Catalysis Letters (2019) 149:916–928

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
R. V. Shafigulin1 · E. O. Filippova1 · A. A. Shmelev1 · A. V. Bulanova1

Received: 10 October 2018 / Accepted: 13 January 2019 / Published online: 7 February 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

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Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and… 917

1 Introduction Germany), dysprosium chloride (abcrGmbH, Germany),

nickel chloride (abcrGmbH, Germany), ammonium hydrox-
The hydrogenation of unsaturated and aromatic hydrocarbons ide (abcrGmbH, Germany), ethanol (abcrGmbH, Germany),
is one of the main reactions of the oil refining and petrochemi- cetyltrimethammonium bromide (CTAB) (abcrGmbH,
cal industries [1–3]. Generally, these processes occur at high Germany), benzene (abcrGmbH, Germany), ethylbenzene
temperatures and pressures, so the search for new efficient and (abcrGmbH, Germany), o-xylene (abcrGmbH, Germany),
selective catalysts that would allow developing energy-saving m-xylene (abcrGmbH, Germany), p-xylene (abcrGmbH,
technologies is a current scientific direction [4–6]. Germany).
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, 2.2 Synthesis of Mesoporous Silica
chemical and mechanical stability, low toxicity and biospecific-
ity. All of these properties make mesoporous silica gels promis- Following samples of mesoporous silica were prepared
ing for their use as sorbents and carriers for catalysts [7–11]. by the template method: an unmodified mesoporous sil-
The surface of mesoporous silica modify with various com- ica (MPS), silica modified with nickel nanoparticles (Ni/
pounds to impart catalytic properties. The obtained materials MPS), silica doped with dysprosium and modified with
combine the initial properties of silica gel and the properties nickel (Dy-Ni/MPS). CTAB (0.78 g) as a structure-forming
of the grafted compound [12, 13]. Modified porous silica are agent (template) was dissolved in a water-alcohol medium
widely used as catalyst carriers for such industrially important at the room temperature with stirring for 30 min. Then
processes as oxidation of organic [14–17] and inorganic [18, TEOS (3.14 mL) was added dropwise, and the solution
19] substances, hydrogenation [20–22], dehydrogenation [23, was stirred for another 30 min. The pH of the reaction mix-
24] and many others [25–28]. ture was adjusted to 10 by adding ammonia solution (27%
Various heterogeneous hydrogenation catalysts have been 8 mL), and then stirred for 5 h. The reaction mixture was
developed and investigated. The range of used metals is very air dried for 24 h at room temperature, and then the sample
wide—from basic (for example, nickel and copper) to noble was placed in the autoclave (NoaLabShaker2.0/Shaker2.1)
metals (for example, platinum and palladium). The d-band for 5 h. To study the effect of pressure on texture and mor-
model has been particularly useful in investigating and systema- phological characteristics of mesoporous silica gels, syn-
tizing the correlation between the electronic structure and the thesis was carried out at different pressures − 2, 5, and
catalytic activity of transition materials. Theoretical study on the 13 atm at 115 °C. After autoclaving, the obtained samples
example of ethylene hydrogenation shows that activation barri- were filtered and washed with deionized water until neutral
ers for hydrogenation and dehydrogenation depend on the loca- (pH = 7 ÷ 7.5). Samples were heated in a muffle furnace
tion of the d-band center of the metal catalyst with respect to the for 5 h at 650 °C to remove the template. The obtained
Fermi level [29, 30]. Several authors prepared S ­ iO2-supported unmodified mesoporous silica was doped with dysprosium
monometallic Ni and bimetallic catalysts with Ni, Pd, Pt, Cu, In as follows: at the beginning of the synthesis, dysprosium
nanoparticles. They were found as catalysts in the hydrogenation chloride (0.02 g) was added while stirring of CTAB and
reaction of benzene, toluene and xylenes [31–35]. TEOS, and then the mixture was autoclaved as described
Catalysts based on mesoporous silica have a number of above. The molar ratio Dy/Si was 0.01. The presence of
advantages, such as wide accessibility of these materials, high dysprosium in the structure of MPS was confirmed by
stability and the potential for repeated use with minimal loss of X-ray fluorescence analysis (XRF) and ICP using spec-
activity, due to the possibility of separation from the reaction trometer PlasmaQuant PQ9000. The concentration of dys-
mixture by filtration or decantation [36]. prosium was 1,3% by weight.
The aim of the work was the synthesis of mesoporous silica
doped with dysprosium and modified with nickel, and a com-
2.3 Catalysts Preparation
parative study of their catalytic properties in the reaction of
hydrogenation of benzene, ethylbenzene and xylenes.
The modification with nickel of synthesized unmodified
(MPS) and dysprosium-doped (Dy/MPS) silica was carried
2 Experiment out as follows: the MPS and Dy/MPS samples weights were
placed in alcoholic solution of nickel (II) chloride and stirred
2.1 Chemicals for 2 h. Ethyl alcohol was evaporated, and then the sample
was heated in a muffle furnace at 450 °C in a stream of
The following commercial reagents were used to synthesize hydrogen for 5 h to reduce nickel. The presence of nickel in
the catalysts: tetraethyl orthosilicate (TEOS) (abcrGmbH, the sample was confirmed by XRF and ICP analyses. The

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918 R. V. Shafigulin et al.

nickel concentration in the samples of mesoporous silica in a static regime at the temperature range 80–170 °C and a
was 8% by weight. hydrogen pressure of 3 atm on an original apparatus allow-
ing an on-line analysis of the reaction mixture (Scheme 1)
2.4 Investigation of Texture Characteristics [37].
and the Surface Morphology of Synthesized 1—tank with carrier gas, 2—reducing valve, 3—valve con-
MPS and Catalysts Obtained on Their Basis trolling the flow rate of the carrier gas, 4—gage measuring
the pressure of the carrier gas in the analytical column, 5—
The texture characteristics of the samples were determined computer and AD converter, 6—heat-conductivity detector,
by nitrogen adsorption–desorption isotherms measurement 7, 16—thermostats, 8—analytical column, 9—6-port three-
at low temperature using Quantochrome Autosorb-1. The way valve, 10—valve at the hydrogen outlet from the reac-
Brunauer-Emmett-Teller model (BET) was used to deter- tor, 11—gage measuring the hydrogen pressure in the reactor,
mine the specific surface area. The total pore volume and 12—hydrogen pressure reducer for delivery of hydrogen into
mesopore size distribution were calculated from the des- the reactor, 13—evaporator (input of reagents into the reactor),
orption curve using the Barrett-Joyner-Khalenda (BJH) 14—hydrogen generator, 15—reactor.
model. The DFT density functional method was used for The apparatus is constituted by the reaction unit (thermo-
the analysis of micropores. The particle size MPS and stat with evaporator for introduction of liquid samples into the
shape of the obtained mesoporous materials were exam- reactor) and analytical unit, a gas chromatograph TraceGC
ined by the electron microscopy using a scanning electron with a flame ionization detector (FID). The units are con-
microscope CarlZeiss EVO 50 with an X-Max 80 energy nected with a 6-port three-way injection valve. The chemical
dispersive attachment. The XRD analysis of synthesized reactor is a steel tube. The catalyst weight is 0.3 g. Reagent
MPS structures and identification of nickel phase were samples were injected into the reactor (volume 1 cm3) with
recorded using a Rigaku Miniflex 600 diffractometer a micro syringe (sample volume 1 µl) in a hydrogen stream.
(Japan) equipped with a detector with a graphite mono- Hydrogen was produced using a hydrogen generator. The first-
chromator and a copper anti-cathode, Cu-Kα radiation order equation was used to calculate the rate constant. Since
(λ = 1.54187 Å). Additionally, samples of catalysts were the reaction was run in excess hydrogen, the reaction kinetics
investigated by transmission electron microscopy (TEM) obeyed the first-order equation [38, 39].
on LEO912 AB OMEGA microscope at an accelerating From the experimental data were determined:
voltage of 100 kV using standard copper grids with a poly- Reaction rate constant:
vinylformal films with a diameter of holes 100 µm. c
1
k= ⋅ ln 0 (1)
t ct
2.5 Study of Catalytic Activity
where ­C0 is the concentration of reagents at the initial
The catalytic activity of the obtained samples was studied on time of the reaction (t = 0) and ­Ct is the concentration of
the example of hydrogenation of benzene, ethylbenzene, o-, reagents at time t.
m-, p-xylenes. The hydrogenation kinetics was carried out

Scheme 1  The original appa-

ratus for hydrogenation and
analysis of the reaction mixture

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Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and… 919

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
The experimental activation energy ­(E≠) was founded of Mesoporous Silica
from the graphical dependence in the coordinates of the
Arrhenius equation (lnk−1/T). The surface area, volume and pore diameter of the synthe-
To determine the contribution of the activation energy sized MPS samples were measured by the methods described
and entropy to the reaction rate constant, the entropy of acti- in Sect. 2.4.
vation was calculated by the equation [37]: Figure 1 shows isotherms of adsorption and desorption
( ) for synthesized samples of unmodified mesoporous silica
Ah obtained at different pressures and different concentrations
(3)
≠
ΔSp = Rln + (1 − x)Rln(RT)
𝜒kTex of CTAB.
where, A is the pre-exponential factor in the Arrhenius The obtained data of the specific surface area and the tex-
equation; R—gas constant; k—Boltzmann constant; h— tural characteristics of synthesized mesoporous silica (MPS)
Plank constant; T—temperature; x—reaction molecularity; are given in Table 1.
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)

13
920 R. V. Shafigulin et al.

Table 1  Effect of different Sample S (BET) ­(m2/g) Vpore (ВJH) Def (BJH) (nm) Def (DFT)
pressures on specific surface (cm3/g) (nm)
areas and textural characteristics
of synthesized mesoporous MPS (2 atm) 666 ± 33 1.462 4/39 2.18
silica
MPS (5 atm, Sur- 579 ± 29 0.913 4 2.38
factant*2)
MPS (5 atm) 600 ± 30 0.828 4 2.38
MPS (13 atm) 563 ± 28 1.266 4/43 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
synthesized at 2 atm is characterized by a maximum pore for Ni/MPS, Dy-Ni/MPS.
volume, and the MPS sample synthesized at 5 atm by a Thus, the presence of nickel and dysprosium in the MPS
minimum pore volume. From the data presented in Table 1 structures and their quantitative content was established by
follows that synthesized samples are characterized by both the ICP method. The content of nickel was 8% by weight,
a monomodal and bimodal distribution of pores. The MPS and dysprosium 1,3% by weight. This indicates a complete
samples synthesized at a pressure of 2 and 13 atm are char- reduction of nickel from nickel chloride using the above
acterized by the presence of mesopores with an effective method, described in paragraph 2.3.
diameter of 39 and 43 nm, respectively. Along with the The textural characteristics for mesoporous silica Dy/
monomodal distribution of pores the sample obtained at a MPS, Ni/MPS, Dy-Ni/MPS are given in Table 2.
pressure of 5 atm is also characterized by their smallest vol- Analyzing Tables 1 and 2, it can be concluded that the
ume, which suggests that nickel will be sorbed in these pores inclusion of dysprosium into the structure of mesoporous sil-
as nanoparticles during the modification. Thus, it follows 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)

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Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and… 921

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
Ni/MPS, Dy-Ni/MPS of nickel in the metal phase form was confirmed by the pres-
Sample S(BET) ­(m2/g) Vpore ВJH Def (BJH) ence of reflections (2Θ = 44.5°, 51.9°, 76.4°) on the diffrac-
(cm3/g) (nm) togram of Ni/MPS and Dy-Ni/MPS samples corresponding
to the reflections of a cubic face-centered cell of metallic
Dy/MPS 514 ± 20 0.457 3.8
nickel with Brava indices (111), (200), (220) respectively.
Ni/MPS 235 ± 12 0.305 4
In addition to XRD method, the obtained samples were
Dy-Ni/MPS 215 ± 12 0.298 4
analyzed using TEM, and the results of which are shown
in Fig. 6.
Analysis by TEM showed that nickel predominantly
to 514 m2/g. The specific surface area of Ni/MPS decreases localized in the pores of materials mesoporous matrix. The
almost by a factor of 2.5 which is possibly due to nickel average particle size of nickel is not significantly differ-
adsorption in the pores of MPS. ent for the Ni/MPS and Dy-Ni/MPS samples and is about
The XRD method was used to confirm the structure of the 3.7 ± 0.5 nm. However, for the Ni/MPS sample, there are
synthesized mesoporous silica. Figure 5 shows the compara- conglomerates with particle sizes of about 20–30 nm.
tive diffraction patterns for the three MPS samples. Figure 7 shows the SEM photographs at different zoom-
Characteristic peaks in the small angle region indicate ing for the two samples, used as catalysts for the hydrogena-
the presence of ordered systems of mesopores (MCM-41 tion reaction of benzene, ethylbenzene and xylenes.
phase) in MPS, Ni/MPS, Dy-Ni/MPS structures. For the Figure 7 shows that the morphology of the surface of
Dy-Ni/MPS sample, the shift of the characteristic peak to mesoporous silica due to doping with dysprosium is trans-
lower angles and a less relative intensity were revealed. formed. Dy-Ni/MPS used as a catalyst is characterized by a
Apparently, these changes are caused by the incorpora- looser structure comparing to Ni/MPS. The average particle
tion of dysprosium into the MPS structure upon doping. size for Ni/MPS is 75 nm, and for Dy-Ni/MPS is 100 nm.
Such changes are not observed for the sample modified The above results show that the Ni/MPS and Dy-Ni/MPS
with nickel, since it is predominantly located in the pores structures are different, therefore, the structure of the active
of the mesoporous matrix in the metallic and does not form centers also differs, which explains the change, namely the

13
922 R. V. Shafigulin et al.

Fig. 5  Diffraction patterns for MPS, Ni/MPS, Dy-Ni/MPS

increase in the catalyst with dysprosium embedded in the and its derivatives. The table shows the selectivity of the
silica structure, as shown in Sect. 3.2. 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-
The determining factor for evaluating the effectiveness of the ear equations of the first-order ­R2 = 0.99. The value of the
catalyst is the conversion of the reactants during the reac- constant was determined from five parallel experiments with
tion. Figure 8 shows the conversions of benzene, ethylben- a relative error not exceeding 3% (the table shows the aver-
zene and xylenes in the hydrogenation reaction on the Ni/ age values of the rate constants).
MPS and Dy-Ni/MPS catalysts at 150 °C and a hydrogen The rate constants, activation energy and entropy of
pressure of 3 atm. the hydrogenation reactions of benzene, ethylbenzene and
Doping with dysprosium and modification with nickel of xylenes at different temperatures on Dy-Ni/MPS catalyst are
doped mesoporous silica leads to an increase of the catalytic shown in Table 4.
activity in the hydrogenation of xylenes and ethylbenzene. Comparing the rate constants, activation energy and
Thus, the conversion of ethylbenzene after 10 min from entropy of the hydrogenation reaction listed in Table 4, it
the start of the reaction is 100% on Dy-Ni/MPS, and only can be concluded that the highest catalytic activity Dy-Ni/
80% on Ni/MPS. O-xylene, m-xylene and p-xylene are fully MPS catalyst exerts with respect to ethylbenzene. For
hydrogenated after 30 min on Dy-Ni/MPS catalyst, and just xylenes, the catalytic activity decreases as follows: from
80% of xylenes are hydrogenated on Ni/MPS catalyst after p-xylene, to m-xylene and o-xylene. The determining factor
30 min from the beginning of the reaction. For comparison, in the hydrogenation of these compounds is the activation
the conversion of benzene, ethylbenzene and xylenes on energy. The lowest catalytic activity Dy-Ni/MPS shows in
Dy-Ni/MPS catalyst is shown in Fig. 9. the hydrogenation of benzene, and the activation rate is the
The hydrogenation reaction was carried out separately for determining factor for the reaction. The hydrogenation of
each benzene derivative. The method of gas chromatography benzene is characterized by the higher values of entropy
showed that the products of hydrogenation were cyclohexane and activation energy in comparison to the ethylbenzene and

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Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and… 923

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- structure of compounds do not significantly affect the reac-
ation of temperature. tion center or structural changes occur far enough from the
The verification of similarity of the reaction mechanisms reaction center. Thus, with linear dependence, it is assumed
can be carried out by analyzing the isokinetic dependence that the reaction mechanisms are similar and do not depend
described by the following equation [40]: from changes in the structure of the initial substances, from
the nature of the medium, and from other factors. Figure 10
ΔH ≠ = 𝛽 ⋅ ΔS≠ (4) shows the compensation curve in the coordinates ­E≠–∆S≠ for
where β—compensation effect (isokinetic temperature); the studied compounds on Dy-Ni/MPS catalyst.
∆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 vation energy and entropy ­(R2 = 0.9959), obtained from
the activated complex ­E≠); ∆S≠—the entropy of activation. experimental data, suggests that the mechanism of gas-
Linear dependences between the energy and the entropy phase hydrogenation of benzene, xylenes and ethylbenzene
are quite common, especially in cases where changes in the on Dy-Ni/MPS has a similar character.

13
924 R. V. Shafigulin et al.

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)

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Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and… 925

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
The mesoporous silica doped with dysprosium and modi- textural characteristics. Moreover, doping mesoporous sil-
fied with nickel (Dy-Ni/MPS) has been synthesized. The ica with dysprosium leads to a decrease in specific surface
study of the synthesis conditions of MPS showed that area from 600 m2/g to 514 m2/g. The catalytic activity of

13
926 R. V. Shafigulin et al.

Fig. 10  Compensation dependence between the activation energy

(kJ*mol−1) and the entropy (J*(mol*K)−1) 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/ that doping mesoporous silica with dysprosium increases
MPS catalyst
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
derivatives on Dy-Ni/MPS catalyst
energy and entropy of the hydrogenation reaction, it can
Compound Product Yield (%) be concluded that the highest catalytic activity Dy-Ni/
MPS catalyst exerts with respect to ethylbenzene and the
Benzene Cyclohexane 100
lowest shows in the hydrogenation of benzene. The mech-
Ethylbenzene Ethylcyclohexane 100
anism of gas-phase hydrogenation of benzene, xylenes
m-xylene cis and trans − 1,3-dimethylcyclohexane 100
and ethylbenzene on Dy-Ni/MPS is similar, which con-
o-xylene cis and trans − 1,2-dimethylcyclohexane 100
firmed by the correlations between activation energy and
p-xylene cis and trans − 1,4-dimethylcyclohexane 100
entropy.

Table 4  The rate constants, activation energy and entropy of the Acknowledgements The work is supported by Russian Foundation for
hydrogenation on Dy-Ni/MPS catalyst Basic Research (project 17-43-630358 r_a).

Compound T°C k, ­min−1 − ΔS≠, E ≠,kJ*mol−1

J*(mol*K)−1
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Affiliations

R. V. Shafigulin1 · E. O. Filippova1 · A. A. Shmelev1 · A. V. Bulanova1

1
* A. V. Bulanova Department of Chemistry, Samara University, Moskovskoe
[email protected] sh. 34, Samara 443086, Russia

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