Applied Surface Science 254 (2008) 5390–5393

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Synthesis and characterization of vanadium nanoparticles on activated carbon

and their catalytic activity in thiophene hydrodesulphurization
Susana Pinto a,b, Lindora D’Ornelas b, Paulino Betancourt a,*
a
Centro de Catálisis, Petróleo y Petroquı´mica, Escuela de Quı´mica, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 40679, Venezuela
b
Centro de Quı´mica Organometálica y Macromolecular, Facultad de Ciencias, Universidad Central de Venezuela, AP, Caracas 47778, Venezuela

A R T I C L E I N F O A B S T R A C T

Article history: Vanadium nanoparticles (7 nm) stabilized on activated carbon were synthesized by the reduction of
Received 23 August 2007 VCl33THF with K[BEt3H]. This material was characterized by inductive coupled plasma-atomic emission
Received in revised form 18 February 2008 spectroscopy (ICP-AES), high-resolution transmission electron microscopy (HRTEM) and X-ray
Accepted 21 February 2008
photoelectron spectroscopy (XPS) analyses. The catalytic performance of the carbon-supported
Available online 6 March 2008
vanadium was studied using thiophene hydrodesulfurization (HDS) as model reaction at 300 8C and
P = 1 atm. The catalytic activity of the vanadium carbide phase on the activated carbon carrier was more
Keywords: significant than that of the reference catalysts, alumina supported NiMoS. The method proposed for the
Nanoparticles
synthesis of such a catalyst led to an excellent performance of the HDS process.
Vanadium carbide
ß 2008 Elsevier B.V. All rights reserved.
V 2 O3
Hydrodesulphurization

1. Introduction
Over the last decade, petroleum refining industry has been
facing important challenges because of the continuously decreas-
ing permissible amount of emissions, such as SOx, NOx and
aromatics from the combustion of fossil fuels. With the currently
used technology, the quality of fuels prescribed by the new
environmental regulations can be attained by the significant
modifications of refining operations. This may include a consider-
able increase in the amount of the consumption of H2 of the
conventional catalyst (e.g. sulphide CoMo or NiMo), and the
decrease of daily throughputs. At certain point, the additional cost
of these modifications can be offset by novel catalysts. An ideal
situation, which would require minimal modifications, involves
the use of a novel multi-functional catalyst, which could replace
conventional catalysts in the currently used reactors. In last
decade, efforts have been made to develop such catalysts for
hydroprocessing. Metal carbides have been identified as the
potential catalysts for such applications. Interstitial carbides of
early transition metals (groups IVB–VIB) are produced by
dissolving carbon atoms into the metal lattices. These carbide
materials have interesting physical and chemical properties, which
combine the characteristic properties of three different classes of
materials: covalent solids, ionic crystals, and transition metals. It
has been suggested that the introduction of carbon into the lattice
of the early transition metals results in an increase of the lattice
parameter. This leads to an increase in the d-electron density
providing that the same number of levels is retained [1]. Then, after
carburization, the early transition metals exhibit the noble metals-
like behavior. Because of their small atomic radius, carbon can nest
in the interstices of the lattice. Additionally, the research and
development of transition metal nanoparticles has received a lot of
attention in many areas of science. This interest is because
nanosized particles show different physical and chemical proper-
ties to those of the same materials in the bulk [2,3]. The main
reasons for these differences originate in the electronic properties
and in the very high ratio between superficial atoms and total
number of atoms in the particles found in these nanomaterials.
Inspired by these ideas, we designed a new method for
preparing carbon-supported vanadium nanopowder by means of
the reduction of the metal adduct VCl33THF with K[BEt3H] at room
temperature, obtaining a mixture of vanadium carbide and V2O3.
This was well confirmed by our experimental results. Compared
with conventional processes (high temperature), the reaction
conditions are much simpler, and the as-obtained vanadium
carbide nanopowder is the main phase and is well dispersed.
2. Experimental

All the reagents are commercially available and of analytical

* Corresponding author. Tel.: +58 212 6051649; fax: +58 212 6051220. grades and used without further purification. All operations were
E-mail address: pbetanco@strix.ciens.ucv.ve (P. Betancourt). carried out under argon atmosphere using Schlenk techniques [4].

0169-4332/$ – see front matter ß 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2008.02.100
 S. Pinto et al. / Applied Surface Science 254 (2008) 5390–5393
2.1. Catalyst preparation
The vanadium nanoparticles were synthesized following the
method established by Bönnemann [5]. A solution of K[BEt3H]
(1 M, 4,6 ml, 4,6 mmol) in tetrahydrofurane (THF) was added
dropwise to a suspension of VCl33THF (0.99 mmol) in THF at room
temperature during 2 h. After 2 h of constant stirring at room
temperature, a dark brown solution was obtained. The KCl formed
during the reaction was removed by filtration. The dark solution
obtained was added to an activated carbon/THF suspension. This
suspension was stirred for at least 24 h, and then dried under
vacuum during 24 h resulting in a black solid. Finally, the
nanometric solid product was exposed to air. No changes in
temperature were observed during synthesis process.
2.2. Characterization
2.2.1. Elemental analysis
Elemental analyses were performed by the Centro de Quı́mica
Analı́tica-UCV, Venezuela. The characterization by ICP-AES of the
obtained product show vanadium content of 0.64% in weight.
2.2.2. X-ray photoelectron spectroscopy studies
The XPS were recorded with a VG ESCALAB 220i-XL spectro-
meter equipped with Al source (Al Ka = 1486.6 eV). The analyzer
was operated in a constant pass energy mode (Epass = 30 eV) using
the electromagnetic mode for the lens. Energy correction was
performed by using the C1s level of carbon as a reference. The
deconvolutions of the XPS spectra were carried out using a XPS
Peak Fitting program Version 4.1.
2.2.3. X-ray diffraction measurements
XRD patterns of the samples were obtained using a Bruker D-8
Advance apparatus (Cu Ka radiation, l = 0.154178 nm, nickel filter)
operating at 35 kV and 30 mA.
2.2.4. Transmission electron microscopy
The morphologies and structures of the obtained product were
observed with a Hitachi H-800 high-resolution transmission
electron microscope at an accelerating voltage of 200 kV. The
diameters were measured directly for particles shaped approxi-
mately circular.
2.2.5. Tiophene hydrodesulfurization
The catalyst was evaluated for the HDS of thiophene at 300 8C,
P = 1 atm. Before the reaction, the materials were activated in situ
under H2/H2S flow for 1 h at 300 8C. A commercial HDS catalyst
(NiMoS/Al2O3; 3.1%Ni and 15%Mo; SSA = 200 m2 g1) was used as
reference catalyst.
The products were analyzed by gas chromatography (Varian
3700, FID), and the reaction rate was calculated according to the
equation R = FX/m, where R is the HDS rate (mmol g1 s1), F the
thiophene molar flow rate, X the thiophene conversion, and m is
the catalyst mass.
3. Results and discussion
The crystallinity of the as-synthesized V/carbon sample was
examined by X-ray diffraction (XRD). The XRD patterns of the
sample, having a low metal concentration (0.64 wt.%) exhibit
several peaks. The XRD pattern consists of peaks corresponding to
V2O3 (JCPDS 34–0187), VC1x (JCPDS 73–0476) and poorly
crystalline carbon. The characteristic peaks of the vanadium
carbide were not apparent because is masked by the support
phase. It is expected that only at high metal contents most peaks
become clearly outlined. VC1x belongs to space group Fm3m with
5391
a small amount of C vacancies, and the vacancies are randomly
distributed in the VC1x lattice [6]. The apparent carbon deficiency
observed for the air exposed solid, could be a consequence of the
presence of oxygen in the lattice [7].
The reactions between VCl3, K[BEt3H] and C may be written as
follows:
THF 3
VCl3  3THF þ 3K½BEt3 H!V0 þ 3BEt3 þ 3KCl þ H2 (1)
2
V0 þ ð1  xÞC ! VC1x (2)
V0 air V2 O3
! (3)
C C
The reaction between VCl3 and K[BEt3H] occurred first (Eq. (1)),
and after started the reaction between V0 and C, so VC1x was
synthesized. As a result of the reaction, the large heat of formation
of VC1x might have accelerated the propagation of the reaction.
Therefore, the reaction could be completed ‘‘easily’’. When this
system was exposed to air (molecular oxygen) probably a partial
oxidation occurs, according to Eq. (3). Martınez-Mendez et al. [8]
have proposed that due to the high reactivity of the THF stabilized
metallic nanoparticles of titanium, vanadium and niobium with
air, the surface analyses only showed the presence of the oxidized
species.
X-ray photoelectron spectroscopy (XPS) was used to investigate
the elemental composition of the V/carbon nanocrystals, and can
further provide evidence for the formation of vanadium carbide.
The XPS spectrum for the vanadium/carbon systems exposed to air
(Fig. 1) shows three different signals in the region for V2p3/2 with
binding energies at 516.6 eV, 515.3 eV and 513.4 eV (as shown in
Fig. 1), indicate the V2p3/2 species of VO2, V2O3 and V8C7 (or V4C3),
respectively [9]. The results agree well with the XPS spectrum of
O1s energy region for vanadium carbide (not shown). The XPS
spectrum of O1s energy region for vanadium carbide contains
three peaks. The peaks at 532.9 eV and 531.7 eV are considered to
be due to O and OH, respectively. These two kinds of oxygen
species are mainly originated from air. The O1s peak with the
binding energy of 530.3 eV is ascribed to V2O3. All assigned binding
energies agree well with the literature values [9,10].
The TEM analysis (micrograph, diffraction pattern and histo-
grams) for the V/carbon system is shown in Fig. 2. This material
shows a homogeneous dispersion on the support and has a sphere-
like morphology. The vanadium system shows nanoparticle sizes
ranging from 2 nm to 24 nm and a mean size of 7 nm (Fig. 3).
Fig. 1. XPS spectrum of V2p for the vanadium/carbon nanostructured system
exposed to air.
5392 S. Pinto et al. / Applied Surface Science 254 (2008) 5390–5393

Fig. 2. Micrography, histogram and ED pattern for as-obtained vanadium nanoparticles, obtained from the reduction of VCl33THF with K[BEt3H].

Distribution is somewhat broad and has a tail extended to particles
with larger size but they are minor in population. Electron
Diffraction (ED) pattern suggests that the powder is polycrystal-
line. The ED diffraction pattern exhibits dominant broad rings
characteristic of an amorphous phase but in addition, there are
other weak rings which are assigned to the vanadium carbide
structure.
Fig. 3 shows the hydrodesulphurization activity during
the run with thiophene. GC analyses showed that the
reaction products consisted of butanes and butenes. Catalyst
supported on the activated carbon is 2-fold times more active
in this reaction than commercial NiMo/Al2O3. The catalyst
showed a significant activity level for hydrogenation and
hydrogenolysis reactions; consequently, this was more selective
 S. Pinto et al. / Applied Surface Science 254 (2008) 5390–5393
Fig. 3. Catalytic activity of nanostructured V/carbon catalyst as a function of time, in
the HDS of tiophene at 300 8C, P = 1 atm.
toward the formation of n-butane and olefins from the HDS of
thiophene.
In general, the catalytic behavior of the unsupported single-
phase carbides is attributed mainly to their particular electronic
structure in which the carbon and nitrogen atoms occupying the
interstices should contribute to the unit cell parameter’s
expansion and add electrons to the d-orbitals, thus enhancing
the metallic character of the transition metal carbides. However,
the supported vanadium carbide is by far a more complex system
with respect to the unsupported single-phase counterparts, and,
at present, they have not been fully characterized. This complexity
increases if one considers the possible inclusion of oxygen atoms
inside the lattice, thus forming oxycarbides. Therefore, at this
point the present work is limited to the exploration of the catalytic
behavior with respect to thiophene HDS; however, the general
features of the catalysts such as the texture and crystallographic
structure are provided in order to search a correlation between
these data and further studies. In this regard, there is still room for
the activity improvement by the optimization of preparation
procedures, combining with additives and other metals, using
different supports, etc.
5393
4. Conclusions
Here, we report a new method to synthesize vanadium carbide
(VC1x) nanopowders at room temperature. Supported vanadium
has been synthesized by reduction of the VCl33THF and
characterized by MET, XRD, and XPS measurements. This model
compound has been tested for the HDS of thiophene in an
atmospheric pressure fixed bed reactor. Its activity has been
compared to that of a commercial NiMo/Al2O3 catalyst.
The results of DRX, TEM and XPS showed the presence of
vanadium oxidic species and vanadium carbide. TEM results
showed that the powders have a good dispersion and are mainly
composed of spherical particles with a mean diameter of 7 nm. In
the HDS of thiophene, the catalytic property of the V/carbon was
outstanding with respect to the reference catalysts based on NiMo/
Al2O3.
Acknowledgements
The authors gratefully acknowledge the financial support of this
work by the FONACIT (Project G-2005000450), Venezuela. We also
wish to thank the BID-FONACIT project QF10 and the Laboratorio
Nacional Analisis Quiımico (FONACIT) for the XPS analyses in the
person of A. Albornoz.
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