Decomposition of hydrogen peroxide on nickel oxide-manganese sesquioxide two-component catalysts and effect of ionizing radiation on them

1981 ◽  
Vol 46 (8) ◽  
pp. 1860-1875 ◽  
Author(s):  
Viliam Múčka

The catalytic and some physico-chemical properties were studied of nickel oxide-manganese sesquioxide two-component catalysts with various proportions of the constituents. Decomposition of hydrogen peroxide in aqueous solution with the initial concentration 1.2 mol l-1 served as testing reaction. The catalyst components affect each other; the effect, being highest in the region of 20-30 mol.% manganese sesquioxide, brings about an enhanced dispersity of the system, with the result of increased surface area, increased amount of overstoichiometric oxygen and deficit in chemical analysis. Furthermore, the mutual component influencing appears in the specific catalytic activity of the system and in the amount of overstoichiometric oxygen per unit surface area, which is highest at 85 mol.% Mn2O3. A model of the mechanism is suggested for the reaction under study, based on the concept of bivalent catalytic centres, assuming that during the reaction, the high valency manganese species are gradually reduced as far as divalent manganese; this accounts for the occurrence of the observed two or three stages of hydrogen peroxide decomposition. Neither the mechanism of interaction of the two oxides nor the mechanism of the hydrogen peroxide decomposition changes on prior gamma irradiation of the catalyst. However, the irradiation affects markedly the catalytic activity of the system, the effect for catalyst of different composition being qualitatively different. Within the suggested concept of the reaction mechanism, the observed changes can be interpreted in terms of formation of non-eqilibrium charge carriers (electrons) resulting from the ionization both in the surface layer and in the catalyst bulk; after stabilization on the surface, the carriers may serve as adsorption centres for chemisorption of oxygen or may recombine with the catalytic centres of the reaction under study.

1979 ◽  
Vol 44 (4) ◽  
pp. 1015-1022 ◽  
Author(s):  
Viliam Múčka

The catalytic properties of two-component catalyst nickel oxide-cadmium oxide with the proportions of the components covering the whole composition region 0-100% were examined by studying the decomposition of hydrogen peroxide in aqueous solution on it. In the range 0-25 mol.% CdO, cadmium oxide is found to affect infavourably the ability of nickel oxide to chemisorb oxygen. The amount of the chemisorbed oxygen increases several times on gamma irradiation of the samples. The effect of cadmium oxide on the catalytic activity of the system shows up in fresh samples only indirectly via the changed amount of the oxygen chemisorbed. In older samples the initial catalytic activity of the system is changed, which can be explained based on the concept of bivalent catalytic centres in terms of the co-action of the catalytic centres of the two oxides, which are in equilibrium. The irradiation of the system under study speeds up the processes leading to the establishing of this equilibrium which is thermally very stable, and results in a substantial increase of the catalytic activity of the samples investigated.


1988 ◽  
Vol 53 (8) ◽  
pp. 1636-1646 ◽  
Author(s):  
Viliam Múčka ◽  
Kamil Lang

Some physical and catalytic properties of the two-component copper(II)oxide-chromium(III)oxide catalyst with different content of both components were studied using the decomposition of the aqueous solution of hydrogen peroxide as a testing reaction. It has been found that along to both basic components, the system under study contains also the spinel structure CuCr2O4, chromate washable by water and hexavalent ions of chromium unwashable by water. The soluble chromate is catalytically active. During the first period of the reaction the equilibrium is being established in both homogeneous and heterogeneous catalytic systems. The catalytic activity as well as the specific surface area of the washed solid is a non-monotonous function of its composition. It seems highly probable that the extreme values of both these quantities are not connected with the detected admixtures in the catalytic system. The system under study is very insensitive with regard to the applied doses of gamma radiation. Its catalytic properties are changed rather significantly after the thermal treatment and particularly after the partial reduction to low degree by hydrogen. The observed changes of the catalytic activity of the system under study are very probably in connection with the changes of the valence state of the catalytically active components of the catalyst.


1981 ◽  
Vol 46 (8) ◽  
pp. 1886-1897 ◽  
Author(s):  
Viliam Múčka

This paper deals with some physico-chemical properties of a two component catalyst NiO-U3O8, prepared with varying ratio of both components. Special interest was given to the catalytic properties - tested by decomposition of aqueous solution of hydrogen peroxide. The study presented evidence of mutual charge interaction between both components of the catalyst. This enables one to explain the observed behaviour of the studied system on the basis of the principle of bivalent sites. A pre-irradiation of a catalyst by gamma rays leads to significant increase of the oxidation states of both catalyst components.


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