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Journal of the Taiwan Institute of Chemical Engineers

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Modified diatomite-supported CuO–TiO2 composite: Preparation,

characterization and catalytic CO oxidation
Saeed Dehestaniathar a,∗, Mohammad Khajelakzay b, Mohammad Ramezani-Farani b,
Hossein Ijadpanah-Saravi c
a
Environmental Health Research Center, Kurdistan University of Medical Sciences, Sanandaj, Iran
b
Materials Science and Engineering Department, Tarbiat Modares University, Tehran, Iran
c
Department of Environmental Engineering, Faculty of Engineering, Tarbiat Modares University, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Modified diatomite (acid treated and ZrO2 -coated diatomite) coated by nano copper and titanium mixed ox-
Received 7 December 2014 ides was used to investigate the catalytic oxidation of carbon monoxide. The prepared catalysts were charac-
Revised 8 May 2015
terized by Brunauer–Emmett–Teller (BET) surface area, field emission scanning electron microscope (FESEM),
Accepted 17 May 2015
X-ray diffraction (XRD), temperature-programmed reduction (TPR), porosimetry, and X-ray photoelectron
Available online xxx
spectroscopy (XPS). Catalytic behavior for CO oxidation was studied in different conditions in a tubular reac-
Keywords: tor packed with catalyst. The variation of catalytic activity of the prepared composite catalysts with different
Diatomite molar fractions of CuO and TiO2 for CO oxidation in different reaction temperatures was investigated. The
Nanocomposite catalytic activity of catalyst was dependent on the concentration of coated catalyst over diatomite, reaction
Carbon monoxide temperature and retention time. The results illustrated that diatomite is the promising candidate for catalyst
Oxidation support due to its unique characteristics. It was found that CO conversion of 100% can be achieved at 220 °C
over catalyst with 70 mol% CuO and 30 mol% TiO2 content.
© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Carbon monoxide (CO) is a highly toxic, colorless, and odorless
gas with a density close to the air, which is produced by natu-
ral processes and anthropogenic sources and is well known for its
potential harmful and poisonous effects on humans. Inhalation of
carbon monoxide gas can impair the heart and the body’s cen-
tral nervous system. Industrial processes and oxidation of hydro-
carbons are the major sources of CO. Automobile emissions are the
major urban source of carbon monoxide [1]. So carbon monoxide
emission must be controlled through engineering principles and
techniques.
Catalytic oxidation is an efficient way to control of CO emis-
sion from automobiles. Substrate, wash-coat, and active component
which are referred as catalyst, are three components of the catalyst
system in a catalytic combustor. The substrate acts as a support for
the other two components and the wash-coat provides a high sur-
∗
Corresponding author. Tel.: +98 871 6625131, +98 912 7100637;
fax: +98 871 6625131.
E-mail addresses: saeed_dehestani@yahoo.com, s.dehestani@muk.ac.ir
(S. Dehestaniathar), lakzayi_malayer@yahoo.com (M. Khajelakzay),
madief2003@gmail.com (M. Ramezani-Farani), hossein.ijad@gmail.com
(H. Ijadpanah-Saravi).
face area to distribute the active component [2]. Exhaust gases must
pass through the support without causing any prohibitive increase in
the back-pressure at the exhaust. Moreover, the support must provide
high surface area for effective dispersion of active phase and rapid
mass transfer [3].
With regard to the catalyst type, the two most common products
available in the market are ceramic and metallic substrates [4]. Both
substrates have relatively low porosity, which makes them unsuit-
able as a catalyst support. A thin layer of a porous material is called
wash-coat applied to increase the developed surface area of the sup-
port. In this regard, γ -Al2 O3 is commonly used as a wash-coat. The
automotive converter substrates need to contain two important me-
chanical properties. These include low thermal expansion coefficient
and high thermal shock resistance. Cordierite (14% MgO, 35% Al2 O3
and 51% SiO2 ) is a good option for an automotive converter due to its
high thermal shock resistance [5]. Among a number of temperature
resistant catalysts for CO oxidation, the complex oxides are of consid-
erable interest. Zirconium dioxide has a high melting point, low ther-
mal conductivity, and a high resistance against the corrosion. More-
over, ZrO2 has an acid–base bifunctional property [6]. SiO2 –Al2 O3 is
a solid acid which can adsorb just basic molecule, but ZrO2 adsorbs
both acidic and basic molecules. Fornasiero and co-workers [7] found
that introduction of ZrO2 into the CeO2 modifies the reduction behav-
ior of the composite. The hypothesis behind this work is that using

http://dx.doi.org/10.1016/j.jtice.2015.05.030
1876-1070/© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: S. Dehestaniathar et al., Modified diatomite-supported CuO–TiO2 composite: Preparation, characterization and
catalytic CO oxidation, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.05.030
JID: JTICE
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2 S. Dehestaniathar et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7
ZrO2 may enhance the catalytic CO oxidation of prepared composite
catalyst.
Different kinds of materials, including active supports, such as
TiO2 and Fe2 O3 , which can be easily reduced, or inert supports, such
as Al2 O3 , silica, MCM-48, Al-SBA-15, activated carbon fibers, Y-type
zeolite and H-BEA zeolite have been used as a support [8–12].
Copper oxide-based catalysts have been extensively investigated
as a possible substitute for noble metal catalysts because they have
much lower cost [13,14]. Copper oxides are well known for their high
activity in oxidation of CO and numerous studies have been carried
out to investigate CO oxidation over copper oxides [15–18]. Due to
the synergistic effect, catalytic activity of composite metal oxides for
CO oxidation is more than individual metal oxides. Moreover catalyst
support significantly influences the catalytic activity. So in this paper
the catalytic performance of diatomite-supported CuO–TiO2 compos-
ite for CO oxidation has been investigated.
Diatomite (diatomaceous earth or kieselguhr) is a lightweight
sedimentary rock consisting principally of silica microfossils of
aquatic unicellular algae, which is available in large deposits around
the world. Silicon dioxide is the main component of diatomite and
some impurities such as iron, alumina and metal oxides are other
components of diatomite. Diatomite products are used in a variety
of ways, such as sound and heat insulation, abrasives and in the man-
ufacture of explosives [19]. Diatomite has some unique characteris-
tics such as: 80–90% pore spaces, numerous fine microscopic pores,
cavities and channels, high porous structure (35–65%), good sorption
ability, low density, high permeability, high surface area, excellent
thermal resistance, wide variety of shapes and sizes, and active hy-
droxyl groups formation on it. These unique properties of diatomite
have led to a number of applications such as filtration media, cat-
alytic support, and adsorbent. Moreover, it has been suggested that
diatomite can be successfully used as a cost-effective alternative to
activated carbon. Commercial activated carbon is 500 times more
expensive than diatomite [20–25]. In this study in order to remove
the impurities and improve the chemical composition and the struc-
ture of natural diatomite, modification of diatomite by acid and ZrO2
treatment has been carried out.
Although copper oxide supported on alumina and other metal
oxides have been widely used in a variety of reactions such as CO
oxidation, [26–28] modified diatomite has not been reported as
a support for copper–titanium mixed oxides for carbon monoxide
oxidation. This study is aimed at investigating the modified diatomite
performance as a supporting host to confine the CuO–TiO2 catalyst
and its catalytic activity for carbon monoxide oxidation.
2. Materials and methods
2.1. Acid treatment and modification (ZrO2 -coated) of support
Diatomite sample was obtained from the mine of Bojnoord in Iran.
Diatomite was washed with tap water to remove impurities then
dried in an oven at 105 °C for 24 h. The dried diatomite was sieved to
a uniform size of 0.8–1 mm. The following procedure was developed
to treat the diatomite: natural diatomite was submitted to calcination
at 900 °C. Calcination was carried out under atmospheric pressure in
a programmable furnace, with a heating rate from room temperature
to the calcination temperature of 10 °C/min, and the samples were
left in the furnace for 5 h at the calcinations temperature. The acid
treatments were carried out with 6 M H2 SO4 and 100 g diatomite, at
about 100 °C for 4 h with reflux conditions. The slurry was cooled in
air and filtered through Whatman no. 42 paper and a Buchner funnel.
The filter cake was repeatedly washed with hot distilled water until
the filtrate pH reached 7. The acid-treated sample was then dried at
105 °C for 12 h.
In order to prepare ZrO2 -coated diatomite, which represented as
M-diatomite, first ZrO2 sol was synthesized using zirconium tetra-
Please cite this article as: S. Dehestaniathar et al., Modified diatomite-supported CuO–TiO2 composite: Preparation, characterization and
catalytic CO oxidation, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.05.030
[m5G;June 6, 2015;21:57]
Table 1
Real composition (molar fraction) of
prepared CuO–TiO2 composite oxides.
Catalyst Cu (mol%) Ti (mol%)
Cu90 Ti10 87.67 12.33
Cu80 Ti20 78.34 21.66
Cu70 Ti30 68.12 31.88
Cu60 Ti40 59.13 40.87
Cu50 Ti50 48.44 51.56
n-propoxide (Zr (OC3 H7 )4 , Aldrich) as previously described [29] and
after that 10 g of acid treated diatomite was added to the solution
containing ZrO2 (0.5% wt) under cont inuous stirring for 3 h at room
temperature, filtered and dried at 120 °C for 12 h.
2.2. Catalyst preparation
2.2.1. Preparation of titanium dioxide particles by the colloidal sol–gel
process
For the production of TiO2 nanoparticles, colloidal particulate sol
was prepared using commercially available alkoxide precursor, which
was hydrolyzed by the addition of excess of H2 O. The TiO2 sol was
obtained by hydrolysis of titanium tetra-isopropoxide (Ti(OC3 H7 )4 )
(TTI, Chemical Merck). TTI was dissolved in isopropyl alcohol on stir-
ring. Hydrolysis was done by reacting the alkoxide precursor with a
large excess water ([H2 O]/ [TTI] = 25). The addition of water was con-
trolled. Then sol was stirred for 2 h. The colloidal sol was prepared by
hydrolysis of alkoxide precursor
Ti(OC3 H7 )4 + xH2 O → Ti(OC3 H7 )4−x (OH)x + xC3 H7 OH
Filtering of the sol and washing of the powder with distilled water
were performed and then, ethanol was used to wash the powder for
three times. The filtered powder was dried in oven at 100 °C for 24 h.
Then the powder was dispersed in water, followed by refluxing step
overnight under the conditions of T = 50 °C and pH 1 using HNO3 .
The final product after peptization was stable fine colloidal TiO2 sol.
2.3. Preparation of CuO–TiO2 /diatomite by wet impregnation method
(WIM)
For the preparation of CuO–TiO2 /diatomite, Cu(NO3 )2 was re-
quired as precursor for metal oxide and added to TiO2 sol and af-
ter that, appropriate amounts of modified diatomite was added to
this solution under continuous stirring for 3 h on a hot plate, until it
was completely dried. The solid material was calcined at 400 °C. The
mixed oxides of Cu–Ti, followed this formula [(CuO)1 −x (TiO2 )x ], in
which x equals 0.1, 0.2, 0.3, 0.4, and 0.5 which represented as Cu90 Ti10 ,
Cu80 Ti20 , Cu70 Ti30 , Cu60 Ti40 , Cu50 Ti50 , respectively. The real compo-
sition of the prepared catalysts was examined using inductively cou-
pled plasma (ICP), and presented in Table 1. It shows that the real
molar ratio of CuO is a little less than the theoretical value.
2.4. Catalyst characterization
In order to determine crystal structure of the prepared catalysts X-
ray diffraction (XRD) analysis was performed using Philips equipment
with Cu Kα radiation at 40 kV and 30 mA in a scanning range of 5–
80° (2θ ). The diffraction peaks of samples were compared with JCPDS
data profiles. The average diameter of the prepared catalysts was es-
timated using the Scherer’s equation. Elemental analysis of pure di-
atomite was determined by XRF technique. The surface areas of the
catalysts were measured by N2 adsorption with the BET method.
Surface morphology of diatomite and coated catalysts were char-
acterized by means of field emission scanning electron microscope
(FESEM-Philips) equipped by EDX (Energy dispersive X-ray mi-
croanalysis). Porous properties of catalyst were determined using
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mercury porosimetry (Pascal 440). Particle size distributions were

analyzed using laser diffraction (Malvern). X-ray photoelectron spec-
troscopy (XPS) analysis of the prepared catalyst was carried out by
Thermo Scientific ESCALAB 250 using monochromated Al (Kα ) radia-
tion source.
The reducibility of CuO–TiO2 /diatomite catalyst was measured by
temperature-programmed reduction (TPR) using a Pulse Chemi Sorb
2705 apparatus equipped with a thermal conductivity detector (TCD).
The experiment was performed under a reducing gas consisting of 5%
H2 in argon flowing (40 ml/min) over 20 mg of catalyst at a heating
ramp rate of 10 °C /min. The amount of hydrogen uptake was deter-
mined by TCD.

2.5. Catalytic activity test

Catalytic tests for the oxidation of CO were carried out at atmo-

spheric pressure in a continuous-flow, fixed-bed stainless steel tubu-
lar reactor (2 cm inner diameter and 20 cm length). About 2 g catalyst
was placed into the reactor. The reaction temperature was increased
from room temperature to 400 °C and the catalyst activity was mea-
sured at steady state condition which has been reached 2 h after
starting of reaction. The temperature being measured by a thermo-
couple was placed into the catalyst bed. Analysis of the reaction prod-
ucts was carried out at a different condition using a multi-component
NDIR gas analyzer (Delta 1600 S-IV). The reaction gas mixture con-
sisting of 5 vol. % CO balanced with air was passed through the cat-
alyst bed at a total flow rates of 0.5 and 1 l/min (gas hourly space
velocity (GHSV) = 15,000 and 30,000 ml/h gcat respectively). The con-
version of CO was given by Eq. (1).
Ci − C0
X (% ) = 100 × (1)
Ci
where Ci is the inlet CO concentration (ppm) and C0 is the outlet CO
concentration (ppm).

3. Results and discussion

3.1. Characterization of support
Natural diatomite has some mineral and organic impurities. So it
is necessary to remove these impurities [30]. Chaisena and Rangsri-
watananon proposed that acid treatment of diatomite alters chemical
compositions and the average size of particle decreases with increas-
ing temperature [31]. Average particle size of diatomite was 21.14 μm.
The particle size distribution of diatomite did not change during acid
treatment. However, the average size of particle decreased with in-
creasing temperature. Elemental analysis of the pure diatomite was
obtained by means of XRF technique. The analysis showed that SiO2
is the main component and the metal oxides (Al2 O3 and Fe2 O3 ) are
the main trace elements. Chemical analysis of diatomite, before and
after the acid treatment, is given in Table 2.
The chemical analysis indicated that acid treatment increased sil-
ica content and leached out organic and inorganic impurities, espe-
cially iron and alumina. Increase of pore volume and surface area are
also important effects of acid treatment and ZrO2 coating. The pore
volume of the diatomite increased from 1.218 to 1.568 cm3 /g after
Table 2
Chemical analysis of diatomite before and after acid treatment.
Component (%) Before treatment After treatment
Fig. 1. XRD patterns of pure diatomite and Cu70 Ti30 /M-diatomite, calcined at different
temperatures: (a) pure diatomite; (b) 400 °C; (c) 500 °C; (d) 600 °C.
the acid treatment. The results of the surface area measurement indi-
cated that the surface area of untreated, acid treated, and ZrO2 coated
diatomite was 21, 30 and 74 m2 /g respectively.
3.2. XRD, FESEM and EDX analysis of support and catalyst
Fig. 1 shows the XRD patterns of pure diatomite and Cu70 Ti30 /M-
diatomite prepared using WIM method. The average diameter of TiO2
and CuO was 30 and 37 nm respectively. Quartz and cristobalite are
the main crystal phases of diatomite as illustrated in this figure. Be-
cause of higher thermal and chemical stability of cristobalite [31] this
crystal phase of silica is preferred to amorphous SiO2 for applying
as a catalyst support. It can be seen that CuO, TiO2 and ZrO2 peaks
appeared.
Fig. 2a, b and c are FESEM photographs of pure diatomite,
ZrO2 /diatomite and Cu70 Ti30 supported on ZrO2 /diatomite respec-
tively and Fig. 2d and e are EDX analysis of Fig. 2b and c respec-
tively. FESEM and EDX analysis declare that porous structure can be
observed on the surface of pure diatomite, while after coating proce-
dure; the surface of diatomite was covered by nanocatalysts. Si, Cu, Ti
and Zr were indicated in EDX elemental analysis.

SiO2 85.25 96.17 3.3. H2 -TPR analysis

Al2 O3 3.87 1.8
Fe2 O3 2.34 0.84
Others 8.54 1.19
The redox characteristic of the prepared catalyst was exam-
ined by H2 -temperature-programmed reduction (TPR). In order to

Please cite this article as: S. Dehestaniathar et al., Modified diatomite-supported CuO–TiO2 composite: Preparation, characterization and
catalytic CO oxidation, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.05.030
JID: JTICE
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Fig. 2. FESEM and EDX analysis of pure diatomite, ZrO2 /diatomite and Cu70 Ti30 supported on ZrO2 /diatomite. (a–c) FESEM photographs of pure diatomite, ZrO2 /diatomite and
Cu70 Ti30 supported on ZrO2 /diatomite respectively. (d) EDX of figure (a) and (e) EDX of figure (c).

investigate the TiO2 and ZrO2 effect on the reducibility of catalyst;
TPR analyses were also carried out for comparison. The TPR profiles
of CuO/diatomite (a), CuO(70 mol%) − TiO2(30 mol%) /diatomite (b) and
CuO–TiO2 /ZrO2 -diatomite (c) are shown in Fig. 3. The CuO/diatomite
has two reduction peaks at about 360 and 380 °C which correspond
to the reduction of Cu2+ . The reduction of copper species depends
on the support, as proposed previously [32]. According to the litera-
ture the reduction profile of pure CuO shows a single peak at about
392 °C [33] and 363 °C [34]. In this study two TPR peaks can be ob-
served, which can be corresponded to the diatomite. Insertion of TiO2
leads to reduction of Cu2+ at lower temperature (260 and 290 °C). It
can be observed that coated ZrO2 enhance the reducibility of catalyst
as reduction of Cu2+ can be occurred at lower temperature (230 and
280 °C). Even though ZrO2 is resistant to the reduction [35] and TiO2
reduction is very difficult at low temperature [36], TiO2 and ZrO2 pro-
mote reduction of CuO. Moreover, these results also point the impor-
tant role of surface area, meaning that over the catalyst with higher
surface area, smaller particles are very likely formed which are more
easily reduced than the bigger particles.
3.4. XPS analysis
Fig. 4 shows the wide XPS spectrum of catalyst. Binding energy
levels of Si 2p, Zr 3d, Ti 2p, O1s, and Cu 2p are depicted. XPS peaks
located at around 934 and 954 are assigned to Cu2p. Cao et al. [37]
reported Cu2p peak at high binding energy (about 934.5 eV) points
out the Cu2+ species in catalyst. The peaks of Si 2p included in the
catalyst ascribed to the diatomite. Moreover, the XPS peaks located
about 182 and 459 eV correspond to Zr 3d and Ti 2p respectively.
3.5. Catalytic activity
The variation of catalytic activity of the prepared catalysts with
different molar fractions of CuO and TiO2 for CO oxidation as a func-
tion of reaction temperature was investigated (Fig. 5). All catalysts
indicate similar behavior as CO conversion increased with increas-
ing the reaction temperature, while carbon monoxide conversion
over pure diatomite (non-coated diatomite) was negligible. Activa-
tion of catalysts occurs after heating up to 100 °C. In other words
below 100 °C, the catalytic activity of catalyst is low, but CO oxida-
tion activity of catalysts increases with increasing the catalytic re-
action temperature. The catalytic activity of catalysts was enhanced
with increasing of TiO2 content from 10 to 30 mol%, but descended
with its further increase. The Cu70 Ti30 catalyst, exhibited the high-
est activity for CO conversion to CO2 [The temperature of 100% CO
conversion (T100 ) was 220 °C]. The better performance of prepared
composite catalyst may be attributed to higher reducibility of cop-
per oxide, which is evidenced also from TPR profiles. It was found
in previous studies that CO conversion over CuO micro powder un-
der oxygen-rich condition and surrounding temperature of 205 °C is
about 15%, [15]. But the results of present study illustrated that at
temperatures about 200 °C, the conversion of CO to CO2 is approx-
imately 95%. As previously demonstrated [38] 99.5% conversion of
CO to CO2 could be achieved at temperatures less than 250 °C using

Please cite this article as: S. Dehestaniathar et al., Modified diatomite-supported CuO–TiO2 composite: Preparation, characterization and
catalytic CO oxidation, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.05.030
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100

90

80

70

CO Conversion (%)
60
Cu90Ti10
50
Cu80Ti20
40 Cu70Ti30
Cu60Ti40
30
Cu50Ti50
20

10

0
0 50 100 150 200 250 300 350
Reaction Temperature (°C)
Fig. 5. Catalytic activity of the prepared catalyst as a function of reaction temperature
for different molar fractions of CuO and TiO2 , calcined at 400 °C for CO oxidation.

100
90
80
CO Conversion (%)

70
60
Fig. 3. H2 -TPR profiles: (a) CuO/diatomite, (b) CuO–TiO2 /diatomite, [Cu70 Ti30 ] and 400 °C
(c) CuO–TiO2 /ZrO2 –diatomite.
50
40 500 °C

30 600 °C
20
10
0
0 50 100 150 200 250
Reaction Temperature (°C)

Fig. 6. Catalytic activity of Cu70 Ti30 /M-diatomite, calcined at different temperatures

for CO oxidation.

Fig. 4. XPS spectrum of CuO–TiO2 /ZrO2 –diatomite catalyst.
copper oxide nanoparticles supported on silica gel. Therefore, the
preparation methods and the catalyst size are critical factor in cat-
alyst’s performance and there is a synergistic effect between cop-
per and titanium oxide supported on modified diatomite for CO
conversion.
The BET analysis demonstrated that “Cu70 Ti30 /diatomite” catalyst
has the highest surface area of 160 m2 /g. The BET values and catalytic
activity for other samples are indicated in Table 3.
It is clear that higher activity is because of higher unsaturated
surface, which results in more active sites exposed to the reactant
gas. This result is quite similar to the results of another study [37].
As they reported, higher surface area and narrower mesopore size
distribution could promote the formation of higher dispersion of
metal or oxide catalyst nanoparticles thus having some beneficial
effects on the catalytic performance whereas, when there is a high
loading of TiO2 , the excess TiO2 have a negative effect on the catalytic
activity, this counterproductive effect is due to bulk TiO2 formation.
The significant enhancement of catalytic activity for CO oxidation on
Au/TiO2 was achieved by dispersing TiO2 on to the high surface area
of SiO2 [39].
In order to investigate the effect of calcination temperature on the
catalytic activity of Cu70 Ti30 /M-diatomite, catalytic oxidation of car-
bon monoxide over prepared catalysts at different calcination tem-
peratures was studied. Fig. 6 illustrates carbon monoxide oxidation
performance of catalyst calcined at different temperatures. As illus-
trated in this figure, slight decrease in catalytic activities of catalysts,
which are calcined at higher temperatures (500 and 600 °C) in com-
parison with lower temperature (400 °C), is due to the decrease of
surface area.
It was found in the previous studies that at temperatures higher
than 500 °C, the decrease in the conversion extent occurs mainly be-
cause of sintering which decreases the number of active sites avail-
able for catalytic process [40]. It was also mentioned that the dif-
ference in the catalytic activities of the catalyst calcined at different
temperatures is due to agglomeration of catalyst and the increase in
particle sizes [37].

Please cite this article as: S. Dehestaniathar et al., Modified diatomite-supported CuO–TiO2 composite: Preparation, characterization and
catalytic CO oxidation, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.05.030
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Table 3
Surface area and catalytic activity of catalyst samples for different calcination temperatures.
Samples
Cu70 Ti30 /M-diatomite
Cu70 Ti30 /M-diatomite
Cu70 Ti30 /M-diatomite
Cu70 Ti30 /diatomite
CuO/M-diatomite
CuO/diatomite
Modified diatomite
100
90
80
CO Conversion (%)
70
60
50
40
30 Flow rate= 0.5 l/min
20 Flow rate= 1 l/min
10
0 [3] Degobert P. Automobiles and pollution. 1st ed. Paris: Technip; 1992.
0 50 100 150 200 250 300 350
Reaction Temperature (°C)
Fig. 7. Influence of flow rate on the catalytic activity of Cu70 Ti30 /M-diatomite.
It can be observed that catalytic activity of catalyst is extremely af-
fected by modified diatomite and high catalytic activity of CuO–TiO2
composite in comparison with single CuO is related to the synergis-
tic effect between CuO and TiO2 . Moreover, ZrO2 coated on diatomite
increases the surface area of diatomite and higher surface area pro-
motes dispersion of catalyst on the support. Thus the higher catalytic
activity of Cu70 Ti30 /M-diatomite calcined at 400 °C is due to well-
dispersion of CuO–TiO2 composite on modified diatomite. As shown
in Table 3, the catalytic activity expressed as T100 depends linearly on
surface area of the catalysts (R2 = 0.93). Furthermore, when catalyst
is supported on a high surface area and porous diatomite, its ther-
mal stability is improved. As previously demonstrated [41] diatomite
support enhanced the thermal stability of magnetite nanoparticles
which is due to the fact that nanoparticles were effectively separated
by diatomite shells.
For investigating the contact time effect on the catalytic activity
of Cu70 Ti30 /diatomite, catalytic oxidation of carbon monoxide over
this catalyst was studied at different GHSVs . As shown in Fig. 7, T50
(140 °C) is lower at low GHSV (15,000 ml/h gcat ) than at a higher GHSV
(30,000 ml/h gcat ), which is due to the effect of contact time.
4. Conclusions
A new catalyst has been prepared by simple wet impregnation
method: filling the pores of diatomite with a solution of copper and
titanium mixed oxides from which the solvent is subsequently evap-
orated followed by drying and calcinations. The variation of catalytic
activity of the prepared composite catalysts with different molar frac-
tions of CuO and TiO2 supported on diatomite for CO oxidation as a
function of reaction temperature catalyst exhibited CO conversion of
100% at 220 °C over catalyst with 70 mol% CuO and 30 mol% TiO2
content. The modification of support using acid treatment and ZrO2
coated promotes dispersion of catalyst on the support. Moreover,
TiO2 and ZrO2 promote reduction of CuO. Based on experimental re-
sults of the present study, CuO–TiO2 composite coated on diatomite
Please cite this article as: S. Dehestaniathar et al., Modified diatomite-supported CuO–TiO2 composite: Preparation, characterization and
catalytic CO oxidation, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.05.030
[m5G;June 6, 2015;21:57]
Calcination Total specific The temperature of 100%
temperature (°C) surface area (m²/g) CO conversion,T100 (°C)
400 160 220
500 154 230
600 145 240
400 140 280
400 125 300
400 118 350
400 74 Negligible
can be recommended as a cost-effective substitute of noble metals
for carbon monoxide oxidation.
Acknowledgment
This research was supported by the Tarbiat Modares University of
Iran.
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