Journal of Radioanalytical and Nuclear Chemistry, Vol. 275, No.

3 (2008) 487495

DOI: 10.1007/s10967-007-7079-1

Effect of gamma-irradiation on surface and catalytic properties of

nanocrystalline CuO, NiO and Fe2O3 supported on alumina
G. A. El-Shobaky,1* M. M. Doheim,2 S. A. Esmail,3 H. A. El-Boohy,3 A. M. Ahmed3
1 National

Research Center (NRC), Dokki, Cairo, Egypt

Petroleum Research Institute (EPRI), Nasr City, Cairo, Egypt
3 National Center for Radiation Research and Technology (NCRRT), Nasr City, Cairo, Egypt
2 Egyptian

(Received April 6, 2007)

The effect of J-irradiation on surface and catalytic properties of CuO/Al2O3, NiO/Al2O3 and Fe2O3/Al2O3 was investigated. The techniques
employed were XRD, nitrogen adsorption at 196 C and catalytic conversion of ethanol and isopropanol at 250400 C using micropulse
technique. The results showed that the supported solids being calcined at 400 C consisted of well crystallized CuO, NiO, Fe2O3 and AlOOH
phases. The AlOOH crystallized into a poorly crystalline J-Al2O3 upon heating at 600 C. All phases present in different solids calcined at 400 and
600 C showed that these solids are of nanocrystalline nature measuring an average crystallite size between 6 and 85 nm. The crystallite size of
crystalline phases present was found to be much affected by the dose of J-rays and the nature of the metal oxide. This treatment resulted in a
progressive increase in the specific surface area reaching to a maximum limit at a dose of 0.8 MGy. The dose of 1.6 MGy exerted a measurable
decrease in the SBET. A radiation dose of 0.2 to 0.8 MGy brought about a progressive significant decrease in the catalytic activity of all the catalytic
systems investigated. All the catalytic systems retained their high activity upon exposure to a dose of 1.6 MGy. The rise in precalcination
temperature of the systems investigated from 400 to 600 C brought about a measurable increase in their catalytic activity in the conversion of
alcohols.

Introduction
Supported transition metals or oxides are commonly
employed to catalyze several reactions including
oxidation-reduction, dehydration, dehydrogenation,
cracking, alkylation, etc.112 The activities and
selectivities for these varieties of solids could be
modified by doping with certain foreign oxides.1319
Ionizing radiations may induce some changes in
textural, surface structural, electric and magnetic
properties of a large variety of solids. Gammairradiation resulted in a decrease in the surface area of
graphite as a result of a progressive blocking of pores as
bulk expansion took place.20 This treatment caused a
significant increase in pore size of steam activated
carbon due to possible radiolytic decomposition of
complexes located on the carbon surface.21 Gammairradiation affected also a decrease in the effective
paramagnetic moment of CuO loaded on Al2O3.10
Gamma-irradiation effected also a significant decrease
in the concentration of surface OH groups on Al2O3support material and CuO/Al2O3 solid.1622
It has been also reported that J-rays led to removal of
chemisorbed oxygen of unloaded Co3O4 and those
loaded on J-Al2O3.5,10,23,24 Furthermore, J-irradiation
effected a progressive decrease in both microstrain and
lattice parameters of Co3O4 crystallites supported on
J-Al2O3 precalcined at 650 C due to removal of excess
oxygen and fragmentation of it crystallites.25 However,
these catalysts undergo deactivation due to the formation
of cobalt aluminate via metal oxide-alumina
interaction.2629

The present work reports the results of an intensive

study on the effects of J-irradiation on physicochemical,
surface and catalytic properties of CuO/Al2O3,
NiO/Al2O3 and Fe2O3/Al2O3 systems. The techniques
employed were XRD, N2 adsorption at 196 C and
conversion of ethanol and isopropanol at 250400 C
using micro pulse technique.
Experimental
Materials
A known mass of finely powdered aluminum
hydroxide was impregnated with a known amount of
copper nitrate or nickel nitrate or ferric nitrate dissolved
in the least amount of doubly distilled water necessary to
make paste. This paste was dried at 120 C to constant
weight and then precalcined at 400, 600 C for 5 hours.
The chemicals employed were of analytical grade and
supplied by the Fluka company.
The nominal compositions of the prepared calcined
mixed solids were 0.2 CuO/Al2O3, 0.2 NiO/Al2O3 and
0.2 Fe2O3/Al2O3. Support samples were prepared by
thermal decomposition of aluminum hydroxide at 400,
600 C for 5 hours. The prepared calcined solids were
exposed to different doses of J-rays namely 0.2, 0.4, 0.8
and 1.6 MGy. The irradiated samples were kept in
sealed tubes for 3 weeks before conducting the different
measurements to avoid any temporary effect that may be
induced by J-irradiation.

* E-mail: elshobaky@yahoo.com
02365731/USD 20.00
2007 Akadmiai Kiad, Budapest

Akadmiai Kiad, Budapest

Springer, Dordrecht

G. A. EL-SHOBAKY et al.: EFFECT OF GAMMA-IRRADIATION ON SURFACE AND CATALYTIC PROPERTIES

Techniques
X-ray diffractograms of different solids calcined at
400, 600 C were carried out using a Bruker
diffractometer (Bruker D8 advance target). The patterns
were run with copper KD with a second monochromator
(O = 1.5405 ) at 40 kV and 40 mA with a scanning
speed of 2 and 0.2 in 2T.min1, for phases
identification and line broadening profile analysis,
respectively. The crystallite size d was estimated using
the Scherrer equation:30
d = k O/B1/2 cos T
where k is the Scherrer constant (0.89), B1/2 is the full
width at half maximum (FWHM) of the main diffraction
line of different phases present, and T is the diffraction
angle of the main line of each phase.
The specific surface areas of the variously prepared
catalyst samples were determined from nitrogen
adsorption isotherms measured at 196 C using a
conventional volumetric apparatus. Before carrying out
such measurements, each sample was degassed under a
reduced pressure of 105 Torr for 2 hours at 200 C.
A Hewlett-Packard 5890 gas chromatograph fitted
with a 30-m HP1 capillary column was used for the
chromatographic studies, inj 200 C, an isothermal oven
temperature of 60 C and an FID 200 C, with the
catalytic conversion of ethanol and isopropanol being
followed using nitrogen free-oxygen as the carrier gas at
a flow rate of 18 ml/min. These catalytic studies were
conducted at temperatures within the range of 250 to
400 C. The ethanol and isopropanol were introduced as
a pulse via a microsyringe, thereby ensuring that only
microquantities of the gaseous vapour (12).103 cm3
were introduced in the form of a pulse over each 50 mg
catalyst sample. The reaction products produced were
transferred directly by the inert carrier gas to the
column.
Results and discussion
XRD investigation of different solids
The X-ray diffractograms of different supported
catalytic systems calcined at 400, 600 C were
determined. The diffractograms of samples exposed to
different doses of J-rays were also determined. The
diffractograms of various solids (not given) showed that
the solids investigated and calcined at 400 C consisted
of well crystallized AlOOH which decomposed
completely by heating at 600 C yielding a poorly
crystalline J-Al2O3.
Examination of the XRD data shows the followings:
(1) The crystalline phases present in solids calcined at
400, 600 C are of nano crystalline nature having
crystallite size varying between 686 nm.
488

(2) Gamma-irradiation resulted in a measurable

change in the crystallite size of different phases. Table 1
summarizes the effects of both calcination temperature
and the dose of J-rays on the crystallite size of different
phases present in various catalytic systems.
(3) It is seen from Table 1 that the rise in the
precalcination temperature of CuO/Al2O3, NiO/Al2O3
and Fe2O3/Al2O3 from 400 to 600 C resulted in a
significant decrease in the crystallite size of CuO, NiO
and D-Fe2O3. This thermal treatment should be normally
accompanied by an increase and not decrease in the
crystallite size of the crystalline phases present. This
expectation arises from an enhanced particle adhesion
processes due to increasing the calcination temperature
from 400 to 600 C. This expectation has not been
verified experimentally (Table 1) this unexpected
behavior could be attributed to the role of the nascently
formed poorly crystalline J-Al2O3 increasing the degree
of dispersion of different transition metal oxides present.
These results showed that AlOOH is devoted with a
dispersion power for various transition metal oxides
smaller than that of a poorly crystalline J-Al2O3.
(4) Exposure of different catalytic systems calcined
at 600 C to J-irradiation (1.6 MGy) resulted in a
measurable increase in the crystallite size of CuO, NiO
and D-Fe2O3.
(5) This treatment, on the other hand, led to a
measurable decrease in the crystallite size of J-Al2O3.
(6) The crystallite size of J-Al2O3 in CuO/Al2O3
calcined at 600 C measured the minimum crystallite
size. It had been reported22 that the J-irradiation of
Co3O4/Al2O3 calcined at 800 C resulted in a significant
decrease in the crystallite size of Co3O4 due to an
energetic fragmentation effect of J-rays. In the present
work opposite effect was observed. It seems that the
nano crystalline nature of CuO, NiO and D-Fe2O3 did
not permit a further decrease in their crystallite size. The
observed significant decrease in the crystallite size of JAl2O3 in Fe2O3/Al2O3 and NiO/Al2O3 precalcined at
600 C due to the exposure of J-rays is expected to be
followed by a measurable increase in the specific surface
areas of different irradiated solids.
Surface areas of different irradiated systems
The specific surface area of bare alumina that has
been used as catalyst's support of the investigated
catalytic systems had been already determined and cited
in ore of the published papers.34 The alumina support
was calcined at 500 C and its SBET measured 234, 236,
263, 290, 295 and 240 m2/g for unirradiated samples and
those exposed to 0.15, 0.3, 0.45, 0.75 and 1.6 MGy,
respectively. The most probable pore radius of the above
mentioned adsorbents measured 2.1, 2.3, 2.45, 2.75,
3.25 and 4.75 nm, respectively.

G. A. EL-SHOBAKY et al.: EFFECT OF GAMMA-IRRADIATION ON SURFACE AND CATALYTIC PROPERTIES

Table 1. Effect of calcination temperature and dose of J-irradiation on crystalline size of

different phases present in various solids
Solids
CuO/Al2O3

Calcination
temperature, C
400
600
600
600

Crystalline phase
present
AlOOH, CuO
Al2O3, CuO
Al2O3, CuO
Al2O3, CuO

Crystallite size,
nm
62, 72
9, 46
6, 48
8, 57

Dose of J-rays,
MGy
0.0
0.0
0.8
1.6

NiO/Al2O3

400
600
600
600

AlOOH, NiO
Al2O3, NiO
Al2O3, NiO
Al2O3, NiO

55, 49
26, 24
13, 57
18, 34

0.0
0.0
0.8
1.6

Fe2O3/Al2O3

400
600
600
600

AlOOH, Fe2O3
Al2O3, Fe2O3
Al2O3, Fe2O3
Al2O3, Fe2O3

85, 47
43, 36
12, 37
11, 45

0.0
0.0
0.8
1.6

The BET-surface areas of NiO/Al2O3, CuO/Al2O3

and Fe2O3/Al2O3 precalcined at 400 and 600 C were
determined from nitrogen adsorption isotherms
conducted at 196 C. The obtained isotherms, not
given, belong to type II of Brunauers classification.31
The different specific surface areas of various
adsorbents were determined from linear BET-plots of
nitrogen adsorption. The investigated adsorbents were
subjected to different doses of J-rays namely 0.2, 0.4,
0.8 and 1.6 MGy. The computed values of SBET for
various adsorbents are given in Table 2. It is clearly
shown from this table that the J-irradiation of 0.2
NiO/Al2O3, 0.2 CuO/Al2O3 and 0.2 Fe2O3/Al2O3
calcined at 400 and 600 C resulted in a progressive
increase in their specific surface areas reaching to a
maximum limit at a dose of 0.8 MGy. Increasing the
dose above this limit brought about a measurable
decrease in the specific surface areas of variously
irradiated solids. These results are very close to those of
bare alumina support exposed to different doses of
J-rays. The maximum increase in the specific surface
areas due to the exposure to a dose of 0.8 MGy attained
28.9%, 27.8% and 21.8 for 0.2 NiO/Al2O3, CuO/Al2O3
and Fe2O3/Al2O3, respectively, precalcined at 400 C,
the percentage increase in the SBET of various solids
precalcined at 600 C due to J-irradiation at 0.8 MGy
was 36.8%, 23% and 30%, respectively.
The effects of J-rays on the specific surface areas of
a big variety of solids had been investigated by
EL-SHOBAKY et al.1318,26 These authors claimed that the
J-irradiation of Co3O4, Co3O4/Al2O3, Co3O4/MgO,
CuO/Al2O3,
CuO/MgO,
NiO/Al2O3,
NiO/MgO,
CuO-ZnO/Al2O3,
Cr2O3/Al2O3,
Fe2O3-Cr2O3/Al2O3,
Fe2O3/Al2O3 and Mn2O3,1318,26 resulted in a measurable
increase in specific surface areas of the previously
mentioned solids. The extent of the increase of the

specific surface areas depends on the nature of irradiated

solids and their calcination condition. The observed
increase in the specific surface areas of different solids
exposed to J-irradiation has been attributed to creation
of new pores and also to splitting of the crystallites of
the irradiated solids. In fact, it has been shown in the
present work in the XRD section that the J-irradiation of
different solids calcined at 400 and 600 C resulted in a
measurable significant decrease in the crystallite size of
their constituting oxides (NiO, CuO, Fe2O3 and Al2O3)
as been shown in Table 1. The measurable decrease in
the SBET of different catalytic systems due to irradiation
at a dose of 1.6 MGy could be attributed to an effective
pore widening as being evidenced from the results of
bare alumina support.34
Catalytic conversion of ethanol and isopropanol
The catalytic conversion of ethanol and isopropanol
was carried out over different catalytic systems
precalcined at 400 and 600 C and subjected to different
doses of J-rays within 0.21.6 MGy.
Tables 3 to 5 include the activities and selectivities
of CuO/Al2O3, NiO/Al2O3 and Fe2O3/Al2O3 calcined at
400 C, respectively. These tables include the
percentage of total conversion for both alcohols and the
selectivity towards dehydration and dehydrogenation as
being influenced by reaction temperature and dose of Jrays.
Figures 1 and 2 depict the effect of reaction
temperature on total conversion of both alcohols carried
out over different solids calcined at 600 C.
Figures 3 to 6 show the effect of reaction
temperature and J-irradiation on the selectivities of
various solids calcined at 600 C towards dehydration
and dehydrogenation of both alcohols.

489

G. A. EL-SHOBAKY et al.: EFFECT OF GAMMA-IRRADIATION ON SURFACE AND CATALYTIC PROPERTIES

Table 2. Specific surface areas of different solids

Solid
0.2 NiO/Al2O3

Calcination
temperature, C
400

600

0.2 CuO/Al2O3

400

600

0.2 Fe2O3/Al2O3

400

600

Dose of J-rays,
MGy
0.0
0.2
0.4
0.8
1.6
0.0
0.2
0.4
0.8
1.6
0.0
0.2
0.4
0.8
1.6
0.0
0.2
0.4
0.8
1.6
0.0
0.2
0.4
0.8
1.6
0.0
0.2
0.4
0.8
1.6

SBET,
m2/g
225
265
275
290
230
190
228
240
260
195
228
263
275
290
237
195
205
215
240
180
238
252
275
290
240
210
285
253
273
203

Examination of Tables 3 to 5 and Figs 1 to 6 shows

the followings: (1) The catalytic activity of various
systems, expressed as total conversion decreases
progressively by increasing the dose of J-rays falling to
a minimum value at a dose of 0.8 MGy.
(2) All catalysts retained their initial high catalytic
activity upon exposure to a dose of 1.6 MGy.
(3) All investigated catalytic systems are highly
selective towards dehydration of ethanol and
isopropanol yielding ethene and propene, respectively.
The dehydrogenation selectivity which is quite smaller
than that of the dehydration selectivity increases
progressively by increasing the reaction temperature.
(4) The rise, in precalcination temperature of all
catalysts investigated from 400 to 600 C brought about
a significant increase in their catalytic activity.
(5) The comparison between the catalytic activities
of various systems calcined at 400 and 600 C in
dehydration and dehydrogenation of ethanol and
isopropanol vary according to the sequence
NiO/Al2O3CuO/Al2O3>Fe2O3/Al2O3. This sequence
turned to CuO/Al2O3>NiO/Al2O3>Fe2O3/Al2O3 for
isopropanol conversion carried out over various
catalysts calcined at 400 C.

490

(6) All investigated solids calcined at 600 C showed

high and comparable activity in alcohols conversion.
The observed measurable increase in the catalytic
activity of various systems upon increasing their
calcination temperature from 400 to 600 C can be
discussed in terms of the following parameters: (a)
conversion of AlOOH into poorly crystallized J-Al2O3;
(b) an effective decrease in the crystallite size of NiO,
CuO and Fe2O3; (c) the decrease in the specific surface
areas of different catalytic systems; (d) the possible
decrease in surface OH groups.
Parameters (c) and (d) are normally accompanied by
a decrease in the catalytic activities of the systems
investigated due to increasing their calcination
temperature from 400 to 600 C. While parameters (a)
and (b) should increase the catalytic activities of
different systems. The fact that the catalytic activity of
various solids were found to increase by increasing the
calcination temperature from 400 to 600 C points out
that parameters (a) and (b) dominante and counteract the
other two parameters.
The observed significant decrease in the catalytic
activity of various systems investigated due to treating
with J-rays from 0.20.8 MGy could be attributed to an
effective decrease in the concentration of Brnsted
acidity (surface OH groups) acting as catalytically active
sites. This treatment, however, brought about an
effective increase in the specific surface area of all
systems investigated. So, the induced effects of
J-irradiation were operating against each other.
However, the role of decreasing the concentration of the
surface OH groups was dominant.
All investigated catalysts gained their initial high
activities upon exposure to a dose of 1.6 MGy. This
finding had been attributed to the reaction of water
molecules liberated in the early stage of the dehydration
reaction of alcohols with the surface of the treated solids
yielding OH groups, which retained on the catalyst
surface.1318 This phenomenon did not take place in the
case of catalysts exposed to doses smaller than 0.8 MGy.
Simply because a dose of 0.8 MGy removed more than
80% of surface OH groups in different solids.34 This
situation favored the creation of these surface OH
groups via an interaction between the liberated water
molecules with the irradiated catalyst surfaces.
Similar results have been reported by EL-SHOBAKY
et al. for the conversion of ethanol and isopropanol
carried out over CuO/MgO, Na2OMn2O3/Al2O3,
Co3O4/Al2O3, ZnOCo3O4/Al2O3, Co3O4/MgO, NiO
Co3O4, CeO2/NiO/Al2O3 and manganese oxides
systems.1318,26,3234

G. A. EL-SHOBAKY et al.: EFFECT OF GAMMA-IRRADIATION ON SURFACE AND CATALYTIC PROPERTIES

Table 3. Total conversion (activity) and selectivities of alcohols over unirradiated and various J-irradiated
CuO/Al2O3 solid catalysts precalcined at 400 C
Dose, MGy

Temperature, C

0.0

250
300
325
350
375
400
250
300
325
350
375
400
250
300
325
350
375
400
250
300
325
350
375
400
250
300
325
350
375
400

0.2

0.4

0.8

1.6

TC
5
25.6
60.9
70.2
77.9
85.9
3.2
15.2
38.2
42.6
55.2
60.2
2.1
9.1
30.2
32.1
39.5
43.6
0
4
6.1
8.1
6.3
11.1
4.3
24.5
60.1
69.1
76.2
84.2

Ethanol
S1
100
18.5
7.4
2.6
1.5
0.9
100
19.7
7.1
5.9
3.8
0
100
20.9
5.6
4.7
3
1.8
0
100
57.4
39.5
20.6
10.8
100
15.5
5.5
4.3
3.7
3.1

S2
0
81.5
92.6
92.6
95.3
96.3
0
80.3
42.9
94
96
97.7
0
79.1
94.4
95
95.9
97.7
0
0
42.6
56.8
74.6
85.6
0
84.5
94.5
95.5
93.8
94.6

TC
18.2
89.6
94.5
95.1
97.4
98.7
8.9
55.5
61.2
65.1
66.4
68.7
5.8
32.5
33.5
38.7
39.9
42.5
2.1
9.8
11.2
13.8
16.8
19.7
16.5
87.5
94.1
94.5
96.5
97.9

Isopropanol
S1
100
16
13
11
7.3
5.6
100
9.2
7.7
3.4
2.0
0.70
100
87.4
80.2
73.4
70
62.4
100
19.4
10.7
8
2.4
0.5
97.6
16.2
12.9
10.7
5.9
4.2

S2
0
83
87
88.3
89.4
90.3
0
90
91
93
94.8
96
0
12
17.6
20.7
27.8
35.4
0
80.6
88.3
90.6
95.2
95.9
2.4
83.8
87.1
88.9
92.2
92.9

TC: Total conversion.

S1: Selectivity towards dehydration.
S2: Selectivity towards dehydrogenation.

Fig. 1. Effect of reaction temperature and J-irradiation on ethanol total conversion of over various catalysts precalcined at 600 C

491

G. A. EL-SHOBAKY et al.: EFFECT OF GAMMA-IRRADIATION ON SURFACE AND CATALYTIC PROPERTIES

Fig. 2. Effect of reaction temperature and J-irradiation on isopropanol total conversion of over various catalysts precalcined at 600 C

Table 4. Total conversion (activity) and selectivities of alcohols over unirradiated and various J-irradiated
NiO/Al2O3 solid catalysts precalcined at 400 C
Dose, MGy

Temperature, C

0.0

250
300
325
350
375
400
250
300
325
350
375
400
250
300
325
350
375
400
250
300
325
350
375
400
250
300
325
350
375
400

0.2

0.4

0.8

1.6

TC: Total conversion.

S1: Selectivity towards dehydration.
S2: Selectivity towards dehydrogenation.

492

TC
10.5
69.5
73.6
75.8
98.9
99.9
6.1
42.1
50.4
55.6
60.2
62.2
4.2
32.4
38.1
42.9
48.2
51.5
0
3.4
7.2
11.2
13.5
15.8
10.1
68.1
72.1
73.6
77.2
78.4

Ethanol
S1
89.5
11.9
10.2
8
5.3
1.9
100
14
8.2
6.5
3
0.2
98
11.7
6.8
5.3
2.5
1
0
100
44.4
27.7
21.5
10.1
100
14.4
13.2
11
9.3
5.4

S2
10.5
88.1
89.8
91.1
92.9
93.5
0
86
91.7
93.7
96.3
96.6
1.4
88.3
93.2
93.5
94.8
95.5
0
0
55.6
66.6
75.6
86.1
0
85.6
86.8
87.2
88.5
89.4

TC
10.5
69.6
73.8
75.9
98.9
99.1
5.2
32.5
36.1
40.2
41.5
44.1
2.1
19.5
22.3
25.8
27.8
30.1
0
2.1
3.5
5.8
6.7
8.9
9.5
58.8
71.8
74.1
77.5
78.7

Isopropanol
S1
100
14.7
13.3
11.7
6.5
4
96.2
14.8
11.9
9.7
1.2
0
100
9.2
5.8
3.1
1.8
0
0
100
51.4
20.7
11.9
0
89.5
13.9
9.3
7
6.2
4.7

S2
0
85.3
86.7
87
87.7
88.6
3.8
85.2
88.1
89.8
96.7
97.6
0
90.8
94.2
94.6
95.3
95.7
0
0
48.6
77.6
85.1
94.4
10.5
86.1
90.5
90.6
91.5
91.9

G. A. EL-SHOBAKY et al.: EFFECT OF GAMMA-IRRADIATION ON SURFACE AND CATALYTIC PROPERTIES

Table 5. Total conversion (activity) and selectivities of alcohols over unirradiated and various J-irradiated Fe2O3/Al2O3
solid catalysts precalcined at 400 C
Dose, MGy

Temperature, C

0.0

250
300
325
350
375
400
250
300
325
350
375
400
250
300
325
350
375
400
250
300
325
350
375
400
250
300
325
350
375
400

0.2

0.4

0.8

1.6

TC
8.1
35.4
46.7
55.7
57.4
60.3
5.2
25.3
32.8
40.2
43.8
45.2
4.1
15.5
19.5
24.8
30.2
32.7
3.1
5.4
6.7
8.2
10.5
12.3
7.1
34.1
46.1
54.2
57.2
60.1

Ethanol
S1
99
22
15.6
11.1
9.4
6.8
96.2
19.4
14.3
10.2
8.4
0
100
25.2
18
12.5
9.3
5.8
100
89.6
87.8
79.1
68
59
100
14.9
2.9
1.7
0.9
0

S2
1
77.9
84.5
89
88.2
91.2
3.8
80.6
85.7
86.3
87.7
94
0
75
82.1
85.1
87.4
89
0
10
11.2
14.6
20.4
36
0
84.1
97.1
98
95.6
96.7

TC
5.2
20.6
57.3
67.8
70.2
75.1
2.3
11.2
30.2
39.5
42.1
46.9
0
6.3
19.8
23.5
26.9
29.9
0
2.3
4.5
6.5
7.8
9.1
4.5
20.1
55.7
67.1
69.2
73

Isopropanol
S1
94.2
20.9
7.1
4.6
3.4
2.8
100
18.8
6
3
1.9
0
0
95.2
28.8
21.7
16.7
12.7
0
87
40
24.6
15.4
9.9
91.1
18.4
5.7
4.5
3.6
2.6

S2
5.2
79.1
93
94.2
95.4
96.4
0
81.3
84
96.2
96.7
97
0
4.8
71.2
72.8
79.9
82.6
0
13
60
72.3
80.8
86.8
8.9
81.6
94.3
94.6
95.5
95.8

TC: Total conversion.

S1: Selectivity towards dehydration.
S2: Selectivity towards dehydrogenation.

Fig. 3. Effect of reaction temperature and J-irradiation on the dehydration of ethanol on various catalysts precalcined at 600 C

493

G. A. EL-SHOBAKY et al.: EFFECT OF GAMMA-IRRADIATION ON SURFACE AND CATALYTIC PROPERTIES

Fig. 4. Effect of reaction temperature and J-irradiation on the dehydrogenation of ethanol on various catalysts precalcined at 600 C

Fig. 5. Effect of reaction temperature and J-irradiation on the dehydration of isopropanol on various catalysts precalcined at 600 C

Fig. 6. Effect of reaction temperature and J-irradiation on the dehydrogenation of isopropanol on various catalysts precalcined at 600 C

Conclusions
The followings are the main conclusions that may be
drawn from the results obtained.
CuO/Al2O3, NiO/Al2O3 and Fe2O3/Al2O3 prepared
by imprignation method and calcined at 400 and 600 C
are nanocrystalline solids measuring particle size
varying between 6 and 85 nm.
The transition metal oxides loaded on aluminium
substrate consisted of well crystallized metal oxides and
a mixture of aluminum oxihydroxide and a poorly
crystalline J-Al2O3.
Increasing the calcination temperature of various
catalytic systems from 400 to 600 C brought about a
measurable decrease in the crystallite size of the CuO,

494

NiO and Fe2O3 and the conversion of AlOOH into a

poorly crystalline J-Al2O3.
Gamma-irradiation changed the crystallite size of
different catalysts constituents. The change is dependent
of the dose of J-rays and the nature of the oxide.
The specific surface areas of different catalytic
systems were found to increase by increasing the dose of
J-rays reaching to a maximum limit at a dose of
0.8 MGy.
The different catalytic systems calcined at 400 and
600 C were highly selective towards dehydration of
alcohols especially for the reaction carried out at a
temperature below 300 C.
The catalytic activities of different solids
investigated much increase by increasing their
calcination temperature from 400 to 600 C.

G. A. EL-SHOBAKY et al.: EFFECT OF GAMMA-IRRADIATION ON SURFACE AND CATALYTIC PROPERTIES

Gamma-irradiation led to a progressive decrease in

the catalytic activity of different solids falling to
minimum values at a dose of 0.8 MGy.
All catalysts investigated retained their initial highly
activity upon exposure to a dose of 1.6 MGy.
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