Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and Heterogeneous Catalyst for the Hydrogenation of Benzene, Ethylbenzene and Xylenes

Article abstract of DOI:10.1007/s10562-019-02678-x

The catalytic activity of synthesized by the template method mesoporous silica doped with dysprosium and modified with nickel (Dy-Ni/MPS) in the hydrogenation of benzene, ethylbenzene and xylenes has been studied. The catalyst is characterized by various techniques such as TEM, SEM, BET, XRD, ICP, XRF analyses. It is shown that the presence of dysprosium in the MPS structure increases the activity of the catalyst. The catalytic activity of the catalyst (Dy-Ni/MPS) has been explored in hydrogenation reaction of benzene derivatives with excellent conversion (96–100%) at low pressure. Graphical Abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s10562-019-02678-x

Catalysis Letters
https://doi.org/10.1007/s10562-019-02678-x
Mesoporous Silica Doped with Dysprosium and Modified with Nickel:
A Highly Efficient and Heterogeneous Catalyst for the Hydrogenation
of Benzene, Ethylbenzene and Xylenes
1
1
1
1
R. V. Shafigulin · E. O. Filippova · A. A. Shmelev · A. V. Bulanova
Received: 10 October 2018 / Accepted: 13 January 2019
©
Springer Science+Business Media, LLC, part of Springer Nature 2019
Abstract
The catalytic activity of synthesized by the template method mesoporous silica doped with dysprosium and modified with
nickel (Dy-Ni/MPS) in the hydrogenation of benzene, ethylbenzene and xylenes has been studied. The catalyst is character-
ized by various techniques such as TEM, SEM, BET, XRD, ICP, XRF analyses. It is shown that the presence of dysprosium in
the MPS structure increases the activity of the catalyst. The catalytic activity of the catalyst (Dy-Ni/MPS) has been explored
in hydrogenation reaction of benzene derivatives with excellent conversion (96–100%) at low pressure.
Graphical Abstract
Keywords Heterogeneous catalyst Dy-Ni/MPS · Hydrogenation of benzene derivatives
Extended author information available on the last page of the article
Vol.:(0
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R. V. Shafigulin et al.
1
Introduction
Germany), dysprosium chloride (abcrGmbH, Germany),
nickel chloride (abcrGmbH, Germany), ammonium hydrox-
ide (abcrGmbH, Germany), ethanol (abcrGmbH, Germany),
cetyltrimethammonium bromide (CTAB) (abcrGmbH,
Germany), benzene (abcrGmbH, Germany), ethylbenzene
(abcrGmbH, Germany), o-xylene (abcrGmbH, Germany),
m-xylene (abcrGmbH, Germany), p-xylene (abcrGmbH,
Germany).
The hydrogenation of unsaturated and aromatic hydrocarbons
is one of the main reactions of the oil refining and petrochemi-
cal industries [1–3]. Generally, these processes occur at high
temperatures and pressures, so the search for new efficient and
selective catalysts that would allow developing energy-saving
technologies is a current scientific direction [4–6].
Over the past few decades, interest in mesoporous silica gels
is increasing due to a number of advantages of these materi-
als, such as chemical inertness, highly developed surface area,
chemical and mechanical stability, low toxicity and biospecific-
ity. All of these properties make mesoporous silica gels promis-
ing for their use as sorbents and carriers for catalysts [7–11].
The surface of mesoporous silica modify with various com-
pounds to impart catalytic properties. The obtained materials
combine the initial properties of silica gel and the properties
of the grafted compound [12, 13]. Modified porous silica are
widely used as catalyst carriers for such industrially important
processes as oxidation of organic [14–17] and inorganic [18,
2.2 Synthesis of Mesoporous Silica
Following samples of mesoporous silica were prepared
by the template method: an unmodified mesoporous sil-
ica (MPS), silica modified with nickel nanoparticles (Ni/
MPS), silica doped with dysprosium and modified with
nickel (Dy-Ni/MPS). CTAB (0.78 g) as a structure-forming
agent (template) was dissolved in a water-alcohol medium
at the room temperature with stirring for 30 min. Then
TEOS (3.14 mL) was added dropwise, and the solution
was stirred for another 30 min. The pH of the reaction mix-
ture was adjusted to 10 by adding ammonia solution (27%
1
9] substances, hydrogenation [20–22], dehydrogenation [23,
4] and many others [25–28].
2
8
mL), and then stirred for 5 h. The reaction mixture was
Various heterogeneous hydrogenation catalysts have been
air dried for 24 h at room temperature, and then the sample
was placed in the autoclave (NoaLabShaker2.0/Shaker2.1)
for 5 h. To study the effect of pressure on texture and mor-
phological characteristics of mesoporous silica gels, syn-
thesis was carried out at different pressures − 2, 5, and
developed and investigated. The range of used metals is very
wide—from basic (for example, nickel and copper) to noble
metals (for example, platinum and palladium). The d-band
model has been particularly useful in investigating and systema-
tizing the correlation between the electronic structure and the
catalytic activity of transition materials. Theoretical study on the
example of ethylene hydrogenation shows that activation barri-
ers for hydrogenation and dehydrogenation depend on the loca-
tion of the d-band center of the metal catalyst with respect to the
1
3 atm at 115 °C. After autoclaving, the obtained samples
were filtered and washed with deionized water until neutral
pH = 7 ÷ 7.5). Samples were heated in a muffle furnace
(
for 5 h at 650 °C to remove the template. The obtained
unmodified mesoporous silica was doped with dysprosium
as follows: at the beginning of the synthesis, dysprosium
chloride (0.02 g) was added while stirring of CTAB and
TEOS, and then the mixture was autoclaved as described
above. The molar ratio Dy/Si was 0.01. The presence of
dysprosium in the structure of MPS was confirmed by
X-ray fluorescence analysis (XRF) and ICP using spec-
trometer PlasmaQuant PQ9000. The concentration of dys-
prosium was 1,3% by weight.
Fermi level [29, 30]. Several authors prepared SiO -supported
2
monometallic Ni and bimetallic catalysts with Ni, Pd, Pt, Cu, In
nanoparticles. They were found as catalysts in the hydrogenation
reaction of benzene, toluene and xylenes [31–35].
Catalysts based on mesoporous silica have a number of
advantages, such as wide accessibility of these materials, high
stability and the potential for repeated use with minimal loss of
activity, due to the possibility of separation from the reaction
mixture by filtration or decantation [36].
The aim of the work was the synthesis of mesoporous silica
doped with dysprosium and modified with nickel, and a com-
parative study of their catalytic properties in the reaction of
hydrogenation of benzene, ethylbenzene and xylenes.
2
.3 Catalysts Preparation
The modification with nickel of synthesized unmodified
MPS) and dysprosium-doped (Dy/MPS) silica was carried
(
out as follows: the MPS and Dy/MPS samples weights were
placed in alcoholic solution of nickel (II) chloride and stirred
for 2 h. Ethyl alcohol was evaporated, and then the sample
was heated in a muffle furnace at 450 °C in a stream of
hydrogen for 5 h to reduce nickel. The presence of nickel in
the sample was confirmed by XRF and ICP analyses. The
2
Experiment
2.1 Chemicals
The following commercial reagents were used to synthesize
the catalysts: tetraethyl orthosilicate (TEOS) (abcrGmbH,
1
3

Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and…
nickel concentration in the samples of mesoporous silica
was 8% by weight.
in a static regime at the temperature range 80–170 °C and a
hydrogen pressure of 3 atm on an original apparatus allow-
ing an on-line analysis of the reaction mixture (Scheme 1)
[37].
2
.4 Investigation of Texture Characteristics
and the Surface Morphology of Synthesized
MPS and Catalysts Obtained on Their Basis
1—tank with carrier gas, 2—reducing valve, 3—valve con-
trolling the flow rate of the carrier gas, 4—gage measuring
the pressure of the carrier gas in the analytical column, 5—
computer and AD converter, 6—heat-conductivity detector,
7, 16—thermostats, 8—analytical column, 9—6-port three-
way valve, 10—valve at the hydrogen outlet from the reac-
tor, 11—gage measuring the hydrogen pressure in the reactor,
12—hydrogen pressure reducer for delivery of hydrogen into
the reactor, 13—evaporator (input of reagents into the reactor),
14—hydrogen generator, 15—reactor.
The texture characteristics of the samples were determined
by nitrogen adsorption–desorption isotherms measurement
at low temperature using Quantochrome Autosorb-1. The
Brunauer-Emmett-Teller model (BET) was used to deter-
mine the specific surface area. The total pore volume and
mesopore size distribution were calculated from the des-
orption curve using the Barrett-Joyner-Khalenda (BJH)
model. The DFT density functional method was used for
the analysis of micropores. The particle size MPS and
shape of the obtained mesoporous materials were exam-
ined by the electron microscopy using a scanning electron
microscope CarlZeiss EVO 50 with an X-Max 80 energy
dispersive attachment. The XRD analysis of synthesized
MPS structures and identification of nickel phase were
recorded using a Rigaku Miniflex 600 diffractometer
The apparatus is constituted by the reaction unit (thermo-
stat with evaporator for introduction of liquid samples into the
reactor) and analytical unit, a gas chromatograph TraceGC
with a flame ionization detector (FID). The units are con-
nected with a 6-port three-way injection valve. The chemical
reactor is a steel tube. The catalyst weight is 0.3 g. Reagent
3
samples were injected into the reactor (volume 1 cm ) with
a micro syringe (sample volume 1 µl) in a hydrogen stream.
Hydrogen was produced using a hydrogen generator. The first-
order equation was used to calculate the rate constant. Since
the reaction was run in excess hydrogen, the reaction kinetics
obeyed the first-order equation [38, 39].
(
Japan) equipped with a detector with a graphite mono-
chromator and a copper anti-cathode, Cu-Kα radiation
λ = 1.54187 Å). Additionally, samples of catalysts were
(
investigated by transmission electron microscopy (TEM)
on LEO912 AB OMEGA microscope at an accelerating
voltage of 100 kV using standard copper grids with a poly-
vinylformal films with a diameter of holes 100 µm.
From the experimental data were determined:
Reaction rate constant:
c0
1
k = ⋅ ln
(
1)
t
ct
2.5 Study of Catalytic Activity
where C is the concentration of reagents at the initial
0
The catalytic activity of the obtained samples was studied on
the example of hydrogenation of benzene, ethylbenzene, o-,
m-, p-xylenes. The hydrogenation kinetics was carried out
time of the reaction (t = 0) and C is the concentration of
t
reagents at time t.
Scheme 1 The original appa-
ratus for hydrogenation and
analysis of the reaction mixture
1
3

R. V. Shafigulin et al.
Conversion (K,%) of the starting reagents:
3 Results and Discussion
ꢀ
ꢁ
ct
K = 1 −
⋅ 100
(2)
3.1 Influence of Synthesis Conditions
c0
on Morphology and Texture Characteristics
of Mesoporous Silica
≠
The experimental activation energy (E ) was founded
from the graphical dependence in the coordinates of the
Arrhenius equation (lnk−1/T).
The surface area, volume and pore diameter of the synthe-
sized MPS samples were measured by the methods described
in Sect. 2.4.
To determine the contribution of the activation energy
and entropy to the reaction rate constant, the entropy of acti-
vation was calculated by the equation [37]:
Figure 1 shows isotherms of adsorption and desorption
for synthesized samples of unmodified mesoporous silica
obtained at different pressures and different concentrations
of CTAB.
ꢀ
ꢁ
Ah
kTex
≠
ΔS = Rln
+ (1 − x)Rln(RT)
(3)
p
ꢀ
The obtained data of the specific surface area and the tex-
tural characteristics of synthesized mesoporous silica (MPS)
are given in Table 1.
where, A is the pre-exponential factor in the Arrhenius
equation; R—gas constant; k—Boltzmann constant; h—
Plank constant; T—temperature; x—reaction molecularity;
and χ—transmission factor.
With an increase of pressure during synthesis, the specific
surface area of MPS samples decreases. The MPS sample
Fig. 1 Adsorption and desorption isotherms (a); pore size distribution determined by the method of BJH (b); and by the DFT (c) for MPS sam-
ples synthesized at 2 atm, 5 atm, 13 atm and 5 atm (surfactant×2) with a doubled concentration of CTAB (surfactant×2)
1
3

Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and…
Table 1 Effect of different
pressures on specific surface
areas and textural characteristics
of synthesized mesoporous
silica
2
Sample
S (BET) (m /g)
V
(ВJH)
Def (BJH) (nm)
D (DFT)
ef
pore
3
(
cm /g)
(nm)
MPS (2 atm)
666± 33
579± 29
1.462
0.913
4/39
4
2.18
2.38
MPS (5 atm, Sur-
factant*2)
MPS (5 atm)
MPS (13 atm)
600± 30
563± 28
0.828
1.266
4
4/43
2.38
2.38
that MPS synthesized at 5 atm has optimal textural char-
acteristics, therefore, only this pressure was used to obtain
samples of catalysts based on MPS further.
Mesoporous silica doped with Dy was synthesized at a
pressure of 5 atm and a Dy/Si molar ratio equal to 0.01.
The presence of dysprosium in the structure of mesoporous
silica was confirmed by X-ray fluorescence and ICP analysis
(
Figs. 2, 3, 4).
The modification of an unmodified mesoporous silica
sample with nickel (Ni/ MPS) and it’s doping with dys-
prosium (Dy-Ni/MPS) was carried out as described above
(
Sect. 2.3).
Fig. 2 X-ray fluorescence analysis of mesoporous silica modified
Figure 3 shows the X-ray fluorescence spectra confirming
with dysprosium (Dy/ MPS)
the presence of nickel in the matrix of mesoporous silica.
Figure 4 shows the spectra obtained by the ICP method
for Ni/MPS, Dy-Ni/MPS.
synthesized at 2 atm is characterized by a maximum pore
volume, and the MPS sample synthesized at 5 atm by a
minimum pore volume. From the data presented in Table 1
follows that synthesized samples are characterized by both
a monomodal and bimodal distribution of pores. The MPS
samples synthesized at a pressure of 2 and 13 atm are char-
acterized by the presence of mesopores with an effective
diameter of 39 and 43 nm, respectively. Along with the
monomodal distribution of pores the sample obtained at a
pressure of 5 atm is also characterized by their smallest vol-
ume, which suggests that nickel will be sorbed in these pores
as nanoparticles during the modification. Thus, it follows
Thus, the presence of nickel and dysprosium in the MPS
structures and their quantitative content was established by
the ICP method. The content of nickel was 8% by weight,
and dysprosium 1,3% by weight. This indicates a complete
reduction of nickel from nickel chloride using the above
method, described in paragraph 2.3.
The textural characteristics for mesoporous silica Dy/
MPS, Ni/MPS, Dy-Ni/MPS are given in Table 2.
Analyzing Tables 1 and 2, it can be concluded that the
inclusion of dysprosium into the structure of mesoporous sil-
ica leads to a decrease in the specific surface area from 600
Fig. 3 XRF-spectra for mesoporous silica samples: a nickel-modified (Ni/MPS); b doped with dysprosium and modified with nickel (Dy-Ni/
MPS)
1
3

R. V. Shafigulin et al.
Fig. 4 Spectra of Ni/MPS, Dy-Ni/MPS obtained by the ICP method: a spectrum of nickel; b dysprosium spectrum; c chlorine spectrum
Table 2 Specific surface area and textural characteristics of Dy/MPS,
additional phases with the mesoporous matrix. The presence
of nickel in the metal phase form was confirmed by the pres-
ence of reflections (2Θ=44.5°, 51.9°, 76.4°) on the diffrac-
togram of Ni/MPS and Dy-Ni/MPS samples corresponding
to the reflections of a cubic face-centered cell of metallic
nickel with Brava indices (111), (200), (220) respectively.
In addition to XRD method, the obtained samples were
analyzed using TEM, and the results of which are shown
in Fig. 6.
Ni/MPS, Dy-Ni/MPS
2
Sample
S(BET) (m /g)
V
ВJH
D (BJH)
ef
pore
3
(
cm /g)
(nm)
Dy/MPS
Ni/MPS
Dy-Ni/MPS
514± 20
235± 12
215± 12
0.457
0.305
0.298
3.8
4
4
Analysis by TEM showed that nickel predominantly
localized in the pores of materials mesoporous matrix. The
average particle size of nickel is not significantly differ-
ent for the Ni/MPS and Dy-Ni/MPS samples and is about
3.7 ± 0.5 nm. However, for the Ni/MPS sample, there are
conglomerates with particle sizes of about 20–30 nm.
Figure 7 shows the SEM photographs at different zoom-
ing for the two samples, used as catalysts for the hydrogena-
tion reaction of benzene, ethylbenzene and xylenes.
Figure 7 shows that the morphology of the surface of
mesoporous silica due to doping with dysprosium is trans-
formed. Dy-Ni/MPS used as a catalyst is characterized by a
looser structure comparing to Ni/MPS. The average particle
size for Ni/MPS is 75 nm, and for Dy-Ni/MPS is 100 nm.
The above results show that the Ni/MPS and Dy-Ni/MPS
structures are different, therefore, the structure of the active
centers also differs, which explains the change, namely the
2
to 514 m /g. The specific surface area of Ni/MPS decreases
almost by a factor of 2.5 which is possibly due to nickel
adsorption in the pores of MPS.
The XRD method was used to confirm the structure of the
synthesized mesoporous silica. Figure 5 shows the compara-
tive diffraction patterns for the three MPS samples.
Characteristic peaks in the small angle region indicate
the presence of ordered systems of mesopores (MCM-41
phase) in MPS, Ni/MPS, Dy-Ni/MPS structures. For the
Dy-Ni/MPS sample, the shift of the characteristic peak to
lower angles and a less relative intensity were revealed.
Apparently, these changes are caused by the incorpora-
tion of dysprosium into the MPS structure upon doping.
Such changes are not observed for the sample modified
with nickel, since it is predominantly located in the pores
of the mesoporous matrix in the metallic and does not form
1
3

Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and…
Fig. 5 Diffraction patterns for MPS, Ni/MPS, Dy-Ni/MPS
increase in the catalyst with dysprosium embedded in the
silica structure, as shown in Sect. 3.2.
and its derivatives. The table shows the selectivity of the
reaction for the products. Table 3 shows the selectivity of
the catalyst for each reagent.
3.2 Kinetic Study of the Hydrogenation
The rate constant was calculated graphically in the coor-
dinates of Eq. (1) the coefficient of determinism for the lin-
2
The determining factor for evaluating the effectiveness of the
catalyst is the conversion of the reactants during the reac-
tion. Figure 8 shows the conversions of benzene, ethylben-
zene and xylenes in the hydrogenation reaction on the Ni/
MPS and Dy-Ni/MPS catalysts at 150 °C and a hydrogen
pressure of 3 atm.
ear equations of the first-order R =0.99. The value of the
constant was determined from five parallel experiments with
a relative error not exceeding 3% (the table shows the aver-
age values of the rate constants).
The rate constants, activation energy and entropy of
the hydrogenation reactions of benzene, ethylbenzene and
xylenes at different temperatures on Dy-Ni/MPS catalyst are
shown in Table 4.
Doping with dysprosium and modification with nickel of
doped mesoporous silica leads to an increase of the catalytic
activity in the hydrogenation of xylenes and ethylbenzene.
Thus, the conversion of ethylbenzene after 10 min from
the start of the reaction is 100% on Dy-Ni/MPS, and only
Comparing the rate constants, activation energy and
entropy of the hydrogenation reaction listed in Table 4, it
can be concluded that the highest catalytic activity Dy-Ni/
MPS catalyst exerts with respect to ethylbenzene. For
xylenes, the catalytic activity decreases as follows: from
p-xylene, to m-xylene and o-xylene. The determining factor
in the hydrogenation of these compounds is the activation
energy. The lowest catalytic activity Dy-Ni/MPS shows in
the hydrogenation of benzene, and the activation rate is the
determining factor for the reaction. The hydrogenation of
benzene is characterized by the higher values of entropy
and activation energy in comparison to the ethylbenzene and
8
0% on Ni/MPS. O-xylene, m-xylene and p-xylene are fully
hydrogenated after 30 min on Dy-Ni/MPS catalyst, and just
8
3
0% of xylenes are hydrogenated on Ni/MPS catalyst after
0 min from the beginning of the reaction. For comparison,
the conversion of benzene, ethylbenzene and xylenes on
Dy-Ni/MPS catalyst is shown in Fig. 9.
The hydrogenation reaction was carried out separately for
each benzene derivative. The method of gas chromatography
showed that the products of hydrogenation were cyclohexane
1
3

R. V. Shafigulin et al.
Fig. 6 TEM photographs and electron diffraction patterns: a MPS modified with nickel (Ni/MPS); b MPS doped with dysprosium and modified
with nickel (Dy-Ni/MPS)
xylenes. The rate constants expectedly increase with evalu-
ation of temperature.
structure of compounds do not significantly affect the reac-
tion center or structural changes occur far enough from the
reaction center. Thus, with linear dependence, it is assumed
that the reaction mechanisms are similar and do not depend
from changes in the structure of the initial substances, from
the nature of the medium, and from other factors. Figure 10
The verification of similarity of the reaction mechanisms
can be carried out by analyzing the isokinetic dependence
described by the following equation [40]:
≠
ΔH = ꢀ ⋅ ΔS
≠
(4)
≠
≠
shows the compensation curve in the coordinates E –∆S for
the studied compounds on Dy-Ni/MPS catalyst.
where β—compensation effect (isokinetic temperature);
≠
∆
H —thermal effect of the formation of the activated com-
The presence of a linear correlation between the acti-
plex (in the present work we used the energy of formation of
2
vation energy and entropy (R = 0.9959), obtained from
≠
≠
the activated complex E ); ∆S —the entropy of activation.
Linear dependences between the energy and the entropy
are quite common, especially in cases where changes in the
experimental data, suggests that the mechanism of gas-
phase hydrogenation of benzene, xylenes and ethylbenzene
on Dy-Ni/MPS has a similar character.
1
3

Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and…
Fig. 7 SEM photographs and particle distribution: a MPS modified with nickel (Ni/ MPS); b MPS doped with dysprosium and modified with
nickel (Dy-Ni/ MPS)
1
3

R. V. Shafigulin et al.
Fig. 8 Dependence of the conversion of benzene derivatives on time at 150 °C and 3 atm on the Ni/MPS and Dy-Ni/MPS catalysts
4
Conclusion
pressure affects textural and morphological characteristics
of the material and MPS synthesized at 5 atm has optimal
textural characteristics. Moreover, doping mesoporous sil-
ica with dysprosium leads to a decrease in specific surface
The mesoporous silica doped with dysprosium and modi-
fied with nickel (Dy-Ni/MPS) has been synthesized. The
study of the synthesis conditions of MPS showed that
2
2
area from 600 m /g to 514 m /g. The catalytic activity of
1
3

Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and…
Fig. 10 Compensation dependence between the activation energy
−
1
−1
(
kJ*mol ) and the entropy (J*(mol*K) ) of the hydrogenation of
benzene, ethylbenzene and xylenes on Dy-Ni/MPS catalyst
Fig. 9 Dependence of the conversion of all compounds under study
on time in hydrogenation reaction at 3 atm and 150 °C on Dy-Ni/
MPS catalyst
that doping mesoporous silica with dysprosium increases
the catalytic activity of the material (Dy-Ni/MPS), compar-
ing to Ni/MPS catalyst.
Table 3 The selectivity of the hydrogenation reaction of benzene
From the obtained data of rate constants, activation
energy and entropy of the hydrogenation reaction, it can
be concluded that the highest catalytic activity Dy-Ni/
MPS catalyst exerts with respect to ethylbenzene and the
lowest shows in the hydrogenation of benzene. The mech-
anism of gas-phase hydrogenation of benzene, xylenes
and ethylbenzene on Dy-Ni/MPS is similar, which con-
firmed by the correlations between activation energy and
entropy.
derivatives on Dy-Ni/MPS catalyst
Compound
Product
Yield (%)
Benzene
Ethylbenzene Ethylcyclohexane
Cyclohexane
100
100
m-xylene
o-xylene
p-xylene
cis and trans −1,3-dimethylcyclohexane 100
cis and trans −1,2-dimethylcyclohexane 100
cis and trans −1,4-dimethylcyclohexane 100
Acknowledgements The work is supported by Russian Foundation for
Table 4 The rate constants, activation energy and entropy of the
Basic Research (project 17-43-630358 r_a).
hydrogenation on Dy-Ni/MPS catalyst
≠
≠
−1
Compound
Benzene
T°C k, min−1
− ΔS ,
E ,kJ*mol
J*(mol*K)−
1
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Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and…
Affiliations
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R. V. Shafigulin · E. O. Filippova · A. A. Shmelev · A. V. Bulanova
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A. V. Bulanova
fileona@mail.ru
Department of Chemistry, Samara University, Moskovskoe
sh. 34, Samara 443086, Russia
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