Journal of Radioanalytical and Nuclear Chemistry, Vol. 254, No.

1 (2002) 151158

Effect of gamma-irradiation on surface and catalytic properties

of Co3O4 and NiO catalysts
H. G. El-Shobaky,1* A. El-Mohsen M. Turky2
2

1
Chemistry Department, Faculty of Science, Cairo University, Cairo, Egypt
Chemistry Department, Faculty of Science, Suez Canal University, Ismailia, Egypt

(Received January 30, 2002)

The effects of -irradiation (0.21.6 MGy) on the particle size, specific surface area and catalytic activity of Co3O4 and NiO solids were
investigated. The investigated solids were prepared by heat treatment of cobalt carbonate at 500 and 700 C and basic nickel carbonate at 400 C.
The techniques employed were XRD, nitrogen adsorption at 196 C and decomposition of H2O2 at 3050 C. The results showed that irradiation resulted in a small decrease in the particle size of the investigated solids and effected a progressive increase in their specific surface
areas. On the other hand, the exposure of Co3O4 and NiO catalysts to a dose of 0.2 MGy resulted in a significant decrease in their catalytic
activities, which suffered further progressive decrease upon increasing the doses up to 1.6 MGy. Gamma-irradiation did not modify the activation
energy of the catalyzed reaction but decreased the concentration of catalytically active sites without changing their energetic nature. These results
were discussed in terms of splitting of the particles of the treated solids and removal of chemisorbed species present in nonstoichiometric cobalt
and nickel oxides.

Introduction
Ionizing radiations may induce some changes in
textural, structural, electric, thermal and magnetic
properties of a large variety of solids.114 These changes
are commonly accompanied by modification in surface,
chemisorptive and catalytic properties of the irradiated
solids.38,1530 Gamma-irradiation has been reported to
cause both an increase and a decrease in the specific
surface areas and the catalytic activities of certain
catalytic systems depending on the nature of the
irradiated solid, the dose of -rays and the nature of
catalyzed reactions. Gamma-irradiation of Pd, Pt-Pd and
Rh catalysts supported on Al2O3 greatly increased
(twofold) their catalytic activities in the hydrogenation of
aromatic unsaturated compounds without changing the
activation energies of the catalytic reactions.16,17,31
Also, -irradiation of Co3O4, Co3O4/Al2O3, CuO/Al2O3,
CuO-ZnO/Al2O3, Cr2O3/Al2O3 solids resulted in a
significant increase in their catalytic activities towards
CO oxidation by O2.11,21,2527,31 Gamma-irradiation of
Al2O3, CuO/Al2O3 and CuO/MgO systems brought
about a significant decrease in their catalytic activities in
alcohol dehydration falling to minimum values at
0.8 MGy then retained their initial activities upon
exposure to 1.6 MGy of -rays.22,29,30,33 Also, irradiation of CuO-ZnO/Al2O3 solids led to a
progressive significant decrease in their catalytic
activities in H2O2 decomposition.34
The present work was devoted to study the effects of
-irradiation on the surface and catalytic properties of
unloaded NiO and Co3O4 precalcined at different

temperatures.The techniques employed were XRD,

nitrogen adsorption studied at 196 C and the catalytic
decomposition of H2O2 at 3050 C.
Experimental
Materials
Co3O4 samples were prepared by thermal
decomposition of cobalt carbonate by heating in air at
500 and 700 C for 5 hours. Nickel oxide sample was
prepared by heat treatment of basic nickel carbonate
2Ni(CO3), 3Ni (OH)2.4H2O in air at 400 C for 5 hours.
The cobalt carbonate and basic nickel carbonate used
were of analytical grade as supplied by Aldrich. The
obtained Co3O4 and NiO solid samples were exposed to
different doses of -rays, of 0.2, 0.4, 0.8 and 1.6 MGy.
The irradiated solids were kept in sealed glass tubes for
3 weeks before carrying out the measurements.
Techniques
X-ray investigation was carried out on un-irradiated
samples of NiO 400 C, Co3O4 500 C and Co3O4
700 C and those treated with 0.8 and 1.6 MGy of -rays
using a Shimadzu diffractometer type (D-D1). The
patterns were run with nickel-filtered copper radiation
( = 1.5405 ) at 40 kV and 30 mA with a scanning
speed of 8 in 2/min.
The specific surface areas of the various samples
were obtained from nitrogen adsorption isotherms
measured at 196 C using a conventional volumetric
apparatus. Before undertaking such measurements, each
sample was degassed under a reduced pressure of 105
Torr for 2 hours at 200 C.

* Author for correspondence.

02365731/2002/USD 17.00
2002 Akadmiai Kiad, Budapest

Akadmiai Kiad, Budapest

Kluwer Academic Publishers, Dordrecht

H. G. EL-SHOBAKY, A. EL-MOHSEN M. TURKY: EFFECT OF GAMMA-IRRADIATION

The catalytic activities of the various samples were

determined by studying the decomposition of H2O2 in
their presence at 30, 40 and 50 C, respectively, using
0.5 ml volume of H2O2 of known concentration diluted
to 10 ml with distilled water. The mass of catalyst
sample taken in each kinetic run was 50 mg for Co3O4
samples precalcined at 500 C and 200 mg for NiO
specimens preheated at 400 C and cobalt oxide samples
precalcined at 700 C. The reaction kinetics were
monitored by measuring the volume of oxygen liberated
at different time intervals until equilibrium was attained.
Results and discussion

difference could be due to the nature of the two solids

and also to the big difference between the particle size of
both phases present in the un-irradiated samples. In fact,
the particle size of Co3O4 phase is about 2-fold that of
NiO phase, thereby the bigger is the size of irradiated
crystallites the easier is their splitting or fragmentation
into smaller crystallites. It has been reported11,13,14 that
-irradiation of Co3O4/Al2O3 precalcined at 650 C and
NiO at 400 C brought about a progressive decrease in
microstrain and lattice defects (Co3+ and Ni3+ ions) in
Co3O4 and NiO solids with subsequent increase in their
lattice parameters. The resulting decrease in residual
microstrain due to exposure to -rays is related to
splitting of Co3O4 and NiO crystallites.

XRD investigation of irradiated catalysts

The X-ray diffractograms of the thermal products of
cobalt carbonate precalcined at 500 and 700 C
exhibited all the diffraction lines associated with the
Co3O4 phase. The intensities of the diffraction lines
increased by increasing the precalcination temperature
from 500 to 700 C due to an increase in the particle size
of Co3O4 phase. The diffractograms of Co3O4 samples
precalcined at 500 an 700 C and being treated with 0.8
and 1.6 MGy -rays were also determined. These
diffractograms were similar to those of the un-irradiated
solids in exhibiting all diffraction lines of Co3O4 phase
but differed in the relative intensities (I/I0) and the
full-width-half-maximum
(FWHM).
The
X-ray
diffractograms of the un-irradiated NiO 400 C
samples and those treated with 0.8 and 1.6 MGy of
-rays consisted of all diffraction lines of NiO phase.
The I/I0 and FWHM of the lines of unirradiated sample
were different from those measured for the lines of the
irradiated samples.
The particle sizes of Co3O4 and NiO phases were
calculated for different solids investigated using Scherer
equation.35
d = B / cos
where d, B, , and are the particle diameter, in , of
the crystalline phase, Scherer constant (0.89),
wavelength of X-ray beam (1.5405 ), full-width-halfmaximum (FWHM) of the main diffraction line of the
investigated phase and its diffraction angle, respectively.
The computed values of particle diameter of unirradiated and -irradiated NiO and Co3O4 phases are
given in Table 1. It is seen from the table that
-irradiation of Co3O4 and NiO solids precalcined at 500
and 400 C, respectively, resulted in a decrease in the
particle size of Co3O4 and NiO phases. The decrease
was, however, more pronounced for Co3O4 phase. The
exposure of Co3O4 and NiO solids to 1.6 MGy of -rays
resulted in a decrease of 27% and 13% in the particle
size of Co3O4 and NiO phases, respectively. This

152

Effect of -irradiation on specific surface areas

of Co3O4 and NiO solids
The specific surface areas of Co3O4 precalcined at
500, 700 C and NiO precalcined at 400 C and
subjected to different doses of -rays between 0.2 and
1.6 MGy were determined from nitrogen adsorption
isotherms conducted at 196 C. The calculated BETsurface areas are given in Table 1. It is seen from the
table that the SBET of both NiO and Co3O4 solids
increases by increasing the dose of -rays. Similar results
have been reported for NiO precalcined at 300 C13 CuO
preheated at 300 C 36CuO-ZnO/Al2O3 600 C,25
Fe2O3-Cr2O3/Al2O3 700 C,28 Co3O4/Al2O3
650 C,11 Al2O3 500 C30 and CuO/MgO precalcined
at 400 C.29 Opposite effects have been reported in the
case of graphite,37 steam-activated carbons,20
CuO/Al2O3 300 C21 and Fe2O3/Al2O3 400 C.24
However, -rays exerted no measurable effect on the
SBET of Mn2O3/Al2O3 preheated at 700 C.22 The
induced changes in the surface characteristics of solids
due to -irradiation could be attributed to splitting of
their crystallites,13,14,19 desorption of chemisorbed
oxygen,8,15 removal of surface hydroxyl groups,30 pore
wall erosion,37 radiolytic decomposition of oxygen
complexes located on the solid surface (carbon)19,38 and
progressive blocking of pores as bulk expansion took
place.37 The observed progressive increase in the SBET
of NiO 400 C which attained about 22% upon
treatment with 1.6 MGy of -rays could result mainly
from desorption of chemisorbed oxygen present in nonstoichiometric NiO with subsequent transformation of
some of Ni3+ ions into Ni2+ ions.39 The increase in the
specific surface area of Co3O4 500 C due to treatment
with -rays (about 22%) could be attributed to both an
effective splitting of its crystallites and desorption of
chemisorbed oxygen present in non-stoichiometric
Co3O4.40 This process is normally accompanied by
conversion of some of Co3+ ions (lattice defects) into
Co2+ ions with subsequent expansion of Co3O4 lattice.11

H. G. EL-SHOBAKY, A. EL-MOHSEN M. TURKY: EFFECT OF GAMMA-IRRADIATION

Table 1. Changes in specific surface areas and particle size of the various solids upon gamma-irradiation
Solid

Calcination
temperature C

Dose of -rays,
MGy

SBET,
m2/g

NiO

400
400
400
400
400

0.0
0.2
0.4
0.8
1.6

61.9
62.3
63.0
64.9
75.4

114
110
109
106
99

Co3O4

500
500
500
500
500

0.0
0.2
0.4
0.8
1.6

37.4
38.7
39.9
43.1
45.5

215
210
200
195
156

Co3O4

700
700
700
700
700

0.0
0.2
0.4
0.8
1.6

12.5
14.7
19.1
27.3
36.8

320
305
293
280
270

The considerable increase in the SBET of Co3O4

700 C due to irradiation with -rays which attained
about 190% upon exposure to 1.6 MGy could be
attributed to an effective increase in the internal surface
area of the treated solid via creation of new pores.
The observed increase in the BET-surface areas of
Co3O4 and NiO solids due to -irradiation, the decrease
in their particle size and desorption of chemisorbed
oxygen are expected to be accompanied by significant
changes in their catalytic activities.

Particle size,

the effects of -irradiation of Co3O4 and NiO catalysts

on their catalytic activities can be investigated by
comparing the values of k measured at different
temperatures over the various solids. Thus, Fig. 4 shows
the variation of k as a function of the dose of -rays for
the reaction carried out at 30 C over Co3O4 500 C,
Co3O4 700 C and NiO 400 C. This figure shows
that the exposure of the solids even to the smallest
dose of -rays (0.2 MGy) resulted in a significant
decrease in their catalytic activities, which decreased
progressively by increasing the dose up to 1.6 MGy.

Effect of -irradiation on the catalytic activities

of Co3O4 and NiO solids
The effect of exposure of Co3O4 and NiO catalysts to
different doses of -rays on their catalytic activities was
investigated by following up the kinetics of H2O2
decomposition in their presence by measuring the
volume of oxygen liberated at different time intervals
until equilibrium was attained. The catalytic reaction was
carried out at 30, 40 and 50 C, respectively. The results
obtained showed that the reaction followed first-order
kinetics in all cases. The slopes of the first-order plots
allowed the determination of the reaction rate constant,
k, measured at a given temperature over a given catalyst.
Figure 1 shows the representative first-order plots for
the catalytic reaction conducted at 30 C in presence of
NiO catalyst samples preheated at 400 C and irradiated
at different doses of -rays. Figures 2 and 3 show
representative first- order plots for the catalyzed reaction
carried out at 30 and 40 C over Co3O4 solids samples,
precalcined at 500 and 700 C, then subjected to
different doses of -rays, respectively. The values of k as
measured at 30, 40 and 50 C over various irradiated
catalysts were calculated as described above. However,

Fig. 1. First order plots of H2O2 decomposition conducted at 40 C

over NiO calcined at 400 C and subjected to various doses of
gamma-irradiation

153

H. G. EL-SHOBAKY, A. EL-MOHSEN M. TURKY: EFFECT OF GAMMA-IRRADIATION

Fig. 2. First order plots of H2O2 decomposition conducted at 30 C

over Co3O4 calcined at 500 C and subjected to various doses of
gamma-irradiation

Fig. 3. First order plots of H2O2 decomposition conducted at 40 C

over Co3O4 calcined at 700 C and subjected to various doses of
gamma-irradiation

The decrease in the catalytic activity measured at 30 C

(k30 C) due to treatment with a dose of 0.2 MGy attained
values of 35%, 29% and 36% for NiO 400 C, Co3O4
500 C and Co3O4 700 C, respectively. The
maximum decrease in the catalytic activity measured at
30 C (k30 C) due to exposure of the catalysts
investigated to 1.6 MGy of -irradiation reached values
of 59%, 60% and 71% for NiO 400 C, Co3O4
500 C and Co3O4 700 C, respectively.

154

Fig. 4. Effect of gamma-irradiation on the rate constant of H2O2

decomposition conducted at 30 C over 1 Co3O4 calcined at 500 C,
2 NiO calcined at 400 C, 3 Co3O4 calcined at 700 C

It has been shown (Table 1) that -irradiation of the

different catalysts investigated brought about an increase
of their specific surface areas. Thus, to account for such
change in SBET, the values of the reaction rate constant

per unit surface area, k , were calculated for the

catalyzed reaction conducted at 30, 40 and 50 C over
the irradiated solids. The data are listed in Table 2. This
table includes also the data of k30 C expressed in
mol/number of metal atoms per minute.
Examination of Table 2 reveals that (1) the specific
catalytic activity of Co3O4 solid samples, even those
precalcined at 700 C, is much bigger than that of NiO
catalyst, (2) the increase of temperature of heat treatment
Co3O4 solid from 500 to 700 C, resulted in a significant
decrease in its specific catalytic activity of about 70%
for the catalyzed reaction carried out at 30 C, (3)
exposure of NiO 400 C, Co3O4 500 C and Co3O4
700 C solids to a dose of 1.6 MGy effected a decrease
of about 67% in the specific catalytic activities,
measured for the catalyzed reaction at 30 C, for both
NiO and Co3O4 500 C, this decrease attained about
90% for Co3O4 precalcined at 700 C and (4) the
catalytic activity of NiO 400 C measured at 30 C,
expressed in mol/number of metal atoms per minute,
suffered a decrease of about 56% upon treatment with
1.6 MGy while a decrease of about 59% and 60% was
observed in the case of Co3O4 precalcined at 500 and
700 C, respectively.
The observed decrease in the catalytic activities of
the solids investigated due to -irradiation might reflect
an effective decrease in the concentration of catalytically
active constituents taking part in catalysis of H2O2

H. G. EL-SHOBAKY, A. EL-MOHSEN M. TURKY: EFFECT OF GAMMA-IRRADIATION

decomposition. NiO and Co3O4 solids precalcined at

temperatures 700 C deviate from the stoichiometric
formula and contain variable amounts of chemisorbed
oxygen which decreases by increasing their
precalcination temperature.4043 Oxygen, being an
electron acceptor gas, its chemisorption on nickel and
cobalt oxides is accompanied by creation of Ni3+ and
Co3+ ions on the top surface layers of NiO and Co3O4
solids. The created trivalent cations increase the
concentration of catalytically active sites via formation
of Ni3+Ni2+ and Co3+Co2+ ions pairs in nickel and
cobalt oxide catalysts, respectively. The increase in the
precalcination temperature of these solids affected the
desorption of some of chemisorbed oxygen thus
decreasing the concentration of trivalent cations present.
This treatment should be accompanied by a decrease in
the catalytic activities of such solids.
So, the observed significant decrease in the specific
catalytic activity of Co3O4 solid (Table 2) upon
increasing the temperature of its thermal treatment from
500 to 700 C could be understood. The observed
significant decrease in the catalytic activities of NiO and
Co3O4 solids due to -irradiation can be attributed to an
effective desorption of chemisorbed oxygen present in
the outermost surface layers of the treated oxides with
subsequent decrease in the concentration of catalytic
active sites taking part in the catalyzed reaction.

It has been reported that the exposure of NiO

300 C to a small dose of -rays (0.2 MGy) led to a
significant decrease in its catalytic activity towards CO
oxidation by O2 at room temperature and 150 C.18 This
decrease has been attributed to an effective decrease in
the amount of chemisorbed oxygen. However, irradiation of unloaded Co3O4 400 C and
Co3O4/Al2O3 650 C brought about an effective
increase in their catalytic activities towards CO
oxidation by O2 conducted at 110140 C and
150200 C, respectively, reaching to a maximum limit
at a dose of 0.4 and 0.8 MGy, respectively then
decreased upon increasing the dose above this limit.19,32
-irradiation
Furthermore,
(0.21.6 MGy)
of
CuOZnO/Al2O3 catalyst precalcined at 600 C led to
an increase of 140% in its catalytic activity, in CO
oxidation by O2 conducted at 150200 C25 and led to a
decrease of 90% in its activity towards H2O2
decomposition at 30 C.34 These results suggested that
the active sites taking part in the catalysis of CO
oxidation by O2 and decomposition of H2O2 present in
different catalytic systems are different from each
other.44 The induced changes in the catalytic activities of
certain solids, towards CO oxidation by O2 and
decomposition of H2O2, due to -irradiation could be
discussed in terms of possible changes in the chemistry
of their surfaces (departure of chemisorbed oxygen,
removal of OH groups) and creation of some kind of
lattice damage.9,11,18,25,34,4547

Table 2. Effect of dose of -rays on the reaction rate constant per unit area (k ) for H2O2 decomposition at
3050 C over NiO and Co3O4 solids
Solid

Calcination
temperature, C

Dose,
MGy

k 30 C,
1/(min.m2)

k 40 C,
1/(min.m2)

k *30 C

NiO

400
400
400
400
400

0.0
0.2
0.4
0.8
1.6

6.9.103
4.5
3.9
3.3
2.3

11.3.103
7.2
6.4
5.4
4.0

12.3.104
9.27
8.03
6.81
5.38

Co3O4

500
500
500
500
500

0.0
0.2
0.4
0.8
1.6

9.6.102
6.6
5.3
4.00
3.2

18.2.102
12.4
9.9
7.7
6.2

12.0.103
9.15
7.34
5.54
4.87

Co3O4

700
700
700
700
700

0.0
0.2
0.4
0.8
1.6

2.8.102
1.5
1.0
0.5
0.3

5.7.102
3.1
2.0
1.0
0.5

11.7.103
7.84
5.23
4.12
3.67

* The catalytic activities are expressed in mol/number of metal atoms per minute.

155

H. G. EL-SHOBAKY, A. EL-MOHSEN M. TURKY: EFFECT OF GAMMA-IRRADIATION

Table 3. Apparent activation energies (E, E*) and frequency factor (lnA) for the catalytic decomposition of
H2O2 over variously irradiated samples
Catalyst

Calcination
temperature, C

Dose,
MGy

E,
kJ/mol

lnA

E*,
kJ/mol

NiO

400
400
400
400
400

0.0
0.2
0.4
0.8
1.6

39.4
40.3
40.7
41.5
44.8

13.20
13.10
13.21
13.3
14.43

39.4
40.5
40.8
41.2
41.4

Co3O4

500
500
500
500
500

0.0
0.2
0.4
0.8
1.6

50.2
49.4
50.2
53.9
54.3

18.23
17.56
17.80
18.97
18.94

50.2
51.1
51.3
52.0
52.2

Co3O4

700
700
700
700
700

0.0
0.2
0.4
0.8
1.6

61.4
58.1
58.1
65.2
65.6

21.69
19.95
19.81
22.18
22.03

61.4
62.0
63.0
63.5
63.7

The determination of the apparent activation energy

(E) for the catalysis of the decomposition of H2O2 over
the irradiated catalyst samples has shed some light on the
possible change in the mechanism of the catalyzed
reaction and the possible change in the concentration and
nature of the catalytically active sites involved. Such
values of E have been obtained from an application of
the Arrhenius equation to the values k measured at 30,
40 and 50 C. The computed E values are listed in
Table 3 which also includes the values of the preexponential factor (A) for the Arrhenius equation. It is
seen from Table 3 that irradiation of NiO with different
doses of -rays resulted in a progressive increase in the
values of E which conforms to the observed decrease in
the catalytic activities of the irradiated solid samples. On
the other hand, exposure of Co3O4 samples precalcined
at 500 and 700 C to different doses of -rays resulted in
fluctuation (both decrease and increase) in the values of
E which did not conform to the observed progressive
decrease in the catalytic activities of the variously
irradiated samples. This apparent discrepancy was
resolved by taking the values of the pre-exponential
constant into account. Table 3 indicates the variation of
the values of lnA for all the solids investigated thus
reflecting the heterogeneous nature of the catalyst
surface and taking this into consideration the values of
lnA for un-irradiated samples of NiO 400 C, Co3O4
500 C and Co3O4 700 C were employed for the
irradiated catalyst samples. The recalculated values of
the activation energy (E*) for the catalyzed reaction
conducted over irradiated solids are listed in the last
column of Table 3. The computed values of E* were
found to be virtually the same within the experimental
error for the un-irradiated and irradiated catalyst samples

156

of NiO 400 C, Co3O4 500 C and Co3O4 700 C.

This finding suggests that exposure of nickel and cobalt
oxide catalysts to different doses of -rays did not
change the mechanism of the catalytic reaction but
simply decreased the concentration of the catalytically
active sites on the surface.
This conclusion was further supported by an analysis
based on the dissipation function for the energy of the
active sites arising from surface heterogeneity48 which
employs the equation:
f(Ei) = a exp (hEi)
where Ei is the interaction energy of site i with the
substrate. This equation may be written into the form:
A = a exp (hE)
which suggests that a plot of ln A versus E for the
variously irradiated solids should give a straight line
whose slope and intercept would allow a ready
determination of the values of the constants h and a for
the catalysts investigated. Such plots are shown in Fig. 5
for the catalytic decomposition of H2O2 over the
catalysts investigated. The values of h thereby computed
were 0.31, 0.30 and 0.30 mol/kJ.min for un-irradiated
and irradiated catalysts samples of NiO 400 C, Co3O4
500 C and Co3O4 700 C solids, respectively. The
computed values of a were 1.98, 19.89 and 9.34 min1
for the previous catalyst samples. Such values indicate
that the exposure of nickel oxide and cobalt oxide
catalysts to different doses of -irradiation (0.21.6 MGy)
did not change the dissipation of active sites on the catalyst
surfaces, i.e., the nature of the surface heterogeneity, but
merely led to a decrease in their concentration.

H. G. EL-SHOBAKY, A. EL-MOHSEN M. TURKY: EFFECT OF GAMMA-IRRADIATION

Conclusions
The exposure of NiO precalcined at 400 C and
Co3O4 preheated at 500 C and 700 C to different doses
of -rays between 0.2 and 1.6 MGy resulted in a
measurable decrease in their particle size. The decrease
was, however, more pronounced in the case of
Co3O4 500 C.
The specific surface areas of NiO and Co3O4
precalcined at various temperatures, were found to
increase as a function of the dose of -irradiation. The
treatment of the various solids investigated with
1.6 MGy of -rays led to an increase of about 22% in the
SBET of NiO 400 C and Co3O4 500 C and 194%
for Co3O4 700 C, which may result from splitting of
the particles of nickel and cobalt oxides and possible
creation of new pores especially in the case of Co3O4
700 C.
Gamma-irradiation resulted in an effective decrease
in the catalytic activities of NiO and Co3O4 solids
towards H2O2 decomposition. The dose of 1.6 MGy
effects a decrease of 66.7% in the specific catalytic

activity, measured at 30 C (k 30), for both NiO 400 C

and Co3O4 500 C and 89.3% for Co3O4 700 C.
This treatment did not change the values of the
activation energy of the catalyzed reaction but decreased
the concentration of catalytically active sites without
changing their nature.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
Fig. 5. Relationship between activation energy and frequency factor
for the catalytic decomposition of H2O2 conducted over: NiO calcined
at 400 C (a); Co3O4 calcined at 500 C (b); Co3O4 calcined at 700 C

10.
11.

The observed decrease in the catalytic activities of NiO

and Co3O4 solids due to treatment with -irradiation is
therefore attributed to an effective decrease in the
concentration of Ni3+ and Co3+ ions, respectively. Such
an effect is accompanied by a decrease in the
concentration of Ni3+Ni2+ and Co3+Co2+ ion pairs on
the catalyst surfaces which acted as active sites involved
the catalytic decomposition of H2O2.

12.
13.
14.
15.
16.
17.
18.

H. R. LEIDER, Phys. Rev., 101 (1956) 56.

J. M. CAFFREY, A. O. ALLEN, J. Phys. Chem., 62 (1985) 33.
A. W. ADAMSON, I. LING, Adv. Chem. Ser., 33 (1961) 51.1.
I. MAXIM, T. BRAUN, J. Phys. Chem. Soils, 24 (1963) 537.
V. MUCKA, Collect. Czech. Chem. Commun., 41 (1976) 159.
V. MUCKA, Collect. Czech. Chem. Commun., 42 (1977) 391.
V. MUCKA, Collect. Czech. Chem.Commun., 44 (1979) 1003.
V. MUCKA, Radiat. Phys. Chem., 41 (1993) 843.
Z. HANAFI, E. M. IBRAHIM, F. M. ISMAIL, Egypt. J. Phys.,
8 (1977) 143.
G. A. EL-SHOBAKY, N. M. GHONEIM, A. M. DESSOUKI,
Thermochim. Acta, 72 (1984) 297.
G. A. EL-SHOBAKY, A. M. EL-SHABINY, A. A. RAMADAN,
A. M. DESSOUKI, Radiat. Phys. Chem., 30 (1987) 233.
A. M. YOUSSEF, S. A. EL-HAKAM, G. A. EL-SHOBAKY, Radiat.
Phys. Chem., 40 (1992) 575.
A. M. EL-SHABINY, G. A. EL-SHOBAKY, A. M. DESSOUKI,
A. A. RAMADAN, Radiat. Phys. Chem., 33 (1998) 19.
A. A. RAMADAN, G. A. EL-SHOBAKY, A. M. DESSOUKI, Radiat.
Phys. Chem., 34 (1989) 787.
V. MUCKA, Radiat. Phys. Chem., 30 (1987) 293.
K. K. KUZEMBAEV, D. V. SKOLSKII, G. T. TUGELBAEVA, Izv.
Akad. Nauk. Kaz. SSR, Ser. Khim., 21 (1980) 21.
K. K. KUZEMBAEV, Zh. Fiz. Khim., 54 (1980) 2359.
G. A. EL-SHOBAKY, N. S. PETRO, T. M. GHAZY, Surface
Technol., 19 (1983) 17.

157

H. G. EL-SHOBAKY, A. EL-MOHSEN M. TURKY: EFFECT OF GAMMA-IRRADIATION

19. G. A. EL-SHOBAKY, G. A. FAGAL, N. S. PETRO, A. M. DESSOUKI,

Radiat. Phys. Chem., 29 (1987) 39.
20. G. A. EL-SHOBAKY, Th. EL-NABARAWY, A. M. DESSOUKI,
Radiat. Phys. Chem., 30 (1978) 161.
21. G. A. EL-SHOBAKY, Th. EL-NABARAWY, G. A. FAGAL,
A. M. DESSOUKI, Radiat. Phys. Chem., 32 (1988) 773.
22. G. A. EL-SHOBAKY, A. M. GHOZZA, G. A. FAGAL,
M. A. SHOUMAN, Materials Lett., 19 (1994) 79.
23. G. A. EL-SHOBAKY, N. H. AMIN, G. A. FAGAL, J. Radioanal.
Nucl. Chem., 178 (1994) 3.
24. G. A. EL-SHOBAKY, A. S. AHMAD, A. M. GHOZZA,
S. M. EL-KHOULY, Adsorp. Sci. Technol., 13 (1996) 163.
25. G. A. EL-SHOBAKY, A. S. AHMAD, M. MOKHTAR, J. Radioanal.
Nucl. Chem., 219 (1997) 89.
26. G. A. EL-SHOBAKY, A. M. GHOZZA, G. M. MOHAMED, Adsorp.
Sci. Technol., 15 (1997) 465.
27. G. A. EL-SHOBAKY, A. M. GHOZZA, G. M. MOHAMED, Adsorp.
Sci. Technol., 16 (1998) 163.
28. G. A. EL-SHOBAKY, G. A. FAGAL, H. G. EL-SHOBAKY,
S. M. EL-KHOULY, Colloids Surfaces, A152 (1999) 275.
29. H. G. EL-SHOBAKY, H. A. EL-BOOHY, M. M. DOHEIM, Adsorp.
Sci. Technol., 18 (2000) 749.
30. A. M. YOUSSEF, G. A. EL-SHOBAKY, Th. EL-NABARAWY,
N. H. AMIN, J. Serb. Chem. Soc., 55 (1990) 21.
31. R. KUDLACEK, A. JUDLOVA, Collect. Czech. Chem. Commun.,
49 (1984) 1933.
32. A. N. AL-NOAIMI, G. A. EL-SHOBAKY, A. S. AHMAD,
H. G. EL-SHOBAKY, J. Radioanal. Nucl. Chem., 185 (1994) 23.
33. N. H. AMIN, G. A. EL-SHOBAKY, G. A. FAGAL, J. Radioanal.
Nucl. Chem., 177 (1994) 211.

158

34. G. A. FAGAL, A. A. ATTIA, H. G. EL-SHOBAKY, Adsorp. Sci.

Technol., 16 (1998) 381.
35. B. D. CULLITY, Elements of X-ray Diffraction, 3rd ed., Addison
Wesley Publishing Company, 1967.
36. A. S. AHMAD, G. A. EL-SHOBAKY, A. N. AL-NOAIMI,
H. G. EL-SHOBAKY, Materials Lett., 26 (1996) 107.
37. C. N. SPALARIS, L. P. BUPP, E. C. GILBERT, J. Phys. Chem.,
61 (1957) 350.
38. A. ABOU-KIAS, N. N. ABOU-KIAS, Acta Phys. Chem., 31
(1985) 109.
39. N. N. GREENWOOD, Inorganic Crystal Lattice Defects and
Nonstoichiometry, Butterworth, London, 1964, p. 37.
40. I. F. HEWAIDY, G. A. EL-SHOBAKY, Bull. Natl. Res. Center Egypt,
6 (1981) 209.
41. N. S. PETRO, G. A. EL-SHOBAKY, N. Z. MISAK, R. S. MIKHAIL,
Surf. Technol., 5 (1977) 315.
42. A. BIELANSKI, K. DYREK, Z. KLUZE, J. STOZNSKI, T. TOMBIASZ,
Bull. Acad. Pol. Sci., 9 (1964) 657.
43. G. A. EL-SHOBAKY, I. F. HEWAIDY, Th. EL-NABARAWY, Surface
Technol., 10 (1980) 311; 10 (1980) 225; Radiat. Phys. Chem.,
33 (1989) 19.
44. G. A. EL-SHOBAKY, F. M. RADWAN, A. M. TURKY,
A. ABD EL-MOEMEN, Adsorp. Sci. Technol., 18 (2000) 799.
45. F. H. LEISEN, Phys. Rev., 123 (1961) 736.
46. M. J. SMITH, J. Appl. Phys., 34 (1963) 2879.
47. G. A. EL-SHOBAKY, A. N. AL-NOAIMI, A. M. DESSOUKI, Surface
Technol., 26 (1985) 117.
48. A. A. BALANDIN, Dokl. Akad. Nauk SSSR, 93 (1953) 55.