strengthening back-donation of electron

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

A.-C. Dupuis / Progress in Materials Science xxx (2005) xxxxxx

[120] Murakami Y, Miyauchi Y, Chiashi S, Maruyama S. Direct synthesis of high-quality single-walled

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