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 has been suggested that the introduction of carbon into the lattice
of the early transition metals results in an increase of the lattice
Over the last decade, petroleum refining industry has been parameter. This leads to an increase in the d-electron density
facing important challenges because of the continuously decreas- providing that the same number of levels is retained [1]. Then, after
ing permissible amount of emissions, such as SOx, NOx and carburization, the early transition metals exhibit the noble metals-
aromatics from the combustion of fossil fuels. With the currently like behavior. Because of their small atomic radius, carbon can nest
used technology, the quality of fuels prescribed by the new in the interstices of the lattice. Additionally, the research and
environmental regulations can be attained by the significant development of transition metal nanoparticles has received a lot of
modifications of refining operations. This may include a consider- attention in many areas of science. This interest is because
able increase in the amount of the consumption of H2 of the nanosized particles show different physical and chemical proper-
conventional catalyst (e.g. sulphide CoMo or NiMo), and the ties to those of the same materials in the bulk [2,3]. The main
decrease of daily throughputs. At certain point, the additional cost reasons for these differences originate in the electronic properties
of these modifications can be offset by novel catalysts. An ideal and in the very high ratio between superficial atoms and total
situation, which would require minimal modifications, involves number of atoms in the particles found in these nanomaterials.
the use of a novel multi-functional catalyst, which could replace Inspired by these ideas, we designed a new method for
conventional catalysts in the currently used reactors. In last preparing carbon-supported vanadium nanopowder by means of
decade, efforts have been made to develop such catalysts for the reduction of the metal adduct VCl33THF with K[BEt3H] at room
hydroprocessing. Metal carbides have been identified as the temperature, obtaining a mixture of vanadium carbide and V2O3.
potential catalysts for such applications. Interstitial carbides of This was well confirmed by our experimental results. Compared
early transition metals (groups IVB–VIB) are produced by with conventional processes (high temperature), the reaction
dissolving carbon atoms into the metal lattices. These carbide conditions are much simpler, and the as-obtained vanadium
materials have interesting physical and chemical properties, which carbide nanopowder is the main phase and is well dispersed.
combine the characteristic properties of three different classes of
materials: covalent solids, ionic crystals, and transition metals. It 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: [email protected] (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 5391

2.1. Catalyst preparation a small amount of C vacancies, and the vacancies are randomly
distributed in the VC1x lattice [6]. The apparent carbon deficiency
The vanadium nanoparticles were synthesized following the observed for the air exposed solid, could be a consequence of the
method established by Bönnemann [5]. A solution of K[BEt3H] presence of oxygen in the lattice [7].
(1 M, 4,6 ml, 4,6 mmol) in tetrahydrofurane (THF) was added The reactions between VCl3, K[BEt3H] and C may be written as
dropwise to a suspension of VCl33THF (0.99 mmol) in THF at room follows:
temperature during 2 h. After 2 h of constant stirring at room
THF 3
temperature, a dark brown solution was obtained. The KCl formed VCl3  3THF þ 3K½BEt3 H!V0 þ 3BEt3 þ 3KCl þ H2 (1)
2
during the reaction was removed by filtration. The dark solution
obtained was added to an activated carbon/THF suspension. This V0 þ ð1  xÞC ! VC1x (2)
suspension was stirred for at least 24 h, and then dried under
vacuum during 24 h resulting in a black solid. Finally, the
V0 air V2 O3
nanometric solid product was exposed to air. No changes in ! (3)
temperature were observed during synthesis process. C C
The reaction between VCl3 and K[BEt3H] occurred first (Eq. (1)),
2.2. Characterization and after started the reaction between V0 and C, so VC1x was
synthesized. As a result of the reaction, the large heat of formation
2.2.1. Elemental analysis of VC1x might have accelerated the propagation of the reaction.
Elemental analyses were performed by the Centro de Quı́mica Therefore, the reaction could be completed ‘‘easily’’. When this
Analı́tica-UCV, Venezuela. The characterization by ICP-AES of the system was exposed to air (molecular oxygen) probably a partial
obtained product show vanadium content of 0.64% in weight. oxidation occurs, according to Eq. (3). Martınez-Mendez et al. [8]
have proposed that due to the high reactivity of the THF stabilized
2.2.2. X-ray photoelectron spectroscopy studies
metallic nanoparticles of titanium, vanadium and niobium with
The XPS were recorded with a VG ESCALAB 220i-XL spectro-
air, the surface analyses only showed the presence of the oxidized
meter equipped with Al source (Al Ka = 1486.6 eV). The analyzer
species.
was operated in a constant pass energy mode (Epass = 30 eV) using
X-ray photoelectron spectroscopy (XPS) was used to investigate
the electromagnetic mode for the lens. Energy correction was
the elemental composition of the V/carbon nanocrystals, and can
performed by using the C1s level of carbon as a reference. The
further provide evidence for the formation of vanadium carbide.
deconvolutions of the XPS spectra were carried out using a XPS
The XPS spectrum for the vanadium/carbon systems exposed to air
Peak Fitting program Version 4.1.
(Fig. 1) shows three different signals in the region for V2p3/2 with
2.2.3. X-ray diffraction measurements binding energies at 516.6 eV, 515.3 eV and 513.4 eV (as shown in
XRD patterns of the samples were obtained using a Bruker D-8 Fig. 1), indicate the V2p3/2 species of VO2, V2O3 and V8C7 (or V4C3),
Advance apparatus (Cu Ka radiation, l = 0.154178 nm, nickel filter) respectively [9]. The results agree well with the XPS spectrum of
operating at 35 kV and 30 mA. O1s energy region for vanadium carbide (not shown). The XPS
spectrum of O1s energy region for vanadium carbide contains
2.2.4. Transmission electron microscopy three peaks. The peaks at 532.9 eV and 531.7 eV are considered to
The morphologies and structures of the obtained product were be due to O and OH, respectively. These two kinds of oxygen
observed with a Hitachi H-800 high-resolution transmission species are mainly originated from air. The O1s peak with the
electron microscope at an accelerating voltage of 200 kV. The binding energy of 530.3 eV is ascribed to V2O3. All assigned binding
diameters were measured directly for particles shaped approxi- energies agree well with the literature values [9,10].
mately circular. The TEM analysis (micrograph, diffraction pattern and histo-
grams) for the V/carbon system is shown in Fig. 2. This material
2.2.5. Tiophene hydrodesulfurization shows a homogeneous dispersion on the support and has a sphere-
The catalyst was evaluated for the HDS of thiophene at 300 8C, like morphology. The vanadium system shows nanoparticle sizes
P = 1 atm. Before the reaction, the materials were activated in situ ranging from 2 nm to 24 nm and a mean size of 7 nm (Fig. 3).
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 Fig. 1. XPS spectrum of V2p for the vanadium/carbon nanostructured system
become clearly outlined. VC1x belongs to space group Fm3m with 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 Fig. 3 shows the hydrodesulphurization activity during
with larger size but they are minor in population. Electron the run with thiophene. GC analyses showed that the
Diffraction (ED) pattern suggests that the powder is polycrystal- reaction products consisted of butanes and butenes. Catalyst
line. The ED diffraction pattern exhibits dominant broad rings supported on the activated carbon is 2-fold times more active
characteristic of an amorphous phase but in addition, there are in this reaction than commercial NiMo/Al2O3. The catalyst
other weak rings which are assigned to the vanadium carbide showed a significant activity level for hydrogenation and
structure. hydrogenolysis reactions; consequently, this was more selective
 S. Pinto et al. / Applied Surface Science 254 (2008) 5390–5393 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.

Fig. 3. Catalytic activity of nanostructured V/carbon catalyst as a function of time, in Acknowledgements

the HDS of tiophene at 300 8C, P = 1 atm.
The authors gratefully acknowledge the financial support of this
toward the formation of n-butane and olefins from the HDS of work by the FONACIT (Project G-2005000450), Venezuela. We also
thiophene. wish to thank the BID-FONACIT project QF10 and the Laboratorio
In general, the catalytic behavior of the unsupported single- Nacional Analisis Quiımico (FONACIT) for the XPS analyses in the
phase carbides is attributed mainly to their particular electronic person of A. Albornoz.
structure in which the carbon and nitrogen atoms occupying the
interstices should contribute to the unit cell parameter’s
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