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Journal of Molecular Catalysis A: Chemical 358 (2012) 2330

Contents lists available at SciVerse ScienceDirect

Journal of Molecular Catalysis A: Chemical


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

Combustion of volatile organic compounds over CuMn based mixed oxide type
catalysts supported on mesoporous Al2 O3 , TiO2 and ZrO2
Pradeep Doggali a , Y. Teraoka b , P. Mungse a , Irfan K. Shah c , S. Rayalu a , Nitin Labhsetwar a,
a
b
c

National Environmental Engineering Research Institute(CSIR-NEERI), Nehru Marg, Nagpur 440020, India
Department of Energy and Material Sciences, Faculty of Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816-8580, Japan
Department of Civil Engineering, Indian Institute of Technology (IIT) Delhi, Hauz Khas, New Delhi 16, India

a r t i c l e

i n f o

Article history:
Received 2 August 2011
Received in revised form 29 January 2012
Accepted 6 February 2012
Available online 28 February 2012
Keywords:
Mesoporous Al2 O3
TiO2 and ZrO2
CuMn catalyst
Acetaldehyde combustion
Benzene combustion
H2 -TPR
O2 -TPD

a b s t r a c t
A series of supported CuMn based catalysts have been synthesized using three different supports
mesoporous Al2 O3 , mesoporous TiO2 and mesoporous ZrO2 . CuMn precursors were incorporated on
mesoporous supports using wet impregnation method. These catalyst supports were prepared by templating method using a natural biopolymer namely, chitosan. The catalytic activity for benzene and
acetaldehyde combustion was studied for these catalysts. The synthesized catalysts have been characterized by XRD, BET-SA, O2 -TPD and H2 -TPR in a view of material characterization, as well as to investigate
the mechanistic aspects of catalytic reactions. The bimetallic supported catalysts follow the activity
sequenceCuMn/TiO2 > CuMn/ZrO2 > CuMn/Al2 O3 for both the reactions studied. These results interestingly show, that the catalytic activity is dependent on the support used, however, quite independent
of the surface area of these supports. The better activity of TiO2 and ZrO2 based catalysts is likely due to
their redox properties. The existence of low temperature peaks in both O2 -TPD and H2 -TPR explain better
redox properties as well as catalytic performance of TiO2 and ZrO2 supported catalysts as compared to
those Al2 O3 supported mixed oxides.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Volatile organic compounds (VOCs) have high vapour pressure
under normal atmospheric conditions and therefore, can be easily
vaporized [1]. VOCs include a variety of different organic compounds including alcohols, ethers, esters, aromatics, chlorinated
hydrocarbons and odorous compounds containing sulphur [2]. The
major sources of VOCs are the paint industry, building materials,
automobile exhaust, combustion exhaust, industrial off gases, personal care products as well as a range of other sources [3]. VOCs
are often toxic [4] and also responsible for the formation of photochemical ozone [5] as well as secondary aerosols in urban air
[6]. Therefore, removal of VOCs from ambient air and controlling VOC emission at source has now been deemed as crucial for
environmental and health point of view. Although various types
of air purication techniques such as adsorption and combustion
processes have been developed and widely used for hazardous
air pollutant removal, they are often not suitable for the removal
of diluted pollutants [7]. The use of catalytic combustion allows
decreasing the temperatures (<600 C) to obtain complete combustion of organic compounds as compared to thermal processes

Corresponding author. Tel.: +91 712 2247828; fax: +91 712 2247828.
E-mail address: nk labhsetwar@neeri.res.in (N. Labhsetwar).
1381-1169/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2012.02.004

(>1000 C) [8]. In addition, the cleaning efciencies can be over 95%,


which is especially important for malodorous VOCs since they are
odorous at very low concentrations [9]. The lowering of reaction
temperatures leads to several advantages in terms of environmental impact by minimizing secondary pollutants as well as energy
saving and reduction of fuel costs [10].
Cu and Mn based oxides are the potential candidates for many
catalytic reactions, environmental importance [1117]. The wellknown CuMn mixed oxide in the form of hopcalite (CuMn2 O4 ) has
been used for ambient CO oxidation, especially in mining industries.
Recently, Christopher Jones et al. studied the effect of calcination on the catalytic CO oxidation activity of CuMn mixed oxide
(CuMnOx ). They observed that aging time does not inuence the
catalytic activity signicantly, when the catalyst is synthesized by
co-precipitation method, and efcient CuMnOx catalysts can be
produced at an optimum calcination temperature of 410 C [18].
One of the advantages to use these catalysts is their low-cost. However; developing a suitable support for the CuMn based catalysts
adds to their potential, while use of catalyst support is often necessarily required for the nal application. Generally the activity of
catalytically active component depends upon both chemical and
physical properties of support used, such as chemical composition,
crystal structure and crucially on the porosity, particle size and surface area. Therefore, several efforts have been focused on tailoring
the pore size and external morphology of supports in a view to

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P. Doggali et al. / Journal of Molecular Catalysis A: Chemical 358 (2012) 2330

improve the catalytic properties of different catalysts dispersed on


them. Li et al. [19] demonstrated high activity of CuMn mixed
oxides with mesoporous MCM-41 support for toluene combustion.
Usually Al2 O3 , TiO2 and ZrO2 are considered to be thermally stable supports with reasonably good chemical stability and low cost.
Extensive studies are therefore reported on transition metals supported on Al2 O3 , TiO2 and ZrO2 for their possible environmental
applications [2023].
Alumina mainly in its -form is the most commonly used catalyst support for a variety of applications. It is an inexpensive and
reasonably stable support materials, which can be processed easily.
High surface area can be achieved with alumina, which is useful for many gas phase catalytic reactions requiring high space
velocities. Many researchers have also investigated the catalytic
properties of TiO2 , as it is a promising reducible semiconductor metal oxide support with excellent stability. TiO2 has been
frequently demonstrated as a useful support as well as a photocatalyst for many reactions to decompose a variety of organics
and other compounds [24]. ZrO2 is also reported to be an active
support for various combustion reactions. The anionic vacancies,
even in small amount, leads to better oxygen mobility in ZrO2
lattice [25,26]. It is an added advantage to make these supports
in mesoporous form, thereby improving their surface area and
pore characteristics, which are likely to result in improved mass
transfer and reactant contacts in catalytic reactions. An abundantly available, low cost, natural biopolymer, chitosan was used
as a template to synthesize these supports. Chitosan, copolymer
of 2-amino-2-deoxy-d-glucopyranose and 2-acetamido-2-deoxyd-glucopyranose, is N-de-acetylated product of chitin, and is the
second most abundant natural polysaccharide in the ecosphere
after cellulose. Both chitin and chitosan are of great interest because
of their unique combination of properties, like biodegradability,
biocompatibility and bioactivity, in addition to attractive physical
and mechanical properties. It has been reported that chitosan has
the higher metal coordinating ability as compared to other natural polymers [27]. In a recent article, we reported the catalytic
behaviour of CuMn supported Al2 O3 , TiO2 and ZrO2 for CO and
PM oxidation reactions [28]. The encouraging results obtained with
these catalysts motivated us to further investigate these catalysts
for benzene and acetaldehyde combustion. The aim of the present
investigation is to develop appropriate support with CuMn mixed
oxide system for the oxidation of benzene and acetaldehyde for
their possible application in control of these VOCs emissions in
indoor environment.
2. Experimental

Mn on mesoporous Al2 O3 , TiO2 and ZrO2 supports. The mixture


of support and metal acetate solutions were stirred in a beaker
for 3 h at 60 C. Metal impregnated supports were then dried
in an oven at 110 C for 4 h. The dried mass thus obtained was
again ground, homogenised and calcined at 400 C in a furnace
for 5 h.

2.3. Characterization
XRD patterns were recorded on a Rigaku Rint-220HF diffractometer, operated at 40 kV and 50 mA with monochromator, and
using Cu K radiation ( = 0.15418 nm). Indexing of XRD peaks was
done, by using the JCPDS database for the respective phases. Surface area was measured by nitrogen adsorption using the automatic
gas adsorption apparatus BELSORP 28SA (produced by Nippon Bell
Co.) and evaluated by following BET method. The samples were
pre-treated at 300 C before the nitrogen adsorption experiments.
Elemental analysis of the catalytic materials was carried out using
PerkinElmer ICP-OES 4100 BV instrument to assess the content
of copper and manganese present. The H2 -TPR and O2 -TPD analysis were performed in a Thermo-Quest TPD/R/O 1100 analyzer,
equipped with a TCD detector. For H2 -TPR test, the quartz tube
reactor was loaded with100 mg sample in powder form. It was
pre-treated in He ow by heating the catalyst from room temperature to 400 C for 30 min (10 mL/min, STP) and cooled to ambient
under helium ow (10 mL/min, STP). The reduction was performed
by owing 5% hydrogen diluted in helium. The sample temperature
was raised at 10 C/min till 400 C under 5% H2 /He (10 mL/min, STP)
ow. The amount of hydrogen consumed in TPR was quantitatively
measured by a thermal conductivity detector (TCD). In the similar way, temperature-programmed oxygen desorption (TPD) was
performed. Prior to each run, the catalyst was heated up to 400 C
under the helium ow (30 N mL/min). After 30 min of isothermal
heating at this temperature, the sample was cooled to 25 C in air
ow. Afterwards, helium was fed to the reactor at 10-mL/min-ow
rate for 1 h at room temperature, in order to purge out any excess
oxygen. The catalyst was then heated up to 400 C at a constant
heating rate of 10 C/min under the same helium ow, and O2 desorbed during the heating was determined to study the TPD pattern.
CHN analysis was carried out on a Shimadzu Elementer. The copper and manganese contents of materials were determined using
ICP-OES technique (PerkinElmer, Model Optima 4100DV). Blank
experiments were conducted throughout the studies and majority of the experiments were repeated thrice and it was observed
that the experimental error was within 2%. The samples were
dissolved in acid before the analysis.

2.1. Materials
All the reagents used for experimental work were of analytical
reagent grade. Acetic acid, ammonia, aluminium nitrate, zirconyl
nitrate, cupric acetate and manganese acetate were obtained from
Merck India Ltd. Chitosan was procured from Chemchito India. Titanium isopropoxide was obtained from Acros India Ltd.
2.2. Methods
Mesoporous Al2 O3 was synthesized following a similar procedure as reported elsewhere [29] and later applied for the synthesis
of TiO2 and ZrO2 in our group [2830]. The supports thus obtained
were ground into powder, homogenised and used for the synthesis of supported catalysts. Aqueous equimolar solutions of the
stoichiometric quantity of Cu(CH3 COO)2 and Mn(CH3 COO)2 were
used to prepare mixed metal solution in deionized water. Catalysts were synthesized by targeted loading of 8 wt% Cu and 8 wt%

2.4. Evaluation of catalytic activity


Catalytic activity of all the synthesized catalysts was investigated for benzene and acetaldehyde combustion (oxidation). The
steady state, xed bed gas evaluation assembly equipped with a
quartz reactor, precise mass ow controllers and heating system
was used in the present study. 100 mg powdered catalyst was
loaded in a xed bed quartz reactor. Catalysts were pre-treated
in He ow at 200 C for 1 h. The reactant gas mixture of 900 ppm
benzene, 10% O2 and He balance was used for benzene combustion while, 500 ppm acetaldehyde, 10% O2 and balance He was used
for the combustion of acetaldehyde. The exit gas stream was analyzed by a Shimadzu Gas chromatograph using a capillary column
for benzene combustion and Porapack-N column for the combustion of acetaldehyde using FID and TCD detector, respectively. A
schematic of the experimental setup is given in Fig. 1.

P. Doggali et al. / Journal of Molecular Catalysis A: Chemical 358 (2012) 2330

25

Fig. 1. Schematic of the experimental setup.

3. Results and discussion


The copper and manganese contents of synthesized
CuMn/Al2 O3 , CuMn/TiO2 and CuMn/ZrO2 was determined
by digesting the CuMn/Al2 O3 , CuMn/TiO2 and CuMn/ZrO2
compounds in aquaregia and analyzing by using ICP-MS technique.
The observed results (Table 1) for Cu and Mn contents for catalytic
materials substantiate the incorporation of targeted amount of
copper and manganese on Al2 O3 , TiO2 and ZrO2 .
The catalysts were characterized for their structure by X-ray
powder diffraction analysis. Figs. 24 illustrates the XRD patterns
for mesoporous Al2 O3 , TiO2 , ZrO2 , CuMn/Al2 O3 , CuMn/TiO2 and
CuMn/ZrO2 catalysts. XRD analysis suggests the formation of alumina phase with presence of the characteristic XRD peaks for
-Al2 O3 phase in the synthesized meso-alumina sample [29]. The
synthesized meso-titania corresponds to TiO2 anatase phase [30].
Patterns correspond to the tetragonal phase was observed in the
synthesized mesoporous ZrO2 sample [28].
The low angle peaks (13 ) characteristic of ordered mesoporous structure were not observed [27]. This implies that the
ordered mesoporous structure is not formed for all the three synthesized supports. The predominant crystalline chitosan peaks at
2 values 8 , 20 and 29 were also not observed [27], which conrm the elimination of organic matter from the oxides formed.
X-ray diffraction analysis of supported catalysts suggests no change
in diffraction pattern after incorporation of CuMn oxide on different supports, prepared by calcination at 400 C. This could be

Table 1
ICP analysis results for Cu and Mn content of mesoporous Al2 O3 , mesoporous TiO2
and mesoporous ZrO2 .
Sample

mg of metal/g of support

CuMn/Al2 O3
CuMn/TiO2
CuMn/ZrO2

78 Cu77 Mn/Al2 O3
77 Cu78 Mn/ZrO2
78 Cu77 Mn/TiO2

because of small crystal sizes of the CuMn species, as well as their


good dispersion on support materials.
Results pertaining to BET surface area and pore size as determined by BJH method for the synthesized catalysts are presented in
Table 2. The surface area results for synthesized mesoporous Al2 O3 ,
TiO2 , ZrO2 are observed to be 312 m2 /g, 130 m2 /g and 34.9 m2 /g,
respectively. The pore sizes of these catalysts are observed as
4.2 nm, 3.2 nm and 3.5 nm, respectively. These results clearly
demonstrate that the investigated supports are mesoporous in
nature and possess high surface area except that of mesoporous
zirconia. However, the surface area of synthesized mesoporous
zirconia was observed to be much higher as compared that of
commercially available zirconia (HIMEDIA chemicals (14 m2 /g)).
The results also indicate that surface area and pore size of the
supports have been slightly decreased after CuMn incorporation (150.9 m2 /g for Al2 O3 , 92.5 m2 /g for TiO2 and 28.5 m2 /g for
ZrO2 ). For mesoporous alumina the pore size was observed to be
4.2 nm, which has been decreased to 3.4 nm after the impregnation of CuMn mixed oxides. Similarly, in case of mesoporous TiO2
and ZrO2 , the pore size has been decreased from 3.2 nm to 2.9 nm
and 3.5 nm to 2.4 nm following the impregnation of CuMn mixed
oxides on these supports. This pore size and surface area results
are in line with the pore volume results of the synthesized catalysts.

Table 2
Surface area pore size and pore volume results for mesoporous Al2 O3 , CuMn/Al2 O3 ,
mesoporous TiO2 , CuMn/TiO2 , mesoporous ZrO2 and CuMn/ZrO2 .
Sample

BET-surface
area (m2 /g)

Pore diameter
(nm)

Pore volume
(cm3 /g)

Mesoporous Al2 O3
CuMn/Al2 O3
Mesoporous TiO2
CuMn/TiO2
Mesoporous ZrO2
CuMn/ZrO2

312
150.9
130
92.5
34.9
28.5

4.2
3.4
3.2
2.9
3.5
2.4

0.36
0.28
0.23
0.10
0.11
0.05

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P. Doggali et al. / Journal of Molecular Catalysis A: Chemical 358 (2012) 2330

Fig. 2. XRD patterns for mesoporous Al2 O3 and CuMn/Al2 O3 .

Fig. 3. XRD patterns for mesoporous TiO2 and CuMn/TiO2 .

P. Doggali et al. / Journal of Molecular Catalysis A: Chemical 358 (2012) 2330

27

Fig. 4. XRD patterns for mesoporous ZrO2 and CuMn/ZrO2 .

The highest pore volume was observed for synthesized mesoporous


alumina (0.36 cm3 /g) for which, the pore size was utmost followed
by titania (0.23 cm3 /g) and zirconia (0.11 cm3 /g). The pore volume
of supports has been decreased to 0.28, 0.10 and 0.05 cm3 /g for
Al2 O3 , TiO2 and ZrO2 , respectively after the incorporation of CuMn
mixed oxides. This could be due to the formation of mixed oxide
crystals on the pores of supports, thereby slightly reducing the pore
size and pore volume.
Table 3 presents the CHN analysis results for CuMn/Al2 O3 ,
CuMn/TiO2 , CuMn/ZrO2 . To conclusively study the presence of
chitosan in synthesized CuMn/supported on Al2 O3 , ZrO2 and TiO2
samples we have subjected the samples to prolonged heating at
400 C. On the other hand, we have also heated the samples at
400 C for longer durations in presence of oxygen. These samples
do not show any signicant difference in C and N contents, thereby
indicating that the chitosan residue is removed almost completely
(approx. 99%) at 400 C.
Although these support materials do not show the ordered
structure, the template synthesis results in mesopores with high
surface area. These properties result in improved mass transfer
and higher number of active sites, important for gas phase catalytic
applications. As the target reactions are not shape or size selective
reactions, the present supports offer the desired requirements for
optimum catalytic activity.

3.1. Catalytic activity measurements


3.1.1. Catalytic activity for benzene decomposition
The catalytic activity results for benzene oxidation as a
function of temperature are shown in Fig. 5. The bimetallic supported catalysts follow the activity sequence of
CuMn/TiO2 > CuMn/ZrO2 > CuMn/Al2 O3 . From Fig. 5, it can
be seen that 100% benzene conversion for CuMn/ZrO2 and
CuMn/TiO2 was observed at 350 C, whereas, it was observed
to be 400 C for CuMn/Al2 O3 , at approximately 30,000 h1
space velocity. These results suggest that Ti (Temperature at
which benzene combustion initiated) and T50 (Temperature at

Table 3
Summary of the % CHN of CuMn/Al2 O3 , CuMn/TiO2 , CuMn/ZrO2 .
Sample

%C

%H

%N

CuMn/Al2 O3
CuMn/TiO2
CuMn/ZrO2

0.58
0.4
0.33

2.2
1.1
0.9

0.1
0.84
0.2

Fig. 5. Benzene combustion over CuMn/Al2 O3 , CuMn/TiO2 and CuMn/ZrO2 catalysts (feed composition: benzene = 900 ppm, O2 = 10% balance He, at approximately
30,000 h1 space velocity).

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P. Doggali et al. / Journal of Molecular Catalysis A: Chemical 358 (2012) 2330

which 50% benzene combustion observed) of CuMn/ZrO2 and


CuMn/TiO2 are comparatively lower than that for CuMn/Al2 O3 .
At 200 C CuMn/Al2 O3 shows no activity, whereas CuMn/ZrO2
and CuMn/TiO2 show about 10% and 15% benzene conversion
respectively. These results clearly infer that CuMn/TiO2 has
enhanced catalytic activity for benzene combustion, followed by
CuMn/ZrO2 and CuMn/Al2 O3 .
Shufeng et al. [31] recently studied the benzene combustion
over alumina pillared clay (Al-PILC) supported transition metals
(M = Cr, Mn, Fe, Co, Ni and Cu with conditions: catalyst weight
300 mg, benzene concentration = 130160 ppm composed of air, at
20,000 h1 space velocity). Among the catalysts reported in this
work, the 8 wt% Mn supported on Al-PILC shows better catalytic
activity as compared to all other catalysts. This catalyst shows 100%
benzene conversion at around 390 C, whereas the present catalysts, CuMn/TiO2 and CuMn/ZrO2 show 100% benzene oxidation
at 350 C, while CuMn/Al2 O3 shows 100% benzene conversion at
400 C. Though the transition metal content in the present study is
comparatively high, the high surface area metal oxide incorporated
alumina pillared clays (MnO2 /Al-PILC and CuOAl-PILC) studied by
Shufeng et al. could also be the possible reason for their superior
activity. The evaluation conditions used in the present study are
much more severe (benzene concentration is several times higher
while space velocity is also one and half times more). Therefore,
the catalytic activity of present catalysts is much better. However,
Shufeng et al. observed the enhancement of catalytic activity for
all the alumina pillared clay (Al-PILC) supported transition metals
after promotion with cerium oxide, and the cerium oxide promoted
Mn/Al-PILC catalyst reported to show 100% benzene oxidation at
about 310 C. This can be explained based on the well known fact
of oxygen storage capacity of cerium oxide. However, even this
catalytic activity can be well compared with the present results
(100% benzene oxidation at 350 C) considering the above mentioned evaluation conditions.
The activity of the investigated catalysts has also been compared
with some of the recently reported noble metal based catalysts.
Nedyalkova et al. studied the catalytic activity of gold catalysts supported on titania and ceria for complete benzene oxidation (CBO).
In that study the authors studied the benzene oxidation under the
following conditions: catalyst weight 500 mg, benzene concentration 4.2 ppm and space velocity 40,000 h1 . Au/CeO2 andAu/TiO2
catalysts investigated by Nedyalkova et al. start showing benzene
conversion at around 150 C and complete oxidation of benzene
was observed at around 260 C. The activity of the catalysts studied in the present research can be considered as much improved
activity as high concentration of benzene (900 ppm) and small
amount of catalyst (100 mg) were used to investigate the catalysts
[32]. Shufeng et al. also studied the 0.2 wt% palladium supported
alumina pillared clays for the complete oxidation of low concentration of benzene. In this study, the authors have carried out the
benzene oxidation in the following conditions: catalyst (300 mg),
benzene (130160 ppm), reactive ow (125 ml/min), space velocity of 20,000 h1 . The authors observed 100% benzene conversion
for 0.2 wt% palladium supported alumina pillared clays at 360 C.
Although the reactive ow of the present study is low (50 ml/min),
considering small amount of catalyst (100 mg), the space velocity
used in the present study is 30,000 h1 which is considerably higher
in addition to several times higher concentration of benzene. This
reects in overall much higher amount of benzene oxidation and
conrms superior activity of CuMn/TiO2 in comparison with the
reported work of Shufeng et al. [33].
3.1.2. Catalytic activity for acetaldehyde decomposition
The CuMn/Al2 O3 , CuMn/ZrO2 and CuMn/TiO2 catalysts
have also been evaluated for their activity towards catalytic acetaldehyde oxidation, as acetaldehydes are among

Fig. 6. Acetaldehyde combustion over CuMn/Al2 O3 , CuMn/TiO2 and CuMn/ZrO2


(feed composition: acetaldehyde = 500 ppm, O2 = 10% balance He, at approximately
30,000 h1 space velocity).

the most common VOC pollutants in indoor air. Fig. 6


shows the acetaldehyde decomposition over CuMn/Al2 O3 ,
CuMn/ZrO2 and CuMn/TiO2 catalysts. The same activity
sequence (CuMn/TiO2 > CuMn/ZrO2 > CuMn/Al2 O3 ) was also
observed in case of acetaldehyde oxidation. The CuMn/Al2 O3 ,
CuMn/TiO2 and CuMn/ZrO2 catalysts get activated after about
60 C and quickly achieve the light-off temperature. 100% decomposition of acetaldehyde for all the catalysts was obtained at
about 200 C at 30,000 h1 space velocity. The Ti (temperature
at which acetaldehyde combustion initiated) and T50 (temperature at which 50% acetaldehyde combustion observed) of
CuMn/ZrO2 and CuMn/TiO2 are comparatively lower than that
for CuMn/Al2 O3 . At 80 C, CuMn/Al2 O3 shows 5% acetaldehyde
conversion, whereas CuMn/ZrO2 and CuMn/TiO2 show 20% and
45% acetaldehyde conversion, respectively.
The catalytic abatement of acetaldehyde over non-noble metal
based catalyst is not frequently reported, therefore the present
results were compared with works of Mitsui et al. [34], in which the
authors have studied the catalytic combustion of acetaldehyde over
SiO2 , TiO2 and CeO2 supported 1 wt% Pt catalysts. A gaseous mixture of 1% acetaldehyde and 99% air was used in the study, and the
catalysts were evaluated at 10,000 h1 space velocity using 600 mg
of catalyst. All the investigated 1 w% Pt supported SiO2 , TiO2 and
CeO2 catalysts show 100% acetaldehyde conversion at 250 C. The
CuMn/Al2 O3 , CuMn/ZrO2 and CuMn/TiO2 catalysts studied in
the present work (Fig. 6) show the 100% acetaldehyde conversion
at 200 C. Although, lower acetaldehyde concentration was used
in the present work as compared to the studies of Mitsui et al.,
considering the small amount of catalyst (100 mg) and higher space
velocity (30,000 h1 ) used in the present investigation, these nonnoble metal catalysts show excellent activity for the combustion of
acetaldehyde.
It has been reported that alumina usually forms less active aluminates with the transition metals, which could be the possible
reason for the inferior activity of CuMn/Al2 O3 catalyst [35]. The
redox and oxygen desorption properties of TiO2 and ZrO2 prevent
the formation of titanates and zirconates with Cu and Mn under the
present synthesis conditions used [36]. In this way, Al2 O3 shows
inferior catalytic activity as compared to TiO2 and ZrO2 , when used
as support for the transition metals, unlike in the case of noble metals like Pt and Pd, which are not reactive towards alumina. The use
of acidic supports and catalysts for the removal of various pollutants is well established for many catalytic reactions of energy and
environmental importance. Tajima et al. [37] studied the decomposition of chlorouorocarbons on different acidic supports such

P. Doggali et al. / Journal of Molecular Catalysis A: Chemical 358 (2012) 2330

29

Fig. 7. O2 -TPD curves for CuMn/Al2 O3 , CuMn/TiO2 and CuMn/ZrO2 .

as SiO2 MgO, SiO2 ZrO2 , SiO2 Al2 O3 and TiO2 ZrO2 . Among the
studied catalysts only TiO2 ZrO2 catalysts show enhanced activity,
though the other catalyst studied were also of acidic nature.
Clearly the present work infers that TiO2 and ZrO2 are better
supports for transition metal based oxide and mixed oxide type catalysts and their physical properties can be signicantly enhanced
through template synthesis.
3.2. O2 -TPD studies
O2 -TPD (temperature programmed oxygen desorption) experiments were performed to understand the oxygen desorption
properties of CuMn/Al2 O3 , CuMn/ZrO2 and CuMn/TiO2 . Two
different types of oxygen species known as and were dened in
our previous O2 -TPD studies on mixed oxide materials for soot oxidation reaction [38]. The peaks at low temperatures are supposed
to be desorbed oxygen species, which are weakly chemisorbed
supercial oxygen species. Fig. 7 shows the O2 -TPD curves for
CuMn/Al2 O3 , CuMn/TiO2 and CuMn/ZrO2 . The -oxygen desorption temperatures are observed around 180, 135 and 120 C
for CuMn/Al2 O3 , CuMn/TiO2 and CuMn/ZrO2 , respectively. The
lower temperature -oxygen desorption further support the better catalytic activity results for CuMn impregnated ZrO2 and TiO2
as compared to CuMn impregnated Al2 O3 . The high activity of
CuMn/TiO2 catalyst also correlates very well with the oxygen
species of peak , i.e. larger area of peak corresponds to higher
combustion activity of the catalyst. From the results it can also
be seen that oxygen releasing temperature of the CuMn/ZrO2
is low, which represents the oxygen desorption properties of
CuMn/ZrO2 at lower temperatures as compared to CuMn/TiO2 .
However, the smaller surface area of this catalyst could also be
responsible for smaller oxygen content of this catalyst. Hence this
catalyst shows slightly inferior activity than that of CuMn/TiO2 .
The catalyst support interaction leading to improved redox properties is the likely cause for the enhanced catalytic activity of
CuMn/TiO2 and CuMn/ZrO2 .
3.3. H2 -TPR studies
Fig. 8 depicts the H2 -TPR (temperature programmed reduction with hydrogen) proles of CuMn/Al2 O3 , CuMn/TiO2 and
CuMn/ZrO2 catalysts. The obtained H2 -TPR proles show two
reduction peaks for CuMn/TiO2 and CuMn/ZrO2 , whereas
CuMn/Al2 O3 shows the single reduction peak. It has been reported
that the low temperature peak/peaks is/are due to highly dispersed
metal oxide particles on supports and the second reduction peak

Fig. 8. H2 -TPR curves for CuMn/Al2 O3 , CuMn/TiO2 and CuMn/ZrO2 .

is usually assigned to the hydrogen consumed in the reaction with


sub-surface lattice oxygen, which can be migrated at higher temperatures from the interior to the surface of the catalyst [39,40].
From the present H2 -TPR results, it is clear that CuMn/TiO2 catalyst is easily reduced followed by CuMn/ZrO2 and CuMn/Al2 O3 . It
has been observed in many studies that the increasing order of catalyst reduction ability can be correlated to their redox ability [40].
Hence the better performance of CuMn/TiO2 catalyst at relatively
lower temperatures could be explained by the ease of reducibility
of this catalyst in comparison with CuMn/ZrO2 and CuMn/Al2 O3 .
The H2 -TPR curves in the temperature range of catalytic activity
can be further correlated to the better catalytic performances of
the investigated catalysts.
4. Conclusion
The results obtained in the present study for the catalytic benzene and acetaldehyde combustion, clearly suggest that Al2 O3 ,
TiO2 and ZrO2 are the potential supports for catalyst dispersion.
The mesoporous nature of these supports without ordered structure offer suitable properties for dispersion of metal oxides and
mixed metal oxides. The higher surface area and open type pore
structure with mesoporous size are observed to be very suitable
for reactions involving VOCs molecules, which could be mainly
due to the improved mass transfer. The redox properties of TiO2
and ZrO2 could be the possible reasons for the better catalytic
activity of CuMn/TiO2 and CuMn/ZrO2 catalysts as compared to
CuMn/Al2 O3 for both combustion of benzene and acetaldehyde.
TPD and TPR experiments further support the enhanced activity
of CuMn/TiO2 through its redox properties. The effect of oxygen,
benzene and acetaldehyde concentration on catalytic performance
will be investigated in the subsequent work. The most striking
observation of the present catalysts is the possibility of development of low cost catalyst compositions as a replacement of those
noble metals. The development of catalyst supports with improved
properties is a signicant advancement in this respect.
Acknowledgements
This work was carried out under the CSIR Supra-institutional
project No. SIP-16 (1.3) as well as, under the research cooperation between NEERI, India and Kyushu University, Japan under the
G-COE programme of Kyushu University. Authors are grateful to
Director NEERI, for providing necessary facilities, while one of the

30

P. Doggali et al. / Journal of Molecular Catalysis A: Chemical 358 (2012) 2330

authors (Pradeep Doggali) is thankful to CSIR India for providing


Senior Research Fellowship.
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