Unsaturated-compound hydrogenation nanocatalysts based on palladium and platinum particles immobilized in pores of mesoporous aromatic frameworks

Article abstract of DOI:10.1134/S0965544117020177

Heterogeneous catalysts for the hydrogenation of unsaturated hydrocarbons have been synthesized on the basis of palladium and platinum nanoparticles immobilized in pores of mesoporous aromatic frameworks, which represent a new class of carbon supports with a diamond-like ordered structure. The resulting materials have been characterized by transmission electron microscopy, IR spectroscopy, and NMR spectroscopy. It has been shown that the catalyst activity in the hydrogenation reaction depends on the substrate molecule size and adsorbability on the surface of nanoparticles. Catalytic activity has been studied in the hydrogenation of a number of unsaturated compounds at temperatures of 60 and 80°C and pressures of 1.0 and 3.0 MPa.

Full text of DOI:10.1134/S0965544117020177

ISSN 0965-5441, Petroleum Chemistry, 2017, Vol. 57, No. 3, pp. 222–229. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © L.A. Kulikov, M.V. Terenina, I.Yu. Kryazheva, E.A. Karakhanov, 2017, published in Neftekhimiya, 2017, Vol. 57, No. 2, pp. 163–170.
Unsaturated-Compound Hydrogenation Nanocatalysts Based
on Palladium and Platinum Particles Immobilized in Pores
of Mesoporous Aromatic Frameworks
L. A. Kulikov, M. V. Terenina, I. Yu. Kryazheva, and E. A. Karakhanov*
Faculty of Chemistry, Moscow State University, Moscow, Russia
*e-mail: kar@petrol.chem.msu.ru
Received September 29, 2016
Abstract⎯Heterogeneous catalysts for the hydrogenation of unsaturated hydrocarbons have been synthesized
on the basis of palladium and platinum nanoparticles immobilized in pores of mesoporous aromatic frame-
works, which represent a new class of carbon supports with a diamond-like ordered structure. The resulting
materials have been characterized by transmission electron microscopy, IR spectroscopy, and NMR spec-
troscopy. It has been shown that the catalyst activity in the hydrogenation reaction depends on the substrate
molecule size and adsorbability on the surface of nanoparticles. Catalytic activity has been studied in the
hydrogenation of a number of unsaturated compounds at temperatures of 60 and 80°C and pressures of 1.0
and 3.0 MPa.
Keywords: nanoparticles, catalysis, mesoporous materials, hydrogenation
DOI: 10.1134/S0965544117020177
One of the most important processes in the mod- organic substrates deep into the pores of the material
ern petrochemical industry is the hydrogenation of than that in the case of conventional inorganic sup-
unsaturated compounds. This process is commonly ports; the structural features of mesoporous aromatic
used to improve the characteristics of motor fuels by supports provide a narrow size distribution of metal
removing polyunsaturated compounds and olefins nanoparticles and their better stabilization compared
from the gasoline and diesel fractions, remove adverse with classical carbon supports. All these features make
undesirable compounds—acetylenes and dienes— PAFs an attractive type of supports for designing
from pyrolysis products, and produce cyclohexane metal-containing catalysts.
and cyclohexanol, which are key intermediates in the
synthesis of adipic acid and caprolactam [1–3]. An
increasingly significant role is played by the selective
hydrogenation of benzene to cyclohexene, which has
already been implemented in industry [4]. In this con-
text, the design of novel catalyst systems exhibiting
high activity and selectivity in the hydrogenation of a
broad range of unsaturated compounds is an urgent
and important problem.
The use of mesoporous aromatic frameworks for
synthesizing hydrogenation catalysts based on ruthe-
nium nanoparticles stabilized by the pores of the
material was previously reported in [12]. The resulting
catalysts were active in the exhaustive hydrogenation
of a broad range of aromatic substrates; in addition, it
was shown that a variation in the pore size in the start-
ing material makes it possible to adjust the average size
of the resulting metal particles and affect the substrate
selectivity of the catalyst.
This study is focused on the synthesis of platinum
and palladium nanoparticles inside the pores of meso-
porous aromatic frameworks and examination of the
activity of the synthesized catalysts in the hydrogena-
tion of unsaturated compounds.
At present, one of the rapidly developing fields of
catalysis is the use of mesoporous polymer supports
for the stabilization of metal nanoparticles and the
design of catalysts for various petrochemical processes
[5–8]. Materials of this type include porous aromatic
frameworks (PAFs), which represent a novel class of
carbon materials with an ordered regular structure (see
below). The main advantages of this material are high
chemical and thermal stability, simple methods of
structure functionalization, and the possibility of
imposing an average pore size in the synthesis of these
materials [9–11]. Furthermore, the aromatic nature of
EXPERIMENTAL
Precursors
The following materials were used as substrates:
the supports contributes to a better diffusion of styrene (Arcos Organics, 97%); α-methylstyrene
222

UNSATURATED-COMPOUND HYDROGENATION NANOCATALYSTS
Table 1. Gas–liquid chromatography analysis conditions
223
Carrier gas
Nitrogen (Р = 200 kPa), volume flow rate of 30 mL/min
styrene, methylstyrene,
phenylacetylene, decene, toluene
octene, octyne,
dimethylhexadiene
groups of substrates
benzene
Detector temperature, °C
Injector temperature, °C
Initial column temperature, °C
Final column temperature, °C
Column heating rate, °C/min
Initial time, min
250
250
60
60
220
10
10
5
35
35
0
20
1
220
10
5
Final time, min
10
(Aldrich, 99%); phenylacetylene (Aldrich, 98%); (P/P0) of 0.05–0.2. Pore volume and pore size distri-
octene-1 (Aldrich, 98%); octyne-4 (Aldrich, 99%);
2,5-dimethylhexadiene-2,4 (Aldrich, 96%); decene-1
(Arcos Organics, 95%); benzene (Irea 2000, analytical
grade); toluene (Khimmed, special purity grade); and
ethylbenzene (Reakhim, high-purity grade). Metha-
nol (Acros Organics, 99+%); ethanol (Irea 2000, ana-
lytical grade); and chloroform (Khimmed, high-
purity grade) were used as solvents.
The solvents were purified according to standard
procedures. PAF-30 was synthesized as previously
described in [12]. To deposit metals into the frame-
work pores, the supports were impregnated with metal
salts, which were subsequently reduced with an alco-
holic solution of sodium borohydride. Metal sources
were palladium(II) acetate (Aldrich, 99.9%) and a 1%
aqueous solution of hexachloroplatinic(IV) acid to
synthesize palladium and platinum catalysts, respec-
tively.
bution were determined from the adsorption branch of
the isotherm using the Barrett–Joyner–Halenda
(BJH) model. Total pore volume (Vtot) was determined
from the amount of nitrogen adsorbed at a relative
pressure of P/P0 = 0.995.
Transmission electron microscopy (TEM). Analysis
of materials by TEM was conducted on a LEO912c AB
OMEGA instrument (magnification of 80× to
500000×; image resolution of 0.2–0.34 nm). The
electron beam potential was 100 eV. The processing of
the micrographs and the calculation of the average
particle size were conducted using the ImageJ soft-
ware program.
Atomic emission spectroscopy. The quantitative
determination of palladium and platinum in the sam-
ples was conducted by inductively coupled plasma
atomic emission spectroscopy on an IRIS Interpid II
XPL instrument (Thermo Electron Corp., United
States) with radial and axial viewing at wavelengths of
310 and 95.5 nm.
Instruments and Investigation Procedures
Gas–liquid chromatography. Analysis of the reac-
tion products was conducted on a ChromPack
CP9001 chromatograph equipped with a flame ion-
ization detector and a 30 m × 0.2 mm column (SE-30
grafted phase) using nitrogen as a carrier gas at a flow
rate of 30 mL/min. Chromatograms were recorded
and analyzed on a computer using the Maestro 1.4
software program. Conversion was determined from
changes in the relative peak areas of the substrate and
the products (in %). The analysis conditions are given
in Table 1.
IR spectroscopy. IR spectra of the synthesized
samples were recorded in a range of 4000–400 cm–1
on a Nicolet IR-2000 instrument (Thermo Scientific)
by the multiple attenuated total internal reflection
method using a Multi-reflection HATR accessory
comprising a 45° ZnSe crystal for different wavelength
ranges with a resolution of 4 nm.
Solid-state NMR spectroscopy. Analysis by polar-
ization-transfer solid-state 13C NMR spectroscopy
(CPMAS) was conducted on a Varian NMR Systems
instrument at an operating frequency of 125 MHz in a
pulse mode at a rotation frequency of 10 kHz.
Low-temperature nitrogen adsorption. Nitrogen
adsorption/desorption isotherms were recorded at a
temperature of 77 K on a Micromeritics Gemini VII
2390 (V1.02t) instrument. Before measurements, the
samples were degassed at a temperature of 110°C for
6 h. The surface area (SBET) was calculated by the
Catalyst Synthesis Procedure
Catalysts were synthesized by impregnating the
support material with solutions of metal salts, which
were subsequently reduced with a methanolic solution
of sodium borohydride. To this end, a 0.01 M solution
of palladium(II) acetate in chloroform was used in the
Brunauer–Emmett–Teller (BET) method on the case of the PAF-30–Pd palladium catalyst; an aque-
basis of adsorption data in a range of relative pressures ous methanol solution of hexachloroplatinic(IV) acid,
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224
KULIKOV et al.
Catalyst activity for each reaction was calculated
which was prepared in a ratio of 5 mL of a 1% aqueous
H2[PtCl6] solution per 20 mL of methanol, was according to the following formula:
employed for the PAF-30–Pt platinum catalyst. In
Conv × n Sub
(
)
both catalysts, the calculated amount of the metal was
5 wt %.
TOFs =
,
Δt × n Me D
(
)
where Conv is the conversion of the substrate to the
product, %; n(Sub) is the substrate content, mol; Δt is
the reaction time, h; n(Me) is the total metal content,
mol; and D is the metal dispersion, which determines
the ratio between the number of surface atoms and the
number of atoms in the bulk of the particle; it is calcu-
lated as follows:
A typical procedure includes the drying of 400 mg
of the original PAF-30 support in a vacuum at 60°C for
1 h and the subsequent impregnation of it with 20 mL
of a palladium acetate solution in chloroform in a
round-bottom flask equipped with a magnetic stirrer
anchor and a reflux condenser at room temperature
under continuous stirring for 12 h. After this time,
40 mL of a freshly prepared 0.33 M solution of sodium
borohydride in methanol was dropwise added to the
resulting suspension. The resulting catalyst was iso-
lated by filtration; to remove the sodium borate
formed as a reaction product, the precipitate was
washed with water and alcohol several times. In either
case, after drying in a vacuum, the resulting products
had the form of a dark gray powder.
6VM Me × k
(
)
6VA
SA × dpt N A × SA × dpt dpt
X
,
D =
=
=
where dpt is the average metal particle size, Å; VA is the
atomic volume of the metal phase; SA is the normal-
ized landing pad area on the particle surface; VM(Me)
is the molar volume of the metal; k is the crystal struc-
ture packing factor; NA is the Avogadro’s number; and
X is the coefficient derived after simplification of the
formula for calculating the metal dispersion by the
substitution of known constants; for palladium and
platinum, X ~ 8.85 and 11.12, respectively [13].
Catalytic Testing Procedure
According to a typical procedure, a calculated
amount of a catalyst and a substrate were placed in a
temperature-controlled steel autoclave equipped with
a test-tube liner and a magnetic stirrer anchor; all cat-
alytic reactions were run without using any solvent.
The autoclave was sealed, filled with hydrogen to a
pressure of 10 or 30 atm, and connected to a thermo-
RESULTS AND DISCUSSION
Characterization of PAF-30
Mesoporous aromatic framework PAF-30 was syn-
stat. The reaction was run under vigorous stirring at thesized of tetrakis[p-bromophenyl]methane and 4,4'-
60°C for 15, 30, or 60 min; after that, the autoclave was biphenyldiboric acid by the Suzuki cross-coupling
cooled below room temperature and depressurized.
reaction as previously described in [12] (Scheme 1).
B(OH)2
Br
Br
Br
Pd(OAc)2, PPh3
DMF/H2O, K2CO3, 140°C
+
Br
B(OH)2
Scheme 1. Schematic synthesis of mesoporous aromatic framework PAF-30.
3100–3600 and 1076 cm–1; this fact confirms the com-
pleteness of the cross-coupling reaction.
The resulting material was characterized by IR
spectroscopy, solid state NMR spectroscopy, and low-
temperature nitrogen adsorption–desorption. The IR
spectrum of the material exhibits a strong absorption
band peaking at 808 cm–1, which corresponds to the
δoop vibrations of the C–H bond, and less intense
absorption bands ν C= Cp-Ar and δip Csp3–CAr peaking
The 13C NMR spectrum of the material exhibits
signals characteristic of sp2-hybridized carbon atoms
of aromatic moieties in the region of 120–150 ppm
and a low-intensity signal at 68 ppm corresponding to
sp3-hybridized carbon atoms in the nodes of tetrap-
henylmethane moieties. Similar to the IR spectros-
at 1485 and 1004 cm–1, respectively. It should be noted
that no absorption bands characteristic of vibrations of
the B–OH and C–Br bonds are observed in regions of copy data, the spectrum of the synthesized framework
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UNSATURATED-COMPOUND HYDROGENATION NANOCATALYSTS
225
does not exhibit a СAr–Br signal (120.0 ppm) character- works. The synthesized polymer frameworks are char-
acterized by lover average specific surface area (SBET
=
istic of tetrakis[p-bromophenyl]methane.
382 m2/g) and pore volume (Vp = 0.17 cm3/g) com-
The low-temperature nitrogen adsorption–
desorption studies of the porosity of the synthesized pared with the previously reported values [14, 15] and
aromatic frameworks revealed an abrupt absorption of an average pore size of 3.5 nm.
nitrogen at low pressures (P/P0 = 0–0.05), which indi-
cates the presence of micropores in the material struc-
Characterization of the Catalysts
ture. In addition, in a relative pressure range of P/P0 =
0.2–0.9, the nitrogen adsorption curve gradually
Both the PAF-30–Pd and PAF-30–Pt catalysts
ascends without exhibiting a plateau; in addition, a synthesized by the immobilization of metal nanoparti-
characteristic hysteresis loop between the adsorption cles in the support pores contained 5 wt % of the metal
and desorption curves is observed; these findings con- (Scheme 2). The resulting materials were character-
firm the mesoporous nature of the resulting frame- ized by atomic emission spectroscopy and TEM.
a. Pd(OAc)2, CHCl3
b. H2[PtCl6], MeOH
NaBH4, MeOH
Scheme 2. Immobilization of metal nanoparticles inside the framework pores.
Figure 1 shows micrographs of the catalysts, the tion of alkynes and dienes to olefins [17, 18]. The main
particle size distribution, and the metal content in the results are shown in Fig. 2 and Table 2.
resulting materials. It should be noted that, in the case
of the PAF-30–Pt catalyst, the particle size distribu-
tion curve exhibits several local minima at 3.5 and
7.0 nm and a maximum at 5.3 nm, while the particle
size distribution for the PAF-30–Pd catalyst is close to
normal (Gaussian) and exhibits a maximum at 3.2 nm.
In addition, the platinum catalyst is characterized
by the formation of large agglomerates of particles
located mostly on the surface. This finding can be
attributed to the ionic nature of the salt and, as a con-
sequence, hindrances to the diffusion of the [PtCl6]2–
ion into the pores of the material.
In the case of the palladium catalyst, the lower
average metal particle size is apparently attributed to
the absence of dissociation of palladium acetate in a
chloroform solution and the existence of the salt in the
form of a cyclic trimer and a linear dimer [16]; this fea-
ture provides a more uniform distribution of the salt
over the support volume.
In all cases, the activity of the platinum-based
PAF-30–Pt catalyst was significantly higher than that
of the palladium-based PAF-30–Pd catalyst, while
the selectivity for products of incomplete hydrogena-
tion of substrates with multiple unsaturated bonds
(phenylacetylene, 2,5-dimethylhexadiene-2,4) was
exhibited by the PAF-30–Pd palladium catalyst. The
catalytic test results are consistent with the literature
data, according to which platinum-containing cata-
lysts exhibit higher activity and lower selectivity than
those of palladium-based catalysts [19, 20].
The hydrogenation ability of the catalysts cor-
relates with the substrate molecule sizes and adsorb-
ability. Thus, the catalyst activity decreases with
increasing number of carbon atoms in the substrate
molecule; this finding is attributed to diffusion limita-
tions during the passage of the substrate through
the framework pores. The presence of a benzene
ring in the substrate structure contributes to the diffu-
sion inside mesoporous aromatic frameworks owing to
π–π stacking interactions with the support material
and facilitates the adsorption of the substrate on
the metal particle surface. Thus, in the case of the
Catalytic Tests
The synthesized materials were tested as catalysts PAF-30–Pt catalyst, the complete conversion of sty-
for the hydrogenation of a series of unsaturated com- rene to ethylbenzene is achieved within 30 min, while
pounds. It was previously shown that Pd and Pt the catalyst activity, which is expressed in terms of the
nanoparticles supported on mesoporous phenol form- turnover number per unit time per number of metal
aldehyde resins are active in the selective hydrogena- atoms on the particle surface, is highest in the case of
PETROLEUM CHEMISTRY Vol. 57 No. 3 2017

226
KULIKOV et al.
(b)
20
15
10
5
dav = 5.3 1.5 nm
W(Pt) = 6.0%
0
2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0
50 nm
(а)
d, nm
(d)
35
30
25
20
15
10
5
dav = 3.2 0.6 nm
W(Pd) = 5.1%
0
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
50 nm
(c)
d, nm
Fig. 1. Micrographs of the catalysts and metal particle size distribution for (a, b) the PAF-30–Pt and (c, d) PAF-30–Pd materials.
styrene; the factors responsible for this feature include
an increase in the electron density of the C=C double
bond owing to the conjugation of the bond with the
aromatic ring [21, 22].
The activity of the synthesized catalysts was com-
pared with the activity of previously described cata-
lysts (Tables 3, 4). To determine the activity of the
The reuse of the synthesized catalysts was studied
using the example of hydrogenation of octene-1. In
either case, a slight decrease in the catalyst activity was
observed; this finding is mostly associated with the
catalyst losses during decantation. After six hydroge-
nation runs, the octene-1 conversion was 64 and 28%
in the case of the platinum-based PAF-30–Pt and pal-
ladium-based PAF-30–Pd catalysts, respectively.
Thus, the synthesized catalysts can be reused without
any significant loss of activity.
300 000
PAF-30–Pt
PAF-30–Pd
250 000
200 000
150 000
100 000
50 000
0
The PAF-30–Pt platinum catalyst was tested in the
hydrogenation of aromatic compounds (Fig. 3). The
main products of the reaction were appropriate cyclo-
hexane derivatives. Similar to the previous results, the
hydrogenation product yield decreases with increasing
substrate molecule size. It should be noted that this
relationship exhibits an inverse linear behavior; this
finding is consistent with the data derived for ruthe-
nium-containing catalysts [12].
Fig. 2. Hydrogenation of unsaturated substrates over the
PAF-30–Pd and PAF-30–Pt catalysts. Reaction condi-
tions: 1 mg of the catalyst; substrate : metal = 27000 :
1 (mol); 1 MPa H ; 60°C; and 30 min (styrene, 15 min;
2
methylstyrene, 60 min).
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UNSATURATED-COMPOUND HYDROGENATION NANOCATALYSTS
227
Table 2. Distribution of unsaturated compound hydrogenation products in the presence of the PAF-30–Pd and PAF-30–
Pt catalysts. Reaction conditions are given in the caption to Fig. 2
Product yield, %
Substrate
Reaction products
PAF-30–Pd
22
PAF-30–Pt
55
44
13
75
33.5
3
0.2
38
71
8
octane
33.6
20
trans-octene-2
cis-octene-2
trans-octene-4
other octenes
cis-octene-4
trans-octene-4
octane
2
Octene-1
Octyne-4
1
1
4.5
24
3
40
0.8
0.2
0.5
0.2
7
2
8
14.5
1
14
82
20
23
68
Decane
Products of decene-1 isom-
erization via double bond
migration
Decene-1
PAF-30–Pd and PAF-30–Pt catalysts in the hydroge-
Thus, it has been found that the synthesized cata-
nation reaction, styrene and phenylacetylene, respec- lysts exhibit high activity and stability in the hydroge-
tively, were selected as a substrate. The tables show nation of a series of unsaturated compounds.
that the catalysts are highly active in the hydrogena- Higher activity is observed for the platinum-based
tion of the selected substrates.
PAF-30–Pt catalyst, while higher selectivity for
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228
KULIKOV et al.
350
300
250
200
150
100
50
2000
1800
1600
1400
1200
1000
800
600
400
200
0
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
Molecular size, Å
Molecular size, Å
Fig. 3. Dependence of the catalyst activity on the substrate molecule size: PAF-30–Pt (left) and PAF-30–Ru (right, plotted
according to the data of [12]). Reaction conditions: 24 mg of the PAF-30–Pt catalyst; substrate : metal = 1500 : 1 (mol);
3 MPa H ; 80°C; and 6 h.
2
Table 3. Comparison of the activity of the PAF-30–Pd catalyst with the activity of other Pd-containing catalysts using the
example of styrene hydrogenation. In all cases, the only reaction product was ethylbenzene
Styrene
conversion, %
TOF, h–1
23760
Catalyst
Reaction conditions
Source
PAF-30–Pd
(5.1% Pd)
1 mg of catalyst, 1.4 mL of styrene, 1 MPa
H2, 60°C, 15 min
22%
This study
PPI–BP-1–Pd (2) 0.95 mg of catalyst, 1 mL of styrene, 1.5 mL
67%
n/a*
44%
34440
2730
[21]
[23]
[24]
(7.61% Pd)
of benzene, 1 MPa H2, 70°C, 15 min
Pd/C*
(3% Pd)
5 mg of catalyst, 1 μL of styrene (0.115 mL),
15 mL of methanol, 0.1 MPa H2, 25°C
Pd–Al2O3
(0.3% Pd)
10 g of catalyst, 31 mL of styrene, 370 mL
of heptane, 3 MPa H2, 40°C, 10 min
2790
* The study provides data on the hydrogenation reaction rate in the linear portion of the time dependence of the product concentration.
Table 4. Comparison of the activity of the PAF-30–Pt catalyst with the activity of other Pt-containing catalysts using the
example of phenylacetylene hydrogenation
Substrate
conversion, % selectivity, %
Styrene
TOF, h–1
42570
Catalyst
Reaction conditions
Source
PAF-30–Pt
(6.0% Pt)
1 mg of catalyst, 1.4 mL of substrate,|
1 MPa H2, 60°C, 15 min
36.5
43
92
89
78
77
This study
MPF–SO3H–Pt (c) 1 mg of catalyst, 1 mL of substrate, 1.5 mL
(0.2% Pt)
55800
1510
[18]
[25]
[26]
of benzene, 1 MPa H2, 80°C, 15 min
0.3 g of catalyst, 2.6 mL of substrate,
35 mL of ethanol, 1 MPa H2, 20°C, 10 min
150 mg of catalyst, 1 mL of substrate
(С = 0.042 М), 200 mL of tetradecane,
0.38 MPa H2, 75°C, 12 min
Pt/C
67
(5% Pt)
Pt–Al2O3
(0.5% Pt)
62
9030
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UNSATURATED-COMPOUND HYDROGENATION NANOCATALYSTS
229
11. J. R. Holst, E. Stockel, D. J. Adams, and A. I. Cooper,
incomplete hydrogenation products is obtained using
the PAF-30–Pd catalyst. Using the example of the
platinum-based PAF-30–Pt catalyst, it has been
shown that the catalyst activity exhibits an inverse lin-
ear dependence on the substrate molecule size in the
exhaustive hydrogenation of aromatic hydrocarbons.
Macromolecules 43, 8531 (2010).
12. A. Maximov, A. Zolotukhina, L. Kulikov, Yu. Karda-
sheva, E. Karakhanov, React. Kinet. Mech. Catal. 117,
729 (2016).
13. J. Anderson, Structure of Metallic Catalysts (Academic,
London, 1975).
14. Y. Yuan, F. Sun, H. Ren, et al., J. Mater. Chem. 21,
ACKNOWLEDGMENTS
13498 (2011).
15. M. Rose, N. Klein, W. Bohlmann, et al., Soft Matter 6,
This work was supported by a grant of the Russian
Science Foundation, project no. 15-19-00099.
3918 (2010).
16. E. S. Stoyanov, Zh. Strukt. Khim. 41, 540 (2000).
17. E. A. Karakhanov, A. L. Maksimov, I. A. Aksenov,
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