Carbon monoxide oxidation by atmospheric oxygen on catalysts prepared by pyrolysis of transition metal β-diketonates on the synthetic foam ceramics

Article abstract of DOI:10.1134/S1070363212010185

The results of development of new catalytic systems for the carbon monoxide oxidation to dioxide are systematized. The catalysts were produced by gas-phase thermal decomposition of the transition metal acetylacetonates on the synthetic foam ceramics. The kinetic and activation parameters of the oxidation on the catalysts were studied and their relative activity was explored. The activity of catalysts at the oxidation with air oxygen were found to depend on the nature of the deposited metal and the carrier. A synergistic effect in the bimetallic copper catalysts was revealed.

Full text of DOI:10.1134/S1070363212010185

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 1, pp. 106–115. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © I.I. Didenkulova, E.I. Tsyganova, V.M. Shekunova, Yu.A. Aleksandrov, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82,
No. 1, pp. 110–119.
Carbon Monoxide Oxidation by Atmospheric Oxygen
on Catalysts Prepared by Pyrolysis of Transition Metal
β-Diketonates on the Synthetic Foam Ceramics
a
a
a
b
I. I. Didenkulova , E. I. Tsyganova , V. M. Shekunova , and Yu. A. Aleksandrov
a
Research Institute of Chemistry, Lobachevskii Nizhny Novgorod National Research University,
pr. Gagarina 23, bld. 5, Nizhny Novgorod, 603950 Russia
e-mail: didenkul@mail.ru
b
Lobachevskii Nizhny Novgorod National Research University, Nizhny Novgorod, Russia
Received October 18, 2010
Abstract—The results of development of new catalytic systems for the carbon monoxide oxidation to dioxide
are systematized. The catalysts were produced by gas-phase thermal decomposition of the transition metal
acetylacetonates on the synthetic foam ceramics. The kinetic and activation parameters of the oxidation on the
catalysts were studied and their relative activity was explored. The activity of catalysts at the oxidation with air
oxygen were found to depend on the nature of the deposited metal and the carrier. A synergistic effect in the
bimetallic copper catalysts was revealed.
DOI: 10.1134/S1070363212010185
Carbon monoxide (CO) is a permanent component
of the Earth’s atmosphere, its natural cotent is 0.01–
Undoubted effectiveness in CO oxidation showed
the catalysts containing noble metals. Therewith, some
catalysts are more active than pure metals [14] due to
the presence of a “size effect” of positive nature: the
reaction rate increases with the decrease in the size of
the supported metal particles. This phenomenon
greatly reduces the cost of some catalysts containing
noble metals. However, at the use of such metals for
catalyst preparation the problem of recycling raises
and the use of additional processes and equipment to
extract the active ingredient. Therefore, the use of the
noble metals in catalytic systems leads to increase in
expenses and thus limits their application to solving
environmental problems.
–
3
0
.09 mg m . By the total mass, CO is the leader
among the polluting emissions [1].
There are different approaches to the purification of
gases: adsorption of polluting gas by a solid,
absorption by a liquid, thermal decomposition, and the
chemical catalytic methods. Among these, the
chemical catalytic oxidation is the most promising, its
application allows converting harmful impurities in the
harmless or less harmful, and even in the useful
substances [2].
Among the catalysts for CO oxidation not based on
a noble metal, the intermetallides Al M (M = Gd, Y)
3
Grainy, granular, and fibrous materials [9], and
cellular metallic carriers with a high mechanical strength
are used as catalysts [15]. A promising support for
catalysts is the porous ceramics, which is advantageous
due to the ability to form blocks.
[
3], CdTe [4], high-temperature superconducting
materials (HTSM) [5, 6] and metal oxides of the
perovskite [7] and spinel [8, 9] structure have been
investigated in sufficient detail. Among the supported
catalysts not inferior in activity to the intermetallides
and metal oxides a copper–cerium oxide catalysts
containing 5 wt % Cu [10–13] should be noted; the
high activity of the catalyst is due to the synergistic
effect caused by the Cu–Ce interaction. Manufacturing
of such supported catalysts is easier and consumes
significantly less amount of active ingredients.
It has been noted that the activity of catalytic
systems is affected not only by the sequence of
depositing oxides on the support [13], but also by the
method of the catalyst preparation. Currently an
intensive research of new methods of catalyst prepara-
tion is performed.
1
06

CARBON MONOXIDE OXIDATION BY ATMOSPHERIC OXYGEN
Table 1. The composition and properties of the ceramic carrier
107
Mechanical
compressive
strength, kg cm
Comp.
no.
Density ρ, Moisture capacity for Specific surface
Porosity, Average pore size,
Basic filler
–
3
2
–1
g cm
10 days, %
area Ssp, m g
%
rav., nm
–
2
Natural claya
Slurry GAZb
0.51
0.65
3.5
2.5
60.0
41.4
30.0
10.8
76
67
51
I
II
50
a
b
3+
2+
3+
Clay of montmorillonite type. Galvanic production wastes of Nizhny Novgorod automobile plant, containing, %: Cr 0.017; Fe , Fe
2
+
2+
3–
2+
2+
2–
–
4
.5; Mn 0.01; Zn 4,5; PO
4
22.37; P
2
O
5
16.72; Cu 0.01; Ni 0.87; SO
4
0.9; Cl 0.9.
In this study are systematized the results of the
trigonal-rhombohedral lattice of SiO (α-quartz) and
2
development of new catalytic systems for the oxidation
of carbon monoxide on the basis of synthetic porous
ceramics, which is durable, heat-resistant, and has a
highly developed surface, being of low cost and
containing a low concentration of active ingredient per
unit of the surface area.
hexagonal lattice of SiO of tridymite structure, and to
2
aluminosilicate, mullite, iron oxide, and aluminum
phosphate lattices. The data obtained are in good
agreement with the composition of the ceramic carrier
I, since for its synthesis natural clay was used contain-
ing in its composition the crystalline phases of alumino-
silicate, quartz, tridymite and mullite; the crystalline
We studied the catalytic activity of the systems
obtained by thermal decomposition of β-diketonates in
a vacuum on a synthetic foam ceramics in the
oxidation of carbon monoxide to dioxide [16–23]. We
investigated the relative activity of various transition
metals deposited on the ceramic media.
phase of AlPO has formed in the ceramic I during its
4
synthesis.
The diffraction pattern of the carrier II because of
the complexity of its chemical composition includes a
large set of peaks indicating a mixture of crystalline
substances [22].
The carriers for the catalysts were prepared using a
modified foam ceramics from HIPEK [24]. Table 1
lists the ceramic carrier composition and character-
istics. The designed carriers and catalysts have
medium density, an extended specific surface, high
strength, high porosity, and low moisture content at
saturation [22].
The IR spectra of samples of ceramics I and II
pressed, pre-crushed with KBr, were recorded on a
Prestige 21 IR spectrometer. The spectra contain a
strong broad band and several low-intensity bands in
–
1
the frequency range 450 to 800 cm , which can be
attributed to the vibrations of silicate and sulfate
groups in the composition of the carrier I. In the
spectrum of carrier II these bands belong only to the
vibrations of sulfate groups, since the silicon in its
structure is absent [26, 27], but the two bands at 400–
Thermograms of the obtained carriers annealed at
00°C for 2 h showed that the mass loss of the carrier I
6
in the whole temperature range (35–900°C) did not
exceed 0.25%. For the carrier II a melting above 760°C
was noted, which limits the use of this carrier for the
preparation of high-temperature catalysts. Thermo-
grams of freshly prepared samples of carriers I and II
showed that the process of structure formation of
ceramic carrier is completed at 600°C [22].
–
1
–1
–1
7
00 cm (572.38 cm and 668.34 cm ) are typical of
complex oxides with perovskite structure [28]. The
–
1
high-frequency band (668.34 cm ) is usually
attributed to the M–O vibrations of a metal in octa-
hedral coordination. The low-frequency band belongs
I
II
to the vibrations of the M –O–M valence bonds.
Deposition of metals on supports I and II did not
change the type of infrared spectra, which is a con-
sequence of low content (less than 5%) of the metal.
The phase composition of the carriers was revealed
by means of X-ray analysis of the annealed carrier I.
Figure 1 shows the diffraction pattern of a sample as
well as the theoretical diffraction patterns for a series
of solid solutions.
On the obtained carriers solid-phase products of
thermal decomposition of transition metal acetyl-
acetonates (M = Cu, Co, Mn, Zr, Fe, Cr), and nickel
The diffraction pattern of annealed ceramic sample
I includes a set of peaks indicating a high degree of
crystallinity of the obtained carrier [25]. The main
reflections of ceramic carrier I correspond to the
hexafluoroacetylacetonate Ni(hfacac) were applied. In
2
order to ensure uniform distribution of active ingre-
dient, the gas-phase thermal decomposition of these
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

1
08
DIDENKULOVA et al.
2
θ, deg
Fig. 1. Diffractogram of the catalysts Co–Cu/I on the ceramic carrier I (1) and the ceramic carrier I itself (2). Theoretical
diffraction patterns according to the ICSD database: (3) aluminosilicate NAlSi , (4) Fe , (5) SiO (α-quartz), (6) SiO
tridymite), (7) Al2.35Si0.64 4.82 (mullite), and (8) AlPO . The non-identified peaks are marked by circles.
2
O
6
2
O
3
2
2
(
O
4
complexes in a vacuum (CVD) was carried out. Nota-
tion of the catalysts, the conditions of their preparation
and processing are given in Table 2.
To calculate the kinetic parameters of the oxidation
of CO to CO in the pulse catalytic system we used the
2
following equation [29]:
ln ln [1/(1–α)] = –E
a
apparent/(RT) + ln k
.
0
It is known that the thermal decomposition of metal
β-diketonates gives composite coatings containing the
metal, the respective oxide, carbide, and free carbon.
All coatings were heated for 1 h at 600°C for the
transformation of the metal in its oxide form and for
the removal the unbound carbon.
The calculation of kinetic parameters with this
equation is possible if the following conditions are
fulfilled: the absence of chromatographic separation of
reactants on the catalyst, the first total reaction order of
the investigated reaction, the absence of the effects of
diffusion factors on the process. These conditions have
been maintained in this study.
The catalytic activity of different catalysts was
compared by testing them in a pulse microcatalytic
system. To compare the conversion approximately
equal contact time: 0.7–0.8 s was used. Each catalyst
was preliminarily heated in a reactor for 3 h at 500°C
in a stream of helium to achieve a steady-state catalytic
activity. The stationary state was reached by each
catalyst after passing 2–3 times through the catalyst
system the CO–air working mixture.
We discovered and then set the conditions and
parameters of the oxidation reaction in the pulse
microcatalytic installation: the carrier gas flow rate
–
1
0.5 ml s , the catalysts dispersion 0.3–0.5 mm, the CO
and O concentrations in the reaction mixture 2.6 and
2
20.0 vol %, respectively, the contact time for each
catalyst 0.7–0.8 s.
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CARBON MONOXIDE OXIDATION BY ATMOSPHERIC OXYGEN
109
Table 2. Composition of the catalysts for CO oxidation to CO
and processing
2
produced by CVD method, the conditions of their preparation
Catalyst composition
Carrier I + 3% Со
Notation
Metal source
Co(acac)
Mn(acac)
Zr(acac)
Deposition conditions
Со/I
Mn/I
Zr/I
2
320°С, 2 h
400°С, 1 h
350°С, 2 h
400°С, 1 h
400°С, 1 h
350°С, 1 h
350°С, 1 h
400°С, 1 h
Carrier I + 3% Mn
Carrier I + 3% Zr
2
4
Carrier I + 3% Fe
Carrier I + 3% Cr
Carrier I + 3% Ni
Carrier I + 3% Cu
Carrier I + 3% Mn + 3% Ni
Fe/I
Fe(acac)
Cr(acac)
3
Cr/I
3
Ni/I
Ni(hfacac)
Cu(acac)
Mn(acac)
Ni(hfacac)
Mn(acac)
2
Cu/I
Mn-Ni/I
2
2
2
Carrier I + 3% Mn + 3% Cu
Carrier I + 3% Cu + 3% Ni
Carrier I + 3% Co + 3% Cu
Carrier I + 3% Co + 3% Ni
Mn-Cu/I
Cu-Ni/I
Co-Cu/I
Co-Ni/I
2
400°С, 1 h
350°С, 1 h
300°С, 2 h
320°С, 1 h
Cu(acac)
2
Cu(acac)
2
Ni(hfacac)
2
Co(acac)
Cu(acac)
2
2
Co(acac)
2
Ni(hfacac)
Co(acac)
Mn(acac)
Zr(acac)
2
Carrier II + 3% Co
Carrier II + 3% Mn
Carrier II + 3% Zr
Carrier II + 3% Fe
Carrier II + 3% Cr
Carrier II + 3% Ni
Carrier II + 3% Cu
Carrier II + 3% Mn + 3%Ni
Co/II
Mn/II
Zr/II
2
320°С, 2 h
400°С, 1 h
350°С, 2 h
400°С, 1 h
430°С, 1 h
350°С, 1 h
300°С, 1 h
400°С, 1 h
2
4
Fe/II
Fe(acac)
Cr(acac)
3
Cr/II
3
Ni/II
Ni(hfacac)
Cu(acac)
Mn(acac)
Ni(hfacac)
Mn(acac)
2
Cu/II
Mn-Ni/II
2
2
2
Carrier II + 3% Mn + 3%Cu
Carrier II + 3% Cu + 3% Ni
Carrier II + 3% Co + 3% Ni
Mn-Cu/II
Cu-Ni/II
Co-Ni/II
2
400°С, 1 h
350°С, 1 h
300°С, 1 h
Cu(acac)
2
Cu(acac)
2
Ni(hfacac)
Co(acac)
Ni(hfacac)
2
2
2
The kinetic experiments conditions and the
activation parameters of the heterogeneous catalytic
oxidation of CO with air oxygen on the catalysts
prepared by the CVD method on the carrier I are
shown in Table 3. Calculation of the apparent
activation energy was performed using the data up to
The carrier I was characterized by a weak catalytic
activity in CO oxidation: the beginning of conversion
occurred at 450°C, and the 50% conversion was
observed at 810°C (Fig. 2). The carrier II showed a
complicated form of the dependence of conversion on
temperature. The conversion begins at 220°C in the
temperature range 300–700°C, the conversion ranges
from 40 to 47% and then raises sharply with increasing
temperature.
5
0% conversion in the region of the absence of side
reactions and the kinetic mode of the process, as
evidence the values of activation energies obtained.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

1
10
DIDENKULOVA et al.
Table 3. Activation parameters of catalytic oxidation of CO to CO on the catalysts prepared by CVD method in the presence
2
of oxygen, on the ascending branch of hysteresis
0
apparent,
а
ΔH298 (M–O),
Temperature range,
°C
Т, °С for
α 50%
Е
Catalysis
Hysteresis mode
log k
0
kJ mol–
1
kJ mol
–1
Co-Cu/I
Cu-Ni/I
Cu/I
–
100–250
97–300
215
215
275
300
300
335
380
400
540
575
600
670
810
240
260
290
323
345
400
470
615
620
725
765
500
4.4±1.1
4.9±0.3
4.3±0.7
4.4±0.5
3.6±0.2
3.7±0.1
2.9±0.2
9.5±1.2
4.3±0.1
7.1±1.6
3.1±0.1
3.2±0.1
2.1±0.2
6.6±0.1
5.8±0.2
8.0±1.2
12.0±1.1
9.8±0.7
4.7±0.3
6.0±1.2
2.7±0.2
2.5±0.1
1.7±0.5
6.0±0.3
9.1±1.2
42.2±2.7
47.9±2.8
48.1±6.7
49.8±2.2
41.2±5.2
44.3±1.1
35.4±2.8
121.0±3.7
68.3±1.8
97.8±4.1
55.6±3.3
60.5±2.1
47.8±2.9
69.1±2.4
61.7±3.4
89.4±2.8
137.9±2.8
112.7±3.5
62.5±3.6
82.2±4.5
48.1±2.4
44.8±1.1
40.6±4.0
121.9±4.9
101.9±3.9
Counterclockwise
266.7
364.1
–
170–370
170–473
150–700
140–450
210–590
255–408
300–690
300–630
300–685
200–780
450–840
200–350
185–632
240–392
170–370
200–394
275–740
250–780
300–700
327–700
450–750
600–800
220–800
Ni/I
Clockwise
Co-Ni/I
Mn-Cu/I
Cr/I
–
Clockwise
456.0
368.3
409.6
757.4
410.1
–
Co/I
Counterclockwise
Mn/I
Counterclockwise
Zr/I
Counterclockwise
Fe/I
–
Mn-Ni/I
Carrier I
Co-Ni/II
Cu/II
–
–
–
266.7
364.1
368.3
410.1
456.0
757.4
–
Ni/II
–
Co/II
Counterclockwise
Fe/II
–
Counterclockwise
Counterclockwise
Clockwise
Clockwise
Clockwise
–
Cr/II
Zr/II
Mn-Ni/II
Mn-Cu/II
Mn/II
Cu-Ni/II
Carrier II
409.6
–
This phenomenon may be due to a change in the
oxidation state of the transition metal in the carrier
composition, and the presence on the carrier surface of
perovskite-like structures (detected by IR spectro-
scopy) that are active catalysts for CO oxidation.
However, the perovskite surface bears not only the
oxidation sites, but also the sites of side reactions, the
latter in the temperature range 300–600°C can strongly
bind up to 95% of CO, thus limiting the conversion
raise in this temperature range [28].
Application of composite coatings on carriers signify-
cantly increased their catalytic activity. We compared
the catalytic activity of catalysts in the presence of
oxygen at the a temperature corresponding to 50% con-
version on the ascending branch of the hysteresis loop.
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CARBON MONOXIDE OXIDATION BY ATMOSPHERIC OXYGEN
111
Т, °C
Fig. 2. Comparison of catalytic activity of the carriers I and
3
–1
II (F = 0.5 cm s , the fraction 0.3–0.5 mm). (1) carrier II,
2) carrier I.
(
The data in Table 3 indicate that the studied
catalysts on the carrier I can be arranged in the
following series by their catalytic activity: Co–Cu ≥
Cu–Ni > Cu > Ni ≥ Co–Ni > Mn–Cu > Cr > Co > Mn
>
Zr > Fe > Mn–Ni. The most active catalysts on the
Т, °C
carrier I were those promoted with the metal-
containing solid products of the thermal decomposition
of the Co–Cu or Cu–Ni β-diketonate mixtures. On
these catalysts the reaction started already at 100°C
Fig. 3. Comparison of catalytic activity of catalysts on the
carrier I (F = 0.5 cm s , the fraction 0.3–0.5 mm).
Catalysts: (1) Cu–Ni/I, (2) Cu/I, (3) Ni/I.
3
–1
and complete conversion of CO to CO was observed
2
occurs in coupling the ions affecting the catalytic
activity on the catalyst surface. It is known [30] that
octahedrally coordinated metal ions on the surface of
complex oxide catalyst play a special role, determining
mainly the catalytic activity. The decrease in the
activity of binary catalysts containing manganese
oxides is a result of relatively easy oxidation of the
Mn to Mn and Mn , which have octahedral
coordination and displace more active ions (in this case
Ni) from the octahedral sites to the tetrahedral.
at 250–300°C. Figures 3 and 4 show the typical
conversion curves for the catalysts on the carrier I.
As seen from Fig. 3, the activity of monometallic
catalysts Cu/I and Ni/I is lower than that of the
bimetallic catalyst Cu–Ni/I. The same effect is
observed in the case of monometallic catalysts Co/I,
Cu/I (Fig. 4) and bimetallic Co–Cu/I.
2+
3+
4+
The high activity of copper–nickel and copper–
cobalt catalysts (Figs. 3 and 4) in the oxidation of CO
is due to a synergistic effect caused by the interaction
of ions Cu–Co and Cu–Ni, where, as in the case of
copper–cerium catalysts [10], copper can be easily
integrated into the lattice of cobalt and nickel oxides.
It was previously found [31] that the rate of
catalytic oxidation of CO to CO varies with changes
2
in the size of deposited particles of the active
component, that is, the CO oxidation is structure-
sensitive. In the case of Mn-containing catalysts
+
The replacement by the Cu leads to the appearance of
oxygen vacancies that causes high mobility of oxygen
in the catalyst lattice resulting in the high activity of
the binary copper catalysts.
(
Mn/I) the “size effect” of the negative nature was
observed (the reaction rate decreased with the decrease
in the size of the particles deposited on the carrier). In
the case of Co-, Cr- and Ni-containing catalysts the
“size effect” is positive in nature (the reaction rate
increases). In the case of Fe-containing catalysts, we
are dealing with structure-insensitive reaction.
The least active in the oxidation of carbon
monoxide was Mn–Ni/I catalyst. Moreover, its activity
was much lower than that of the monometallic
catalysts Ni/I and Mn/I. In this case an antagonism
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

1
12
DIDENKULOVA et al.
bimetallic ones. The monometallic catalysts based on
the carrier II give the following series by their
catalytic activity in CO oxidation with atmospheric
oxygen: Cu > Ni > Co > Fe > Cr > Zr > Mn. This
series of catalysts is in good agreement with the values
of the energy of the metal–oxygen bond.
It should be noted that the plots of conversion of
CO to CO on the catalysts based on carrier II have
2
complex undulate form, with maxima and minima in
the kinetic curves (Figs. 5 and 6). This nature of the
conversion is due to the complex composition of the
carrier II that consists mainly of salts (chlorides,
sulfates, and phosphates) of transition metals and
contains the perovskite-like structures on its surface.
The curves of the conversion–temperature
dependence of some catalysts supported on I and II
reflect the phenomenon of “hysteresis,” when the
values of conversion is not the same at the raise and
decrease in the temperature (Figs. 3, 5). The hysteresis
is observed both “counterclockwise,” e.g., Co/I, Mn/I,
Cu–Ni/I, Zr/I (carrier I) and Co/II, Cr/II, Zr/II (carrier
II), and, commonly seldom, “clockwise;” Ni/I and
Mn–Cu/I (carrier I), and Mn/II, Mn–Cu/II and Mn–
Ni/II (carrier II). The occurrence of hysteresis can be
due to different factors: the presence of critical
phenomena and the multiplicity of stationary states, the
change in the phase composition of the catalyst and the
different forms of adsorbed oxygen, as well as by local
overheating of active centers and low thermal
conductivity of porous media.
Т, °C
Fig. 4. Comparison of catalytic activity of the oxidation
catalysts on carrier I (F = 0.5 cm s , the fraction 0.3–
.5 mm). Catalysts: (1) Co–Cu/I, (2) Cu/I, (3) Co/I.
3
–1
0
The studied monometallic catalysts based on the
carrier I form the following series by their catalytic
activity in CO oxidation with atmospheric oxygen (at
the temperature of 50% conversion, along the
ascending branch of the hysteresis loop): Cu > Ni >
Cr > Co > Mn > Zr > Fe.
The activity in the presence of oxygen of all the
studied catalysts, with the exception of the Mn-
containing ones, forms the following series (a the
temperature of 50% conversion):
This series is in accordance with the values of the
metal–oxygen bond energy (Table 3): the lower is the
M–O bond energy, the more active is the catalyst.
The study showed that the most active on the
carrier I are the bimetallic catalysts, especially copper-
containing, except for the Mn–Ni catalyst. The cata-
lysts prepared on the basis of carrier I operate stabely
over a wide temperature range up to 1000°C.
The study of the catalysts on the carrier II gave the
following series of activities: Co–Ni > Cu > Ni > Co >
Fe > Cr > Zr > Mn–Ni ≥ Mn–Cu > Mn > Cu–Ni.
The reaction on the most active Co–Ni catalyst
begins at 200°C, and the complete conversion of CO to
CO was observed at 350°C. The least active was the
Cu–Ni/I > Cu/II > Cu/I > Ni/II Ni/I > Co/II > Fe/II
>
Cr/I Co/I = Cr/II > Zr/II > Zr/I > Fe/I > Cu–Ni/II.
This sequence indicates that monometallic catalysts
of oxidation on the support II are more active than
those on the support I. Also a great difference is seen
in the activity of Cu–Ni catalysts supported on I or II
(ΔT = 550°C at 50% conversion), which may be
associated with the presence of poisoning the catalyst
by chloride ions in the carrier II. This series is also in
good agreement with the energy of the M–O bond.
Thus, by the study of catalytic systems for CO
oxidation obtained by CVD method on the carriers I
and II it was found that the activity of the catalysts
depends not only on the activity of the metal on the
2
Cu–Ni catalyst. It should be noted that in contrast to
the catalysts based on the carrier I, on the carrier II the
monometallic catalysts are more active than the
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CARBON MONOXIDE OXIDATION BY ATMOSPHERIC OXYGEN
113
Т, °C
Т, °C
Fig. 6. Comparison of catalytic activity of Mn-containing
3
–1
Fig. 5. Comparison of catalytic activity of catalyst on the
carrier II (F = 0.5 cm s , the fraction 0.3–0.5 mm).
Catalysts: (1) Fe/II, (2) Cr/ II, (3) Zr/ II.
catalysts for CO oxidation on a carrier II (F = 0.5 cm s ,
the fraction 0.3–0.5 mm). Catalysts: (1) Mn–Ni/II, (2) Mn–
Cu/II, (3) Mn/II, (4) carrier II itself.
3
–1
carrier surface, but also on the nature of the carrier
itself. Supported catalyst on I are more versatile,
because they retain the activity in a wide range of
temperatures, while the carrier II melts at the
temperature above 760°C.
while in the heterogeneous catalysis the oxidation of
CO proceeds on the outer surface of the catalyst. A
similar pattern was observed for the Co-containing
catalysts. The best was Co-containing catalyst on a
carrier II, produced by CVD method: on this catalyst
the conversion began at 170°C, and 80% conversion
probability was achieved at 340°C.
Previously [16, 17] by the example of Cu- and Co-
containing catalysts prepared on a carrier II we have
shown that the mode of the metal deposition affects the
catalyst. The greatest catalytic activity up to 50%
conversion had the catalyst prepared by pyrolysis of
Thus, the catalysts prepared by deposition in a
vacuum from the gas phase (CVD) are superior by
their catalytic properties to catalysts prepared by
conventional impregnation. The catalysts on an inert
carrier I (the base is natural clay of the montmori-
llonite type) are heat resistant up to 1000°C. The most
active are the catalysts promoted with metal-containing
solid product of thermal decomposition of a mixture of
Co-Cu or Cu-Ni β-diketonates.
Cu(acac) along the CVD method. The catalyst
2
prepared by impregnating the carrier with the
(
CH COO) Cu solution is close to it by the activity.
3
2
This is due to the similarity of the solid phase
compositions formed at the decomposition of copper
acetate and acetylacetonate. The lowest activity had
Cu/II catalyst prepared with the introduction of copper
nitrate in the carrier composition at the preparation of
the latter. Its activity was the same as the activity of
the carrier II itself. This is explained by location of
CuO inside the carrier bulk and in its internal pores,
EXPERIMENTAL
Preparation of carriers for catalysts based on a
“HIPEK” ceramics was performed in accordance with
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

1
14
DIDENKULOVA et al.
TU 5759-010-10657190-97 [24], by introducing various
fillers and additives to the system. To prepare the
catalyst were taken the ceramic samples annealed for
5. Berentsveig, V.V., Lagutkina, O.I., and Shabatin, V.P.,
Kinetika i Kataliz, 1992, vol. 33, nos. 5–6, p. 1174.
6. Bobolev, A.V., Borisov, Yu.V., and Vydrin, S.N.,
Fizikokhimiya i tekhnologiya vysokotemperaturnykh
sverkhprovodyashchikh materialov (Physical Chemistry
and Technology of High-Temperature Superconducting
Materials), Moscow: Nauka, 1989.
1
h at 500°C (fraction of 0.3–0.5 mm).
The carrier-promoting additive ratios are given in
Table 2. A weighed sample of the carrier with pre-
calculated amount of a β-diketonate was placed in a 60
ml glass ampule, the ampule was evacuated and placed
in a furnace heated to a desired temperature. The
optimum conditions for thermal decomposition of β-
diketonates were chosen [32]. The obtained catalysts
were annealed at 600°C in air for 1 h.
7
8
9
. Panich, N.M., Pirogova, G.N., Korosteleva, R.I., and
Voronin, Yu.V., Izv. Akad. Nauk, Ser. Khim., 1999,
no. 4, p. 698.
. Pirogova, G.N., Panich, N.M., Korosteleva, R.I., Voro-
nin, Yu.V., and Popova, P.N., Izv. Akad. Nauk, Ser.
Khim., 2000, no. 9, p. 1547.
. Eyubova, S.M. and Yagodovskii, V.D., Zh. Fiz. Khim.,
Kinetics of heterogeneous catalytic oxidation of CO
2
007, vol. 81, no. 4, p. 637.
to CO was studied using a pulsed version of gas
2
1
1
0. Il’ichev, A.N., Firsova, A.A., and Korchak, V.N.,
chromatographic method. Conversion was calculated
Kinetika i Kataliz, 2006, vol. 47, no. 4, p. 602.
from the intensity of CO peaks using the method of
2
1. Snytnikov, P.V., Stadnichenko, A.I., Semin, G.L.,
Belyaev, V.D., Boronin, L.I., and Sobyanin, V.A.,
Kinetika i Kataliz, 2007, vol. 48, no. 3, p. 472.
calibration. The technique of kinetic measurements is
described in [33].
The IR spectra of pressed samples pre-crushed with
KBr of the carriers I and II and catalysts based on
them were recorded on a Shimadzu infrared Fourier
spectrometer IR Prestige 21.
1
2. Snytnikov, P.V., Stadnichenko, A.I., Semin, G.L.,
Belyaev, V.D., Boronin, L.I., and Sobyanin, V.A.,
Kinetika i Kataliz, 2007, vol. 48, no. 3, p. 463.
1
3. Firsova, A.A., Il’ichev, A.N., Khomenko, T.N.,
Gorobinskii, L.V., Maksimov, Yu.V., Suzdalev, I.P.,
and Korchak, V.N., Kinetika i Kataliz, 2007, vol. 48,
no. 2, p. 298.
The X-ray diffraction (XRD) studies were
performed on a DRON-3M diffractometer using CuK
α
radiation with a graphite monochromator on the
diffracted beam. Registration was carried out in the
angular range 2θ = 10°–60° with 0.05° steps of 2θ at
1
1
1
4. Boudart, M., Advances in Catalysis, 1969, vol. 20,
p. 153.
5. Semikolenov, V.A., Zh. Prikl. Khim., 1997, vol. 70,
2
s exposure per point.
no. 5, p. 785.
Thermogravimetric (TGA) analysis was performed
6. Tsyganova, E.I., Didenkulova, I.I., Shekunova, V.M.,
Faerman, V.I., and Aleksandrov, Yu.A., Zh. Obshch.
Khim., 2004, vol. 74, no. 11, p. 1770.
on a Perkin-Elmer PYRIS 6 TGA unit. The 24 mg
samples were placed in platinum crucibles. The linear
polythermal heating option was used for the analysis
1
7. Tsyganova, E.I., Didenkulova, I.I., Shekunova, V.M.,
and Aleksandrov, Yu.A , Zh. Obshch. Khim., 2004,
vol. 74, no. 5, p. 742.
–
1
with the rate of 5°C min in air. The air flow rate was
–
1
8
9
0 ml min . The maximum heating temperature was
00°C. The sensitivity of the instrument is 1 μg, the
accuracy 0.2%.
18. Tsyganova, E.I., Didenkulova, I.I., Shekunova, V.M.,
and Aleksandrov, Yu.A., Zh. Obshch. Khim., 2005,
vol. 75, no. 9, p. 1426.
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