Activity of Mo(W)S2/SBA-15 Catalysts Synthesized from SiMoW Heteropoly Acids in 4,6-Dimethyldibenzothiophene Hydrodesulfurization

Article abstract of DOI:10.1134/S0965544119120077

Abstract: Mo(W)/SBA-15 catalysts are prepared using heteropoly acids H₄SiMo₁₂O₄₀, H₄SiW₁₂O₄₀, and H₄SiMo₃W₉O₄₀. The catalysts in the sulfide form are studied by low-temperature nitrogen adsorption, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. Catalytic properties are tested in the hydrodesulfurization of 4,6-dimethyldibenzothiophene. It is shown that the gas-phase sulfiding of Mo(W)/SBA-15 catalysts leads to increase in the average length of particles and the number of Mo(W)S₂ layers in active phase particles compared with liquid-phase sulfiding with the use of dimethyl sulfide. The replacement of a quarter of tungsten atoms with molybdenum ones makes it possible to considerably improve the catalytic activity of the mixed catalyst Mo + W/SBA-15 compared with the monometallic counterparts. This effect can be enhanced due to the use of mixed heteropoly acid H₄SiMo₃W₉O₄₀ as a precursor of the active phase of the MoW/SBA-15 catalyst, which is apparently associated with the formation of MoWS₂ active sites.

Full text of DOI:10.1134/S0965544119120077

ISSN 0965-5441, Petroleum Chemistry, 2019, Vol. 59, No. 12, pp. 1293–1299. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Nanogeterogennyi Kataliz, 2019, Vol. 4, No. 2, pp. 104–110.
Activity of Mo(W)S2/SBA-15 Catalysts Synthesized
from SiMoW Heteropoly Acids
in 4,6-Dimethyldibenzothiophene Hydrodesulfurization
A. S. Koklyukhina, b, M. S. Nikul’shinaa, A. A. Sheldaisov-Meshcheryakova, b, A. V. Mozhaeva,
C. Lancelotb, P. Blanchardb, C. Lamonierb, and P. A. Nikul’shina, c,
*
aSamara State Technical University, Samara, 443100 Russia
bUniversité Lille1, UCCS, Cité Scientifique, Lille, 590000 France
cAll-Russia Research Institute of Oil Refining, Moscow, 111116 Russia
*e-mail: p.a.nikulshin@gmail.com
Received June 3, 2019; revised July 9, 2019; accepted September 8, 2019
Abstract—Mo(W)/SBA-15 catalysts are prepared using heteropoly acids H4SiMo12O40, H4SiW12O40, and
H4SiMo3W9O40. The catalysts in the sulfide form are studied by low-temperature nitrogen adsorption, high-
resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. Catalytic properties are
tested in the hydrodesulfurization of 4,6-dimethyldibenzothiophene. It is shown that the gas-phase sulfiding
of Mo(W)/SBA-15 catalysts leads to increase in the average length of particles and the number of Mo(W)S2
layers in active phase particles compared with liquid-phase sulfiding with the use of dimethyl sulfide. The
replacement of a quarter of tungsten atoms with molybdenum ones makes it possible to considerably improve
the catalytic activity of the mixed catalyst Mo + W/SBA-15 compared with the monometallic counterparts.
This effect can be enhanced due to the use of mixed heteropoly acid H4SiMo3W9O40 as a precursor of the
active phase of the MoW/SBA-15 catalyst, which is apparently associated with the formation of MoWS2
active sites.
Keywords: hydrotreatment, heteropoly acid, MoWS2 active phase, 4,6-dimethyldithiobenzothiophene
DOI: 10.1134/S0965544119120077
The consumption of ultrapure motor fuels contin- in [9], the formation of bimetallic МоW oxide precur-
ues to grow, while the quality of the processed raw sors ensures formation of mixed metal sulfides,
materials worsens considerably. Secondary fractions (up whereas in the case of the mechanical mixture two dif-
to 30% or above) are more frequently involved in the pro- ferent Mo and W compounds particles of individual
cess of diesel fraction hydrofining [1, 2]; as a result, the monometallic sulfides prevail on the surface of the
proportion of hard-to-remove heteroatomic (diben- MoWS2/Al2O3 catalyst [9].
zothiophene derivatives) and aromatic compounds
increases. These changes in the feedstock chemical com-
position are responsible for more strict requirements on
deep hydrotreating catalysts, and demands for catalysts
will only increase because of the current and long-term
environmental standards restricting the content of sulfur
and polycyclic aromatic hydrocarbons in motor fuels and
lubricant oils [3, 4].
Catalytic activity is considerably affected not only
by oxide precursors but also by the support used. The
support nature influences the dispersity of catalyst
oxide and sulfide phases, the size distribution of active
component particles, and the degree of their sulfiding
[6, 10]. The absolute leader among hydrotreating cat-
alyst supports is Al2O3; however, information about
advantages of mesostructured silica having a higher
In recent years, the attention of researchers has specific surface area, equal sizes of channels, which
been focused on the design of mixed hydrotreating are nanoreactors for targeted chemical reactions,
catalysts including just two structure-forming active inactivity toward formation of low-activity sulfide par-
phase metals—molybdenum and tungsten. This inter- ticles, and thermal stability, has appeared in recent
est is associated with a high catalytic activity of mixed decades. The most widespread representatives of these
MoWS2 systems [4–6]. Oxide precursors of the sulfide materials are SBA-15 [11], MCM-41 [12], and HMS
[13]. It was reported that CoMoS and Mo(W)S2 cata-
active phase play a crucial role in the process of cata-
lyst synthesis. Current research in this field more fre- lysts deposited on SBA-15 show a higher activity in the
quently concerns using molybdenum and tungsten hydrogenation and hydrodesulfurization reactions
Keggin structure heteropoly acids [7, 8] and their because of a high dispersity and optimal morphology
derivatives, which in turn show high solubility and sta- of active-phase particles [14–16]. Mendoza-Nieto et
bility and are in wide use in the industry. As was shown al. [17] demonstrated that the activity of trimetallic
1293

1294
KOKLYUKHIN et al.
catalysts NiMoW/SBA-15 in the hydrodesulfurization
To study the physicochemical properties the synthe-
(HDS) of dibenzothiophene and 4,6-dimethyldithio- sized oxide samples were activated (sulfided) in a flow of
benzothiophene (4,6-DMDBT) was higher compared H2S/H2 (10 vol % H2S) under heating at a rate of
with their counterparts deposited on Al2O3.
5°С/min followed by holding at 400°С for 2 h.
The textural characteristics of the catalysts were mea-
sured by low-temperature nitrogen adsorption on a
Quantachrome Autosorb-1 adsorption porosimeter. The
specific surface area was calculated according to the
Brunauer–Emmett–Teller (BET) model at Р/Р0 =
0.05–0.3. The total pore volume and pore size distribu-
tion were calculated from the desorption curve in terms
of the Barrett–Joyner–Halenda model.
The composition of active-phase particles of the syn-
thesized Mo(W)/SBA-15 catalysts in the sulfide form
was studied by X-ray photoelectron spectroscopy on a
Kratos Axis Ultra DLD spectrometer using AlKα radia-
tion (hν = 1486.6 eV). The samples were applied on a
double-sided nonconducting adhesive tape. The
charging effect arising during the photoemission of elec-
trons was minimized through irradiation of the sample
surface by a beam of low-energy electrons. The binding
energy (Еb) scale was preliminarily calibrated against
positions of the peaks of core levels Au 4f7/2 (84.0 eV) and
Cu 2p3/2 (932.67 eV). Calibration was made against the
C1s line (284.8 eV) of carbon present on the catalyst sur-
face. The energy step was 1 eV for the survey spectrum
and 0.1 eV for individual lines C 1s, Si 2p, S 2p, Mo 3d,
and W 4f. For all sulfide catalysts the relative concentra-
tions of W6+ (Mo6+) particles in the oxide environment,
oxysulfides WSxOy (MoSxOy), and sulfides WS2 (MoS2)
were determined.
As was shown in [15], the monometallic catalysts
MoS2/SBA-15 and WS2/SBA-15 and the bimetallic
mixed sample (Mo + W)S2/SBA-15, which were sul-
fided by the liquid-phase method with the use of
dimethyl disulfide, exhibit a higher activity in the
hydrodesulfurization of dibenzophiophene and naph-
thalene compared with Al2O3-deposited counterparts
and are characterized by a better dispersity of active-
phase particles. The goal of this study was the synthesis of
the MoWS2/SBA-15 catalyst with the use of mixed bime-
tallic heteropoly acid H4SiMo3W9O40 containing both
metals in its anion as an oxide precursor and the compar-
ison of composition and characteristics of sulfide parti-
cles on the surface of SBA-15-deposited catalysts with
those of monometallic samples based on H4SiMo12O40
and H4SiW12O40 and the bimetallic counterpart prepared
from the mechanical mixture of the mentioned hetero-
poly acids. The catalytic properties of the
Mo(W)S2/SBA-15 catalysts sulfided by the gas-phase
method were studied in the 4,6-DMDBT hydrodesul-
furization. This sulfur-containing compound was chosen
because it concentrates in the high-boiling part of mid-
dle-distillate oil fractions and its activity is much lower
active than that of dibenzothiophene because of steric
hindrances to σ-adsorption on edge active sites.
EXPERIMENTAL
The catalyst samples in the sulfide form were also
analyzed by high-resolution transmission electron
SBA-15 was synthesized in accordance with previ-
ously described techniques [18]. Triblock copolymer microscopy (HR TEM) on a Tecnai G2 20 instrument at
Pluronic P123 (М = 5800, EO20PO70EO20, Aldrich) an accelerating voltage of 200 kV. Parameters, such as the
was used as a structure-forming agent, and tetraethyl
orthosilicate was used as a source of silica. A weighed
portion of Pluronic Р123 (4 g) was dissolved in water
(30 cm3) containing 2 М HCl (120 cm3) at a temperature
of 35°С. The weighed portion of tetraethyl orthosilicate
(8.5 g) was added dropwise under vigorous stirring to the
obtained solution, and the resulting mixture was held for
20 h at 35°С. After holding, the still solution was trans-
ferred to a polypropylene bottle (1000 cm3) and placed in
a thermostat for 48 h at a temperature of 80°С. The prod-
uct was cooled to room temperature, filtered, washed
with deionized water, dried at 60, 80, and 100°С for 5, 2,
and 5 h, respectively; and finally calcined at 240 and
540°С for 4 and 6 h, respectively.
( )
average length of particles
Mo(W)S2 layers per stack
and the number of
L
(
)
were determined by the
N ,
statistical treatment of 400–600 particles situated in 10–
15 different areas of the catalyst surface. The dispersity
(D) of active-phase particles was calculated in terms of
the Kasztelan hexagonal model [21]:
6n − 6
i
i=1..t
Me + Mc
(1)
D =
=
,
3n2 − 3n + 1
MT
i
i

i=1..t
where Me is the number of Mo(W) atoms on the edges of
middle crystallite Mo(W)S2, Mc is the number of Mo(W)
atoms on the corners of middle Mo(W)S2 crystallite, MT
is the total number of Mo(W) atoms in the middle parti-
cle of the active phase; ni is the number of Mo atoms
along one side of the Mo(W)S2 crystallite defined by its
length; and t is the total number of stacks in the crystallite
according to HR TEM.
The catalytic properties of the catalyst samples were
tested in the process of 4,6-DMDBT (0.6 wt %)
hydrodesulfurization in toluene in a flow unit equipped
with a microreactor. A steel reactor was charged with the
Mo(W)/SBA-15 catalysts were synthesized by the
single incipient wetness impregnation of the synthesized
SBA-15 with the solution of corresponding heteropoly
acid followed by drying at 100°С for 12 h without calcina-
tion. Precursors were Keggin structure monometallic
H4SiMo12O40 and H4SiW12O40 heteropoly acids and
mixed heteropoly acid H4SiMo3W9O40 [19, 20]. All sam-
ples had the same surface concentration of metals
(Mo + W) equal to ~1.2 at/nm2.
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ACTIVITY OF Mo(W)S2/SBA-15 CATALYSTS SYNTHESIZED
1295
catalyst (0.4 g, fraction 0.25–0.50 mm) diluted with car- dimethylbiphenyl. This result be attributed to steric hin-
borundum at a ratio of 1 : 4. Tests were run under the fol- drances caused by methyl substituents, which hinder the
lowing conditions: temperature, 320°С; pressure, σ-adsorption of a sulfur molecule on the active site. The
3.0 MPa; feed space velocity, 5–10 h–1; and Н2 : feed-
stock, 500 nL/L. Before testing, the catalysts were sul-
fided in a flow of H2S/H2 (10 vol % H2S) under heating
at a rate of 5°С/min followed by holding at 400°С for 2 h.
Liquid samples were analyzed by gas-liquid chromatog-
raphy on a Kristall-5000 chromatograph.
The rate constant of 4,6-DMDBT hydrodesulfuriza-
tion was calculated with allowance for the pseudo-first
order of this reaction according to the following equation:
reaction products contain only trace 4,6-tetrahydro- and
perhydrodibenzothiophenes. The selectivity of the
hydrogenation route for direct desulfurization SHYD/DDS
was calculated in accordance with the reaction scheme of
4,6-DMDBT transformation:
СMCHT +СDMBCH
(3)
SHYD/DDS
=
.
СDMBP
The turnover frequency (TOFHDS, s–1) for the 4,6-
DMDBT hydrodesulfurization over the edge sites of
Mo(W)S2 particles was calculated as follows [22]:
F
kHDS = − 4,6-DMDBT ln(1 − x4,6-DMDBT 100),
(2)
m
is the rate constant (mol g–1 h–1) of 4,6-
F4,6-DMDBT x4,6-DMDBT
where
kHDS
DMDBT hydrodesulfurization,
(4)
TOFHDS
=
,
С
СMoS
2 

WS2
is the conver-
x4,6-DMDBT
m
+
D × 3600



Ar
ArMo
sion of 4,6-DMDBT (%),
is the molar con-
F4,6-DMDBT

W
sumption of the reagent (mol h–1), and m is the catalyst
where
is the consumption of 4,6-DMDBT
F4,6-DMDBT
weight (g).
(mol h–1);
is the conversion of 4,6-DMDBT
x4,6-DMDBT
The hydrogenation of 4,6-DMDBT aromatic rings
(Scheme 1) followed by the hydrogenolysis of C–S–С
bonds and the formation of methylcyclohexyltoluene
and 3,3'-dimethylbicyclohexyl occurs at a rate several
times higher than the rate of direct hydrogenolysis of C–
(%); m is the catalyst weight (g);
and
is the
С
С
WS2
MoS2
content (wt %) of W and Mo in WS2 and MoS2 particles,
respectively; D is the dispersity of Mo(W)S2 particles;
and ArW and ArMo are the atomic masses of tungsten
S–C bonds accompanied by the formation of 3,3'- (183.9 g/mol) and molybdenum (95.9 g/mol).
3,3'-DMBP
H3C
CH3
DDS
S
H3C
CH3
4,6-DMDBT
HYD
4,6-DM-TH-DBT
MCHT
S
H3C
CH3
H3C
CH3
4,6-DM-PH-DBT
3,3'-DMBCH
S
H3C
CH3
H3C
CH3
Scheme 1. Routes of 4,6-dimethyldibenzothiophene hydrodesulfurization, HYD is the preliminary hydrogenation path, and
DDS is the path via the direct removal of sulfur atoms (3,3'-DMBP is 3,3'-dimethylbiphenyl, 4,6-DMDBT is 4,6-dimethydiben-
zothiophene, 4,6-DM-TH-DBT is 4,6-dimethyltetrahydrodibenzothiophene, MCHT is methylcyclohexyltoluene, 4,6-DM-
PH-DBT is 4,6-dimethylperhydrodibenzothiophene, and 3,3'-DMBCH is 3,3'-dimethylbicyclohexyl).
PETROLEUM CHEMISTRY Vol. 59 No. 12 2019

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KOKLYUKHIN et al.
RESULTS AND DISCUSSION
of its small content in the samples and a high sulfiding
rate.
The content of edge active sites on the catalyst sur-
The composition and textural characteristics of the
synthesized samples and the geometry characteristics
of active-phase particles are shown in Table 1. The
original SBA-15 possessed high specific surface area
(850 m2/g) and pore volume (1.18 cm3/g). Naturally,
after metal deposition the specific surface area
decreased to 450–500 м2/g and the pore volume
decreased to 0.55–0.80 cm3/g.
face was determined which for the synthesized sam-
ples varied within 0.32–0.60 × 1020 at/g. The activa-
tion method (gas-phase or liquid-phase) insignifi-
cantly affected the degree of metal sulfiding. These
results are consistent with the data obtained for the
catalysts synthesized on alumina [9].
The data on the catalytic activity of the
Mo(W)/SBA-15 catalysts in the 4,6-DMDBT
hydrodesulfurization are summarized in Table 3. The
reactant conversion varied from 11.7 to 43.5%. The
lowest activity in all the studied reactions was exhib-
ited by the sample prepared from SiW12HPA. This can
be explained by a low content of active sites and a
lower degree of tungsten sulfiding because of a stron-
ger W–O bond. The sample synthesized using the
mechanical mixture of monometallic heteropoly acids
(Mo3 + W9)/SBA-15 exhibited a higher catalytic activ-
ity compared with Mo12/SBA-15 with the content of
active sites being comparable (Table 2). These results
can be probably explained by the enhanced hydrating
function owing to the presence of tungsten in the sam-
ple. The Mo3W9/SBA-15 catalyst provided the maxi-
mal 4,6-DMDBT conversion (43.5%) among the
tested samples; in this case, the content of edge active
sites was the smallest.
The TEM images of the sulfide catalysts are shown
in Fig. 1. Black threadlike bands correspond to the lay-
ers of Mo(W)S2 crystallites with a characteristic inter-
planar distance of about 0.65 nm [23].
It should be noted that the Mo(W)/SBA-15 cata-
lysts sulfided by the gas-phase method are character-
ized by a larger average number of Mo(W)S2 layers in
a crystallite and a larger average length of crystallites
compared with the catalysts sulfided by the liquid-
phase method. The dispersity of particles for the
Mo(W)/SBA-15 samples sulfided by the gas-phase
method was lower and amounted ~0.28 against ~0.32
for the samples sulfided by the liquid-phase method.
These changes are apparently related to different sul-
fiding kinetics of oxide particles: in the case of the gas-
phase method, as is known [24], the transformations
of supported oxide precursors begin at room tempera-
ture to form oxysulfides and subnanosized MоS3 par-
ticles, which further at higher temperatures (>300°C)
convert to two-dimensional MoS2 crystallites. As
regards the liquid-phase activation process, the cata-
lyst sulfiding starts at 170–220°С—the decomposition
temperatures of the sulfiding agent—and the forma-
tion of active-component particles is coupled with the
catalyst running-in by the feedstock and the stabiliza-
tion of the formed nanosized particles by amorphous
carbon. As a result, the number of Mo(W)S2 layers in
the stack in the case of the liquid-phase method is
smaller compared with the gas-phase method.
The TEM images show small rounded dark spots
which are particles of the unreacted precursor or oxy-
sulfide phases [11]. Almost all active-phase particles
are localized inside support channels, as is also seen
from the images. The average length of Mo(W)S2 par-
ticles is not above 5 nm, which is evidently related to
the size of SBA-15 channels (5.6 nm) hampering the
growth of sulfide particles in the process of catalyst
sulfiding.
The composition of particles on the surface of
the synthesized catalysts was investigated in detail by
X-ray photoelectron spectroscopy (Table 2). The
tested samples possess a high degree of metal sulfid-
ing. A high degree of tungsten sulfiding should be
mentioned (above 60 rel. %), which is, however,
slightly lower than the degree of molybdenum sulfid-
To level off the amount of active-phase particles in
the synthesized catalysts the turnover frequencies
(TOF) normalized to the content of edge active sites in
the Mo(W)S2 crystallites was calculated (Fig. 2).
In the 4,6-DMDBT hydrodesulfurization the sam-
ples based on monometallic heteropoly acids and their
mechanical mixtures demonstrated comparable turn-
over frequencies (about 8 × 10–4 s–1). However, for the
Mo3W9/SBA-15 sample prepared using of the mixed
heteropoly acid H4SiMo3W9O40 the turnover fre-
quency was more than two times higher than the
respective value for the mixed counterpart. This find-
ing provides evidence for formation of the mixed sul-
fide phase MoWS2 which is more active than conven-
tional catalytic systems. Actually, the application of
high-angle annular dark-field scanning transmission
electron microscopy (HAADF) and extended X-ray
absorption fine structure spectroscopy (EXAFS)
revealed that the use of the Keggin structure mixed
SiМо3W9 heteropoly acid as an oxide precursor of the
MoW/Al2O3 hydrotreating catalyst provides the spatial
proximity of Mo and W atoms and thus facilitates for-
mation of the mixed MoWS2 phase with the even
inclusion of Mo atoms in the structure of WS2 crystal-
lites [9, 25, 26].
Thus, we showed that for the Mo(W)/SBA-15 cat-
ing in Mo12/SBA-15 (74 rel. %). Molybdenum in the alysts the use of gas-phase sulfiding makes it possible
to increase the average length of sulfide particles and
the average number of layers in the Mo(W)S2 stack
MoW/SBA-15 samples fully passes to the sulfide
phase during the process of catalyst sulfiding because
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ACTIVITY OF Mo(W)S2/SBA-15 CATALYSTS SYNTHESIZED
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Table 1. Composition, textural characteristics, and morphology of sulfide particles for the synthesized Mo(W)/SBA-15 cat-
alysts
Content,
wt %
Textural characteristics
Geometry characteristics
average
Catalyst
average
particle
length
nm
number
of Mo(W)S2
layers in
dispersity
of Mo(W)S2
particles, D
pore
diameter ∅,
surface area pore volume
MoO3 WO3
SBET, m2/g
Vp, cm3/g
L,
nm
crystallite
N
SBA-15
–
18.0
–
–
850
492
453
452
447
1.18
0.68
0.55
0.78
0.64
5.6
5.6
5.6
5.6
5.6
–
–
–
4.1 (3.8)а
4.4 (3.5)
3.9 (3.6)
4.1 (3.8)
2.7 (2.1)а
2.6 (1.9)
2.3 (2.1)
2.7 (2.0)
Mo12/SBA-15
–
0.29
0.27
0.30
0.29
W12/SBA-15
26.2
20.1
20.1
Mo3W9/SBA-15
(Mo3+W9)/SBA-15
4.2
4.2
a
The parenthesized values refer to the catalysts sulfided by the liquid-phase method [15].
Mo12/SBA-15
W12/SBA-15
10 nm
10 nm
Mo3W9/SBA-15
(Mo3 + W9)/SBA-15
10 nm
10 nm
Fig. 1. TEM images of the sulfided Mo(W)/SBA-15 catalysts.
PETROLEUM CHEMISTRY Vol. 59 No. 12 2019

1298
KOKLYUKHIN et al.
Table 2. Surface composition of active-phase particles of sulfided Mo(W)/SBA-15 catalysts according to transmission elec-
tron microscopy and X-ray photoelectron spectroscopy
Number of edge sites, 1020 at g–1
Content of Mo, rel. %
MoS2 MoSxOy
74 (73)а 13 (12) 14 (15)
Content of W, rel. %
Catalyst
IV
edge
IV
edge
IV
edge
IV
Mo6+
W6+
WS2
WSxOy
+
Mo
W
ΣMo
Wedge
Mo12/SBA-15
–
–
–
0.56
0.00
0.32
0.25
0.30
0.56
0.32
0.39
0.60
W12/SBA-15
61 (67)
64 (65)
68 (65)
12 (9) 25 (24)
14 (8) 22 (27) 0.14
8 (6) 19 (29) 0.29
–
–
–
–
Mo3W9/SBA-15
(Mo +W )/SBA-15
95 (100) 3 (0)
100 (100) 0 (0)
2 (0)
0 (0)
3
9
а
The parenthesized values refer to the composition of particles on the surface of catalysts sulfided by the liquid-phase method [15].
Table 3. Catalytic properties of Mo(W)/SBA-15 catalysts in the 4,6-dimethyldibenzothiophene hydrodesulfurization
Rate constant kHDS
,
Selectivity SHYD/DDS
Catalyst
Conversion, %
×105 mol g–1 h–1
Mo12/SBA-15
26.7
11.7
43.5
35.7
6.4
5.9
6.3
5.4
11.6
4.5
W12/SBA-15
Mo3W9/SBA-15
(Mo3 + W9)/SBA-15
17.1
13.5
compared with the liquid-phase sulfiding providing MoWS2 sulfide phase. Thus, the use of the mixed het-
the use of dimethyl disulfide.
eropoly acid H4SiMo3W9O40 as an oxide precursor and
mesostructured silica SBA-15 as a support allows one
to synthesize the highly active hydrotreating catalyst.
The bimetallic MoW/SBA-15 catalysts are distin-
guished by a higher activity in the 4,6-DMDBT
hydrodesulfurization compared with the monometal-
lic counterparts. The synergistic effects makes itself
evident to a higher extent when mixed heteropoly acid
are used as an oxide precursor. The turnover frequen-
cies for the Mo3W9/SBA-15 catalyst are two times
higher than the corresponding values for the reference
samples. This indicates formation of a more active
FUNDING
This work was supported by the Ministry of Education
and Science of the Russian Federation (project
no. 14.586.21.0054, unique project identifier RFME-
FI58617X0054) and the Ministry of Foreign Affairs and
International Development (France) and the Ministry of
National Education, Higher Education, and Science
(France) within the framework of the Partenariats Hubert
Curien (PHC) program Kolmogorov for 2017–2019.
Turnover frequency ×104, s–1
25
CONFLICT OF INTEREST
20.8
20
The authors declare that there is no conflict of interest.
15
ADDITIONAL INFORMATION
A.S. Koklukhin, ORCID: https://orcid.org/0000-0002-
4737-120X
M.S. Nikul’shina, ORCID: https://orcid.org/0000-
0001-7081-7049
9.0
10
5
8.4
7.6
A.A.
https://orcid.org/0000-0001-7084-1583
A.V. Mozhaev, ORCID: https://orcid.org/0000-0003-
3781-6073
C. Lancelot, ORCID: https://orcid.org/0000-0002-
0691-0721
Sheldaisov-Meshcheryakov,
ORCID:
0
Mo12
W12
Mo3W9
Mo3 + W9
Fig. 2. Turnover frequency (TOF) in the 4,6-DMDBT
hydrodesulfurization over edge active sites of Mo(W)S
crystallites in the Mo(W)/SBA-15 catalysts.
2
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ACTIVITY OF Mo(W)S2/SBA-15 CATALYSTS SYNTHESIZED
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P. Blanchard, ORCID: https://orcid.org/0000-0003- 13. B. Pawelec, S. Damyanova, R. Mariscal, J. L. G. Fier-
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C. Lamonier, ORCID: https://orcid.org/0000-0002-
5100-8139
P.A. Nikul’shin, ORCID: https://orcid.org/0000-0002-
3243-7835
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Translated by T. Soboleva
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