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Environmental Technology
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Degradation of phenol via wet-air oxidation over

CuO/CeO2–ZrO2 nanocatalyst synthesized employing
ultrasound energy: physicochemical characterization
and catalytic performance
ab ab ab
Mohsen Parvas , Mohammad Haghighi & Somaiyeh Allahyari
a
Chemical Engineering Faculty, Sahand University of Technology, PO Box 51335-1996, Sahand
New Town, Tabriz, Iran
b
Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, PO Box
51335-1996, Sahand New Town, Tabriz, Iran
Published online: 09 Dec 2013.

To cite this article: Mohsen Parvas, Mohammad Haghighi & Somaiyeh Allahyari (2014) Degradation of phenol via wet-air
oxidation over CuO/CeO2–ZrO2 nanocatalyst synthesized employing ultrasound energy: physicochemical characterization and
catalytic performance, Environmental Technology, 35:9, 1140-1149, DOI: 10.1080/09593330.2013.863952

To link to this article: http://dx.doi.org/10.1080/09593330.2013.863952

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 Environmental Technology, 2014
Vol. 35, No. 9, 1140–1149, http://dx.doi.org/10.1080/09593330.2013.863952

Degradation of phenol via wet-air oxidation over CuO/CeO2 –ZrO2 nanocatalyst synthesized
employing ultrasound energy: physicochemical characterization and catalytic performance
Mohsen Parvasa,b , Mohammad Haghighia,b∗ and Somaiyeh Allahyaria,b
a Chemical Engineering Faculty, Sahand University of Technology, PO Box 51335-1996, Sahand New Town, Tabriz, Iran;
b Reactorand Catalysis Research Center (RCRC), Sahand University of Technology, PO Box 51335-1996,
Sahand New Town, Tabriz, Iran
(Received 30 April 2013; accepted 30 October 2013 )

Catalytic wet air oxidation (CWAO) of phenol was carried out under atmospheric pressure of oxygen at 160◦ C in a stirred
batch reactor over copper catalysts supported by CeO2 –ZrO2 . The copper with different loadings were impregnated over
the composite support by a sonication process. The catalysts were characterized by X-ray diffraction (XRD), field emission
scanning electron microscopy (FESEM), energy dispersive X-ray analysis (EDX), Brunauer-Emmett-Teller (BET) specific
Downloaded by [University of Bath] at 05:57 09 October 2014

surface area and Fourier-transformed infrared analyses. Characteristic peaks attributed to copper were not found in XRD
patterns even at high loadings, but based on EDX results, the existence of copper particles was confirmed. It means that
sonochemical synthesis method even at high loadings produced small copper particles with low crystallinity and excellent
dispersion over the CeO2 –ZrO2 composite. FESEM micrographs indicated just slight enhancement in particle size at high
loadings of Cu. Blank CWAO experiments illustrated low conversion of phenol using bare CeO2 –ZrO2 support. Although
some agglomeration of particles was found at high loadings of copper but owning to the fact that almost all ZrO2 particles
incorporated into the CeO2 lattice at high contents of Cu, catalyst activity not only did not decrease but also the phenol
conversion reached to the higher values. The optimal catalyst loading for phenol degradation was found to be 9 g/l. Complete
conversion of phenol was achieved using CuO/CeO2 –ZrO2 in 9 g/l catalyst loading with initial phenol concentration of
1000 ppm after 3 h of reaction.
Keywords: wet air oxidation; phenol; copper; CeO2 –ZrO2 ; sonochemistry; nanocatalyst

1. Introduction and odour even at concentrations below 0.001 mg/l.[13]

Waste water treatment typically includes a combination of
methods classified as physical, chemical and biological.
Biological treatment is not suitable for toxic compounds,
needs dilute waste waters and produces sludge with dis-
posal issues.[1] Nowadays, chemical methods like wet air
oxidation (WAO) that totally converts organic pollutants
to CO2 , N2 and H2 O emerge and find promising appli-
cations for the treatment of concentrated toxic effluents
of industrial processes.[2–7] The degree of oxidation is
mainly a function of pollutant stability, reaction temper-
ature, oxygen partial pressure and residence time.[8–11]
Higher temperatures and pressures in which the degree of
oxidation is noticeable bring extra operational costs. There-
fore, an alternative to reduce the costs is the use of suitable
catalysts able to promote the WAO under milder operating
conditions and shorter residence times. Many wastewaters
originating from chemical, pharmaceutical and petrochem-
ical industries are phenol contaminated,[12] conferring a
heavy burden to the environment. Phenol and its deriva-
tives are known to be detrimental to human health and
aquatic life, giving water a particularly disagreeable taste
Heterogeneous catalysts presenting high activity and stabil-
ity in WAO have been investigated over the years [14–17]
since they can be easily removed by filtration from the
treated solution.[18,19] Among WAO catalysts, transition
metal oxide catalysts due to lower cost compared with
noble metals are widely studied as an alternative in the
WAO even if they show rather lower activity.[15,20–22]
To improve the activity of these catalysts, some efficient
supports like CeO2 and TiO2 have been considered to
facilitate the oxygen transfer from the dissolved phase to
the active sites.[23] CeO2 –ZrO2 composite support with
high oxygen mobility is widely applied in the removal of
organic compounds from wastewaters.[24–28] The addition
of ZrO2 to CeO2 can improve its oxygen storage capacity,
redox properties, thermal resistance and catalytic activity
at low temperatures.[29] Copper oxides that are one of
the most commonly used transition metal catalysts also
have good activity in WAO.[30–32] In the work of Gulin,
CuO(10 wt.%)/CeO2 catalyst was applied for the removal
of aniline from wastewater.[11] This catalyst seemed to be
active having an aniline removal of 45.7%. Researchers via

∗ Corresponding author: Email: haghighi@sut.ac.ir; web: http://rcrc.sut.ac.ir

© 2013 Taylor & Francis

 Environmental Technology
increasing the transition metal loading attempt to make up
lower activity of them compared with noble metals. Even
this high loading of metal does not bring huge extra costs
because of low cost of transition metals. Kim et al. [31]
investigated the effect of copper loading (1–25%) and found
that chemical states of copper in the CuOx /Al2 O3 catalysts
varying with copper loading: the highly dispersed Cu2+
cluster for 5 wt.% and 7 wt.% converted to bulk CuO for
10–25 wt.%. They showed that the optimum copper load-
ing was 7 wt.% and at higher contents of copper, dispersion
of active phase declined. Although increasing the metal
content results in more activity of the catalyst in phenol
degradation but at high loadings, agglomeration of met-
als and in other words, reduction of dispersion results in a
decline in activity.
According to the direct effect of the synthesis method on
the structure and hence the activity of the catalyst, the sono-
Downloaded by [University of Bath] at 05:57 09 October 2014
chemistry method is proposed as a suitable way for settling
metallic nanoparticles with high dispersion over different
supports without damaging the structure.[33] To our knowl-
edge, little work has been performed to find a method to
synthesize a transition metal catalyst that even at high load-
ings of active phase can degrade phenol extensively. There-
fore, in this study CuO/CeO2 –ZrO2 catalyst with different
loadings of copper (0–20 wt.%) was synthesized by sono-
chemistry method and its structure and activity in catalytic
wet air oxidation (CWAO) of phenol were investigated. The
Brunauer-Emmett-Teller (BET) specific surface area, X-ray
diffraction (XRD), Fourier-transformed infrared (FTIR),
field emission scanning electron microscopy (FESEM) and
energy dispersive X-ray analysis (EDX) were adopted to
characterize the CuO/CeO2 –ZrO2 nanocatalyst and the
phenol concentration of each sample was determined using
UV–Vis. detector.
2. Materials and methods
2.1. Materials
All the chemicals used in this study were obtained from
the companies of repute. The following chemicals were
employed for the preparation of nanocatalysts: cerium
nitrate (Ce(NO3 )3 ·6H2 O; 98.5 wt.%; Merck), zirconium
nitrate (ZrO(NO3 )2 ·6H2 O; 99 wt.%; Aldrich), as a precur-
sor in the synthesis of the nanocatalyst support; copper
chloride (CuCl2 ·2H2 O; 99 wt.%; Merck), as a precursor
using in active phase, ammonia (NH3 ; 33 wt.%; Merck)
as a precipitant. Phenol from Merck Company was used
as a representative of organic pollutants for the investiga-
tion of nanocatalysts activity. All the reagents were used as
received and were not purified further.
2.2. Preparation and procedures
The schematic flow chart for the preparation steps
of CuO/CeO2 –ZrO2 nanocatalysts synthesized via
1141
co-precipitation and ultrasound-assisted method is shown
in the figure (Supplementary material).
The mixed oxide support CeO2 –ZrO2 with Ce/Zr
molar ratio of 3:1 used as a support was prepared via
co-precipitation method. Appropriate amounts of nitrate
salts (cerium nitrate: Ce(NO3 )3 ·6H2 O and zirconyl nitrate:
ZrO(NO3 )2 ·2H2 O) were dissolved in distilled water. The
precipitate of Ce(OH)3 -Zr(OH)4 was obtained by adding
aqueous ammonia (28%) drop wise into a mixed aqueous
solution at room temperature with stirring until the pH of the
mother liquor reached about 7.0. The obtained precipitate
was filtered and washed with distilled water, and then dried
at 110◦ C overnight. Finally, ceria–zirconia mixed oxide was
obtained by calcination in air flow at 450◦ C for 6 h.
In the second stage, transition metal (Cu) was impreg-
nated on CeO2 –ZrO2 by different loadings of active phase
(5, 10, 15 and 20 wt.%). The synthesized nanocatalysts are
designated as C0CZ, C5CZ, C10CZ, C15CZ and C20CZ
with Cu-loadings of 0, 5, 10, 15 and 20 wt.%, respectively.
These nanocatalysts were prepared by the sonochemistry
method using an aqueous solution of CuCl2 ·6H2 O and the
prepared CeO2 –ZrO2 support. Sonication was carried out
on a SONOPULS HD 3200. The slurry irradiated with
a high-intensity ultrasonic employing a direct immersion
titanium horn of 1 cm2 (20 kHz, power output 90 W/cm2 )
which was inserted 1 cm below the solution, under a flow of
argon for 45 min. The sonication flask was fixed in a water
bath at room temperature (20 − 25◦ C) during the reaction,
whereas the temperature inside the sonication flask was
around 70 − 80◦ C. Then, the mixture was dried at 110◦ C
for 12 h. After drying, the precipitate was calcined in air at
the temperature of 500◦ C for 5 h.
2.3. Characterizations
The crystal structures of nanocatalyst were confirmed by
means of a diffractometer SIENENF B5000: Advance-D8
using Cu-Kα radiation. Intensities were obtained in the 2θ
range between 20◦ and 90◦ with a scanning speed of 0.04◦
per second. The average crystallite size of nanocatalyst was
estimated using the Debye–Scherrer equation:
0.90λ
D= (1)
β cos θ
where D is the crystallite size (nm), λ is the wavelength
(λ = 0.154056 nm), β is the corrected full width at half
maximum (radian) and θ is the Bragg angle (radian).
The samples were characterized at acceleration voltage of
15 kV. Morphology and particle size of the nanostructure
catalysts were observed by FESEM (HITACHI S-4160)
analyser. EDX was carried out by VEGA\\ TESCAN,
BSE DETECTOR. The BET surface area was determined
using a CHEMBET-3000 (Quantachorom) apparatus from
adsorption of nitrogen at relative pressure between 0.05 and
0.3. FTIR technique was used at Fourier transform-infrared
 1142 M. Parvas et al.

spectrophotometer (Unicam 4600) to identify the surface

functional groups on the nanocatalysts. The samples were
characterized at wavelength between 4000 and 400 cm−1 .

2.4. Oxidation procedure

The oxidation experiments were carried out at atmospheric
pressure of O2 in a 200 ml autoclave equipped with a mag-
netically driven impeller. The cylinder reactor made of
SS-316 stainless steel was equipped with a teflon liner to
prevent severe corrosion problems. A thermal sensor and
external heating element are also provided in the reactor for
temperature control with an accuracy of ±1◦ C. Typically,
in an oxidation run, 100 ml of aqueous solution, containing
the pollutant (1000 g/l of phenol) and the desired amount
of nanocatalyst powder, was loaded inside the cold reactor.
After 5-min flushing with O2 , the reactor was heated to the
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reaction temperature. After it was sealed, the reactor was

rapidly heated to the desired temperature. Initial O2 pres-
sure was 1 atm. The operating temperature was chosen to be
160◦ C. The mixer was set at 800 rpm to minimize the inter-
facial mass resistance between the gas and liquid phases
and to ensure uniform temperature and concentration pro-
files in the liquid phase. The nanocatalyst loading in reactor
(g/l) and active phase loading on support (%) were varied
over wide experimental intervals. Once the set temperature
was achieved, the time of reaction was initialized and was
defined as the start time (t = 0). Each run lasted for 3 h.
At the end of the reaction, liquid samples were withdrawn,
rapidly cooled, centrifuged to remove any catalyst particle
in the liquid samples and analysed. The phenol concentra-
tion of each sample was determined using UV–Vis. detector.
The UV–Vis. detector was used with a 272 nm wavelength.
The conversion of phenol (%) was calculated according to
the following equation:
[PhOH]i − [PhOH]t
Phenol degradation (%) = × 100,
[PhOH]i
(2)
where [PhOHi ] and [PhOH]t are the initial and the instan-
taneous concentration of phenol (mol/l), respectively.
3. Results and discussions
3.1. Nanocatalysts characterizations
3.1.1. XRD analysis
The XRD patterns of synthesized samples with copper load-
ings of 0, 5, 10, 15 and 20 wt.% over CeO2 –ZrO2 are
illustrated in Figure 1(a), (b), (c), (d), and (e), respectively.
As shown in the figure, the XRD analysis demonstrates
the formation of CeO2 as indicated by the diffraction
peak at 2θ = 28.8, 33.2, 47.7, 56.6, 59.4, 69.8, 77.1, 79.5
and 88.9 corresponding to the planes of CeO2 (JCPDS:
01-075-0076). As shown in Table 1, the average crystallite
size of CeO2 in prepared support was 10.4 nm, calculated
from the X-ray line broadening technique employing the
Figure 1. XRD patterns of CuO/CeO2 –ZrO2 nanocatalysts with
different Cu loadings: (a) C0CZ: 0 wt.%, (b) C5CZ: 5 wt.%, (c)
C10CZ: 10 wt.%, (d) C15CZ: 15 wt.% and (e) C20CZ: 20 wt.%.
Scherrer equation. The crystallite size of the CeO2 remains
constant up to 10 wt.% of Cu (C10CZ) and increased for the
samples C15CZ and C20CZ. The ZrO2 support was poorly
crystallized, which implied that ZrO2 was incorporated into
the CeO2 lattice. The diffraction lines of synthesized ceria
and zirconia are typical of the cubic and tetragonal crystal
structure, respectively.
The CuO/CeO2 –ZrO2 nanocatalysts had the same pat-
terns as the pure CeO2 –ZrO2 support, and no diffraction
peak characteristic to copper even at high loadings could
be observed on the XRD patterns. Actually, the existence
of copper has been confirmed according to the following
EDX dot mapping analysis, and these observations sug-
gest that copper was either in an amorphous form or was
too small (and hence well dispersed) to be detected by the
XRD technique. The sonochemical synthesis of a volatile
precursor (Cu·Cl2 in this case) occurs in cavity region in
which the cooling rate is high. Therefore, the crystallinity
of metal oxide formulated from this precursor will be low.
Careful examination indicates that the shoulder attributed
to ZrO2 has been disappeared at high loadings of copper
that means almost all ZrO2 incorporated in the CeO2 lattice
at higher copper content. It seems sonochemistry at higher
contents of copper conduct more ZrO2 particles into the
CeO2 network to create more space for copper particles.
 Environmental Technology
Table 1. Structural properties of CeO2 –ZrO2 support and CuO/CeO2 –ZrO2 nanocatalysts synthe-
sized via co-precipitation and ultrasound-assisted methods.
Crystallite sizea (nm)
Catalyst/support Cu (wt.%) CuO CeO2
C0CZ 0 – 10.4
C5CZ 5 – 10.4
C10CZ 10 – 10.4
C15CZ 15 – 13
C20CZ 20 – 14.9
a Crystallite size estimated by Scherre’s equation.
b Reference code (JCPDS): 01-080-1268.
c Reference code (JCPDS): 01-075-0076.
d Reference code (JCPDS): 00-024-1164.
3.1.2. FESEM analysis
One of the aspects that significantly affect the catalytic
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activity of ceria is the size of nanocatalyst particles.[34,35]
Figure 2(a), (b), (c), (d) and (e) illustrate FESEM micro-
graphs and particle size histogram of the nanocatalysts with
different loadings of copper: 0, 5, 10, 15 and 20 wt.%,
respectively. Almost all micrographs show uniform mor-
phology. Bare CeO2 –ZrO2 support had minimum size of
20.9 nm and maximum particle size of 77.7 nm, whereas
the average particle size was 30.7 nm. While bare CeO2 –
ZrO2 support had a uniform morphology, introduction of
5 wt.% copper makes some irregularity in the structure. The
average size of particles in C5CZ nanocatalyst increased to
39.8 nm with minimum and maximum size of 25.2 nm and
188.9 nm respectively. Obvious agglomeration of particles
can be observed in the C5CZ nanocatalyst. With increas-
ing the copper content, the results have highlighted the
general progressive covering of active phase in nanocata-
lysts. The FESEM micrographs of the C10CZ (Figure 2(c))
indicate that the CuO/CeO2 –ZrO2 nanocatalyst particles
were tiny and spherical which this can be related to high
nucleation rate when sonication is applied at this concentra-
tion. C10CZ nanocatalyst has a minimum size of 25.4 nm
and maximum particle size of 118.3 nm with the average
size of 42.7 nm. Moreover, it can be seen that the synthe-
sized particles in C10CZ nanocatalyst have narrow particle
size distribution compared with C5CZ nanocatalyst. C15CZ
nanocatalyst had a very similar morphology to C10CZ
nanocatalyst. It has a minimum size of 26.4 nm and max-
imum particle size of 119.3 nm with the average size of
46.3 nm. C20CZ nanocatalyst exhibited rather non-uniform
morphology. Some agglomeration of particles was found
and the size of particles grew to a average size of 52.9 nm.
The minimum size of particles was 36.8 nm and maximum
was 137.2 nm. It was expected that at high loadings of cop-
per (20 wt.%) bigger particles with drastic agglomeration of
particles was observed but owe to sonochemistry method,
high dispersion of particles prevents sever agglomeration of
particles. Due to this fact, rather uniform and low agglom-
erated morphology even at high loadings of copper was
1143
Crystallite phase
ZrO2 CuOb CeOc2 ZrOd2
– Monoclinic Cubic Tetragonal
– Monoclinic Cubic Tetragonal
– Monoclinic Cubic Tetragonal
– Monoclinic Cubic Tetragonal
– Monoclinic Cubic Tetragonal
observed in C20CZ nanocatalyst. Low vapour pressure of
Cu·Cl2 leads to collapse of cavity at high temperatures,
which due to enhanced nucleation rate produces small and
dispersed particles with uniform morphology.
3.1.3. EDX dot mapping
The EDX dot mapping of the CuO/CeO2 –ZrO2 nanocata-
lysts with different loadings of copper (0, 5 and 20 wt.%) is
illustrated in Figure 3. All of the elements used in the syn-
thetic procedure can be observed in the EDX spectra. This
analysis shows that the Cu, Ce and Zr are highly uniform dis-
persed in the attributed nanocatalysts. Applying ultrasound
to the starting solution, homogeneous nucleation occurs and
is followed by the growth of the particles and subsequent
aggregation. But in the presence of a support, microjets
produced from collapse of the bubbles near the solid sur-
face will drive the formed nucleus in solution to the surface
of the solid support and immobilize them before they are
severely aggregated in solution. Therefore, sonochemical
method provides better dispersion of copper species over
the support.
No sintering or particle growth was observed in the cop-
per particles even at high loadings, which is completely
consistent with the XRD and FESEM results. It can be stated
that dispersion of copper is relatively better for high load-
ings of copper (C20CZ) rather than low loadings (C5CZ)
in good agreement with particle size histograms of related
nanocatalysts. Although at high concentrated solutions of
precursor, agglomeration of particles is more likely but
applied power of the ultrasound in present work is high
enough to control the dispersion. Therefore, no severe
agglomeration or particle growth has been observed in
C20CZ nanocatalyst. High dispersion of copper particles
on the CeO2 –ZrO2 support can have a direct effect on the
nanocatalyst activity in phenol removal.
3.1.4. BET analysis
Surface area is one of the important features that highly
influence the nanocatalyst activity. The specific surface area
 1144 M. Parvas et al.
60 55.9
Min: 20.9 nm (a) C0 CZ: Cu( 0 wt.%)/CeO 2 - ZrO 2
50 Max: 77.7 nm
Average = 30.7 nm
Particles < 100 nm: 100 %

Frequency (%)
40
Standard deviation: 8.2
30 28.0

20 15.4

10
0.0 0.0 0.0 0.0 0.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0 300 nm
0-10 30-40 60-70 90-100 120-130 150-160 180-190
Particle size (nm)
60
Min: 25.2 nm (b) C 5 CZ: Cu( 5 wt.%)/CeO 2 - ZrO 2
50
Max: 188.9 nm
Average = 39.8 nm
Frequency (%)

40 36.6 Particles < 100 nm: 97.4 %

Standard deviation: 20.8
30 26.2
23.0

20
10.5
Downloaded by [University of Bath] at 05:57 09 October 2014

10
0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.0 2.1 0.0 0.0 0.0 0.0 0.0 0.5 0.0
0 300 nm
0-10 30-40 60-70 90-100 120-130 150-160 180-190
Particle size (nm)
60
Min: 25.4 nm (c) C 10 CZ: Cu( 10 wt.%)/CeO 2 - ZrO 2
50 Max: 118.3 nm
Average = 42.7 nm
Particles < 100 nm: 98.2 %
Frequency (%)

40
30.1
Standard deviation: 15.5
30 25.3
22.9

20 18.1

10
0.0 0.0 0.0 1.2 0.6 0.0 0.6 1.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0 300 nm
0-10 30-40 60-70 90-100 120-130 150-160 180-190
Particle size (nm)
60
Min: 26.4 nm (d) C15CZ: Cu(15 wt.%)/CeO2-ZrO2
50 Max: 119.3 nm
Average = 46.3 nm
Particles < 100 nm: 97.5 %
Frequency (%)

40
31.4 Standard deviation: 16.5
30 26.4
24.8

20
12.4
10
1.7 0.8 1.7
0.0 0.0 0.0 0.0 0.8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 300 nm
0
0-10 30-40 60-70 90-100 120-130 150-160 180-190
Particle size (nm)

60
Min: 36.8 nm (e) C20CZ: Cu(20 wt.%)/CeO2-ZrO2

50 Max: 137.2 nm
Average = 52.9 nm
40 36.6 38.0 Particles < 100 nm: 95.7%
Frequency (%)

Standard deviation: 18.8

30

20 16.9

10
2.8 1.4 2.8
0.0 1.4 0.0 0.0
0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
300 nm
0-10 30-40 60-70 90-100 120-130 150-160 180-190
Particle size (nm)

Figure 2. FESEM analysis and particle size histogram of CuO/CeO2 –ZrO2 nanocatalysts with different Cu loadings (a) C0CZ: 0 wt.%,
(b) C5CZ: 5 wt.%, (c) C10CZ: 10 wt.%, (d) C15CZ: 15 wt.% and (e) C20CZ: 20 wt.%.
 Environmental Technology 1145
Ce Zr
(a) C0CZ

cps 1.0µm 1.0µm

SEM O

1.0µm

1.0µm 1.0µm
0 2 4 6 8 10 12 14 16 18 20
keV
Ce Zr
(b) C5CZ
Downloaded by [University of Bath] at 05:57 09 October 2014

cps

1.0µm 1.0µm

Cu O

1.0µm

1.0µm 1.0µm
0 2 4 6 8 10 12 14 16 18 20
keV
Ce Zr
(c) C20CZ
cps

1.0µm 1.0µm

Cu O

1.0µm

1.0µm 1.0µm
0 2 4 6 8 10 12 14 16 18 20
keV
Figure 3. EDX dot mapping analysis of CuO/CeO2 –ZrO2 nanocatalysts with different Cu loadings: (a) C0CZ: 0 wt.%, (b) C5CZ: 5 wt.%
and (c) C20CZ: 20 wt.%.

of the CeO2 –ZrO2 support was 62.7 m2 /g. This surface
area is comparable to those reported by Biswas and Kun-
zru [36] and Liang et al. [37] for ceria–zirconia. The
amount of surface area for nanocatalysts with copper 5,
10, 15 and 20 wt.% has been 13.9, 32.1, 28.6 and 19.4,
respectively. After 5% of copper introduction (C5CZ), a
significant decrease in BET value is observed, due to pore
blocking by big agglomerated metals according to FESEM.
The reduction in surface area from 5 to 10 wt.% is not
so much. The surface area of C10CZ and C15CZ is very
close, in good agreement with FESEM and particle size
histograms of these two nanocatalysts that indicated similar
morphology. Low surface area observed in C20CZ nanocat-
alyst is attributed to some agglomerations and also to high
loading of copper that blocks the support pores.
3.1.5. FTIR analysis
Figure 4 shows the recorded FTIR patterns of CeO2 –ZrO2
support and CuO/CeO2 –ZrO2 nanocatalysts with different
loadings of transition metal. The nanocatalysts displayed
infrared absorption bands at 415, 1400 and 1620 cm−1 . The
characteristic peaks were assigned as follows: the bands at
1400 cm−1 are the stretching vibration absorption spectra of
 1146
1620
(a) C0CZ: CeO2-ZrO2
(b) C5CZi: Cu(5%)/CeO2-ZrO2
(c) C10CZ: Cu(10%)/CeO2-ZrO2
(d) C15CZ: Cu(15%)/CeO2-ZrO2
(a)
(e) C20CZ: Cu(20%)/CeO2-ZrO2
(b)
Transmittance (a.u.)
(c)
(d)
(e)
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4000 3500 3000 2500 2000
Wavenumber (cm–1)
Figure 4. FTIR spectrum of CuO/CeO2 –ZrO2 nanocatalysts
with different Cu loadings: (a) C0CZ: 0 wt.%, (b) C5CZ: 5 wt.%,
(c) C10CZ: 10 wt.%, (d) C15CZ: 15,wt.% and (e) C20CZ:
20 wt.%.
H–O. The band at 1625 cm−1 is assigned to the deformation
vibration mode of the adsorbed water.[38,39] No peak of
chloride precursor has ever appeared in the pattern, which
shows that chloride precursor was completely removed by
repeatedly washing with water. Surprisingly, no peak at
3450 cm−1 was found indicative of hydrogen-bonded O–H
species.
The peaks at 415 cm−1 corresponding to the metal–
oxygen–metal bond (M–OM).[38] This band can also be
related to the stretching vibration absorption spectrum of
Ce(Zr)-O. Since this peak changes with increasing Cu
content and according to XRD, copper has no crystalline
structure; therefore, attribution of this peak to Ce(Zr)-O
is more likely. This peak got sharper with increasing Cu
content that reveals more crystalline structure at high Cu
loadings. This observation is exactly consistent with XRD
results that shows at high loadings of copper, CeO2 got
higher crystalline structure.
3.2. Catalytic performance of synthesized
nanocatalysts for oxidation of phenol
As the ultimate part of this work, the activities of different
copper nanocatalysts were compared. The effect of active
metal content and nanocatalyst loading on phenol removal
was investigated.
3.2.1. Effect of Cu-loading on catalytic performance of
synthesized nanocatalysts
Figure 5(a) indicates the effect of different loadings of active
components on catalytic performance of CuO/CeO2 –ZrO2
M. Parvas et al.
1400
460
415
nanocatalyst in phenol conversion. To evaluate the effect
of bare support, reaction experiment was carried out with-
out metal for 3 h under phenol concentration of 1000 mg/l
and nanocatalyst loading of 4.0 g/l. Blank experiments with
CeO2 –ZrO2 proved that the support was not very active in
the oxidation of phenol at 160◦ C. Phenol conversion stabi-
lized around 11.4 wt.% in blank experiments. Four different
CeO2 –ZrO2 supported copper nanocatalysts, containing 5,
10, 15 and 20 wt.%, were loaded. The active phase dis-
persion on the support might vary as a function of the
active phase loading and the catalytic performances might
be consequently affected. The nanocatalyst loading is an
important parameter affecting the CWAO initial reaction
rate and phenol destruction. The increase in metal load-
ing means the increase in the nanocatalyst active sites. It
can be seen that the doping of Cu species on the CeO2 –
ZrO2 improved catalytic activity in WAO of phenol. The
1500 1000 500
degradation increased from 42.1%, 48.3%, 51.0% to 56.8%
after 180 min reaction when the Cu loading changed from
5, 10, 15 to 20 wt.%, respectively. Reduction in nanocat-
alyst activity was expected at 20 wt.% copper, because of
relatively weak morphology, but surprisingly highest activ-
ity was observed for this nanocatalyst. The reason for this
observation will be explained in Section 3.3 in detail.
3.2.2. Effect of catalyst loading on catalytic performance
of synthesized nanocatalysts
Figure 5(b) shows the effect of nanocatalyst loading on
catalytic performance of synthesized nanocatalysts. The
efficiency of WAO of phenol increased with nanocata-
lyst loading from 1.0 to 9.0 g/l. The phenol was com-
pletely removed after 180 min reaction in the presence of
Cu nanocatalyst with 9.0 g/l of nanocatalyst loading but
decreased noticeably when the loading was increased to
10.0 g/l. Higher nanocatalyst loadings correspond to higher
active sites and it is expected to increase the removal of
phenol; however, an optimum phenol removal at 9.0 g/l
of nanocatalyst loading exists. Therefore, increasing the
nanocatalyst loading not necessarily increases the phenol
removal. In fact, higher nanocatalyst loading may cause
mass transfer limitations and on the other hand some of
nanocatalysts may not incorporate in the reaction.
3.3. Reaction mechanism of phenol oxidation over
synthesized nanocatalysts
In the reaction occurring via heterogeneous catalysis, the
primary step to be considered is the adsorption of both
the reactants and molecular oxygen.[40] In their research,
Balcaen et al. [41] concluded that the existence of copper
oxide on ceria increases active surface lattice O species.
The increase in active surface lattice O species leads to the
increase in phenol conversion. The phenol uses the exist-
ing lattice O species in ceria and copper oxide and creates
 Environmental Technology 1147

(a) 70 O2 H2O
(8)
Catalyst: Cu/CeO2-ZeO2 C6H5OH CO2
Ce/Zr ratio = 3 (mol/mol) (5) (7)
60 Catalyst/Waste water ratio = 4 g/l 56.8 (1)
OL,s
Phenol concentration = 1000 ppm Oads (3)
51.0
50 48.3
Phenol conversion (%)

H2O
42.1 (4) CuO or (2)
CO2
40 (6) CeO2
OL,b

30
Support: CeO2 -ZrO2

20
11.4
10

C0CZ C10CZ C20CZ 200nm

0 1.0µm 500nm
0 5 10 15 20
Cu Content (%)
Figure 6. Simplified reaction pathway for CWAO of phenol over
(b) Catalyst: Cu(5 wt.%)/CeO2-ZeO2
CuO/CeO2 –ZrO2 nanocatalysts.
100.0
100 Ce/Zr ratio = 3 (mol/mol)
Phenol concentration = 1000 ppm
Downloaded by [University of Bath] at 05:57 09 October 2014

82.9 82.0
80
8. Oxidation of phenol by weakly adsorbed oxygen
Phenol conversion (%)

species, Oads to CO2 .

61.6
60
52.1 54.3
42.1
40
20
0
4 5 6 7 8 9
Catalyst/wastewater ratio (g/l)
Figure 5. Effect of different Cu loadings (a) and effect of cat-
alyst loading (b) on catalytic performance of CuO/CeO2 –ZrO2
nanocatalyst in phenol degradation.
vacancies in these metal oxides. These vacancies are replen-
ished either by adsorption of gas phase O2 , via surface
diffusion of oxygen adsorbed on CuO and CeO2 , or via
diffusion of oxygen from the bulk lattice. The formation of
weakly adsorbed oxygen species is also attributed to the
interaction of O2 with CuO and CeO2 .[41] Ceria and cop-
per oxide adsorb and desorb oxygen within a redox cycle
(Ce4+ /Ce3+ for ceria and Cu2+ /Cu1+ for copper oxide).
The phenol adsorbs and oxides on ceria and copper oxide.
Figure 6 illustrates a scheme of different steps of phenol
oxidation:
1. Oxidation of phenol by surface lattice oxygen
species, OL,s to CO2 and H2 O.
2. Spillover of CO2 from CuO and CeO2 and to CeO2 –
ZrO2 .
3. Desorption of CO2 from CeO2 –ZrO2 .
4. Diffusion of bulk lattice oxygen, OL,b to the surface.
5. Production of Oads species by dissociative adsorption
of gas phase O2 .
6. Replenishment of OL,b species from Oads species.
7. Associative desorption of Oads species.
The role of zirconia when incorporated in ceria is to facil-
itate the reduction of Ce4+ to Ce3+ and to preserve the
oxygen vacancies that are the source of oxygen storage
capacity in ceria-based nanocatalyst supports.[42] With
increasing the copper content although the active sites
increases but agglomeration of particles results in reduc-
10 tion in activity. But as shown in Figure 5 the highest activity
has been observed for nanocatalyst with 20 wt.% copper. As
mentioned in Section 3.1.1, at high loadings of copper more
ZrO2 migrates to CeO2 lattice so that ZrO2 shoulder cannot
be detected any more at 15% and 20 wt.% copper. It causes
more oxygen transfer for this nanocatalyst via facilitating
the reduction of Ce4+ to Ce3+ . Therefore, even at high load-
ings of copper that agglomeration and surface reduction has
been occurred, the maximum activity for the nanocatalyst
was observed.
The mechanism of reaction associates with adsorption
and desorption of the produced molecules and intermediate
materials during the reaction on the nanocatalyst surface.
The various mechanisms presented by the researchers [43–
45] are an evidence of the claim. The formed intermediate
materials during the reaction have been partially unstable
and are converted to materials of lower and lighter molecule
species (less numbers of carbons) in reaction conditions.
Phenol oxidation starts by a hydroxylation of the
molecule leading to hydroquinone or catechol.[43] Con-
tinuously, these compounds are converted to acids of low
molecular weight, including formic acid, oxalic acid, maleic
acid and so on. At final stages, some of the reactants are
converted to acetic acid, which is a part of the products
hardly converted to carbon dioxide and water. As acetic
acid is refractory to oxidation, the decomposition of this
carboxylic acid is one of the rate-determining steps of the
wet oxidation of various organic compounds.[43] Besides
the role of copper in initial phenol oxidation, another role
 1148 M. Parvas et al.
of copper may be the enhancement of the rate of oxidation
of small organic compounds that are resistant and not easily
degraded by the CeO2 –ZrO2 mixed oxide.[46,47]
4. Conclusions
The main conclusions of the present study can be summa-
rized along these lines:
• The sonochemically Cu catalysts prepared on CeO2 –
ZrO2 demonstrated suitable phenol oxidation under
experimental conditions.
• Although at high loadings of copper some agglom-
eration of particles has been observed but owning to
sonochemical synthesis method, it can be stated that
the particles are still small and well dispersed.
• It seems sonochemistry at higher contents of copper
Downloaded by [University of Bath] at 05:57 09 October 2014
conduct more ZrO2 particles to the CeO2 network to
create more space for copper particles.
• Although according to some agglomeration in
Cu(20 wt.%)/CeO2 –ZrO2 , lower phenol degradation
is expected but due to higher oxygen capacity in
Cu(20 wt.%)/CeO2 –ZrO2 (incorporation of all ZrO2
into the CeO2 lattice) the highest phenol conversion
was observed.
• A maximum of phenol conversion is observed as
the nanocatalyst loading increases. This maximum
occurs at nanocatalyst loading of 9.0 g/l.
• About 100 wt.% phenol is removed after 180 min
reaction at a reaction temperature of 160◦ C, atmo-
spheric oxygen partial pressure, phenol concentration
of 1000 ppm and at nanocatalyst loading of 9.0 g/l.
Funding
The authors gratefully acknowledge Sahand University of Tech-
nology for the financial support of the project as well as Tabriz
Refinery Company and Iran Nanotechnology Initiative Council
for complementary financial support.
References
[1] Cybulski A, Trawczynski J. Catalytic wet air oxidation of
phenol over platinum and ruthenium catalysts. Appl Catal B
Environ. 2004; 47:1–13.
[2] Wei H, Yan X, He S, Sun C. Catalytic wet air oxidation of
pentachlorophenol over Ru/ZrO2 and Ru/ZrSiO2 catalysts.
Catal Today. 2013; 201:49–56.
[3] Ovejero G, Rodríguez A, Vallet A, García J. Catalytic wet air
oxidation of a non-Azo dye with Ni/MgAlO catalyst. Chem
Eng J. 2013; 215–216:168–173.
[4] Li Y, Zhang F, Liang X, Yediler A. Chemical and toxicolog-
ical evaluation of an emerging pollutant (enrofloxacin) by
catalytic wet air oxidation and ozonation in aqueous solution.
Chemosphere. 2013; 90:284–291.
[5] Luan M, Jing G, Piao Y, Liu D, Jin L. Treatment of refrac-
tory organic pollutants in industrial wastewater by wet air
oxidation. Arab J Chem. in press.
[6] Collado S, Laca A, Diaz M. Decision criteria for the selec-
tion of wet oxidation and conventional biological treatment.
J Environ Manage. 2012; 102:65–70.
[7] Kim K-H, Ihm S-K. Heterogeneous catalytic wet air oxida-
tion of refractory organic pollutants in industrial wastewa-
ters: a review. J Hazard Mater. 2011; 186:16–34.
[8] Renard B, Barbier J Jr, Duprez D, Durecu S. Catalytic wet
air oxidation of stearic acid on cerium oxide supported noble
metal catalysts. Appl Catal B Environ. 2005; 55:1–10.
[9] Yang S, Wang X, Yang H, Sun Y, Liu Y. Influence of the
different oxidation treatment on the performance of multi-
walled carbon nanotubes in the catalytic wet air oxidation of
phenol. J Hazard Mater. 2012; 233–234:18–24.
[10] Ovejero G, Rodríguez A, Vallet A, García J. Ni supported on
Mg–Al oxides for continuous catalytic wet air oxidation of
Crystal Violet. Appl Catal B Environ. 2012; 125:166–171.
[11] Ersöz G, Atalay S. Treatment of aniline by catalytic wet
air oxidation: comparative study over CuO/CeO2 and
NiO/Al2 O3 . J Environ Manage. 2012; 113:244–250.
[12] Liotta LF, Gruttadauria M, Di Carlo G, Perrini G, Librando V.
Heterogeneous catalytic degradation of phenolic substrates:
catalysts activity. J Hazard Mater. 2009; 162:588–606.
[13] Pintar A, Levec J. Catalytic liquid-phase oxidation of phenol
aqueous solutions. A kinetic investigation.Indus Eng Chem
Res. 1994; 33:3070–3077.
[14] Liu J, Yu C, Zhao P, Chen G. Comparative study of supported
CuOx and MnOx catalysts for the catalytic wet air oxidation
of naphthol. Appl Surf Sci. 2012; 258:9096–9102.
[15] Hua L, Ma H, Zhang L. Degradation process analysis of
the azo dyes by catalytic wet air oxidation with catalyst
CuO/Al2 O3 . Chemosphere. 2013; 90:143–149.
[16] Vallet A, Ovejero G, Rodriguez A, Peres JA, Garcia J.
Ni/MgAlO regeneration for catalytic wet air oxidation of
an azo-dye in trickle-bed reaction. J Hazard Mater. 2013;
244–245:46–53.
[17] Hung C-M. Activity of Cu-activated carbon fiber catalyst in
wet oxidation of ammonia solution. J Hazard Mater. 2009;
166:1314–1320.
[18] Gomes HT, Machado BF, Ribeiro A, Moreira I, Rosário M,
Silva AMT, Figueiredo JL, Faria JL. Catalytic properties of
carbon materials for wet oxidation of aniline. J Hazard Mater.
2008; 159:420–426.
[19] Jing G, Luan M, Chen T. Progress of catalytic wet air
oxidation technology. Arab J Chem. in press.
[20] Zhou S, Qian Z, Sun T, Xu J, Xia C. Catalytic wet peroxide
oxidation of phenol over CuNiAl hydrotalcite. Appl Clay
Sci. 2011; 53:627–633.
[21] Arena F, Italiano C, Spadaro L. Efficiency and reactivity
pattern of ceria-based noble metal and transition metal-oxide
catalysts in the wet air oxidation of phenol. Appl Catal B
Environ. 2012; 115–116:336–345.
[22] Arena F, Italiano C, Raneri A, Saja C. Mechanistic and
kinetic insights into the wet air oxidation of phenol
with oxygen (CWAO) by homogeneous and heterogeneous
transition-metal catalysts. Appl Catal B Environ. 2010;
99:321–328.
[23] Wang J, Zhu W, He X, Yang S. Catalytic wet air oxida-
tion of acetic acid over different ruthenium catalysts. Catal
Commun. 2008; 9:2163–2167.
[24] Masui T, Imadzu H, Matsuyama N, Imanaka N. Total oxida-
tion of toluene on Pt/CeO2 –ZrO2 –Bi2 O3 /γ -Al2 O3 catalysts
prepared in the presence of polyvinyl pyrrolidone. J Hazard
Mater. 2010; 176:1106–1109.
[25] Cai T, Liao Y, Peng Z, Long Y, Wei Z, Deng Q. Photocatalytic
performance of TiO2 catalysts modified by H3 PW12 O40 ,
ZrO2 and CeO2 . J Environ Sci. 2009; 21:997–1004.
 Environmental Technology
[26] Saidina Amin NA, Chong CM. SCR of NO with C3 H6 in the
presence of excess O2 over Cu/Ag/CeO2 –ZrO2 catalyst.
Chem Eng J. 2005; 113:13–25.
[27] Kim K-H, Kim J-R, Ihm S-K. Wet oxidation of phenol over
transition metal oxide catalysts supported on Ce0.65 Zr0.35 O2
prepared by continuous hydrothermal synthesis in supercrit-
ical water. J Hazard Mater. 2009; 167:1158–1162.
[28] Delgado JJ, Chen X, Pérez-Omil JA, Rodríguez-Izquierdo
JM, Cauqui MA. The effect of reaction conditions on the
apparent deactivation of Ce–Zr mixed oxides for the catalytic
wet oxidation of phenol. Catal Today. 2012; 180:25–33.
[29] Pengpanich S, Meeyoo V, Rirksomboon T. Methane partial
oxidation over Ni/CeO2 –ZrO2 mixed oxide solid solution
catalysts. Catal Today. 2004; 93–95:95–105.
[30] Gomes HT, Selvam P, Dapurkar SE, Figueiredo JL, Faria
JL. Transition metal (Cu, Cr, and V) modified MCM-41
for the catalytic wet air oxidation of aniline. Microporous
Mesoporous Mater. 2005; 86:287–294.
[31] Kim S-K, Kim K-H, Ihm S-K. The characteristics of wet air
oxidation of phenol over CuOx /Al2 O3 catalysts: effect of
copper loading. Chemosphere. 2007; 68:287–292.
Downloaded by [University of Bath] at 05:57 09 October 2014
[32] Kim K-H, Ihm S-K. Characteristics of titania supported cop-
per oxide catalysts for wet air oxidation of phenol. J Hazard
Mater. 2007; 146:610–616.
[33] Liu H, Zhang S, Zhou Y, Zhang Y, Bai L, Huang L.
Effect of ultrasonic irradiation on the catalytic performance
of PtSnNa/ZSM-5 catalyst for propane dehydrogenation.
Ultrasonics Sonochem. 2011; 18:19–22.
[34] Abbasi Z, Haghighi M, Fatehifar E, Saedy S. Synthesis
and physicochemical characterizations of nanostructured
Pt/Al2 O3 -CeO2 catalysts for total oxidation of VOCs.
J Hazard Mater. 2011; 186:1445–1454.
[35] Abbasi Z, Haghighi M, Fatehifar E, Saedy S. Synthe-
sis and physicochemical characterization of nanostructured
Pt/CeO2 catalyst used for total oxidation of toluene. Int J
Chem Reactor Eng. 2011; 9:1–19.
[36] Biswas P, Kunzru D. Oxidative steam reforming of ethanol
over Ni/CeO2 –ZrO2 catalyst. Chem Eng J. 2008; 136:
41–49.
1149
[37] Liang Q, Wu X, Weng D, Lu Z. Selective oxidation of
soot over Cu doped ceria/ceria-zirconia catalysts. Catal
Commun. 2008; 9:202–206.
[38] Saberi A, Golestani-Fard F, Sarpoolaky H, Willert-Porada M,
Gerdes T, Simon R. Chemical synthesis of nanocrystalline
magnesium aluminate spinel via nitrate–citrate combustion
route. J Alloys Compounds. 2008; 462:142–146.
[39] Pae Y, Shin DC, Sohn JR. CeO2 -promoted highly active cat-
alyst, NiSO4 /CeO2 –ZrO2 for ethylene dimerization. Bull
Korean Chem Soc. 2006; 27:1989–1996.
[40] Gomes HT, Figueiredo JL, Faria JL, Serp P, Kalck P. Carbon-
supported iridium catalysts in the catalytic wet air oxidation
of carboxylic acids: kinetics and mechanistic interpretation.
J Mol Catal A Chem. 2002; 182–183:47–60.
[41] Balcaen V, Roelant R, Poelman H, Poelman D, Marin GB.
TAP study on the active oxygen species in the total oxidation
of propane over a CuO-CeO2 /Al2 O3 catalyst. Catal Today.
2010; 157:49–54.
[42] Srinivas D, Satyanarayana CVV, Potdar HS, Ratnasamy
P. Structural studies on NiO-CeO2 –ZrO2 catalysts for
steam reforming of ethanol. Appl Catal A Gen. 2003;
246:323–334.
[43] Duprez D, Delanoe F, Barbier J Jr, Isnard P, Blanchard G.
Catalytic oxidation of organic compounds in aqueous media.
Catal Today. 1996; 29:317–322.
[44] Quintanilla A, Casas JA, Mohedano AF, Rodríguez JJ. Reac-
tion pathway of the catalytic wet air oxidation of phenol with
a Fe/activated carbon catalyst. Appl Catal B Environ. 2006;
67:206–216.
[45] Santos A, Yustos P, Quintanilla A, Rodríguez S, García-
Ochoa F. Route of the catalytic oxidation of phenol in
aqueous phase. Appl Catal B Environ. 2002; 39:97–113.
[46] Gallezot P, Chaumet S, Perrard A, Isnard P. Catalytic wet
air oxidation of acetic acid on carbon-supported ruthenium
catalysts. J Catal. 1997; 168:104–109.
[47] Barbier J Jr, Delanoë F, Jabouille F, Duprez D, Blanchard
G, Isnard P. Total oxidation of acetic acid in aqueous
solutions over noble metal catalysts. J Catal. 1998; 177:
378–385.