Colloids and Surfaces A: Physicochem. Eng.

Aspects 274 (2006) 138144

Effect of -irradiation and ZnO-doping of CuO/TiO2 system on its

catalytic activity in ethanol and isopropanol conversion
H.G. El-Shobaky a, , A.S. Ahmed a , N.R.E. Radwan b
a
b

Cairo University, Faculty of Science, Department of Chemistry, Cairo 12262, Egypt

Suez Canal University, Faculty of Education, Department of Chemistry, Suez, Egypt

Received 11 October 2004; received in revised form 26 August 2005; accepted 29 August 2005
Available online 29 September 2005

Abstract
The effects of -irradiation (0.41.6 MGy) and ZnO-doping (16 mol%) of CuO/TiO2 system on its surface and catalytic properties were
investigated using XRD, nitrogen adsorption at196 C and ethanol and isopropanol conversion. The catalytic reactions were carried out at
250400 C using micro pulse technique. The results revealed that all investigated solids heated at 400 and 600 C consisted of TiO2 (anatase)
as major phase besides TiO2 (rutile) as minor phase together with CuO phase. The anatase and CuO phases existed as nano-crystallized solids
having crystallite size varying between 5.5 and 21.3 nm and between 8.2 and 23.5 nm for anatase and CuO phases, respectively. ZnO-doping and
-irradiation brought about a progressively significant decrease in the crystallite size of TiO2 and CuO phases which increased by increasing the
calcination temperature of the system investigated from 400 to 600 C. ZnO-doping and -irradiation increased the specific surface areas of the
treated solids to an extent proportional to the amount of dopant added and the dose of -rays absorbed. All solids investigated were highly selective
in ethanol and isopropanol conversion reactions, which proceed via dehydration yielding only ethene and propene, respectively. The catalytic
activity of all solids was found to decrease by increasing the calcination temperature from 400 to 600 C. ZnO-doping conducted at 400 C exerted
no significant change in the activity of doped solids. -Irradiation of the solids calcined at 400 C led to a limited increase in their catalytic activities.
On the other hand, ZnO-doping and -irradiation (0.4 MGy) of solids calcined at 600 C resulted in an increase in their catalytic activities. The
increase was, however, more pronounced in case of -irradiation at a dose of 0.4 MGy.
2005 Elsevier B.V. All rights reserved.
Keywords: Dehydration of alcohols; CuO/TiO2 ; ZnO-doping; -Irradiation

1. Introduction
Titania has been widely employed as catalyst and catalyst
support for variety of applications [1,2]. In particular, the TiO2
(anatase) has been extensively used for several photocatalytic
reactions for the elimination of many organic pollutants from
waste water [35]. It is well known that the type of support
plays an important role for the catalytic properties and for a given
catalytic reaction the activity and selectivity of the catalyst can
be improved by use of an appropriate support oxide [6].
Doping TiO2 with different substrates like noble metals, transition metals, lead, thallium and cadmium has been carried out
[7]. The effect of doping is to change the equilibrium concentration of electrons or creating holes leading to an effective

Corresponding author. Tel.: +20 2 5676575; fax: +20 2 370931.

E-mail address: hala elshobaky@yahoo.com (H.G. El-Shobaky).

0927-7757/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2005.08.046

modification in its electrical and optical properties [8]. The electrical and photocatalytic properties of titania can be changed by
varying its crystallite size [9]. The catalytic properties of noble
metal catalysts supported on titania depend on many variables
such as the thermal treatment, doping with cations or anions,
the synthesis process and different titania crystalline phases
[1012]. Titania is one of the most convenient support material
for copper to be used as catalyst, which determines its dispersion
and active surface area [1316].
Titania (anatase) supported vanadia and molybdena catalysts
have been used in the reaction of NOx reduction with NH3
[1719]. TiO2 -SiO2 solgel catalyst has been used for dehydration of 2-butanol [20]. The catalytic activities of TiO2 -MgO
mixed oxides with magnesia concentrations between 10 and
90 wt.% prepared by solgel method were measured for dehydration of 2-propanol and 2-butanol [21].
Ionizing radiations and doping with certain metal oxides
brought about significant changes in the chemistry of surface of

H.G. El-Shobaky et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 274 (2006) 138144

most of solid catalysts. These changes might be normally accompanied by changes in textural, structural and catalytic properties
of the treated solids [2226].
The present work is devoted to study the effect of ZnOdoping and -irradiation on surface and catalytic properties
of CuO/TiO2 system. The techniques employed were XRD,
adsorption of nitrogen at 196 C and catalytic dehydration
of ethanol and isopropanol alcohols at temperatures within
250400 C.
2. Experimental
2.1. Materials
Ti(OH)4 gel was obtained at room temperature by the addition of concentrated ammonia solution (35% NH3 ) dropwise to
a vigorously stirred dilute solution of TiCl4 until a pH 9 was
attained. The ammonia solution was added dropwise to prevent particle adhesion and sudden grain growth of particles. The
white hydrous Ti(OH)4 was filtered, washed several times with
bidistilled water till free from chloride ions. The resulting precipitate was dried at 120 C for 12 h and then calcined at 300
and 500 C for 6 h to get titania.
Pure copper oxide sample supported on titania having the formula 0.2CuO/TiO2 was prepared by wet impregnation method
using a fixed weight of Ti(OH)4 solid, subjected to careful grinding, with calculated amount of copper nitrate dissolved in the
least amount of distilled water making a paste. The paste was
dried at 120 C till constant weight, then calcined in air at 400
and 600 C for 6 h. Four zinc oxide doped CuO/TiO2 samples
were prepared by impregnating a known mass of finely powdered Ti(OH)4 with different amounts of zinc nitrate dissolved
in the least amount of distilled water prior to impregnation with
Cu(NO3 )2 . The obtained doped solids were dried at 120 C, then
calcined at 400 and 600 C. The dopant concentrations were 1,
2, 4 and 6 mol% of ZnO.
Pure catalyst samples calcined at 400 and 600 C were
exposed to different doses of -rays using a 60 Co source.
The doses were 0.4, 0.8 and 1.6 MGy at a dose rate of
2.7 107 MGy s1 . The irradiated samples were left for 2
weeks in sealed tubes before the different measurements were
carried out.
2.2. Techniques
X-ray powder diffraction patterns of different calcined solids
not subjected to -irradiation and those treated with 0.8 and
1.6 MGy of -irradiation were recorded using a Shimadzu
diffractometer type (D-D1). Data were collected with nickel at 60 kV and 25 mA with
filtered copper radiation ( = 1.5405 A)
a scanning speed of 8 and 0.2 in 2 min1 in phase identification and in line broadening profile analysis, respectively.
The mean crystallite size d of TiO2 and CuO phases in pure
and doped solids was determined using Scherrer equation [27].
d=

B
cos

139

where d is the mean crystallite diameter, B the Scherrer constant

the
(0.89), the wave length of the X-ray beam (1.5405A),
full width at half maximum FWHM of CuO or TiO2 diffraction
peaks and is the diffraction angle.
The specific surface areas of the various prepared catalyst
samples were determined from nitrogen adsorption isotherms
measured at 196 C using conventional volumetric apparatus. Before carrying out such measurements, each sample was
degassed under a reduced pressure of 105 Torr for 2 h at
200 C.
A Helwett-Packard 5890 gas chromatograph with an Hp1,
30 m capillary column, inj. 200 C, oven 60 C isotherm, FID
200 C, N2 as a carrier gas flowing at a rate of 20 ml min1
was employed in studying the catalytic conversion of alcohols.
The catalytic reaction temperature was varied between 250 and
400 C.
The investigated alcohols (ethanol and isopropanol) were
introduced in microquantities (12 103 cm3 ) by the aid of
a microsyringe in the form of pulse, into a small amount of catalyst (50 mg). The reaction products were transferred directly by
an inert carrier gas (nitrogen) to the gas chromatograph.
3. Results and discussion
3.1. XRD investigation of different solids
X-ray diffractograms of pure and variously doped solids precalcined at 400 and 600 C were collected. The obtained diffractograms, not given, revealed that: (i) all investigated solids precalcined at 400 C consisted of TiO2 (anatase) as a major phase,
TiO2 (rutile) as a minor phase together with CuO phase; (ii)
the rise in calcination temperature from 400 to 600 C resulted
in complete conversion of rutile into anatase phase and also to
an effective increase in the degree of crystallinity of both TiO2
(anatase) and CuO phase. The effects of ZnO-doping and irradiation on the crystallite size of TiO2 (anatase) and CuO
phases in CuO/TiO2 system were investigated via analysis of
X-ray diffraction data of the solids investigated. The computed
values of the average crystallite size of anatase and CuO phases
in various CuO/TiO2 systems precalcined at 400 and 600 C are
given in Table 1. Examination of Table 1 showed the following: (a) The various catalysts constitutes are of nanocrystalline
nature. (b) Both ZnO-doping and -irradiation of CuO/TiO2
system brought about a measurable progressive decrease in the
crystallite size of anatase and CuO dopant added. -Irradiation
has been reported to decrease the crystallite size of Co3 O4
phase in Co3 O4 /Al2 O3 precalcined at 650 C via fragmentation
of its crystallites [28]. Similarly, ZnO-doping of Co3 O4 /Al2 O3
and CuO/Al2 O3 systems increase the degree of dispersion of
Co3 O4 and CuO crystallites via decreasing the crystallite size
of cobalt and copper oxides loaded on alumina [29,30]. The
mechanism of this action had been tentatively attributed to coating cobalt oxide crystallite by ZnO film that may hinder the
particle adhesion of the doped oxide solids [29]. (c) The rise in
precalcination temperature of all solids investigated from 400
to 600 C led to an increase in the crystallite size of catalysts
constituents.

140

H.G. El-Shobaky et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 274 (2006) 138144

Table 1
Effects of ZnO-doping and -irradiation on the crystallite size of TiO2 (anatase) and CuO phases in CuO/TiO2 solids precalcined at 400 and 600 C
Calcination temperature ( C)

Dopant concentration (mol% ZnO)

Dose of -rays (MGy)

Crystallite size (nm)

TiO2

CuO

0.0
1.0
2.0
4.0
6.0

400
400
400
400
400

0.0
0.0
0.0
0.0
0.0

12.5
11.2
10.3
9.1
7.9

0.5
0.5
0.5
0.5
0.5

13.1
12.0
11.2
10.1
8.2

0.5
0.5
0.5
0.5
0.5

0.0
0.0
0.0
0.0

400
400
400
600

0.4
0.8
1.6
0.0

8.1
7.0
5.5
21.3

0.5
0.5
0.5
0.5

9.0
8.5
6.5
23.5

0.5
0.5
0.5
0.5

1.0
2.0
4.0
6.0

600
600
600
600

0.0
0.0
0.0
0.0

20.1
19.2
18.3
16.9

0.5
0.5
0.5
0.5

21.7
20.8
19.2
18.7

0.5
0.5
0.5
0.5

0.0
0.0
0.0

600
600
600

0.4
0.8
1.6

19.2 0.5
18.9 0.5
17.5 0.5

3.2. Specic surface areas of different adsorbents

21.7 0.5
20.2 0.5
19.3 0.5

substrate was added in the form of zinc nitrate) [30,31]. The

observed increase in the BET-surface areas of various systems
can be attributed to creation of new pores resulting from liberation of nitrogen oxide gases due to thermal decomposition
of dopant nitrate in course of heating the doped solids [30,31].
The observed increase in the SBET of the CuO/TiO2 system due
to ZnO-doping could be attributed to an effective decrease in
the crystallite size of its constituents and creation of new pores
as being claimed in case of ZnO-doped CuO/Al2 O3 [30] and
Co3 O4 /Al2 O3 [31] systems. The observed decrease in the crystallite size of both CuO and TiO2 due to ZnO-doping of the
system investigated might be attributed to the well known role
of ZnO in coating the surfaces of grains of catalysts constituents
that hinders their particle adhesion opposing their grain growth
[32].
-Irradiation of different catalytic systems, viz.
Co3 O4 /Al2 O3 [29], CuO-ZnO/Al2 O3 [33], CuO/MgO [34],
NiO/MgO [35] has been reported to increase their specific
surface areas. The significant increase in the specific surface
areas of these different catalytic systems due to exposure to
different doses of -rays had been discussed by El-Shobaky et

The specific surface areas of CuO/TiO2 system as being influenced by calcination temperature, ZnO-doping and -irradiation
were determined from nitrogen adsorption isotherms measured
at 196 C. These isotherms, not given, belong to type II of
Brunauers classification showing hystersis loops of different
shapes and areas closing at p/po = 0.3. The computed BETsurface areas of different adsorbents are given in Table 2. This
table shows that: (i) ZnO-doping of the system investigated followed by heating at 400 and 600 C resulted in a measurable
increase the specific surface areas. The maximum increase in
the SBET due to ZnO-doping attained 13 and 42% for the solids
calcined at 400 and 600 C, respectively. (ii) -Irradiation of
CuO/TiO2 system resulted also in a measurable increase in its
specific surface area. The maximum increase in the SBET due
to exposure to a dose of 1.6 MGy attained 22 and 60% for the
solids precalcined at 400 and 600 C, respectively.
ZnO-doping of CuO/Al2 O3 [30], Co3 O4 /Al2 O3 [31] had
been reported to increase their specific surface areas to an
extent proportional to the amount of dopant added (zinc dopant

Table 2
Specific surface areas of different treated solids calcined at 400 and 600 C
Dopant concentration (mol% ZnO)

Calcination temperature ( C)

SBET (m2 /g)

0.0
1.0
2.0
4.0
6.0

400
400
400
400
400

135
140
145
149
153

0.0
1.0
2.0
4.0
6.0

600
600
600
600
600

60
69
75
81
87

Dose of -rays (MGy)

Calcination temperature ( C)

SBET (m2 /g)

2
2
2
2
2

0.4
0.8
1.6

400
400
400

147 2
156 2
165 2

1
1
1
1
1

0.4
0.8
1.6

600
600
600

71 1
83 1
96 1

H.G. El-Shobaky et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 274 (2006) 138144

141

Table 3a
Dependance of catalytic activity of CuO/TiO2 system precalcined at 400 C on reaction temperature and dose of -rays in ethanol and isopropanol conversion
reactions
Dose of -rays (MGy)

0.0
0.4
0.8
1.6

Ethanol conversion (%) for the reaction carried out at

different temperatures ( C)

Isopropanol conversion (%) for the reaction carried out at

different temperatures ( C)

250

300

325

350

375

400

250

300

325

350

375

400

9
10
12
15

56
59
55
75

67
69
58
76

73
74
60
79

88
76
62
82

89
88
71
86

4
4
2
6

12
12
3
1.6

29
22
22
30

44
35
32
45

63
39
34
61

70
48
34
75

al. [3336]. The observed increase in the SBET of these systems

had been explained in terms of: (i) fragmentation of catalysts
constituents; (ii) creation of new pores; (iii) removal of surface
contaminants as adsorbed oxygen or hydroxyl groups [3336].
It has been also reported that a dose of 0.8 MGy causes the
hydrolytic decomposition of more than 80% of the total surface
acidity of -Al2 O3 [36]. The effective decrease in crystallite
size of both CuO and TiO2 phases due to -irradiation (cf.
Tables 1 and 2) might account for the observed increase in the
SBET of CuO/TiO2 system exposed to different doses of -rays.
However, one cannot overlook the contribution of possible
creation of new pores and removal of surface OH groups in
increasing the specific surface areas of -irradiated CuO/TiO2
system.
The observed increase in the SBET of the system investigated
due to ZnO-doping or -irradiation are expected to modify its
activity.
3.3. Catalytic activity of different CuO/TiO2 catalysts
The catalytic activity of pure and ZnO-doped CuO/TiO2 was
investigated using ethanol and isopropanol conversion at temperatures within 250400 and 300400 C for solids precalcined
at 400 and 600 C, respectively.
Preliminary experiments showed that TiO2 calcined at 400 C
showed a measurable catalytic activity in ethanol and isopropanol conversion reactions and acted as dehydration catalyst.
However, TiO2 sample preheated at 600 C completely lost its
catalytic activity in alcohols conversion. So, in CuO/TiO2 system preheated at 600 C titania plays the role of catalyst support.
The catalytic conversion of ethanol and isopropanol was conducted over pure and, ZnO-doped and -irradiated CuO/TiO2
precalcined at 400 and 600 C. The results showed that all

solids investigated precalcined at 400 C exhibited high catalytic

activity in ethanol and isopropanol conversion reactions which
proceed via dehydration yielding ethane and propene, respectively.
Table 3a includes the total conversion of both alcohols carried
out at 250400 C over variously irradiated CuO/TiO2 system
precalcined at 400 C. This table shows that -irradiation of the
system investigated up to 0.8 MGy resulted in a measurable progressive decrease in the percentage conversion of isopropanol
for the reaction carried out at 300 C. The catalyst retained its
initial activity upon increasing the irradiation dose to 1.6 MGy.
Similar results have been reported in case of Co3 O4 / MgO [37],
CuO/MgO [38], Co3 O4 /Al2 O3 [29] and -Al2 O3 [39] systems.
These results have been attributed to an effective removal of
surface OH groups due to -irradiation up to 0.8 MGy, which
removed almost completely these groups, which contribute in
dehydration of isopropanol. The attainment of the initial catalytic activity upon exposure to a dose of 1.6 MGy has been
attributed to the creation of surface OH groups due to interaction
between the catalyst sample and water liberated during the early
stages of dehydration reaction [3739]. It can be seen also from
Table 3a that -irradiation of CuO/TiO2 system precalcined at
400 C led to a limited change in the percentage conversion of
ethanol, especially when the catalytic reaction was carried out
325 C.
The effect of ZnO-doping on the catalytic activity (percentage
conversion) of the system investigated in dehydration of ethanol
and isopropanol carried out 300400 C over various solids precalcined at 400 C was investigated and the results obtained
are given in Table 3b. This table shows clearly that the doping
process did not much affect the catalytic activity of CuO/TiO2
system in dehydration of ethanol and isopropanol carried out at
<350 C. A small increase in the catalytic activity was, however,

Table 3b
Dependance of catalytic activity (% conversion) of CuO/TiO2 system precalcined at 400 C on reaction temperature and amount of ZnO dopant in ethanol and
isopropanol conversion reactions
Dopant concentration (mol% ZnO)

0.0
1.0
2.0
4.0
6.0

Ethanol conversion (%) for the reaction carried out at

different temperatures ( C)

Isopropanol conversion (%) for the reaction carried out at

different temperatures ( C)

300

325

350

375

400

300

325

350

375

400

56
58
58
65
72

56
59
55
73
77

73
73
79
81
83

88
90
85
89
89

89
95
93
93
94

12
13
15
17
20

29
29
28
29
30

44
45
50
52
58

63
65
71
73
75

70
74
75
78
82

142

H.G. El-Shobaky et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 274 (2006) 138144

Fig. 1. Variation of total conversion of ethanol as a function of reaction temperature for the reaction conducted over pure and doped solids calcined at 600 C.

Fig. 2. Variation of total conversion of isopropanol as a function of reaction

temperature for the reaction conducted over pure and doped solids calcined at
600 C.

observed for reaction carried out at <350 C. This increase may

be directly related to the resulting decrease in the crystallite size
of catalysts constituents with subsequent increase in the specific
surface area of CuO/TiO2 (cf. Tables 1 and 2).
The effect of -irradiation and ZnO-doping of CuO/TiO2
system calcined at 600 C on its catalytic activity in alcohols
conversion was also investigated. The results obtained are graphically illustrated in Figs. 14.

Fig. 3. Variation of total conversion of ethanol as a function of reaction temperature for the reaction conducted over variously irradiated solids precalcined at
600 C.

Fig. 4. Variation of total conversion of isopropanol as a function of reaction temperature for the reaction conducted over variously irradiated solids precalcined
at 600 C.

Fig. 1 depicts the variation of total conversion of ethanol as a

function of reaction temperature for pure and variously ZnOdoped solids precalcined at 600 C. It is shown from Fig. 1
that ZnO doping of CuO/TiO2 system followed by heating at
600 C resulted in a progressive increase in its catalytic activity to an extent proportional to the amount of dopant added.
The maximum increase in the catalytic activity, in ethanol conversion due to doping with 6 ml% ZnO attained 53 and 40%
for the reaction carried out at 350 and 400 C, respectively.
Fig. 2 illustrates the variation of total conversion of isopropanol
conversion as a function of reaction temperature for pure and
different ZnO-doped solids precalcined at 600 C. Similar to
ethanol conversion, ZnO-doping of the system investigated
much increased its catalytic activity in isopropanol conversion. The maximum increase in the catalytic activity, towards
isopropanol conversion due to doping with 6 mol% reached
150% and 130% for the reaction carried out at 375 and 400 C,
respectively.
The observed increase in the catalytic activity of CuO/TiO2
due to ZnO-doping can be directly attributed to the effective
increase in the concentration of active sites involved in the catalytic reactions via decreasing the crystallite size of CuO and
TiO2 phases (cf. Table 1). Similar results have been reported
[29] in case of Co3 O4 /Al2 O3 system doped with ZnO in ethanol
and isopropanol conversion. It has been also reported that ZnOdoping of CuO/Al2 O3 system precalcined at 600 C increased
the degree of dispersion of CuO phase via decreasing its crystallite size [25]. The same effect has been found in case of
ZnO-doped CoO/Al2 O3 [40,42].
Figs. 3 and 4 illustrate the variation of percentage conversion
of ethanol and isopropanol by the reaction temperature and dose
of -rays for the catalytic reaction carried out over CuO/TiO2
system precalcined at 600 C. It is clearly shown from these
figures that exposure of the system investigated to a dose of
0.4 MGy of -rays brought about a considerable increase in its
catalytic activity in dehydration of ethanol and isopropanol. This
increase amounts several folds the activity of unirradiated catalyst sample. Figs. 3 and 4 also show that increasing the dose of
-rays up to 0.8 MGy resulted in a measurable decrease in the

H.G. El-Shobaky et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 274 (2006) 138144

catalytic activity of the treated catalysts, in alcohols conversion,

but still remained bigger than that of the unirradiated solids.
These solids retained their considerably high catalytic activity
upon exposure to a dose of 1.6 MGy.
It has been reported that -irradiation (up to 0.8 MGy) of a
big variety of solids decreased their catalytic activities in ethanol
and isopropanol conversion. These solids include Co3 O4 /Al2 O3
[29], CuO/Al2 O3 [42], CuO/MgO [38] and Al2 O3 [39]. The
observed decrease in the catalytic activities of these catalytic systems due to exposure to -rays 0.8 MGy had been attributed to
an effective removal of most of surface Bronsted OH groups by
irradiation. These surface groups acts as active sites for dehydration of alcohols the removal of which decrease drastically
the concentration of the surface sites involved in dehydration
process [38,41,37]. It has been also reported that the previously
mentioned catalytic systems retained their initial catalytic activities in dehydration of ethanol and isopropanol upon exposure to
dose of -rays >0.8 MGy. It was expected that -irradiation of
CuO/TiO2 system might decrease its catalytic activity in dehydration of ethanol and isopropanol similar to the previously published works on other catalytic systems. It seems that the surface
concentration Bronsted OH sites in case of CuO/TiO2 system
precalcined at 600 C showed minimum value that could not
be much reduced by exposure to -irradiation and the observed
increase in dehydration activity could be tentatively discussed
in terms of: (i) the effective decrease in the crystallite size catalysts constituents (CuO and TiO2 phases); (ii) the possible
transformation of Lewis acid sites and Bronsted acidity by the
action of water molecules librated from an early dehydration
of ethanol and isopropanol on the 0.4 MGy-irradiated catalyst
samples. The drastic decrease found in dehydration activity of
CuO/TiO2 solid by increasing the dose up to 0.8 MGy might
be attributed to an effective removal of the Bronsted acidity
created.
4. Conclusions
The following are the main conclusions that may be drawn
from the results obtained:
1- CuO/TiO2 system precalcined at 400 and 600 C consisted of
anatse as major phase besides rutile as minor phase together
with CuO that had a moderate degree of crystallinity.
2- ZnO-doping and -irradiation of the system investigated
brought about a measurable decrease in the crystallite size
of both anatase and CuO phases to an extent proportional to
the amount of dopant added and dose of -rays used. These
treatments led to an increase in the specific surface areas of
various solid adsorbents.
3- Pure and variously treated CuO/TiO2 samples were highly
selective in alcohols conversion which proceeds via dehydration yielding only ethane and propene in case of ethanol
and isopropanol, respectively.
4- The catalytic activities of various solids decreased by increasing their calcination temperature from 400 to 600 C.
5- ZnO-doping followed by calcination at 400 C did not affect
the catalytic activity of the doped solids. While -irradiation

143

of these solids exerted a limited increase in their catalytic

activities.
6- -Irradiation (0.4 MGy) and ZnO-doping of the solid samples precalcined at 600 C increased their catalytic activities.
The increase was, however, more pronounced in case of irradiation.

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