Journal of Sol-Gel Science and Technology

https://doi.org/10.1007/s10971-018-4792-x

REVIEW PAPER: SOL–GEL AND HYBRID MATERIALS FOR CATALYTIC,

PHOTOELECTROCHEMICAL, AND SENSOR APPLICATIONS

One-pot synthesis of Nb-modified Al2O3 support for NiMo

hydrodesulfurization catalysts
Esneyder Puello-Polo1 Edgar Marquez2 J. L. Brito3,4
● ●

Received: 11 April 2018 / Accepted: 24 August 2018

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
The effect of Nb as a support modifier on the NiMo6/Al2O3–Nb2O5(x) (x = 0, 1, 4, and 8 wt% Nb) catalysts was studied. The
supports were prepared by one-pot coprecipitation from soluble precursors. The XRF analysis of the catalysts showed that
the contents of Mo and Ni increased slightly with the presence of Nb. Micropore area and pore volume augmented
importantly with Nb content, resulting in pore diameters between 5.3 and 9.3 nm. XPS analysis showed that the presence of
Nb decreases the active metal–support interaction, improving the Mo and Ni sulfidation degree. The Raman spectra of
1234567890();,:
1234567890();,:

sulfided catalysts suggested an increase in the number of layers of MoS2 in the presence of Nb. Generally, the thiophene
HDS activity at normal pressure of sulfided NiMo6/Al2O3–Nb2O5(8) was greater than that of the sulfided catalysts with x =
0, 1, and 4 wt% Nb, which can be attributed to the Nb promotion that would have an effect on the type of active site
(Brønsted or Lewis acidic sites), since the number of sites by CO chemisorption for sulfided NiMo6/Al2O3–Nb2O5(x) did not
show correlation with the catalytic activity. The high-pressure HDS activity of dibenzothiophene was also greater in the
presence of Nb, and the hydrogenation route was preferred for the Nb-promoted solid, while the unpromoted one showed a
larger yield of direct desulfurization products.

Graphical Abstract

* Esneyder Puello-Polo Norte, Barranquilla, Colombia

snypollqco@yahoo.com 3
Laboratorio de Fisicoquímica de Superficies, Centro de Química,
1 Instituto Venezolano de Investigaciones Científicas, IVIC.
Grupo de Investigación en Oxi/Hidrotratamiento Catalítico y
Apartado 20632, Caracas 1020-A, Venezuela
Nuevos Materiales, Programa de Química-Ciencias Básicas
4
Universidad del Atlántico, Barranquilla, Colombia Yachay Tech University, Urcuqui 100119 Imbabura, Ecuador
2
Grupo de investigación en Química y Biología, Universidad del

Highlights
● The niobium-containing catalyst presented the best catalytic activity.
● Niobium promotion influenced the type of active site.
● The presence of Nb improves the sulfidation degree of Mo and Ni.
● Nb increases the number of Lewis acid sites related to HDS activity.
Keywords Anderson-type heteropolyoxomolybdate Hydrodesulfurization Niobia–alumina One-pot synthesis
● ●
1 Introduction
Hydrodesulfurization (HDS) catalysts are fundamental to
decrease pollutant emissions, because sulfur compounds in
fuels cause environmental problems due to the production
of SOx [1, 2]. Alumina is the most used support for
hydrotreatment (HDT) catalysts, since it has excellent
mechanical and dispersion properties [3, 4]. However, alu-
mina shows relatively strong metal–support interactions
with the components of the active phase, which leads to the
formation of compounds non-active for HDT (Ni(Co)
Al2O4) and consequently to partial sulfiding of metal spe-
cies [5, 6]. Although this can be improved by first covering
the alumina surface with a MoO3 monolayer before Ni or
Co impregnation [5], during activation by sulfiding, the
MoO3 monolayer is disrupted and thus direct interaction
promoter-support becomes almost unavoidable. By con-
sidering these limitations, recent studies have shown that it
is convenient to modify the surface properties of the alu-
mina to decrease the metal–support interaction and, in this
regard, the acid–base characteristics of the support would
play a fundamental role in the structure and activity of these
catalysts [4, 6]. Niobium-containing solids have attracted
special attention due to their applications as active phases,
supports, or promoters [7, 8]. However, the use of pure
niobium oxide as support for hydroprocessing catalysts is
limited since it also presents strong metal–support interac-
tion, which affects the catalytic properties [9, 10]. On the
other hand, the addition of niobia as a support promoter to
the catalysts used in HDT could be of interest, as it
apparently leads to increase of the catalytic activities [11].
One of the reasons for this could be attributed to the
occupation of tetrahedral sites by niobium, inhibiting the
formation of Ni(Co) aluminates and resulting in an increase
in the amount of nickel (cobalt) species that can participate
in the decoration of MoS2 slabs by forming “Ni(Co)–Mo–
S” phase, as has been demonstrated for gallium, silicon, and
other alumina-modifier elements [12–14]. The addition of
niobia for the preparation of NiMo/Al catalysts, either as
surface niobium–aluminum oxide phases or as bulk nio-
bium–aluminum oxides has been reported by Weissman,
who suggested that the enhanced activity with the addition
of niobia was due to the increase in the support acidity.
Maximum rates of sulfur and nitrogen removal occurred for
Journal of Sol-Gel Science and Technology
●
niobium–aluminum oxide catalysts containing 5 wt%
Nb2O5 (the highest Lewis acidity) [15]. Rocha et al. com-
pared the activity of NiMoS catalysts supported on niobia,
alumina, and niobia/alumina in HDS and HDN reactions. It
was shown that on a niobia/alumina support, the formation
of the NiMoS phase can be directly linked to alumina not
covered by niobia [16].
Palcheva et al. [17] and Cedeño et al. [18] have reported
the preparation and study of Nb-modified SBA-15, HMS,
and MCM-41 as supports of NiMo. The HDS activity of the
NiMo catalysts supported on Nb-SBA-15, Nb-HMS, and
Nb-MCM-41 was assigned to a better dispersion of Ni and
Mo promoted by Nb. Recently, Mendez et al. studied HDS
over Nb-modified MCM-41-supported NiMo and CoMo
catalysts [19]. The results show that the incorporation of
small amounts of Nb (3–5 wt%) increased the catalytic
activity of both types of catalysts and affected their selec-
tivity. In all these cases, the incorporation of Nb is carried
out by applying a conventional impregnation method. On
the other hand, the incorporation of additional metal com-
ponents during the synthesis of mesoporous materials by a
one-pot process possesses special advantages because the
metal components can be highly dispersed and better resist
against sintering even on suffering from a high-temperature
treatment, as has been shown in a recent study by Lai [20].
In this regard, the present work reports the effect of the
addition of niobium during the synthesis of mesoporous
alumina supports by a one-pot process on some physico-
chemical characteristics of the resulting NiMo/Al2O3–
Nb2O5 catalysts and their HDS activity.
2 Experimental
2.1 Preparation of alumina modified with niobium
The Al2O3–Nb2O5 catalytic supports with different Nb
contents were prepared by a modification of the one-pot
synthesis method of Lai [20]. Appropriate amounts of
AlCl3·6H2O (Sigma-Aldrich, 99%) and urea (Merck,
99.5%) were dissolved in deionized water under constant
stirring at pH between 5 and 6, and then a given quantity of
starch (Sigma-Aldrich, ACS reagent) and the appropriate
amount of ammonium niobate(V) oxalate hydrate (Sigma-
Journal of Sol-Gel Science and Technology

Aldrich, 99.9%) dissolved in a citric acid (Merck, 99.5%)

wt% percentage by weight, SBET BET surface area, Smicro micropores surface area, Sext external surface area, Smicro/SBET fraction of the micropore area to the total surface area, VT total volume of
Mo (wt%) Ni (wt%) Nb (wt%) SBET (m2/g) Sext (m2/g) Smicro (m2/g) Dp (nm) Vmeso (cm3/g) Vmicro (cm3/g) VT (cm3/g) Smicro/SBET (%) Vmicro/VT (%)
solution were slowly added to form a uniform pasty mix-
ture. Finally, the paste was stirred at 363 K for 2 h. Then,

11.9
2.8
6.9
4.7

8.7
the as-made sample was further dried at 423 K for 12 h
overnight and the sample was moved to a tubular furnace
and treated with air at a flow rate of 50 cm3 min−1. Calci-
nation of the precursor was carried out at 873 K for 6 h. The
obtained solid sample was milled and the particles of 100–

13
21
19
30
24
140 mesh were collected for use (denoted as Al2O3–Nb2O5
(x), x = 0, 1, 4, or 8 wt% Nb). The mass ratio of
AlCl3·6H2O:urea:starch:citric acid: (ammonium niobate

0.470
0.282
0.396
0.243
0.222
oxalate) was 1:0.17:0.84:0.1: (0; 0.16; 0.65; or 1.3) so that
the final catalyst contained nominally 0, 1, 4, or 8 wt% Nb.

pores, Dp mean pore diameter, Vmeso mesopore volume, Vmicro micropore volume, Vmicro/VT fraction of the micropore volume to the total volume
2.2 Preparation of catalyst precursors supported on

0.0132
0.0194
0.0190
0.0289
0.0193
Table 1 Composition and textural properties of NiMo6/Al2O3–Nb2O5(x) catalyst varying the content of niobium (x = 0, 1, 4, and 8 wt%)
niobium-modified alumina

The Anderson ammonium salt (NH4)4[NiMo6O24H6]•5H2O

(hereafter named NiMo6) was obtained as described else-
where [21]. The supported precursor from hetero-

0.457
0.263
0.377
0.214
0.203
Specific surface area and porous structure characteristics
polyoxomolybdate complexes was impregnated in excess of
pore volume, adding dropwise an aqueous solution of
NiMo6 (15 wt% Mo and 1.6 wt% Ni) to a flask containing 5

8.1
7.2
9.3
5.9
5.3
g of support, under stirring at 323 K and pH around 5–6.
The impregnation step lasted until removal of the solvent by
evaporation. Finally, the mass obtained was further dried at
423 K for 12 h.
The (NH4)4[NiMo6O24H6]•5H2O supported on alumina
34
49
50
72
48
modified with niobium will be identified as NiMo6/Al2O3–
Nb2O5(x), where x is the weight content of niobium (x = 0,
1, 4, or 8 wt%).
227
184
218
170
150

2.3 Catalyst characterization

The elemental analysis for NiMo6/Al2O3–Nb2O5(x) was

261
233
268
242
198

determined by X-ray fluorescence using a MagixPro PW-

2440 Philips instrument. The results for all compounds were
in agreement, within experimental accuracy, with the
0.920
4.30
7.70

nominal metal contents (Table 1). The textural properties

Experimental composition

–
0

were determined by means of the physisorption of N2 at 77

K using a Micromeritics 3FLEXTM instrument. Prior to the
1.30
1.80
1.90
2.10

measurements, the samples were degassed at 573 K for 16 h

–

in vacuum of 10−6 mmHg. The surface areas of samples

were calculated by the Brunauer–Emmett–Teller (BET)
multipoint method, and the total pore volume and pore size
NiMo6/Al2O3–Nb2O5(0) 13.0
NiMo6/Al2O3–Nb2O5(1) 14.4
NiMo6/Al2O3–Nb2O5(4) 16.2
NiMo6/Al2O3–Nb2O5(8) 16.4
–

distribution were determined from the adsorption branch of

the isotherm using the Barret–Joyner–Halenda (BJH)
model. The total mesopore volume (Vme) and mean pore
diameter (Dp) were provided by the BJH method, while the
Al2O3–Nb2O5(0)

micropore volume (Vmicro) and external surface area (Sext)

were evaluated by the t-plot method. Hence, the total pore
volume was estimated by the addition of microporous and
Solid

mesoporous volumes. The surface area due to micropores


(Smicro) was obtained from the equation: Smicro = SBET−Sext
[21–23]. XRD analysis of the samples was carried out using
a SIEMENS D-5005 diffractometer with a Cu Kα radiation
source (λ = 1.5418 Å) and Ni filter, within the range 5° ≤
2θ ≤ 90°, step size of 0.02°, and acquisition speed of 0.08°/
s. For the identification of the crystallographic phase(s), the
JCPDS data files were preferentially used of Powder Dif-
fraction File, ICDD, Newtown Square, Philadelphia (1995).
The surface composition of both the most active catalyst
and of the unpromoted one (NiMo6/Al2O3–Nb2O5(x) with x
= 8 and 0, respectively) was determined by means of X-ray
photoelectron spectroscopy (XPS) with a Thermo Scientific
K-Alpha spectrometer, equipped with a dual (non-mono-
chromatic) Mg/Al anode, operated at 400 W and under a
vacuum better than 10−9 torr. Calibration of the instrument
was done employing the Au 4f7/2 line at 83.9 eV. The
internal referencing of binding energies was made using the
dominating Al 2p band of the support at 74.4 eV [21].
Before XPS analysis, samples were sulfided ex situ as
described below, afterward immersed in purified n-hexane,
and quickly transferred to the XPS instrument, where the
solvent was slowly removed under vacuum. Curve fitting of
the spectra was carried out by means of the XPSPEAK
version 4.1 and XPS GRAPH programs, using a standard
nonlinear least-squares curve-fitting routine, employing
mixed Gaussian/Lorentzian peak shapes of variable pro-
portion, after baseline subtraction by the Shirley method.
Raman spectra of the catalysts after sulfiding at 593 K
were obtained in a Horiba Scientific Raman micro-
spectrometer LabRAM HR Evolution at room temperature
using the 532-nm line and between 41.1 and 56.1 μW He–
Ne laser as the excitation source through an Olympus TM
BX41 optical microscope. The pyridine adsorption experi-
ments (FTIR Py) of sulfided NiMo6/Al2O3–Nb2O5(x) were
performed with the aim to monitor both the type (Brønsted
or Lewis) of surface acid sites and their relative abundance
[24]. Spectra were recorded in 256 scans using a Nicolet
FTIR spectrometer and the data analysis was performed
with the spectrometer software Omnic 8.1. The spectrum
recorded before adsorption of pyridine was subtracted from
spectra taken after pyridine adsorption. Band intensities
were corrected for slight differences in the weight of the
wafer and normalized to a disk of 8 mg cm−2.
The CO chemisorption analyses of sulfided NiMo6/
Al2O3–Nb2O5(x) were carried out under static volumetric
conditions in a Micromeritics ASAP 2020 apparatus.
Samples were sulfided ex situ and transferred in an inert
atmosphere. Prior to measurement, samples were treated
in situ in H2 at 673 K (30 min) and evacuated at 308 K and
105 kPa for 10 h. The chemisorption isotherm was obtained
by measuring the amount of CO adsorbed between 13.3 and
93.3 kPa at 308 K. The chemisorption stoichiometry
Journal of Sol-Gel Science and Technology
considered to calculate the number of active sites was 1:1.
Likewise, an additional correction for chemisorption on
pure alumina or alumina modified with niobium was
determined under conditions identical to those of the cata-
lyst [25].
2.4 Catalytic tests
Prior to the HDS catalytic reactions, NiMo6/Al2O3–Nb2O5
(x) catalysts were activated by sulfiding in situ under a
feedstock of CS2 (2% in heptane) and 70 cm3 min−1 of
hydrogen at 573 K for 4 h to attain a reproducible and stable
initial state of the catalytic surface. The thiophene HDS
reaction was carried out in a fixed-bed tubular stainless-steel
reactor (30 cm long, 20 mm I.D.) with an axial thermowell
containing a thermocouple centered in the catalyst bed, at
623 K and atmospheric pressure. The HDS test conditions
were 500 mg of catalyst, flow of 0.333 cm3 min−1 of the
thiophene (2%)/C7H16 mixture, 70 cm3 min−1 of H2, 0.1
MPa, and kept for 4.5 h of reaction time.
The HDS of dibenzothiophene (DBT) of NiMo6/Al2O3–
Nb2O5(8), the most active catalyst for thiophene HDS, and
of NiMo6/Al2O3–Nb2O5(0), the unpromoted one, was car-
ried out in a high-pressure batch reactor. In order to mini-
mize internal diffusion limitations, all catalysts were
thoroughly ground in a mortar to a fine powder. After
presulfiding ex situ as described above, the sample was
cooled down to room temperature under a hydrogen flow.
The sulfided catalyst (ca. 500 mg) was then introduced into
the batch reactor containing 100 mL of DBT in cyclohexane
(0.032 mol/L) under the following reaction conditions: the
reactor was pressurized to 8.2 MPa with hydrogen and
heated up to 593 K, and kept for 6 h of reaction time at 700
rpm. The total DBT conversion was calculated as DBT
disappearance, and direct desulfurization (DDS) and
hydrogenation (HYD) selectivities were defined as Eqs. (1)
and (2), respectively:
DDS : ðBPÞ  100%=ðCHB þ BP þ THDBT þ BCHÞ
ð1Þ
HYD : ðCHB þ THDBT þ BCHÞ  100%=
ð2Þ
ðCHB þ BP þ THDBT þ BCHÞ;
where BP, CHB, THDBT, and BCH are biphenyl,
cyclohexylbenzene, tetrahydrodibenzothiophene, and bicy-
clohexyl, respectively.
The course and products of the thiophene and DBT HDS
reaction was followed using a GC–MS Agilent Technolo-
gies 7890B GC System-5977A MSD and a Shimadzu GC-
2014 gas chromatograph, with sampling of the liquid
effluent occurring at 60-min intervals, and the catalytic
Journal of Sol-Gel Science and Technology

350

300

250
Adsorbed volume (cm 3 g-1)

200

150

100

50

0
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
P/P0

Fig. 1 Adsorption/desorption isotherms of N2 at 77 K on the γ-Al2O3

and NiMo6/Al2O3–Nb2O5(x) catalyst varying the content of niobium
(x = 0, 1, 4, and 8 wt%). (□) γ-Al2O3; (▲) NiMo6/Al2O3–Nb2O5(0);
(♦) NiMo6/Al2O3–Nb2O5(1); (■) NiMo6/Al2O3–Nb2O5(4); (●)
NiMo6/Al2O3–Nb2O5(8)

activities of the catalysts were determined. The alumina

support and the Nb-modified alumina showed negligible
thiophene and DBT conversion. Absence of mass and heat-
flow transport effects was verified according to established
procedures [26].
All experiments reported in this work (synthesis proto-
cols, characterizations, and catalytic activity measurements)
were carried out at least in duplicate. Good reproducibility
was verified, better than 10% in all quantitative Fig. 2 XRD of NiMo6/Al2O3–Nb2O5(x) catalyst varying the content of
measurements. niobium (x = 0, 1, 4, and 8 wt%). (●) γ-Al2O3

3 Results and discussion
3.1 Textural properties
The N2 physisorption isotherms of γ-Al2O3 and NiMo6/
Al2O3–Nb2O5(x) are shown in Fig. 1 and the textural data
derived from the isotherms are summarized in Table 1. All
the isotherms belong to type IV in the IUPAC classification.
In their initial part, they show a fast increase that reflects
significant micropore surface area and volume which aug-
ment importantly with Nb content. Thus, when comparing
the undoped γ-Al2O3 with NiMo6/Al2O3–Nb2O5(x), Smicro/
SBET varies between 13 and 30% and Vmicro/VT between 2.8
and 11.9%. These trends can be attributed to the generation
of microporosity induced by Nb (see Table 1). The hys-
teresis loops can be observed at intermediate and high
relative pressures (P/P0 > 0.5), which is mainly due to the
presence of ink-bottle type of mesopores [27]. The overall
surface area was found to increase as follows: NiMo6/
Al2O3–Nb2O5(8) < NiMo6/Al2O3–Nb2O5(0) < NiMo6/
Al2O3–Nb2O5(4) < Al2O3 < NiMo6/Al2O3–Nb2O5(1), while
the total pore volume follows roughly the same trend. From
the corresponding pore size distributions, the precursors and
supports mostly locate in the range of mesopores (2–50
nm), with values of BJH mesopores mean size between 5.3
and 9.3 nm.
As listed in Table 1, the presence of Nb causes a more
pronounced decrease of the surface area for samples con-
taining Mo and Ni with respect to the bare support (except
NiMo6/Al2O3–Nb2O5(1) which can be related to the large
generation of micropores in this case). Such behavior can be
related to the migration of the metallic phases into the
support pores during the impregnation process and/or
synthesis of the material that decreases their pore volume
and therefore the surface area [28].
3.2 XRD analysis
The XRD analysis of NiMo6/Al2O3–Nb2O5(x) with x = 0, 1,
4, and 8 wt% Nb, irrespective of the presence of Nb,
revealed no lines other than those characteristics of γ-Al2O3
at 2θ = 67.10; 45.90; and 37.48 (card No. 10-0425, see Fig.

Fig. 3 X-ray photoelectron spectra Mo 3d, Ni 2p, and S 2p regions of sulfided NiMo6/Al2O3–Nb2O5(x) catalyst varying the content of niobium
(x = 0 and 8 wt%)
2) and it did not show appreciable changes on XRD pat-
terns. Diffraction peaks due to (NH4)4[NiMo6O24H6]•5H2O
or Nb2O5 were absent probably because the crystallites are
too small to give XRD signals or the particles of POMs and
Nb2O5 were well dispersed on the support.
3.3 XPS analysis
Figure 3 presents the XPS spectra of the Mo 3d5/2–3/2 region,
showing signals that confirm the presence on the surface of
Mo4+ (229 eV) attributable to sulfide-phase Mo5+ (230.3
eV) that can be assigned to oxysulfide species and Mo6+
(232.5 eV) which can be identified as MoO3-like com-
pounds [29, 30]. It can be seen that Nb presence is reflected
in a higher amount of Mo4+ (sulfided) species and lower
concentrations of surface oxidic phases (Mo5+ and Mo6+).
Likewise, in the XPS spectral Mo 3d5/2 region, a quite
visible shoulder is found at 226.5 eV, corresponding to the
2-s signal of sulfur. This can be confirmed by the presence
of three bands in the S 2p3/2 region [30]: a signal at 161.7
eV due to terminal disulfide and/or sulfide (S2–) ligands in
MoS2 or NiS phases, another signal at 163.1 eV corre-
sponding to bridging disulfide (S22−) ligands, and the signal
at 168.9 eV which can be assigned to SO42−. The signals
due to sulfide and disulfide species are much more
Journal of Sol-Gel Science and Technology
important for the Nb-containing sample, which showed no
presence of sulfates.
The Ni 2p region spectra show four Ni 2p3/2–1/2 peaks at
853.1–853.6; 854.2, 856.1–856.7; and 862 eV [31]. These
signals suggest the presence of NixSy sulfide phases (Ni2S3,
Ni9S8, or NiS), the so-called NiMoS phase, the NiMoO4
species, and the strong shake-up lines characteristic of Ni2+
species in a Ni–Mo–O matrix. Note that the signal assigned
to NiMoS is more prominent for the Nb-containing catalyst,
at the expense of the NiMoO4 one. In this regard, the (Ni +
Mo)/S atomic ratio is higher for NiMo6/Al2O3–Nb2O5(0)
than for NiMo6/Al2O3–Nb2O5(8) (Table 2).
The XPS spectra of Nb 3d5/2–3/2 (not shown), reported a
doublet centered at 207.6 and 210.3 eV which can be
assigned to Nb5+ as in Nb2O5 [32].
In spite of the variation of the types of species of Mo, Ni,
and S at the surface by the presence of Nb, their total atomic
percentages do not have significant differences. This is
possibly because the synthesis of both catalysts from an
Anderson–Evans-type heteropolyanion guarantees uni-
formity in the deposition of the precursor as it has been
reported by Puello et al. [13, 21]; hence, the Ni/Mo atomic
ratios were in agreement (see Table 2). On the other hand,
the species of Mo and Ni partially sulfided of these catalysts
have been evidenced in a variety of studies [33]. These
Journal of Sol-Gel Science and Technology

Atomic ratio—

SO42− 168.9 eV Mo/Ni (Mo +

Ni)/S

1.5

1.3
XPS

6.8

6.8
NiMo6/Al2O3-Nb2O5(8)

36.8
(%)

NiMo6/Al2O3-Nb2O5(4)
–
S22−163.1 eV
Table 2 Distribution of Mo, Ni, and S surface species in sulfided NiMo6/Al2O3–Nb2O5(x) catalyst varying the content of niobium (x = 0 and 8 wt%)

12.4

15.5
(%)
Ni2+ 856.7 eV S2− 161.7 eV
S 2p3/2–2p1/2

NiMo6/Al2O3-Nb2O5(1)
50.8

84.5
(%)

NiMo6/Al2O3-Nb2O5(0)

320 350 380 410 440 470 500

40.0

30.9
(%)

Raman shift (cm-1)

Mo4+ 229 eV Mo5+ 230.3 eV Mo6+ 232.5 eV NixSy 853.3 eV NiMoS 854.2 eV

Fig. 4 Raman spectra of sulfided NiMo6/Al2O3–Nb2O5(x) catalyst

varying the content of niobium (x = 0, 1, 4, and 8 wt%)
26.7

32.3
(%)

works showed that it is possible that the catalysts react with

the gaseous H2S produced during the HDS reaction to
Ni 2p3/2–2p1/2

become completely sulfided.

3.4 Raman analysis and FTIR of adsorbed pyridine

19.5

18.4
(%)

The Raman spectra (see Fig. 4) collected after sulfidation at

593 K for NiMo6/Al2O3–Nb2O5(x) catalysts display two
main Raman active modes characteristic of the bulk or
25.7

24.6

multilayered MoS2, the E2g1 (in-plane vibration) and A1g

(%)

(out-of-plane vibration) [34]. It has been demonstrated that

the frequency difference between E2g1 and A1g modes can
be used as a robust and convenient preliminary diagnostic
of the layer thickness of MoS2 samples [34]. In this regard,
11.9
(%)

9.7

the Raman spectra of the catalysts independently of the

Mo 3d5/2–3d3/2

presence of Nb exhibit this doublet characteristic of MoS2

with Δω = 26 to Δω = 24, suggesting an increase in the
number of layers of MoS2 (around 3–4 layers) [34]. Figure
62.3

65.8
(%)

4 also shows that the E2g1 and A1g bands in the spectrum of
NiMo6/Al2O3–Nb2O5(x) with x = 0, 4, and 8 are broader
than the corresponding bands of NiMo6/Al2O3–Nb2O5(1),
NiMo6/Al2O3–

NiMo6/Al2O3–

which is likely induced by the growth of the MoS2 crystal

Nb2O5 (0)

Nb2O5 (8)

size.
Figure 5 shows the IR bands characteristics of the pyr-
Solid

idine adsorbed on Lewis acid sites (LAS) and Brønsted acid

 Journal of Sol-Gel Science and Technology

sites (BAS) of the sulfided NiMo6/Al2O3–Nb2O5(x) [35].
LAS sites are evidenced by a ν8a band at around 1610 cm−1
and a ν19b band at around 1450 cm−1. Adsorption of Py on
BAS leads to a ν8a band at around 1630 cm−1 and to a ν19b
band at around 1545 cm−1, and a peak at 1490 cm−1 is
assignable to a mixture of LAS and BAS. Quantitative
results are shown in Table 3, and the amount of Brønsted
sites is high in NiMo6/Al2O3–Nb2O5(1) and NiMo6/Al2O3–
Nb2O5–Nb2O5(4) catalysts, which is in agreement with the
LAS
LAS
more intense envelope in the FT–IR spectra of the OH
region for these catalysts (not shown). On the other hand,
NiMo6/Al2O3+Nb(x) with x = 1, 4, and 8 wt% exhibit a
larger amount of LAS than NiMo6/Al2O3+Nb(0). The
amount of LAS and total acidity was found to increase as
follows: NiMo6/Al2O3–Nb2O5(0) < NiMo6/Al2O3–Nb2O5
(1) < NiMo6/Al2O3–Nb2O5(4) < NiMo6/Al2O3–Nb2O5(8).
This steady increase in acidity and consequent improved
interaction with the NiMo6 precursor could explain the
slight augment of Mo and Ni concentrations with increasing
Nb content (Table 1).
3.5 Catalytic test

BAS Thiophene HDS activities (Table 3) are reported as con-

version percent after ~4.5 h of reaction time (steady state).
BAS
LAS + BAS No correlation was found between textural properties (sur-
face area and pore volume) and the conversion of thio-
phene. On the other hand, the amount of Nb had a large
NiMo6/Al2O3-Nb2O5(8) effect as shown in Table 3; hence, the overall activities of
the thiophene HDS (sulfided precursors) correlated well
with the Nb content, as follows: NiMo6/Al2O3–Nb2O5(0) =
41% < NiMo6/Al2O3–Nb2O5(1) = 47% < NiMo6/Al2O3–
Nb2O5(4) = 50% < NiMo6/Al2O3–Nb2O5(8) = 54%.
NiMo6/Al2O3-Nb2O5 (4)
The CO chemisorption values of the freshly sulfided
catalysts are included in Table 3. Clearly, a significant
correlation between thiophene conversion and the CO
chemisorption capacity is not observed. This means that the
differences in thiophene conversion observed for these
NiMo6/Al2O3-Nb2O5(1) catalysts are not due to increasing concentrations of surface
active sites, but to differences due to the nature of the sites
depending on the Nb content in the catalysts. One clear
difference seems to be the concentration of LAS (Table 3)
NiMo6/Al2O3-Nb2O5(0) which would be related to the adsorption of thiophene on or
close to the active sites. Another one would be the optimal
sulfiding of the surface, guaranteeing the formation of the
1700 1650 1600 1550 1500 1450 1400
NiMoS active phase as suggested from the XPS results.
wavenumber (cm-1) Thus, the results of catalytic activity obtained in this work
Fig. 5 FTIR spectra of pyridine adsorbed over sulfided NiMo6/Al2O3– may be correlated with the presence at the surface of
Nb2O5(x) catalyst varying the content of niobium (x = 0, 1, 4, and 8 wt molybdenum and nickel species, such as Mo4+ and NiMoS
%)

Table 3 Steady-state thiophene HDS activity, proportion of Lewis/Brönsted surface acid sites, and CO uptake of NiMo6/Al2O3–Nb2O5(x) catalyst
varying the content of niobium (x = 0, 1, 4, and 8 wt%)
Catalysts Activity × 106 (mol Th conv/g Cat min) Pyridine adsorption(μmol Py/ CO uptake
gCatalyst)
LAS BAS Total acidity μmol/gCatalyst μmol/m2

NiMo6/Al2O3–Nb2O5(0) 16.74 2.93 0.260 3.19 31.91 0.137

NiMo6/Al2O3–Nb2O5(1) 19.18 3.07 2.07 5.14 32.91 0.131
NiMo6/Al2O3–Nb2O5(4) 20.41 5.45 1.48 6.93 21.67 0.090
NiMo6/Al2O3–Nb2O5(8) 22.04 6.33 3.67 10.0 27.02 0.136
LAS Lewis acid sites, BAS Bronsted acid sites
Journal of Sol-Gel Science and Technology
Table 4 Steady-state
Catalysts Product distribution at 40% of DBT conversion
dibenzothiophene HDS
conversion, product distribution, DDS
and HYD/DDS ratio (at 40% of
DBT conversion) of NiMo6/ BP (%) CHB (%) BCH (%) THDBT (%)
Al2O3–Nb2O5(x) catalyst
varying the content of niobium NiMo6/Al2O3– 29.6
(x = 0 and 8 wt%) Nb2O5(0)
NiMo6/Al2O3-Nb2O5 17.0
(8)
(Table 2). It is clear that the presence of Nb induces a
greater catalytic activity, suggesting that the surface species
of NiMo6/Al2O3–Nb2O5(x) are important for the HDS
reaction.
To further test the catalysts in more real conditions, high-
pressure experiments of DBT HDS were carried out with
the Nb-unpromoted catalyst and the promoted one showing
higher thiophene HDS conversion. Table 4 shows the DBT
conversions obtained with NiMo6/Al2O3–Nb2O5(0) and
NiMo6/Al2O3–Nb2O5(8) at 6 h of reaction time and the
product distributions observed at 40% of DBT conversion.
The HDS reaction occurs through two different routes: DDS
yielding BP and HYD that yields THDBT, CHB, and
dicyclohexyl (DCH). Nb-containing catalysts proved to be
more active than catalysts without Nb and relative amounts
of the obtained products depended on the Nb presence. The
main desulfurized reaction products obtained were BP,
CHB, and THDBT. The DDS product was formed in a
larger proportion for the NiMo6/Al2O3–Nb2O5(0) catalyst,
while the products of the HYD route (THDBT + CHB +
DCH) were predominantly formed with the NiMo6/Al2O3–
Nb2O5(8) catalyst, which is reflected in the HYD/DDS ratio.
This result is in good agreement with previous literature
reports for Nb-modified NiMo/Al2O3 catalysts [19].
4 Conclusions
One-pot synthesis method was successful in introducing Nb
into Al2O3 as a fast preparation way to supports for HDS
catalysts. The characterization techniques demonstrated that
Nb presence influences the physicochemical properties of
the NiMo-impregnated catalysts. Ni and Mo contents
slightly increased in Nb presence, but no crystalline phases
such as the heteropolymolybdate precursor or Nb2O5 were
detected. XPS analysis showed for the sulfided NiMo6/
Al2O3–Nb2O5(0) and NiMo6/Al2O3–Nb(8) similar species
of Mo and Ni on the surface; however, the S species type
and relative proportions of Mo, Ni, and S species depended
on the presence of Nb, suggesting less active metal–support
interaction that improves the sulfidation degree of Mo and
Ni. The Raman spectra for sulfided NiMo6/Al2O3–Nb2O5(x)
suggest an increase with Nb of the S/Mo atomic ratio of
DBT conversion (%) at
6h
HYD HYD/
DDS
3.15 0.10 1.46 0.16 71
20.6 0.00 3.10 1.36 83
MoS2 and crystal sizes of around 3–4 layers for the latter. It
was found that the overall thiophene HDS conversion par-
allels the Nb content of the catalysts, but did not show any
correlation with the textural properties (surface area or pore
volume) nor with the total number of sites, as measured by
CO chemisorption. Instead, a good correlation with the
amount of LAS, probably arising from the presence of Nb,
was found. Thus, the effect of Nb seems to be modifying
the nature and not the number of active sites. Results of
HDS of DBT confirmed that the catalyst containing Nb is
more active than the unpromoted one, and showed pre-
ference for the HYD route against the DDS route observed
for the catalyst supported on alumina.
Acknowledgements The authors would like to acknowledge financial
support to Universidad del Atlántico-Colombia (through Project
CB21-FGI2016 “7ma Convocatoria 2016”). E.P.P. dedicates this work
to Ofelia Polo (R.I.P.).
Compliance with ethical standards
Conflict of Interest The authors declare that they have no conflicts of
interest.
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