Vous êtes sur la page 1sur 7

JID: JTICE

ARTICLE IN PRESS [m5G;June 6, 2015;21:57]

Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7

Contents lists available at ScienceDirect

Journal of the Taiwan Institute of Chemical Engineers


journal homepage: www.elsevier.com/locate/jtice

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 face area to distribute the active component [2]. Exhaust gases must
pass through the support without causing any prohibitive increase in
Carbon monoxide (CO) is a highly toxic, colorless, and odorless the back-pressure at the exhaust. Moreover, the support must provide
gas with a density close to the air, which is produced by natu- high surface area for effective dispersion of active phase and rapid
ral processes and anthropogenic sources and is well known for its mass transfer [3].
potential harmful and poisonous effects on humans. Inhalation of With regard to the catalyst type, the two most common products
carbon monoxide gas can impair the heart and the body’s cen- available in the market are ceramic and metallic substrates [4]. Both
tral nervous system. Industrial processes and oxidation of hydro- substrates have relatively low porosity, which makes them unsuit-
carbons are the major sources of CO. Automobile emissions are the able as a catalyst support. A thin layer of a porous material is called
major urban source of carbon monoxide [1]. So carbon monoxide wash-coat applied to increase the developed surface area of the sup-
emission must be controlled through engineering principles and port. In this regard, γ -Al2 O3 is commonly used as a wash-coat. The
techniques. automotive converter substrates need to contain two important me-
Catalytic oxidation is an efficient way to control of CO emis- chanical properties. These include low thermal expansion coefficient
sion from automobiles. Substrate, wash-coat, and active component and high thermal shock resistance. Cordierite (14% MgO, 35% Al2 O3
which are referred as catalyst, are three components of the catalyst and 51% SiO2 ) is a good option for an automotive converter due to its
system in a catalytic combustor. The substrate acts as a support for high thermal shock resistance [5]. Among a number of temperature
the other two components and the wash-coat provides a high sur- 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-

Corresponding author. Tel.: +98 871 6625131, +98 912 7100637; over, ZrO2 has an acid–base bifunctional property [6]. SiO2 –Al2 O3 is
fax: +98 871 6625131. a solid acid which can adsorb just basic molecule, but ZrO2 adsorbs
E-mail addresses: saeed_dehestani@yahoo.com, s.dehestani@muk.ac.ir
both acidic and basic molecules. Fornasiero and co-workers [7] found
(S. Dehestaniathar), lakzayi_malayer@yahoo.com (M. Khajelakzay),
madief2003@gmail.com (M. Ramezani-Farani), hossein.ijad@gmail.com
that introduction of ZrO2 into the CeO2 modifies the reduction behav-
(H. Ijadpanah-Saravi). 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
ARTICLE IN PRESS [m5G;June 6, 2015;21:57]

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 Table 1


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

S. Dehestaniathar et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7 3

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 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.
Natural diatomite has some mineral and organic impurities. So it
is necessary to remove these impurities [30]. Chaisena and Rangsri- the acid treatment. The results of the surface area measurement indi-
watananon proposed that acid treatment of diatomite alters chemical cated that the surface area of untreated, acid treated, and ZrO2 coated
compositions and the average size of particle decreases with increas- diatomite was 21, 30 and 74 m2 /g respectively.
ing temperature [31]. Average particle size of diatomite was 21.14 μm.
The particle size distribution of diatomite did not change during acid 3.2. XRD, FESEM and EDX analysis of support and catalyst
treatment. However, the average size of particle decreased with in-
creasing temperature. Elemental analysis of the pure diatomite was Fig. 1 shows the XRD patterns of pure diatomite and Cu70 Ti30 /M-
obtained by means of XRF technique. The analysis showed that SiO2 diatomite prepared using WIM method. The average diameter of TiO2
is the main component and the metal oxides (Al2 O3 and Fe2 O3 ) are and CuO was 30 and 37 nm respectively. Quartz and cristobalite are
the main trace elements. Chemical analysis of diatomite, before and the main crystal phases of diatomite as illustrated in this figure. Be-
after the acid treatment, is given in Table 2. cause of higher thermal and chemical stability of cristobalite [31] this
The chemical analysis indicated that acid treatment increased sil- crystal phase of silica is preferred to amorphous SiO2 for applying
ica content and leached out organic and inorganic impurities, espe- as a catalyst support. It can be seen that CuO, TiO2 and ZrO2 peaks
cially iron and alumina. Increase of pore volume and surface area are appeared.
also important effects of acid treatment and ZrO2 coating. The pore Fig. 2a, b and c are FESEM photographs of pure diatomite,
volume of the diatomite increased from 1.218 to 1.568 cm3 /g after 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
Table 2 observed on the surface of pure diatomite, while after coating proce-
Chemical analysis of diatomite before and after acid treatment. dure; the surface of diatomite was covered by nanocatalysts. Si, Cu, Ti
Component (%) Before treatment After treatment 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
ARTICLE IN PRESS [m5G;June 6, 2015;21:57]

4 S. Dehestaniathar et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7

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; catalyst ascribed to the diatomite. Moreover, the XPS peaks located
TPR analyses were also carried out for comparison. The TPR profiles about 182 and 459 eV correspond to Zr 3d and Ti 2p respectively.
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 3.5. Catalytic activity
has two reduction peaks at about 360 and 380 °C which correspond
to the reduction of Cu2+ . The reduction of copper species depends The variation of catalytic activity of the prepared catalysts with
on the support, as proposed previously [32]. According to the litera- different molar fractions of CuO and TiO2 for CO oxidation as a func-
ture the reduction profile of pure CuO shows a single peak at about tion of reaction temperature was investigated (Fig. 5). All catalysts
392 °C [33] and 363 °C [34]. In this study two TPR peaks can be ob- indicate similar behavior as CO conversion increased with increas-
served, which can be corresponded to the diatomite. Insertion of TiO2 ing the reaction temperature, while carbon monoxide conversion
leads to reduction of Cu2+ at lower temperature (260 and 290 °C). It over pure diatomite (non-coated diatomite) was negligible. Activa-
can be observed that coated ZrO2 enhance the reducibility of catalyst tion of catalysts occurs after heating up to 100 °C. In other words
as reduction of Cu2+ can be occurred at lower temperature (230 and below 100 °C, the catalytic activity of catalyst is low, but CO oxida-
280 °C). Even though ZrO2 is resistant to the reduction [35] and TiO2 tion activity of catalysts increases with increasing the catalytic re-
reduction is very difficult at low temperature [36], TiO2 and ZrO2 pro- action temperature. The catalytic activity of catalysts was enhanced
mote reduction of CuO. Moreover, these results also point the impor- with increasing of TiO2 content from 10 to 30 mol%, but descended
tant role of surface area, meaning that over the catalyst with higher with its further increase. The Cu70 Ti30 catalyst, exhibited the high-
surface area, smaller particles are very likely formed which are more est activity for CO conversion to CO2 [The temperature of 100% CO
easily reduced than the bigger particles. conversion (T100 ) was 220 °C]. The better performance of prepared
composite catalyst may be attributed to higher reducibility of cop-
3.4. XPS analysis per oxide, which is evidenced also from TPR profiles. It was found
in previous studies that CO conversion over CuO micro powder un-
Fig. 4 shows the wide XPS spectrum of catalyst. Binding energy der oxygen-rich condition and surrounding temperature of 205 °C is
levels of Si 2p, Zr 3d, Ti 2p, O1s, and Cu 2p are depicted. XPS peaks about 15%, [15]. But the results of present study illustrated that at
located at around 934 and 954 are assigned to Cu2p. Cao et al. [37] temperatures about 200 °C, the conversion of CO to CO2 is approx-
reported Cu2p peak at high binding energy (about 934.5 eV) points imately 95%. As previously demonstrated [38] 99.5% conversion of
out the Cu2+ species in catalyst. The peaks of Si 2p included in the 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
JID: JTICE
ARTICLE IN PRESS [m5G;June 6, 2015;21:57]

S. Dehestaniathar et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7 5

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.

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
Fig. 4. XPS spectrum of CuO–TiO2 /ZrO2 –diatomite catalyst. 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
copper oxide nanoparticles supported on silica gel. Therefore, the catalytic activity of Cu70 Ti30 /M-diatomite, catalytic oxidation of car-
preparation methods and the catalyst size are critical factor in cat- bon monoxide over prepared catalysts at different calcination tem-
alyst’s performance and there is a synergistic effect between cop- peratures was studied. Fig. 6 illustrates carbon monoxide oxidation
per and titanium oxide supported on modified diatomite for CO performance of catalyst calcined at different temperatures. As illus-
conversion. trated in this figure, slight decrease in catalytic activities of catalysts,
The BET analysis demonstrated that “Cu70 Ti30 /diatomite” catalyst which are calcined at higher temperatures (500 and 600 °C) in com-
has the highest surface area of 160 m2 /g. The BET values and catalytic parison with lower temperature (400 °C), is due to the decrease of
activity for other samples are indicated in Table 3. surface area.
It is clear that higher activity is because of higher unsaturated It was found in the previous studies that at temperatures higher
surface, which results in more active sites exposed to the reactant than 500 °C, the decrease in the conversion extent occurs mainly be-
gas. This result is quite similar to the results of another study [37]. cause of sintering which decreases the number of active sites avail-
As they reported, higher surface area and narrower mesopore size able for catalytic process [40]. It was also mentioned that the dif-
distribution could promote the formation of higher dispersion of ference in the catalytic activities of the catalyst calcined at different
metal or oxide catalyst nanoparticles thus having some beneficial temperatures is due to agglomeration of catalyst and the increase in
effects on the catalytic performance whereas, when there is a high 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
JID: JTICE
ARTICLE IN PRESS [m5G;June 6, 2015;21:57]

6 S. Dehestaniathar et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7

Table 3
Surface area and catalytic activity of catalyst samples for different calcination temperatures.

Samples Calcination Total specific The temperature of 100%


temperature (°C) surface area (m²/g) CO conversion,T100 (°C)

Cu70 Ti30 /M-diatomite 400 160 220


Cu70 Ti30 /M-diatomite 500 154 230
Cu70 Ti30 /M-diatomite 600 145 240
Cu70 Ti30 /diatomite 400 140 280
CuO/M-diatomite 400 125 300
CuO/diatomite 400 118 350
Modified diatomite 400 74 Negligible

100 can be recommended as a cost-effective substitute of noble metals


90 for carbon monoxide oxidation.
80 Acknowledgment
CO Conversion (%)

70
60 This research was supported by the Tarbiat Modares University of
Iran.
50
40 References
30 Flow rate= 0.5 l/min
[1] Raub JA, Marthieu-Nolf M, Hampson NB, Thom SB. Carbon monoxide poisoning—a
20 Flow rate= 1 l/min public health perspective. Toxicol 2000;145:1–14.
[2] Garten RL, Dalla-Betta RA, Schlatter JC. Catalytic combustion. Environmental
10 catalysis. Ertl G, Knozinger H, Weitkamp J, editors. New York: Wiley-VCH; 1997.
0 [3] Degobert P. Automobiles and pollution. 1st ed. Paris: Technip; 1992.
[4] Kaspar J, Fornasiero P, Hickey N. Automotive catalytic converters: current status
0 50 100 150 200 250 300 350 and some perspectives. Catal Today 2003;77:419–49.
Reaction Temperature (°C) [5] Santos H, Costa M. Evaluation of the conversion efficiency of ceramic and metallic
three way catalytic converters. Energy Conver Manage 2008;49:291–300.
Fig. 7. Influence of flow rate on the catalytic activity of Cu70 Ti30 /M-diatomite. [6] Yamaguch T. Application of ZrO2 as a catalyst and a catalyst support. Catal Today
1994;20:199–218.
[7] Fornasiero P, Balducci G, Di Monte R, Kasper J, Sergo V, Gubitosa G, et al. Modifi-
cation of the redox behaviour of CeO2 induced by structural doping with ZrO2 . J
It can be observed that catalytic activity of catalyst is extremely af- Catal 1996;164:173–83.
fected by modified diatomite and high catalytic activity of CuO–TiO2 [8] Bandyopadhyay M, Korsak O, Vanden B, Grunert W, Birkner A, Li W, et al. Gold
nano-particles stabilized in mesoporous MCM-48 as active CO-oxidation catalyst.
composite in comparison with single CuO is related to the synergis-
Microporous Mesoporous Mater 2006;89:158–63.
tic effect between CuO and TiO2 . Moreover, ZrO2 coated on diatomite [9] Bulushev DA, Yuranov I, Suvorova EI, Buffat PA, Kiwi-Minsker L. Highly dis-
increases the surface area of diatomite and higher surface area pro- persed gold on activated carbon fibers for low-temperature CO oxidation. J Catal
2004;224:8–17.
motes dispersion of catalyst on the support. Thus the higher catalytic
[10] Chiang CW, Wang A, Mou CY. CO oxidation catalyzed by gold nanoparticles con-
activity of Cu70 Ti30 /M-diatomite calcined at 400 °C is due to well- fined in mesoporous aluminosilicate Al-SBA-15: pretreatment methods. Catal To-
dispersion of CuO–TiO2 composite on modified diatomite. As shown day 2006;117:220–7.
in Table 3, the catalytic activity expressed as T100 depends linearly on [11] Derouane EG, Schmidt I, Lachas H, Christensen CJH. Improved performance of
nano-size H-BEA zeolite catalysts for the Friedel-Crafts acetylation of anisole by
surface area of the catalysts (R2 = 0.93). Furthermore, when catalyst acetic anhydride. Catal Lett 2004;95:13–17.
is supported on a high surface area and porous diatomite, its ther- [12] Lin JN, Wan BZ. Effects of preparation conditions on gold/Y-type zeolite for CO
mal stability is improved. As previously demonstrated [41] diatomite oxidation. Appl Catal B Environ 2003;41:83–95.
[13] Cao JL, Shao GS, Wang Y, Liu Y, Yuan ZY. CuO catalysts supported on attapulgite
support enhanced the thermal stability of magnetite nanoparticles clay for low-temperature CO oxidation. Catal Commun 2008;9:2555–9.
which is due to the fact that nanoparticles were effectively separated [14] Rau JY, Chen JC, Huang ST, Hung WT, Wey MY. Removals of fly ash and NO
by diatomite shells. in a fluidized-bed reactor with CuO/activated carbon catalysts. J Hazard Mater
2011;187:190–8.
For investigating the contact time effect on the catalytic activity [15] Avgouropoulos G, Ioannides T. Selective CO oxidation over CuO-CeO2 cata-
of Cu70 Ti30 /diatomite, catalytic oxidation of carbon monoxide over lysts prepared via the urea–nitrate combustion method. Appl Catal A Gen
this catalyst was studied at different GHSVs . As shown in Fig. 7, T50 2003;244:155–67.
[16] Huang TJ, Tsai DH. CO oxidation behavior of copper and copper oxides. Catal Lett
(140 °C) is lower at low GHSV (15,000 ml/h gcat ) than at a higher GHSV
2003;87:173–8.
(30,000 ml/h gcat ), which is due to the effect of contact time. [17] Jernigan GG, Somorjai GA. Carbon monoxide oxidation over three different oxi-
dation states of copper: metallic copper, copper (I) oxide, and copper (II) oxide-a
surface science and kinetic study. J Catal 1994;147:567–77.
4. Conclusions [18] Sadykov VA, Tikhov SF. Comment on “carbon monoxide oxidation over three dif-
ferent oxidation states of copper: metallic copper, copper (I) oxide, and copper (II)
oxide-a surface science and kinetic study. J Catal 1997;165:279–83.
A new catalyst has been prepared by simple wet impregnation [19] Jia Y, Han W, Xiong G, Yang W. Diatomite as high performance and environmen-
method: filling the pores of diatomite with a solution of copper and tal friendly catalysts for phenol hydroxylation with H2 O2 . Sci Technol Adv Mater
titanium mixed oxides from which the solvent is subsequently evap- 2007;8:106–9.
[20] Arik H, Eur J. Synthesis of Si3 N4 by the carbo-thermal reduction and nitridation
orated followed by drying and calcinations. The variation of catalytic
of diatomite. J Eur Ceram Soc 2003;23:2005–14.
activity of the prepared composite catalysts with different molar frac- [21] Bahramian B, Doulati Ardejani F, Mirkhani V, Badii K. Diatomite-supported man-
tions of CuO and TiO2 supported on diatomite for CO oxidation as a ganese Schiff base: an efficient catalyst for oxidation of hydrocarbons. Appl Catal
A Gen 2008;345:97–103.
function of reaction temperature catalyst exhibited CO conversion of
[22] Chaisena A, Rangsriwatananon K. Synthesis of sodium zeolites from natural and
100% at 220 °C over catalyst with 70 mol% CuO and 30 mol% TiO2 modified diatomite. Mater Lett 2005;59:1474–9.
content. The modification of support using acid treatment and ZrO2 [23] Hadjar V, Hamdi B, Jaber M, Brendle J, Kessaissia Z, Balard H, et al. Elaboration
coated promotes dispersion of catalyst on the support. Moreover, and characterisation of new mesoporous materials from diatomite and charcoal.
Microporous Mesoporous Mater 2008;107:219–26.
TiO2 and ZrO2 promote reduction of CuO. Based on experimental re- [24] Martinovic S, Vlahhovic M, Boljanac T, Pavlovic L. Preparation of filter aids based
sults of the present study, CuO–TiO2 composite coated on diatomite on diatomites. Int J Mineral Process 2006;80:255–60.

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
ARTICLE IN PRESS [m5G;June 6, 2015;21:57]

S. Dehestaniathar et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–7 7

[25] Nenadovic S, Nenadovic M, Kovacevic R, Matovic LJ, Matovic B, Jonanovic Z, [33] Xiaoyuan J, Guanglie L, Renxian Z, Jianxin M, Yu C, Xiaoming Z. Studies of
Grbovic J. Influence of diatomite microstructure on its adsorption capacity for pore structure, temperature-programmed reduction performance, and micro-
Pb(II). Sci Sinter 2009;41:309–17. structure of CuO/CeO2 catalysts. Appl Surf Sci 2001;173:208–20.
[26] Liu X, Wang A, Li L, Zhang T, Mou CY, Lee J. Structural changes of Au-Cu bimetallic [34] Cao JL, Shao GS, Ma TY, Wang Y, Ren TZ, Wu SH, et al. Hierarchical meso-
catalysts in CO oxidation: in situ XRD, EPR, XANES, and FT-IR characterizations. J macroporous titania-supported CuO nanocatalysts: preparation, characterization
Catal 2011;278:288–96. and catalytic CO oxidation. J Mater Sci 2009;44:6717–26.
[27] Wan H, Wang Z, Zhu J, Li X, Liu B, Gao F, et al. Influence of CO pretreatment on [35] Dobrosz-Gomez I, Kocemba I, Rynkowski JM. Carbon monoxide oxidation over
the activities of CuO/γ -Al2 O3 catalysts in CO + O2 reaction. Appl Catal B Environ Au/Ce1- x Zrx O2 catalysts: effects of moisture content in the reactant gas and cata-
2008;79:254–61. lyst pretreatment. Catal Lett 2009;128:297–306.
[28] Wan H, Li D, Dai Y, Hu Y, Zhang Y, Liu L, et al. Effect of CO pretreatment on the [36] Li K, Wang Y, Wang S, Zhu B, Zhang S, Huang W, et al. A comparative study of
performance of CuO/CeO2 /γ -Al2 O3 catalysts in CO + O2 reactions. Appl Catal A CuO/TiO2 -SnO2 , CuO/TiO2 and CuO/SnO2 catalysts for low-temperature CO oxi-
Gen 2009;360:26–32. dation. J Nat Gas Chem 2009;18:449–52.
[29] Gestel TM, Kruidhof H, Blank DHA, Bouwmeester HJM. ZrO2 and TiO2 membranes [37] Cao JL, Wang Y, Yu XL, Wang SR. Mesoporous CuO-Fe2 O3 composite catalysts for
for nanofiltration and pervaporation. Part 1. Preparation and characterization of a low-temperature carbon monoxide oxidation. Appl Catal B Environ 2008;79:26–
corrosion-resistant ZrO2 nanofiltration membrane with a MWCO< 300. J Membr 34.
Sci 2006;284:128–36. [38] White B, Yin M, Hall A, Le D, Stolbov S, Rahman T, et al. Complete CO oxidation
[30] Akhtar F, Rehman Y, Bergstrom L. A study of sintering of diatomaceous earth over Cu2 O nanoparticles supported on silica gel. Nano Lett 2006;6:2095–8.
to produce ceramic monoliths with bimodal porosity and high strength. Powder [39] Wang ZW, Wang XV, Zeng DY, Chen MS, Wan HL. Enhance catalytic activity for
Technol 2010;201:253–7. CO oxidation over titania supported gold catalysts that dispersed on SiO2 . Catal
[31] Chaisena A, Rangsriwatananon K. Effects of thermal and acid treatments on some Today 2011;160:144–52.
physico-chemical properties of lampang diatomite. J Sci Technol 2004;11:289– [40] Khedr MH, Abdel Halim KS, Nasr MI, El-Mansy AM. Effect of temperature on
299.30; Mahani H, Kazemeini M. Treatment of diatomaceous earth to obtain its the catalytic oxidation of CO over nano-sized iron oxide. Mater Sci Eng A
catalyst support. Sci Iran 2003;10(3):350. 2006;430:40–5.
[32] Wang Z, Liu Q, Yu J, Wu T, Wang G. Surface structure and catalytic behavior of [41] Yuan P, Liu D, Fan M, Yang D, Zhu R, Ge F, et al. Removal of hexavalent chromium
silica-supported copper catalysts prepared by impregnation and sol–gel methods. [Cr(VI)] from aqueous solutions by the diatomite-supported/unsupported mag-
Appl Catal A Gen 2003;239:87–94. netite nanoparticles. J Hazard Mater 2010;173:614–21.

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