Palladium–Ruthenium Catalyst for Selective Hydrogenation of Furfural to Cyclopentanol

Article abstract of DOI:10.1134/S0023158418030151

Bimetallic Pd–Ru/C catalyst was shown to be much more active in the aqueous-phase hydrogenation of furfural (473 K, 8 MPa) in comparison with both Pd/C and Ru/C catalysts. The enhanced hydrogenation activity manifested itself as an increased yield of cyclopentanol (77%) at a complete conversion of furfural. The observed synergistic effect between palladium and ruthenium in the tested reaction can be related to changes in the electronic state and particle size of supported metals upon interaction with each other and the Pd–Ru alloy formation.

Full text of DOI:10.1134/S0023158418030151

ISSN 0023-1584, Kinetics and Catalysis, 2018, Vol. 59, No. 3, pp. 339–346. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © R.M. Mironenko, O.B. Belskaya, A.V. Lavrenov, V.A. Likholobov, 2018, published in Kinetika i Kataliz, 2018, Vol. 59, No. 3, pp. 347–354.
Palladium–Ruthenium Catalyst for Selective Hydrogenation
of Furfural to Cyclopentanol1
R. M. Mironenkoa, b, *, O. B. Belskayaa, c, A. V. Lavrenova, and V. A. Likholobova, c, d
aInstitute of Hydrocarbons Processing, Siberian Branch, Russian Academy of Sciences,
Omsk, 644040 Russia
bDostoevsky Omsk State University, Omsk, 644077 Russia
cOmsk State Technical University, Omsk, 644050 Russia
dOmsk Scientific Center, Siberian Branch, Russian Academy of Sciences,
Omsk, 644024 Russia
*e-mail: mironenko@ihcp.ru
Received September 5, 2017
Abstract⎯Bimetallic Pd–Ru/C catalyst was shown to be much more active in the aqueous-phase hydroge-
nation of furfural (473 K, 8 MPa) in comparison with both Pd/C and Ru/C catalysts. The enhanced hydro-
genation activity manifested itself as an increased yield of cyclopentanol (77%) at a complete conversion of
furfural. The observed synergistic effect between palladium and ruthenium in the tested reaction can be
related to changes in the electronic state and particle size of supported metals upon interaction with each
other and the Pd–Ru alloy formation.
Keywords: furfural, selective hydrogenation, cyclopentanol, supported Pd–Ru catalysts, synergistic
effect
DOI: 10.1134/S0023158418030151
obviated if the hydrogenation is performed in water
medium. Finally, water may be involved in the cata-
lytic transformations during the hydrogenation of fur-
fural. This enables to obtain a large number of valuable
chemicals [14‒22].
The catalytic processing of biomass-derived com-
pounds has recently attracted much attention due to
the possibility of obtaining valuable chemical products
from renewable raw materials [1‒3]. Furfural is an
important platform compound produced commer-
cially from plant polysaccharides. The catalytic hydro-
genation of furfural yields a wide range of useful inter-
mediates [4‒11]. By now, various supported catalysts
containing noble metals have been proposed to per-
form this reaction with the selective obtaining of furfu-
ryl alcohol (FA) [5, 7, 8], 2-methylfuran (MF) [5, 9],
tetrahydrofurfuryl alcohol (THFA) [5, 10], 1,2-pen-
tanediol (PDL) [11] and 1,5-pentanediol [10].
Previously [14‒16], it has been found that the
aqueous-phase hydrogenation of furfural over Pt/C,
Pd/C and Ru/C catalysts at temperatures more than
413 K and pressures above 3 MPa is accompanied by a
Piancatelli-type rearrangement with participation of
water as nucleophile (Scheme 1).
The subsequent hydrogenation of rearrangement
product allowed obtaining cyclopentanone (CPN)
with a high yield (up to 76.5%) [14, 16]. Among the by-
products, THFA and 2-methyltetrahydrofuran (MTHF)
have been detected. However, further hydrogenation of
CPN to cyclopentanol (CPL) is suppressed, which is
caused by blocking of catalytically active sites by the
products of polycondensation of FA [15].
Currently, the using of water as reaction medium in
furfural hydrogenation is attractive and preferable for
the following reasons. Firstly, water is non-toxic and
inexpensive solvent. It is important from the viewpoint
of environmental and green chemistry [12]. Secondly,
furfural is obtained in industry as aqueous solutions
[13]. Thus, costly separation of furfural–water can be
1
The article was translated by the authors.
339

340
MIRONENKO et al.
O
−CO
O
O
Furan
Furfural
OH
OH
H2O
CH3
CH3
O
MF
O
FA
O
O
CPN
OH
CPL
OH
O
O
THFA
MTHF
Scheme 1. Reaction pathways of furfural hydrogenation in aqueous medium.
In order to retain or even improve the catalytic (both >98%, Aurat, Russia) were used for catalyst
activity and stability to deactivation, the second metal preparation without further purification. Furfural
can be introduced into the supported catalyst [23–29]. (99%, Sigma-Aldrich) was purified by distillation
Among numerous bimetallic catalysts, the palladium- before use. For qualitative analysis of reaction mix-
ruthenium composites have attracted attention due to tures, the authentic samples of MF (99%, Carl Roth),
their much improved or novel catalytic properties [28]. THFA (99%, Sigma-Aldrich), MTHF (99%, Acros
Very recently, we have found that bimetallic Pd–Ru/C Organics), CPN (99%, Sigma-Aldrich), CPL (99%,
catalysts are much more active in the liquid-phase Sigma-Aldrich), 1-butanol (>98%, Reakhim), 2-pen-
hydrogenation of benzaldehyde than the Pd/C and tanol (98%, Sigma-Aldrich), 1-pentanol (>98%,
Ru/C monometallic catalysts [29]. Depending on the Acros Organics), PDL (96%, Acros Organics), tetra-
nature of carbon supports, Pd–Ru/C catalysts allow hydrofuran (>98%, Reakhim) were used. Hydrogen
significant increase in the yield of benzyl alcohol or gas (99.99%, Novosibirsk Chemical Concentrates
toluene at a complete conversion of benzaldehyde.
Plant, Russia) was used for reduction of the catalysts
and the catalytic hydrogenation.
The present work deals with the study of supported
palladium, ruthenium and palladium–ruthenium cat-
alysts based on carbon nanotubes (CNTs) in the aque-
ous-phase hydrogenation of furfural. The choice of
carbon support was caused by high activity of Pd–
Ru/CNTs catalyst in liquid-phase hydrogenation of
benzaldehyde [29]. Moreover, there are other reasons
for choice of CNTs as the support, namely: a devel-
oped system of mesopores is to be favorable for using
in liquid-phase catalytic processes, a relatively low
content of oxygen functional groups on the surface
obstructs the side acid–base reactions [30, 31]. It
should be noted that due to their physicochemical
characteristics, CNTs are widely used as the support of
highly effective hydrogenation catalysts [32, 33].
Catalyst Preparation
Before the preparation of the catalysts, the carbon
support was dried overnight in air at 393 K to remove
the adsorbed water. The catalysts were obtained by
incipient wetness impregnation of CNTs with the
solutions of chloride precursors as described elsewhere
[29, 30, 34]. The content of palladium and ruthenium
in monometallic catalysts was 1.5 wt %. Bimetallic
catalyst contained 0.85 wt % Pd and 0.80 wt % Ru (the
Pd : Ru molar ratio of 1.0). After the impregnation, the
samples were dried in air at room temperature. Before
characterization and catalytic experiments, the cata-
lysts were additionally dried in argon flow at 423 K for
0.5 h and then reduced in flowing hydrogen at 523 K
for 2 h.
EXPERIMENTAL
Catalyst Characterization
Materials and Reagents
Palladium and ruthenium contents in the catalysts
were estimated by atomic emission spectrometry with
inductively coupled plasma on a Varian 710-ES spec-
trometer (Agilent Technologies, United States) after
complete dissolution of the samples in a mixture of
The multi-wall CNTs Baytubes® C 150 HP (Bayer
Material Science AG, Germany) were used as the sup-
port. Physicochemical properties of CNTs were stud-
ied in previous works [30, 34]. PdCl2 and Ru(OH)Cl3
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PALLADIUM–RUTHENIUM CATALYST
341
nitric and perchloric acids (palladium determination) ratio of 1.0 was tested in the aqueous-phase hydroge-
or nitric and hydrochloric acids (ruthenium determi-
nation).
nation of furfural at a temperature of 473 K and total
pressure of 8 MPa. Results of the catalytic measure-
ments were compared with the data obtained under
identical conditions for monometallic 1.5%Pd/CNTs
and 1.5%Ru/CNTs catalysts. The identification of
High resolution transmission electron microscopy
(HRTEM) images of the catalysts were taken by a
JEM-2100 (JEOL, Japan) instrument with the grating
resolution of 0.14 nm at the accelerating voltage of
200 kV. The samples were prepared by dispersing the
catalysts in ethanol and spraying the suspension on a
perforated carbon-coated copper grid. The energy dis-
persive X-ray (EDX) analysis was performed with an
INCA 250 (Oxford Instruments, Great Britain) spec-
trometer.
X-ray photoelectron spectroscopy (XPS) measure-
ments of the catalysts were carried out on a SPECS
(SPECS Surface Nano Analysis, Germany) spec-
trometer at a residual pressure of 7 × 10−7 Pa in the
analyzer chamber. To avoid oxidation of supported
metals, contact with air of the pre-reduced samples
was minimized. The spectra were recorded using
monochromatic AlKα radiation (hν = 1486.7 eV). Pre-
liminarily, the binding energy scale of the spectrome-
ter was calibrated against signals obtained from metal-
lic gold and copper, Au4f7/2 (84.0 eV) and Cu2p3/2
(932.6 eV). The spectra were calibrated with respect to
C1s line of the carbon support (284.6 eV).
13
reaction products was carried out by C NMR spec-
troscopy. Analysis of 13C NMR spectra allowed to
establish the presence of THFA, MTHF and CPL in
the reaction mixtures. The qualitative composition of
the mixtures of products was confirmed by GC analy-
sis with comparison of the retention times using
authentic samples. Thus, MF, CPN, PDL, 2-penta-
nol, 1-pentanol, 1-butanol, furan and tetrahydrofuran
were additionally detected. The analysis revealed no
traces of FA and intermediates of its conversion to
CPN (4-hydroxy-2-cyclopentenone, 2-cyclopente-
none). Despite this, based on literature data as well as
analysis of reaction products, it is reasonable to sug-
gest that the conversion during the aqueous-phase
hydrogenation of furfural over the catalysts proceeds
according to the above scheme.
In the presence of Pd–Ru/CNTs catalyst, a com-
plete conversion of furfural is achieved already after
1 h of the reaction and CPL predominates among the
products (Fig. 1a). Further hydrogenation of CPN
leads to increase in the selectivity for CPL up to about
77% (Table 1). In the presence of monometallic
Pd/CNTs catalyst, a complete conversion of furfural is
also achieved. However, the yield of CPL is only about
14% even after 3 h of the reaction and CPN prevails
among the products (Fig. 1b, Table 1). The ruthenium
catalyst is even less active compared to Pd/CNTs and
Pd–Ru/CNTs samples. In the presence of this cata-
lyst, a full conversion of furfural with the formation
mainly of CPN (selectivity up to 51%) is achieved only
at the end of the experiment (Fig. 1c, Table 1). It is
interesting to note that, unlike Pd and Pd–Ru sam-
ples, the main route of furfural transformation over
Ru/CNTs catalyst at the beginning of the reaction is
decarbonylation to furan. During the experiment, the
selectivity for furan decreases from 41 to 10% due to
the parallel reduction reactions of furfural to other
Catalytic Experiments and Analysis
of Reaction Products
The hydrogenation of furfural in the presence of
the synthesized catalysts was performed in a limbo li
(Büchi AG, Switzerland) periodic reactor. A catalyst
sample (500 mg) was placed into the autoclave with
water (95 cm3) and furfural (5.0 cm3). Then, the auto-
clave was purged by argon and filled by hydrogen. The
hydrogenation was carried out for 3 h at a temperature
of 473 K and a total pressure of 8 MPa under vigorous
stirring (1500 min–1) of the reaction mixture. Sampling
from the reactor (1 cm3) was performed every 0.5 h.
The reaction products were identified by 13C NMR
spectroscopy. The spectra were recorded on an
Avance-400 (Bruker, United States) spectrometer at
the Larmor frequency of 100.6 MHz using J-modu-
lated pulse sequence [35]. The quantitative composi- products (Fig. 1c).
tion of the reaction mixtures was determined using gas
chromatography (GC) on a Hewlett Packard 5890
Series II chromatograph equipped with a capillary col-
umn HP-PONA (50 m × 0.20 mm, Agilent Technol-
ogies) and a flame ionization detector.
As has been mentioned above, the aqueous-phase
hydrogenation of furfural over noble metal-based cat-
alysts allows obtaining CPN with a high selectivity,
whereas further reduction to CPL is suppressed
[14‒16]. A comprehensive search on published
sources showed that 5%Ru/C catalyst, which is most
active in the target reaction (among the other supported
catalysts based on noble metals), allows producing CPL
RESULTS AND DISCUSSION
Pd–Ru/CNTs catalyst with the total content of
supported metals of 1.65 wt % and the Pd : Ru molar with relatively low selectivity (up to 47%) [5].
KINETICS AND CATALYSIS Vol. 59 No. 3 2018

342
MIRONENKO et al.
(a)
(b)
Conversion or selectivity, %
100
(c)
Conversion or selectivity, %
100
Conversion or selectivity, %
100
1
5
1
3
1
3
5
80
80
60
40
80
60
60
3
6
40
40
4
6
2
6
2
4
20
20
2
20
4
5
0
0.5 1.0 1.5 2.0 2.5 3.0
Time, h
0
0.5 1.0 1.5 2.0 2.5 3.0
Time, h
0
0.5 1.0 1.5 2.0 2.5 3.0
Time, h
Fig. 1. Furfural conversion (1, j) and selectivities for THFA (2, d), CPN (3, s), MTHF (4, r), CPL (5, e) and furan (6, m) vs.
time during aqueous-phase hydrogenation over catalysts Pd–Ru/CNTs (a), Pd/CNTs (b) and Ru/CNTs (c) at a temperature of
473 K and pressure of 8 MPa.
It is interesting that the yield of the products of FA
In order to elucidate the reasons for the observed
hydrogenation (predominantly, THFA and MTHF) differences in the catalytic properties, the samples
was low, independently of the catalyst used. In all
cases, the reaction route involving water prevails.
Apparently, this is due to such reaction conditions
(473 K, 8 MPa), which are favorable to involve water
in the furan ring rearrangement. Under much milder
conditions (<363 K, <2 MPa), water does not participate
in transformations and the aqueous-phase furfural
hydrogenation yields mainly FA and THFA [30, 34].
were investigated by XPS and HRTEM. XPS was used
to estimate the oxidation state of supported metals.
The XPS data can indicate the interaction between
palladium and ruthenium in bimetallic catalyst. The
Pd3d5/2 and Pd3d3/2 spectra recorded for Pd/CNTs
and Pd–Ru/CNTs catalysts can be decomposed into
two overlapping peaks, which indicates that supported
palladium has two electronic states (Fig. 2a). The
positions of the signals with lower binding energy val-
ues (3d5/2 region) are close to those observed for
metallic palladium (335.7 0.3 eV [36, 37]), whereas
the signals with higher values of binding energy can be
attributed to the electron-deficient palladium species
Pdδ+ (337.9 0.3 eV for PdCl2 [36, 37]). To estimate
the oxidation state of ruthenium in the Ru/CNTs and
Thus, bimetallic Pd–Ru/CNTs catalyst exhibits
superior performance in the aqueous-phase hydroge-
nation of furfural to CPL compared to monometallic
Pd/CNTs and Ru/CNTs catalysts. Under the chosen
reaction conditions (473 K, 8 MPa), the bimetallic
catalyst allows achieving a high selectivity for CPL (up
to about 77%) at a complete conversion of furfural.
Table 1. Catalytic properties of Pd/CNTs, Ru/CNTs and Pd–Ru/CNTs samples in the aqueous-phase hydrogenation of
furfural*
S, %**
Catalyst
x, %**
other
products***
THFA
CPN
MTHF
CPL
furan
Pd/CNTs
100
100
100
10.3
7.0
36.2
0.8
17.9
4.5
1.1
14.1
76.8
18.4
0.1
1.9
21.4
9.0
Pd–Ru/CNTs
Ru/CNTs
4.8
51.3
10.2
14.2
3
3
* Reaction conditions: 95 cm of water, 5.0 cm of furfural, 500 mg of catalyst, Т = 473 К, P = 8 MPa, duration of 3 h.
** x is the conversion of furfural according to GC, S is the selectivity of products formation according to GC.
*** Among the other products, MF, PDL, 2-pentanol, 1-pentanol, 1-butanol and tetrahydrofuran were detected by NMR and GC.
KINETICS AND CATALYSIS Vol. 59 No. 3 2018

PALLADIUM–RUTHENIUM CATALYST
Pd–Ru/CNTs samples (Fig. 2b), the Ru3p3/2 peak was
343
(a)
Intensity
employed, since the signals from ruthenium in the
Ru3d region overlap with the C1s line from the sup-
port [38, 39].
Pd3d
Pdδ+
Pd0
As follows from the analysis of spectra, a notable
shift of the maxima of Pd0 and Pdδ+ lines toward high
binding energy values and a decrease in the Pd0 : Pdδ+
atomic ratio are observed for Pd–Ru/CNTs with
respect to Pd/CNTs catalyst (Fig. 2a, Table 2). At the
same time, a negative shift of Ru3p3/2 peak occurs for
Pd–Ru/CNTs sample with respect to monometallic
Ru/CNTs catalyst (Fig. 2b, Table 2). The Ru3p3/2 sig-
nal in the spectrum of bimetallic sample can be
assigned to metallic ruthenium. Such changes in the
oxidation state of supported palladium and ruthenium
in bimetallic Pd–Ru system have been found earlier
[29, 40, 41] and can be caused by the interaction of
metals with each other during the formation of Pd–Ru
alloy. The direction of electron transfer (from palla-
dium to ruthenium) is possibly related to a greater sur-
face electronegativity of ruthenium in comparison
with palladium [42].
Pd/CNTs
Pd–Ru/CNTs
334
336
338
340
342
344
346
Binding energy, eV
(b)
Intensity
Ru3p
The formation of Pd–Ru bimetallic nanoparticles
was confirmed by HRTEM with EDX analysis of
reduced Pd–Ru/CNTs catalyst. As shown in one of
the HRTEM images (Fig. 3b), this sample has
nanoparticles with a d-spacing of 0.217 nm, which
does not correspond to any lattice spacings of Pd or Ru
and very close to that of the (111) facet of face-cen-
tered cubic lattice for Pd–Ru alloy (0.219 nm [28,
43]). The EDX spectrum (Fig. 3c) recorded from the
region emphasized in Fig. 3b includes signals corre-
sponding to Pd and Ru. This confirms that supported
nanoparticles in Pd–Ru/CNTs catalyst are bimetallic.
Ru/CNTs
Pd–Ru/CNTs
456
458
460
462
464
466
468
Binding energy, eV
As shown by a comparison of HRTEM data for the
Pd/CNTs, Ru/CNTs and Pd–Ru/CNTs catalysts, the
dispersion of nanoparticles in bimetallic sample is
noticeably higher than that in the corresponding
monometallic systems. The bimetallic nanoparticles
have a spherical shape and the average size is equal to
1.6 nm (Fig. 3d), whereas the palladium and ruthe-
Fig. 2. Pd3d (a) and Ru3p (b) spectra of Pd/CNTs, Pd–
Ru/CNTs and Ru/CNTs catalysts.
catalysts have the average size of 2.3 and 1.8 nm,
respectively. A decrease in size of nanoparticles upon
Pd–Ru alloy formation is in agreement with CO
nium nanoparticles in corresponding monometallic chemisorption data obtained earlier [29, 30].
Table 2. Results of XPS analysis of Pd/CNTs, Ru/CNTs and Pd–Ru/CNTs catalysts
Binding energy of Pd3d5/2, eV
Pd0 : Pdδ+ atomic
ratio
Binding energy
Catalyst
of Ru3p3/2, eV
Pd0
Pdδ+
Pd/CNTs
336.2
336.4
‒
337.9
338.2
‒
‒
1.0
0.7
‒
Pd–Ru/CNTs
Ru/CNTs
462.2
462.5
KINETICS AND CATALYSIS Vol. 59 No. 3 2018

344
MIRONENKO et al.
Thus, an increased activity of bimetallic Pd–
(a)
(b)
(c)
Ru/CNTs catalyst in the aqueous-phase hydrogena-
tion of furfural can be caused by the mutual interac-
tion of supported Pd and Ru, which increases the dis-
persion of nanoparticles and changes the electronic
state of metals. A decrease in size of metal nanoparti-
cles increases the fraction of active sites accessible to
reactants. A change in electronic state can promote the
activation of hydrogen and substrate molecules. In
viewpoint of the electronic factor, it is difficult to
unequivocally establish a participation of palladium
and ruthenium species as active sites in the reaction.
The most plausible mechanism of promoting action of
the second metal involves the formation of so-called
mixed sites where both metal components participate
in the catalytic transformations, but one of them is not
fully reduced in the running conditions of the reaction
[44, 45]. In this case, the promotion effect is due to the
presence of electron-deficient metal species which
enhance the polarization of C=O bond of furfural as
well as CPN formed during the reaction (Fig. 4). The
electron transfer from Pd to Ru increases the fraction
of electron-deficient palladium species in the cata-
lysts, which serve as the electrophilic sites of adsorp-
tion and activation of the C=O bond in the molecules
of carbonyl compounds. As a result of electrophilic
activation, the C=O bond is weakened, thus facilitat-
ing a subsequent addition of chemisorbed hydrogen
[46]. Moreover, due to electron transfer from palla-
dium to ruthenium, the latter is present in the Pd–
Ru/CNTs catalyst as Ru0. It is known that activation of
the hydrogen molecule and cleavage of the H–H bond
are less hindered if the metallic sites have an increased
number of accessible electrons at the external d-orbital
[47]. So, the preferential sites of H2 adsorption and
activation are represented most likely by the electron-
rich supported ruthenium species.
20 nm
0.217 nm
1 nm
20 nm
Intensity
C
Ru Pd
O
Si
2.0 2.5 3.0 3.5
Cu
0.5 1.0 1.5 2.0 2.5 3.0 3.5
Energy, keV
(d)
Distribution, %
CONCLUSIONS
50
40
30
20
10
0
In summary, we found that bimetallic Pd–Ru cat-
alyst based on carbon nanotubes exhibits superior per-
formance in the aqueous-phase hydrogenation of fur-
fural to cyclopentanol compared to monometallic pal-
ladium and ruthenium catalysts prepared by using the
same support. Under the chosen reaction conditions
(473 K, 8 MPa), the bimetallic catalyst allows achiev-
ing selectivity for cyclopentanol up to about 77% at a
complete conversion of furfural. The data obtained for
the catalysts by HRTEM and XPS suggest that an
increased hydrogenation activity of bimetallic sample
in the tested reaction can be related to changes in the
electronic and dispersion states of supported metals
upon interaction with each other and formation of
Pd–Ru alloy. In terms of the electronic factor, the
dav = 1.6 nm
0.5 1.0 1.5 2.0 2.5 3.0 3.5
Particle diameter, nm
Fig. 3. HRTEM images (a and b), EDX spectrum from the
region emphasized in micrograph (c) and the particle size
distribution histogram (d) of Pd–Ru/CNTs catalyst.
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PALLADIUM–RUTHENIUM CATALYST
345
η1–(O)
η2–(C, O)
η1–(O)
η2–(C, O)
O
H
O
H
O
O
O
O
Pdδ+
Pdδ+
Pd0
Pdδ+
Pdδ+
Pd0
Fig. 4. Supposed modes of adsorption and activation of furfural and CPN molecules on the surface of Pd–Ru nanoparticles.
2. Sheldon, R.A., Green Chem., 2014, vol. 16, p. 950.
observed synergistic effect between palladium and
ruthenium can be caused by facilitation of electro-
philic activation of the C=O bonds in furfural and
intermediate cyclopentanone owing to an increased
fraction of electron-deficient palladium species.
The obtained result may be useful for the develop-
ment of efficient catalysts for the hydrogenation of
furfural to cyclopentanol, which is a starting com-
pound in the synthesis of pharmaceuticals, fragrances,
fungicides [17, 18, 48]. Conventionally, cyclopentanol
is produced by oxidation of cyclopentene or cycliza-
tion of 1,6-hexanediol with subsequent reduction of
cyclopentanone. At the same time, the aqueous-phase
hydrogenation of furfural can be regarded as one-pot
synthesis of cyclopentanol from a renewable source.
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ACKNOWLEDGMENTS
Today, 2015, vol. 247, p. 33.
The study was financially supported by FASO Rus-
sia according to the Program of Fundamental Scien-
tific Researches of the State Academies of Sciences for
2013–2020, project V.47.1.3.
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The work was performed using facilities of the
Omsk Regional Center of Collective Usage, Siberian
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