Short Communication

Guaiacol derivatives and inhibiting species adsorption over MoS

2
and CoMoS
catalysts under HDO conditions: A DFT study
Michael Badawi, Jean-Franois Paul , Sylvain Cristol, Edmond Payen
Unit de Catalyse et Chimie du SolideUniversit Lille 1UMR-CNRS 8181, 59650 Villeneuve d'Ascq Cedex, France
a b s t r a c t a r t i c l e i n f o
Article history:
Received 28 September 2010
Received in revised form 2 February 2011
Accepted 9 February 2011
Available online 18 February 2011
Keywords:
Density functional theory (DFT)
Guaiacol
Phenol
Hydrodeoxygenation (HDO)
MoS
2
CoMoS
CO
Adsorption
We have investigated using DFT calculations the
1
adsorption of guaiacol, phenol, anisole and phenol over CoMoS
and MoS
2
phases under HDO conditions. This adsorption mode should lead to a direct deoxygenation (DDO)
reaction, which is low hydrogen-consuming. The most stable mode is an adsorption through the OH group of the
molecule. Thecalculationof adsorptionGibbs freeenergies of inhibitingcompounds (H
2
O, H
2
S, andCO) whichcanbe
present under reaction conditions shows that these molecules adsorb more strongly than oxygenated compounds,
which suggests that CO will be a major inhibitor of the HDO process of real feeds.
2011 Elsevier B.V. All rights reserved.
1. Introduction
New fuel production based on liquids derived from pyrolysis of
lignocellulosic biomass [13] may be usedfor respecting the environment
norms on the CO
2
emissions. However these wood-derived bio-oil
fractions contain important amounts (up to 45 wt.%) of oxygenated
compounds having multiple functions like aldehyde, ketone, acids, esters
and alcohols [13], which leads to deleterious properties such as high
viscosity, thermal andchemical instability[2,4] andpoor engineefciency.
Hence, upgrading of bio-oils by reducing their oxygencontent is therefore
required. Hydrodeoxygenation (HDO) of these bio-oils, which refers to a
high temperature hydrogen treatment could be performed to obtain
oxygen-free molecules and water as by-product.
Hydrotreating catalysts such as CoMo/Al
2
O
3
and NiMo/Al
2
O
3
, the
active phases of which consist of well dispersed MoS
2
nanocrystallites
promoted by Co or Ni atoms appear as good candidates for HDO
processing [1,415]. These catalysts, which are used in hydrodesulfuriza-
tion (HDS) and hydrodenitrogenation (HDN) processes have been
investigated extensively experimentally and theoretically [1622]. The
active sites are located on the edges of the nanocrystallites corresponding
to the (100) MoS
2
edge planes that exhibit alternative rows of sulfur-
terminated layers (1

010) (hereafter called S, or sulfur edge) and

molybdenum-terminated layers (101

0) (hereafter called M, or molybde-

numedge) [19,20]. Stability of the catalysts is a crucial issue, as interaction
with water and oxygen-containing compounds may modify the sulde
structure of the active phases' edges [1,7,10,14]. Recently, we have shown
using DFT calculations that the stability of the sulde phase under typical
HDOconditions depends onthe H
2
O/H
2
S pressure ratio [14]. Introduction
of a small amount of H
2
S in the feedstock may then be required to avoid
oxygenation of the catalysts as observed experimentally [7,10,11]. Today,
a growing number of experimental studies deal with the HDO of
lignocellulosic model compounds in model feeds [3,611] or in co-
hydrotreatment with petroleum fractions [2,12,13]. Molecules like
guaiacol [6,12,13,15], anisole [6,7] or phenol [5,7,9] have been proved to
be among the most refractory ones to the HDO process. The presence of
oxygenatedcompounds likeesters couldleadtoCOformationthroughthe
reduction of CO
2
[1,8,12]. Furthermore H
2
O and H
2
S molecules are also
present under HDO conditions. We have therefore to consider the
competitive adsorption of H
2
O, H
2
S and CO molecules with the
oxygenated compounds. In this context, we investigated theoretically by
DFTcalculations theadsorptionof guaiacol, phenol andtheir derivatives as
well as the aforementioned possible inhibiting molecules over the CoMoS
and MoS
2
phases under HDO conditions. We focused on the direct
deoxygenation (DDO) reaction pathway since it limits hydrogen
consumption compared to the hydrogenation one [10,11] and is thus
the major target of research works. Indeed previous studies [14,23]
showed that
1
adsorption should lead to direct heteroatom removal
whereas at adsorptionwouldfavor full hydrogenationof aromatic ring. A
better understanding of this
1
adsorption mode would provide hints to
improve the DDO pathway. After a brief presentation of the calculations
Catalysis Communications 12 (2011) 901905
Corresponding author.
E-mail address: jean-francois.paul@univ-lille1.fr (J.-F. Paul).
1566-7367/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2011.02.010
Contents lists available at ScienceDirect
Catalysis Communications
j our nal homepage: www. el sevi er. com/ l ocat e/ cat com
methods, we will present the adsorption results and their consequences
on the reaction and inhibiting effects.
2. Computational methods
The density-functional theory (DFT, PW91 [24]) calculations were
performed with the Vienna Ab initio Simulation Package (VASP) [25]
using the PAW method [26]. The solution of the KohnSham equations
was improved self-consistently until a difference lower than 10
5
eVwas
obtained between successive iterations. The calculations were performed
witha cut-off energy of 450 eV(675 eVfor the density) anda Methfessel
Paxton smearing with =0.1 eV.
Throughout this work, we used a large super cell (12.641
12.29425.000
3
), which contains four elementary MoS
2
units in the
x and z directions, and two layers along the y-axis (Fig. 1). Ak-point mesh
(3,1,1) has been chosen to give an accurate sampling of the supercell's
Brillouin zone. Previous studies [19,23,27] showed that this model is
suitable to predict the electronic and structural properties of the MoS
2
surface. A vacuum layer of 15 is located above the MoS
2
slab in the z
direction to avoid interactions between slabs. Since the molecules are
adsorbedonly ononeside of the slab, dipolar corrections have beenadded
in the z direction. The two upper rows were allowed to relax until forces
acting on ions are smaller than 3.10
2
eV
1
. The two lower rows were
kept xed to simulate bulk constraints [1923,27].
Under HDO conditions, the presence of H
2
, H
2
S and H
2
O may
modify the stoechiometry and the nature of the atoms on the edges of
the catalyst active phase. For T=350 C and the following partial
pressure ranges: 0.05bH
2
S/H
2
b10,000, 0.05bH
2
O/H
2
b10,000, H
2
S/
H
2
ON0.025, the most MoS
2
stable surface [14] is presented in Fig. 1.
This gure shows that the molybdenum edge is covered with sulfur
atoms, yielding sixfold-coordinated Mo edge atoms [20,27]. Within
the same partial pressure and temperature range, the sulfur edge is
reduced leading to fourfold-coordinated molybdenum atoms.
In order to take into account the experimental conditions in the
adsorption reaction (Eq. (1)) and to evaluate the inhibiting effect, we
compute the adsorption free energies (Eq. (2)).
surface X surface X 1

r
G = surface X surface X 2
Fig. 1. On the left, cell showing the perfect MoS
2
(100) surface. On the right, cell showing the stable MoS
2
surface when 0.05bH
2
S/H
2
b10,000 [27] and H
2
S/H
2
ON0.025 [14] that will
be used as reference. Molybdenum atoms are in blue, sulfur atoms are in yellow.
Fig. 2. Representation of DDO adsorption sites over MoS
2
and CoMoS catalysts: A) vacancy on the MoS
2
M-edge, B) vacancy on the MoS
2
S-edge, C) stable 50% promoted CoMoS
M-edge, D) vacancy on the 100% promoted CoMoS S-edge. Color code: Mo in green, S in yellow, Co in blue.
902 M. Badawi et al. / Catalysis Communications 12 (2011) 901905

r
G =
r
G
0
R

ln P X =P

3
where
r
G
0
=
r
E+(T) with
r
E=E(surfaceX)E(surface)
E(X).
The variation of the chemical potential of compound X between its
gas and adsorbed phase, (T), is computed using the translational
and rotational partition function for ideal gas [28]; the vibrational
contribution is assumed to be unaffected by the adsorption process.
The calculations were performed at T=350 C, which corresponds to
the reaction temperature, for X partial pressure ratios between 10
4
and 10 bar.
3. Results
3.1. Direct deoxygenation (DDO) sites over MoS
2
and CoMoS phases
3.1.1. MoS
2
phase
It is generally assumed that HDS, HDN and HDO reactions proceed
on the CUS (Coordinative Unsaturated Sites) of the MoS
2
edges
[16,17]. Adsorption of small molecules, such as CO or H
2
S has been
reported on the stable edges. However all the calculations with
phenol like molecules lead to the molecule desorption. Hence, starting
from the edge stable under reducing conditions, we have to consider
the adsorption on vacancies generated either by removing (as H
2
S)
one sulfur atomfromone of the edges or by displacing one sulfur atom
and forming one S-S dimere on the S-edge [29] (Fig. 2). Besides,
1
adsorption of oxygenated compounds will be a good starting point for
the DDO reaction pathway since it leads to CO bond activation. This
adsorption mode will be possible on the considered CUS of MoS
2
(Fig. 2-A and 2-B). Vacancy formation is an endothermic reaction and is
more difcult on the S-edge (E=1.66 eV for the displacement and
E=1.98 eV for the removal [23]) than on the M-edge (E=0.62 eV).
3.1.2. CoMoS phase
Experimentally, addition of cobalt or nickel in the sulde phase
increases the HDOactivity [17]. Based on STMobservations [30,31], it has
been proposed that the Co atoms are mostly localized on the S-edge.
However, IR experiments [32,33] suggest that parts of Co atoms, in the
case of highCo/Mo ratio, are also locatedonthe M-edge. According to DFT
studies [31,3436], the S-edge is supposed to be fully promoted while the
M-edge is only partially substituted. We have then considered for this
study the fully promoted S-edge and the 50% promoted M-edge. This 50%
promoted M-edge (Fig. 2-C) presents stable CUS under typical hydro-
treating conditions [36]. In contrast, vacancy creation on the 100%
promotedS-edge(Fig. 2-D) is still requiredandis anendothermic reaction
(E=1.05 eV).
3.2. Guaiacol and derivatives adsorption
Several reaction schemes for guaiacol HDO ([1,12] and references
therein, [15] and anisole [1,6,12]) have been proposed. The classical
HDO reaction scheme for guaiacol (Fig. 3) considers rst an
hydrogenolysis of the methoxy group producing cathecol (1,2-
benzenediol) and methane, followed by the elimination of a cathecol
hydroxyl group, forming phenol, which, in the DDO pathway, is
subsequently decomposed in benzene. However, anisole may be
produced in the rst step, instead of cathecol. In order to get a
complete picture of the adsorption properties and of the possible
competitive effects, guaiacol, cathecol, anisole and phenol adsorption
have been investigated on the considered DDO sites of the MoS
2
and
CoMoS phases (adsorption structures supplied in the Supporting
Information).
Adsorption of guaiacol was rst investigated. Several congura-
tions were tested on the MoS
2
M-edge (Table 1 and Fig. 4). Among
the various possibilities (adsorption by the OH or the OCH
3
group,)
the most stable mode is always an adsorption by the OH function
(Fig. 4-A). The calculated adsorption energies, reported in Table 2,
show that the adsorption energy order is the same for all sites on Mo
and CoMo catalysts:
cathecol Nguaiacol N phenol anisole
This order reects the lack of reactivity of the ether function. The
small energy differences between the molecules for the OH
adsorption modes are a good indication that the steric effects are
limited. The energies follow the donor effect of the substituents.
Taking into account the vacancy formation process (see Table 2),
the most probable adsorption site on the MoS
2
phase is on the M-
edge. On the CoMoS phase, adsorption on the 50% M-edge will be
favored due to the presence of stable vacancies (Fig. 5).
3.3. Inhibiting effects
H
2
O and H
2
S molecules are present under HDO conditions.
Furthermore, bio-oils resulting from pyrolysis of lignocellulosic
OH
O
OH
OH
OH
+H
2
-CH
4
+H
2
+H
2
-H
2
O -H
2
O
Fig. 3. Deoxygenation reaction scheme of guaiacol (adapted from [12]).
Table 1
Guaiacol adsorption energy on the MoS
2
M-edge.
Conguration E (eV) MO distance ()
OH coordinated, OCH
3
upward (Fig. 3-A) 0.45 2.59
OH coordinated, OCH
3
downward (Fig. 3-B) 0.33 2.60
Both OH and OCH
3
coordinated (Fig. 3-C) 0.22 2.98+3.40
OCH
3
coordinated, OH down 0.17 3.10
OCH
3
coordinated, OH top 0.08 3.05
Fig. 4. Adsorption of guaiacol on the MoS
2
M-edge. A) OH coordinated, OCH
3
upward;
B) OH coordinated, OCH
3
downward; C) both OH and OCH
3
coordinated. Color code:
Mo in green, S in yellow, O in red, C in grey, H in white.
903 M. Badawi et al. / Catalysis Communications 12 (2011) 901905
biomass contain ester molecules [13] which will be decarboxylated
in the reaction conditions [1,8,12] and the produced CO
2
will be
reduced, producing either CO or coke. We have then to consider the
competitive adsorption of these molecules with oxygenated com-
pounds. Our calculated adsorption energies (Table 3) are in good
agreement with previous works (CO [37] and H
2
S [38] over MoS
2
).
The present results show that CO would adsorb more strongly than
other molecules on all sites. Therefore CO inhibiting effect on the
adsorption of guaiacol would be very large on all the possible DDO
adsorption sites. On the non-promoted catalyst, the H
2
S and H
2
O
adsorption energies are similar to the guaiacol ones. A small inhibiting
effect is therefore expected. Over CoMoS sites (Fig. 5), H
2
S and H
2
O
are more strongly adsorbed than guaiacol. The addition of H
2
S into the
feed, which is needed to stabilize the catalytic phase [7,14], would
have to be as low as possible to prevent this poisoning effect.
4. Discussion
The previous results indicate that CO will be the more inhibiting
molecule among the tested ones. This effect can be evaluated
computing the adsorption free energies taking into account the
reaction conditions according to Eq. (3). These
r
G values are
reported in Table 4. Such corrections are more important for large
molecules such as guaiacol and phenol than for the lighter ones. The
inhibiting effect may then be important, even if the adsorption
energies are similar as indicated in Table 3. The promoted catalyst
being more active in DDO than the unpromoted one [11], we only
considered the CoMoS 50% M-edge catalytic site. For this site, we have
plotted the adsorption free energies versus the logarithm of the
partial pressures at 350 C (Fig. 6). Using this diagram, we can see that
the inhibiting of CO molecules will be very large and that the effect of
the H
2
O will be more important than the H
2
S one.
The effect of water and H
2
S would be quite similar. On the
opposite, the CO molecule will have a very strong effect since its
adsorption will be favored whatever the experimental conditions.
This phenomenon, which did not occur in the classical HDS reaction,
due to the lack of oxygenated compound in the feedstock, will lead to
a drastic decrease of the catalytic activity. Indeed, such a negative
impact of CO on the transformation of a model FCC gasoline over a
CoMoS/Al
2
O
3
catalyst was recently reported [39].
The classical reaction scheme (Fig. 3) may thus be discussed taking
into account the DFT calculations. The most stable adsorption mode
(adsorption by the OH group) would favor hydroxyl removal instead
of the methoxy one and will prevent the activation of the OCH
3
group.
These results suggest that the rst step of the reaction of the DDO
pathway proposed in the literature, i.e. CH
3
group removal, occurs on
other active sites as the acid sites of supports such as alumina [9].
5. Conclusion
We have investigated using DFT calculations the
1
adsorption of
guaiacol, phenol and their derivatives over CoMoS and MoS
2
phases
under HDO conditions, leading to the direct deoxygenation (DDO)
Table 2
Guaiacol and derivatives adsorption energies (eV) over MoS
2
and CoMoS catalytic sites
vacancy formation energies (eV) are reported in brackets.
Molecule MoS
2
M-edge
(0.62)
MoS
2
S-edge
(1.66)
CoMoS 50%
M-edge
(0)
CoMoS 100%
S-edge
(1.05)
Cathecol 0.60 1.36 0.50 0.68
Guaiacol 0.45 1.26 0.49 0.59
Phenol 0.38 1.07 0.37 0.42
Anisole 0.22 1.03 0.21 0.33
Fig. 5. Adsorption on the 50% promoted CoMoS M-edge: A) cathecol, B) H
2
S, C) CO.
Color code: Mo in green, S in yellow, Co in blue, O in red, C in grey, H in white.
Table 3
Inhibiting molecules adsorption energies (eV) over MoS
2
and CoMoS catalytic sites
(vacancy formation energies (eV) are reported in brackets).
Molecule MoS
2
M-edge
(0.62)
MoS
2
S-edge
(1.66)
CoMoS 50%
M-edge
(0)
CoMoS 100%
S-edge
(1.05)
Guaiacol 0.45 1.26 0.49 0.59
H
2
O 0.69 1.10 0.97 0.68
H
2
S 0.45 1.55 1.03 1.46
CO 1.02 2.06 1.68 1.85
Table 4
Corrected molecules adsorption energies (eV) over the CoMoS 50%M-edge catalytic
site.
Molecule
r
E (T)
r
G(T)
guaiacol 0.49 1,97 1,48
H
2
O 0.97 1,27 0,30
H
2
S 1.03 1,38 0,35
CO 1.68 1,33 0,35
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
-5 -4 -3 -2 -1 0 1 2
Log (P(X) / P
O
)

G

a
d
s
o
r
p
t
i
o
n

(
e
V
)
guaiacol
CO
H
2
S
H
2
O
Fig. 6. Gibbs free energy of adsorption of X species on the 50% promoted CoMoS M-edge
at 350 C versus log (P(X)/P) where X=guaiacol, H
2
S, H
2
O or CO.
904 M. Badawi et al. / Catalysis Communications 12 (2011) 901905
reaction. For the studied oxygenated compounds, the most stable
mode is an adsorption by the OH function. The adsorption order is the
same for all considered sites on both catalysts:
cathecol N guaiacol N phenol anisole
H
2
O, H
2
S and CO molecules are present under HDO conditions.
Adsorption Gibbs free energies of these inhibiting compounds were
computed at 350 C and are always lower than guaiacol one. H
2
O and
H
2
S will have similar effects while CO will have the greater effect
among the tested molecules. The presence of CO will be a major
limitation in the HDO process.
Acknowledgements
This work has been performed within the ANR funded Programme
National de Recherche sur les Bionergies-ECOHDOC, a joint project of
the Centre National de la Recherche Scientique (CNRS), the
university of Caen, Lille and Poitiers, and TOTAL. We acknowledge
the USTL Centre de Ressources Informatiques (partially funded by
FEDER) for allocating CPU time.
Appendix A. Supplementary data
Supplementarydatatothis articlecanbefoundonlineat doi:10.1016/j.
catcom.2011.02.010.
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