The thermal decomposition of cobalt, nickel, manganese, zinc, and copper nitrates supported on nanometric alumina was investigated and compared with decomposition of corresponding bulk nitrates. TG, DTA, and MS measurements in air were performed. The supported nitrates decompose in lower temperatures than the bulk ones and their decomposition proceeds in fewer stages which are better separated. Synthesized materials and bulk nitrates before degradation of nitrates groups undergo dehydration. For decomposition of manganese and copper nitrates, the last step of water vapour releasing is combined with degradation of nitrate groups thus formation of anhydrous metal nitrate during decomposition is not achievable. Thermal decomposition of bulk nitrates leads to oxides-Co 3 O 4 , NiO, MnO 2 , ZnO, and CuO-respectively, as the solid residue. The nickel, zinc, copper, and manganese nitrates while supported on alumina decompose to corresponding oxides (NiO, ZnO, CuO, MnO 2 ) as well. For decomposition of cobalt nitrate while supported on Al 2 O 3 as the solid residue CoAl 2 O 4 were identified. The correlation between dehydration and degradation of nitrates groups temperatures for bulk and supported nitrates was analysed in terms of atomic properties of d-metals.
Fourier transform ion cyclotron resonance mass spectrometry has been employed to study the reactions of gas-phase cationic cobalt clusters, Co(n) (+) (n=4-30), with nitric oxide, NO, and nitrous oxide, N(2)O, under single collision conditions. Isolation of the initial cluster permits detailed investigation of fragmentation channels which characterize the reactions of all but the largest clusters studied. In reaction with N(2)O, most clusters generate the monoxides Co(n)O(+) without fragmentation, cobalt atom loss accompanying only subsequent reactions. By contrast, chemisorption of even a single NO molecule is accompanied by fragmentation of the cluster. The measured rate coefficients for the Co(n) (+)+N(2)O reaction as a function of cluster size are significantly smaller than those calculated using the surface charge capture model, while for NO the rates are comparable. The reactions have been studied under high coverage conditions by storing clusters for extended periods to permit multiple reactions to occur. This leads to interesting chemistry on the surface of the cluster resulting in the formation of stable oxide clusters and/or the decomposition of nitric oxide on the cluster with the resulting loss of molecular nitrogen.
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