Capillary microreactor with a catalytic coating based on mesoporous titanium dioxide for the selective hydrogenation of 2-methyl-3-butyn-2-ol

Article abstract of DOI:10.1134/S0023158416040091

A continuously working capillary microreactor with a catalytic coating based on mesoporous titanium dioxide with embedded Pd nanoparticles was tested in a reaction of the selective hydrogenation of 2-methyl-3-butyn-2-ol (MBI). The catalytic coatings were obtained by the supporting of a carrier sol, which contained colloidal Pd nanoparticles, onto the internal wall of a quartz capillary with a diameter of 250 μm in the dynamic mode. The effects of the concentration of MBI in methanol (0.05–0.2 mol/L), the partial pressure of hydrogen (0.28–1.0 atm), and the reaction temperature (308–333 K) on the catalyst activity and the selectivity of reaction were studied. High selectivity for the formation of the semi-hydrogenated product 2-methyl-3-buten-2-ol was reached at 313 K in an atmosphere of pure hydrogen. At a conversion of 99.9%, the selectivity was 92.3%, which is 15.5% higher than that in a batch reactor. The rate of hydrogenation on the Pd/TiO₂ coating was higher by one order of magnitude than that on a commercial Lindlar catalyst. The coating remained stable upon the continuous passage of the flow of a reaction mixture for 500 h.

Full text of DOI:10.1134/S0023158416040091

ISSN 0023-1584, Kinetics and Catalysis, 2016, Vol. 57, No. 4, pp. 497–503. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © L.B. Okhlopkova, M.A. Kerzhentsev, Z.R. Ismagilov, 2016, published in Kinetika i Kataliz, 2016, Vol. 57, No. 4, pp. 501–507.
Capillary Microreactor with a Catalytic Coating Based
on Mesoporous Titanium Dioxide for the Selective Hydrogenation
of 2-Methyl-3-Butyn-2-ol
a,
a
a, b
L. B. Okhlopkova *, M. A. Kerzhentsev , and Z. R. Ismagilov
a
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
b
Institute of Coal Chemistry and Chemical Materials Science, Siberian Branch, Russian Academy of Sciences,
Kemerovo, 650000 Russia
*
e-mail: mila65@catalysis.ru
Received September 8, 2015
Abstract—A continuously working capillary microreactor with a catalytic coating based on mesoporous tita-
nium dioxide with embedded Pd nanoparticles was tested in a reaction of the selective hydrogenation of
2
-methyl-3-butyn-2-ol (MBI). The catalytic coatings were obtained by the supporting of a carrier sol, which
contained colloidal Pd nanoparticles, onto the internal wall of a quartz capillary with a diameter of 250 μm
in the dynamic mode. The effects of the concentration of MBI in methanol (0.05–0.2 mol/L), the partial
pressure of hydrogen (0.28–1.0 atm), and the reaction temperature (308–333 K) on the catalyst activity and
the selectivity of reaction were studied. High selectivity for the formation of the semi-hydrogenated product
2
-methyl-3-buten-2-ol was reached at 313 K in an atmosphere of pure hydrogen. At a conversion of 99.9%,
the selectivity was 92.3%, which is 15.5% higher than that in a batch reactor. The rate of hydrogenation on the
Pd/TiO coating was higher by one order of magnitude than that on a commercial Lindlar catalyst. The coat-
2
ing remained stable upon the continuous passage of the flow of a reaction mixture for 500 h.
Keywords: capillary microreactor, catalytic coating, sol–gel method, palladium nanoparticles, titanium diox-
ide, selective hydrogenation, 2-methyl-3-butyn-2-ol
DOI: 10.1134/S0023158416040091
INTRODUCTION
Capillary microreactors are very promising in the
development of a selective method for the manufac-
ture of fine organic synthesis products. They make it
possible to reach high selectivity because of a possibil-
ity to control the contact time of reagents with a cata-
lyst and the reaction temperature and also as a result of
the absence of limitations related to mass and heat
transfer [3]. Recently, the number of publications on
the studies of thin catalytic coatings in microcapillary
reactors continuously increased [4–6]. However, only
a few of them were dedicated to the development of
modified quartz and glass capillaries with specified
parameters. Bolton et al. [7] considered the problem
of the instability of coatings caused by the loss of an
active component. Rohr et al. [8] proposed to modify
a coating with the use of a grafted layer. The synthesis
and characterization of catalytic coatings on the inter-
nal surface of a quartz capillary containing active
mono- and bimetallic nanoparticles in order to deter-
mine a relationship between the catalytic and physico-
chemical properties of these coatings remains a prob-
lem of considerable current interest.
The semi-hydrogenation of triple carbon–carbon
bonds with the formation of alkenes is one of the most
common methods for the industrial production of
vitamins; however, the catalyst and reaction condi-
tions should be thoroughly chosen in order to reach
high selectivity. Methylbutenol (MBE) is a starting
compound for the production of food additives. It is
obtained by the semi-hydrogenation of a correspond-
ing alkyne—methylbutynol (MBI)—in a loading-type
batch reactor [1] in accordance with the following
reaction scheme:
MBI
MBE
MBA
CH3
CH3
CH3
H2
I
H2
II
OH
OH
OH
2H2
III
Modified palladium catalysts, in particular, the Lind-
lar catalyst, exhibit the highest activity and selectivity
in this reaction [2].
Porous materials with the well-controlled micro,
meso, and macro structures are widely used in hetero-
497

4
98
OKHLOPKOVA et al.
The morphology of the samples, the average size of
geneous catalysis. The high dispersion of an active
component and its accessibility to a bulky organic sub- Pd nanoparticles, and the particle size distribution
strate and the rapid transport of reagents and reaction were determined on a JEM–2010 electron microscope
products are the desirable characteristics of any cata- (JEOL, Japan) with a lattice resolution of 0.14 nm at
lytic process. Mesostructured materials with mono- an accelerating voltage of 200 kV. Chemical analysis
disperse mesopores were synthesized based on tita- was carried out using an EDAX energy-dispersive
nium dioxide with the use of anionic, cationic, and spectrometer (EDAX Inc., United States) supplied
nonionic organic templates [9]. The strong metal– with a Si(Li) detector with a resolution of 130 eV. The
support interaction with the use of mesoporous tita- samples for transmission electron microscopy (TEM)
nium dioxide increases the stability of a catalyst and its analysis were supported onto perforated carbon base
selectivity [10]. Thin catalytic films with a high spe- layers immobilized on copper grid. Scanning electron
cific surface area can be supported onto the internal microscopy (SEM) images were obtained on a JSM-
wall of microstructured channels [11]. They are syn- 6460 LV microscope (JEOL) with a resolution of 3
thesized by a sol–gel method with the use of a solvent nm. The palladium content of the powder catalysts
evaporation-induced self-assembly (EISA) technique, was determined by X-ray fluorescence spectroscopy
which makes it possible to obtain a mesoporous struc- on a VRA-30 analyzer (ThermoFisher Scientific,
ture with a crystalline framework and to control the Switzerland) with a Cr-anode X-ray tube.
porosity and the thickness of films [12].
In this work, we considered the possibility of using
a coating based on titanium dioxide as a matrix for cat-
alyst immobilization on the walls of a microcapillary
reactor. The nanoparticles of Pd were implanted into
the support at the stage of sol formation; thus, coatings
with a controlled nanoparticle size and a specified
porosity were synthesized [13, 14]. We performed a
comparative study of the catalytic activity and selectiv-
ity of Pd nanoparticles in the process of MBI hydroge-
nation in both a batch reactor at a pressure of 5 atm
and a temperature of 333 K and a microcapillary reac-
tor. We optimized the conditions of the reaction per-
Catalytic Tests
For obtaining powder, the catalyst was preliminarily
ground in an agate mortar. It was placed in a 130-mL
autoclave and reduced in situ at a temperature of 523 K
and an H pressure of 5 atm for 2 h; then, it was cooled
2
to room temperature and blown with argon. The solu-
tion of MBI in methanol (50 mL) was blown with argon
and transferred into the reactor. Hydrogenation was
performed at 333 K and a hydrogen pressure of 5 atm
with intense stirring at a rate of 2000 rpm.
Coatings on the internal surface of a quartz capil-
lary were tested in a temperature range from 303 to
formed on Pd/TiO coatings.
2
3
33 K. The gas, which consisted of a mixture of hydro-
gen with helium, and the solution of MBI in methanol
0.05–0.2 mol/L) were mixed in a T-shaped mixer.
The inside diameter of the supply line capillaries was
(
EXPERIMENTAL
2
50 μm. The flow rates of the liquid and a mixture of
Synthesis and Physicochemical Characterization
H –He were varied from 5 to 60 μL/min and from 0.1
of Pd/TiO in Powdered Form and as a Coating
2
2
to 4.0 mL/min, respectively. Under these conditions,
A solvent reduction method was used for the prepa- an annular two-phase flow was observed [17].
ration of a colloidal solution of Pd nanoparticles [15]
The reaction mixture was analyzed in the off-line
with Pd(CH COO) as a metal precursor and polyvi-
3
2
mode on a Kristall 2000M gas chromatograph (Khro-
matek, Russia) supplied with an SKTFT-50X capillary
column with a diameter of 0.22 mm and a length of
nyl pyrrolidone (PVP) as a stabilizer (the PVP : metal
molar ratio was 10 : 1). Coatings with a Pd concentra-
tion of 1 wt % was obtained by a sol–gel method in the
presence of a Pluronic F127 template in accordance
with a procedure described earlier [14, 16]. The
3
(
0 m and a flame-ionization detector. 1-Butanol
0.1 mol/L) was used as an internal standard. The con-
version of MBI, selectivity for the formation of MBE,
the yield of MBE, and the catalyst productivity were
calculated in percentages from the following equations:
Ti(O‒iPr) : Pluronic F127 : C H OH : H O : HNO
3
4
2
5
2
molar ratio in the sol was 1 : 0.009 : 40 : 1.3 : 0.13. A
portion of the sol was applied onto the internal surface
of a microcapillary with a diameter of 250 μm and a
length of 10 m in the dynamic mode at a flow velocity
of 1 cm/s. Before the supporting, the quartz capillary
was preliminarily washed with a 1 M solution of
NaOH at 313 K for 30 min in order to improve the
adhesion of the coating. The capillary and the remain-
der of the sol were kept in a tightly closed box for 24 h
at a relative humidity of 80%; then, they were calcined
to 573 K with a heating rate of 1 K/min at a pressure of
СMBI,0 − СMBI
х =
×100,
СMBI,0
C
MBE
SMBE
=
×100,
СMBI,0 − СMBI
А
MBE = (СMBE
С
MBI,0) ×100,
СMBI,0 АMBE
V
Q =
×100,
13 mbar for the removal of the surfactant.
tmCat
KINETICS AND CATALYSIS
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CAPILLARY MICROREACTOR WITH A CATALYTIC COATING
is the initial concentration
499
respectively, where C
of MBI; C and C
MBI,0
are the current concentrations
MBE
MBI
of MBI and MBE, respectively; Q is the catalyst pro-
ductivity; V is the reaction volume; t is the current
reaction time in the autoclave or the contact time in
0.225 nm PP d(111)
the microcapillary; and m is the catalyst sample
Cat
weight.
5
nm
RESULTS AND DISCUSSION
The mesoporous coatings based on titanium diox-
ide with an ordered pore structure on quartz base lay-
ers can be obtained by the EISA method. A stable hex-
agonal mesostructure is formed at the molar ratio sur-
factant : Ti = 0.009 and pH 1.5 [18]. These conditions
were used for the synthesis of catalysts with embedded
nanoparticles. Bimetallic nanoparticles were obtained
by a colloid method, which makes it possible to syn-
thesize particles of size ≥2 nm with a narrow pore-size
distribution [13]. The nanoparticles were stabilized by
a polymer (polyvinyl pyrrolidone) for the prevention
of their agglomeration both at the stage of colloid
preparation and on the subsequent thermal treatment
performed for the removal of the template [14].
According to the SEM data, the thickness of a
5
0 nm
Fig. 1. TEM image of the Pd/TiO coating.
2
decreases the selectivity because the complete hydro-
genation of MBI begins to predominate. At a decrease
in the flow rate of H from 4 to 1 mL/min, the selec-
2
Pd/TiO coating after twice supporting with the subse-
2
tivity of MBE formation at a 86% conversion of MBI
decreased from 93 to 76%. If the ratio between the gas
and liquid flow rates decreased, the film thickness
increased to cause an increase in the residence time in
the reactor, a decrease in the concentration of MBI
and the adsorption of MBE, and the hydrogenation of
this latter to MBA. According to available data, a
change in the selectivity can be caused by the influ-
ence of particle size. The size effect was explained by
the different adsorption of alkynes and alkenes on the
faces of Pd; the fraction of each of these faces depends
on the particle shape and size [22]. Okhlopkova et al.
quent heat treatment in a vacuum at 573 K and a pres-
sure of 13 mbar was about 300 nm. The pore size of a
titanium dioxide matrix varied from 3 to 4 nm (Fig. 1).
The micrographs show the quasi-hexagonal structure
of pores. This mesoporous structure with an open pore
system ensures the accessibility of an active compo-
nent and improves the transport of substrate mole-
cules. The absence of periodicity can be caused by a
low humidity at the stage of film aging. An excess of sol
was removed from the capillary in a flow of dry argon.
According to Choi et al. [19], in terms of the mecha-
nism of mesophase formation proposed by Soler-Illia
and Sanchez [20], a quasi-hexagonal pore structure is
formed at a relative moisture content of less than 80%.
The crystal lattice parameters of embedded Pd nano-
clusters (0.225 nm) correspond to the face-centered
lattice of Pd (JCPDS-40-1043).
[
14] reported the average particle size of ~2 nm in
powder catalysts and coatings according to TEM data.
The higher selectivity reached in a microcapillary
reactor (see the table) can be explained by a decrease
in the contact time between a reagent and a catalyst. In
a batch reactor, the transport of MBI to the catalyst
surface under the action of internal [19] and external
[
23] diffusion is hindered; the concentration of MBE
Effect of the Reactor Type
increases and it is converted into MBA. Thus, in the
microcapillary reactor, the catalyst is used more effec-
tively and its productivity and selectivity are twice as
high as these characteristics in the batch reactor (see
the table). Furthermore, if the reaction is performed in
the microcapillary, there is no need for separating the
catalyst from the reaction solution.
Alkynes are more strongly adsorbed on a catalyst
than alkenes; therefore, the surface is mainly covered
with an alkyne, and the reaction of С≡С bond hydro-
genation predominantly occurs with the formation of
corresponding olefins (reaction I in the above dia-
gram) [1]. At a low concentration of MBI, the result-
ing product undergoes hydrogenation up to the forma-
tion of 2-methyl-2-butanol (MBA) (reaction II). The
direct hydrogenation of MBI to an alkane (reaction III)
is possible with the formation of an ethylidine inter-
mediate [21]. In order to ensure the high selectivity of
Activity and Selectivity under Different Conditions
We studied the influence of the residence time of
hydrogenation, it is necessary to control contact time liquid, the initial concentration of MBI, the partial
in a microcapillary. An increase in the contact time pressure of hydrogen, and temperature on the conver-
KINETICS AND CATALYSIS Vol. 57 No. 4 2016

5
00
OKHLOPKOVA et al.
Effect of catalyst and reactor type on the hydrogenation of 2-methyl-3-butyn-2-ol
Activitya,
Sb, %
Q, gMBE (gCat)–1 h–1
Catalyst
Reactor type
АMBE, %
molMBI (mol ) s–1
–1
Pd
0.9c
2.6d
0.04e
Pd/TiO2
Microreactor
Batch reactor
Batch reactor
92.7
77.2
–
92.3
74.4
–
61
34
–
Pd/TiO2
Pd + Pd/CaCO3
a
At a 20% MBI conversion.
Selectivity for the formation of MBE at a 96% MBI conversion.
b
c
СMBI,0 = 0.2 mol/L (in methanol), v = 2.0 mL/min, РН2 = 1 atm, T = 313 K, mCat = 0.4 mg, V = 0.49 mL.
g
d
e
СMBI,0 = mol/L (in methanol), РН2 = 5 atm, T = 333 K, mCat = 20 mg, V = 50 mL.
СMBI,0 = 0.1 mol/L (in water), РН2 = 5 atm, T = 308 K, mCat = 18 mg, V = 200 mL.
sion of MBI and selectivity for the formation of MBE. exhibited activity that was higher by an order of mag-
Figure 2 shows the dependence of the conversion of nitude than the activity of the Lindlar catalyst (see the
MBI and S
on flow rate at a constant temperature table).
MBE
of 313 K. Based on these data, we plotted the depen-
dence of S on the conversion of MBI (Fig. 3). At a
The effect of the initial MBI concentration on the
catalytic properties of a coating was studied in a range
MBE
conversion of higher than 20%, the selectivity of C
from 0.05 to 0.2 mol/L (Fig. 5). The rate of
MBI,0
remained almost constant and equal to 92.7% (at a
conversion of 96%). The complete hydrogenation of
MBI was observed at a 100% conversion.
hydrogenation was almost independent of the initial
MBI concentration, and the order of reaction was
0.03, which is consistent with published data [26, 27].
Figure 6 shows the dependences of the conversion
In the annular two-phase flow in a microcapillary,
gas passes at the center of a tube, whereas liquid flows
along the walls of a channel to form a film. The liquid
of MBI and selectivity for the formation of MBE on
the pressure of hydrogen and temperature. As the par-
hold-up and the residence time were calculated from tial pressure РН2 was increased from 0.28 to 1 atm, the
the Lockhart–Martinelli–Chisholm equation [24]. It rate of reaction increased in the entire temperature
should be noted that the occurrence of an induction range (313–323 K). At conversions of 3.8 and 40.9%,
period (to a 20% conversion of MBI) (Fig. 4) is, prob- selectivity for the formation of MBE was 97.9%
ably, related to the formation of catalytic centers [25]. (Fig. 6a). At a conversion of 88.7%, S
decreased to
MBE
The catalysts in batch and microcapillary reactors 92.9%. It was established that the reaction has the first
Conversion, %
Selectivity, %
SMBE
00
1
2
8
0
0
80
80
1
4
40
60
3
0
0
20
40
60
80
100
x, %
0
5
10
15
20
vl, mL/min
Fig. 3. Dependence of selectivity for the formation of MBE
Fig. 2. Effects of liquid flow rate on (1) the conversion of
MBI and selectivity for the formation of (2) MBE and
on the conversion of MBI. Initial MBI concentration,
0
.1 mol/L; liquid flow rate v = 0.02 mL/min; gas flow
l
(
3) MBA. Initial MBI concentration, 0.2 mol/L; gas flow
rate v = 2.0 mL/min; H pressure, 1 atm; and tempera-
rate v = 2.0 mL/min; H pressure, 1 atm; and tempera-
g
2
g
2
ture, 313 K.
ture, 313 K.
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CAPILLARY MICROREACTOR WITH A CATALYTIC COATING
501
Concentration, mol/L
.2
Activity, molMBI (mol ) s–1
–1
Pd
0
1
1.0
2
0.1
0.5
3
0
200
400
600
800 1000 1200
t, s
0
0.1
0.2
Concentration, mol/L
Fig. 4. Dependences of the concentrations of (1) MBI and
the hydrogenation products (2) MBE and (3) MBA on the
reaction time. Initial MBI concentration, 0.2 mol/L; gas
Fig. 5. Effect of the initial concentration of MBI on the
rate of hydrogenation at a conversion of 20%. Liquid flow
rate, from 0.003 to 0.06 mL/min; gas flow rate,
flow rate v = 2.0 mL/min; H pressure, 1 atm; and tem-
g
2
perature, 313 K.
2.0 mL/min; H pressure, 1 atm; and temperature, 313 K.
2
order with respect to hydrogen. The experimental washed off into the reaction solution. The coating
results are consistent with published data, according to remained stable upon passing a continuous flow for
which the kinetics of triple bond hydrogenation is 500 h; therefore, this technology can be used under
described by the Langmuir–Hinshelwood mechanism industrial conditions.
[
25] under the following assumptions: (1) the adsorp-
It is well known that the yield of the olefin products
of hydrogenation considerably increases upon the
introduction of reaction modifiers into the reaction
mixture [29] or modifying metals into the catalyst on
its synthesis [30–32]. The modifier increases electron
density on the surface of palladium because a coordi-
nation ligand or metal are electron donors, and this
changes a ratio between alkyne and alkene adsorption
constants. Selectivity for the formation of an alkene
can be increased by the addition of an electron-donor
metal (Zn) to the particles of Pd [33]. The bimetallic
catalyst exhibited high efficiency and selectivity and
ensured a high reaction rate. The aim of our further
studies will be to optimize the Pd/Zn ratio in order to
increase the activity and selectivity of reaction.
tion of reagents is competitive; (2) the hydrogenation
of MBI occurs by the consecutive addition of hydro-
gen atoms; the addition of the second H atom is a slow
step, and the addition of the first atom is a quasi-equi-
librium step [28]; and (3) hydrogen is more weakly
adsorbed on Pd than an alkyne [26].
Selectivity for the formation of MBE weakly
depends on temperature. As the temperature was
increased, the selectivity decreased (Fig. 6b); this is
consistent with published data on the hydrogenation
of MBI on Pd Zn /TiO [5]. A maximum MBE yield
25
75
2
of 92.3%, which was reached at 313 K, is 5% higher
than that found by Rebrov et al. [5]. At temperatures
above 328 K, the activity of catalysts decreased
(
Fig. 6b). This can be explained by a shift of adsorp-
tion–desorption equilibrium between all of the reac-
tion components, including a solvent (the boiling
point of methanol is 338 K), and by an increase in the
rate of desorption of MBI [25]. The apparent activa-
tion energy of the hydrogenation of MBI was
CONCLUSIONS
In this work, we developed nanosized thin-film
palladium catalysts based on mesoporous titanium
dioxide and studied their activity in the hydrogenation
reaction of 2-methyl-3-butyn-2-ol. In contrast to cat-
alysts used in a standard batch reactor, including the
commercial Lindlar catalyst, these coatings can be
63 kJ/mol, which is consistent with the value found
earlier by Rebrov et al. [5].
Note that a test sample sufficient for analysis can be used in a continuously working microcapillary reactor.
collected at a liquid flow rate of 10 μL/min in 60 min They manifest high activity and selectivity, and they
(
10 test samples per day and 220–250 test samples per also make it possible to effectively separate the reac-
month). The catalyst was not deactivated for two tion products from the catalyst and to control the con-
months of operation at a temperature of 313 K. Our tact time of the catalyst with the reagents. The opti-
results showed that the colloidal nanoparticles intro- mum conditions of the hydrogenation of MBI in a
duced into a matrix of titanium dioxide were not microcapillary reactor were found: the greatest yield of
KINETICS AND CATALYSIS Vol. 57 No. 4 2016

5
02
OKHLOPKOVA et al.
(
а)
(b)
SMBE, %
SMBE, %
x, %
00
x, %
2
1
2 100
2 80
80
60
40
8
0
0
0
0
3
13 К
323 К
6
4
2
60
40
20
0
1
1
1
20
0
20
40
60
80
100
PH2
305 310 315 320 325 330 335
T, K
Fig. 6. Effects of (a) the partial pressure of H and (b) temperature on (1) the conversion of MBI and (2) selectivity for the for-
2
mation of MBE. Initial MBI concentration, 0.1 mol/L; liquid and gas flow rates, 0.01 and 2.0 mL/min, respectively. (b) The H
pressure is 1 atm.
2
the unsaturated alcohol 2-methyl-3-buten-2-ol
92.3%), which is higher by 17.9% than the yield in a
batch reactor, was obtained in an atmosphere of pure 10. Singh, U.K. and Vannice, M.A., J. Mol. Catal. A:
Chem., 2000, vol. 163, p. 233.
9. Zhang, R., Elzatahry, A.A., Al-Deyab, S.S., and Zhao, D.,
(
Nano Today, 2012, vol. 7, p. 344.
hydrogen at 313 K.
1
1. Rebrov, E.V., Berenguer-Murcia, Á., Johnson, B.F.G.,
and Schouten, J.C., Catal. Today, 2008, vol. 138, p. 123.
ACKNOWLEDGMENTS
1
2. Lee, U.-H., Lee, H., Wen, S., Mho, S., and Kwon, Y.-U.,
We are grateful to Cand. Sci. (Chem.) E.Yu. Gera-
simov and A.N. Serkova for their assistance in the
physicochemical analysis of the samples.
This work was supported by the Russian Academy
of Sciences and the Federal Agency of Scientific Orga-
nizations (FANO) of Russia (project no. V45.1.10).
Microporous Mesoporoua Mater., 2006, vol. 88, p. 8.
1
3. Okhlopkova, L.B., Kerzhentsev, M.A., Tuzikov, F.V.,
Larichev, Y.V., Prosvirin, I.P., and Ismagilov, Z.R.,
J. Nanopart. Res., 2012, vol. 14, no. 9. doi doi
10.1007/s11051-012-1089-9
14. Okhlopkova, L.B., Kerzhentsev, M.A., Tuzikov, F.V.,
Larichev, Y.V., and Ismagilov, Z.R., J. Nanopart. Res.,
2012, vol. 14, no. 9. doi 10.1007/s11051-012-1088-x
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