Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Effect of Core Morphology on the Decomposition of CCI₄ over the Surface of Core/Shell Structured Fe₂O₃/MgO Composite Metal Oxides

  • Published : 1997.08.20
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Abstract

Core/shell structured composite metal oxides of Fe2O3/MgO were prepared by thermal decomposition of Fe(acac)3 adsorbed on the surface of MgO cores. The morphology of the composites conformed to that of the MgO used as the cores. Broad powder X-ray diffraction peaks shifted toward larger d, large BET surface area (∼350 m2/g), and the size of crystalline domains in nano range (4 nm), all corroborate to the nanocrystallinity of the Fe2O3/MgO composite which was prepared by using nanocrystalline MgO as the core. By use of microcrystalline MgO as the core, microcrystalline Fe2O3/MgO composite was prepared, and it had small BET surface area of less than 35 m2/g. AFM measurements on nanocrystalline Fe2O3/MgO showed a collection of spherical aggregates (∼80 nm dia) with a very rough surface. On the contrary, microcrystalline Fe2O3/MgO was a collection of plate-like flat crystallites with a smooth surface. The nitrogen adsorption-desorption behavior indicated that microcrystalline Fe2O3/MgO was nonporous, whereas nanocrystalline Fe2O3/MgO was mesoporous. Bimodal distribution of the pore size became unimodal as the layer of Fe2O3 was applied to nanocrystalline MgO. The macropores in a wide distribution which the nanocrystalline MgO had were absent in the nanocrystalline Fe2O3/MgO. The decomposition of CCl4 was largily enhanced by the overlayer of Fe2O3 on nanocrystalline MgO making the reaction between nanocrystalline Fe2O3/MgO and CCl4 be nearly stoichiometric. The reaction products were environmentally benign MgCl2 and CO2. Such an enhancement was not attainable with the microcrystalline samples. Even for the nanocrystalline MgO, the enhancement was not attained, if not with the Fe2O3 layer. Without the layer of Fe2O3, it was observed that the nanocrystalline domain of the MgO transformed into microcrystalline one as the decomposition of CCl4 proceeded on its surface. It appeared that the layer of Fe2O3 on the particles of nanocrystalline Fe2O3/MgO blocked the transformation of the nanocrystalline domain into microcrystalline one. Therefore, in order to attain stoichiometric reaction between CCl4 and Fe2O3/MgO core/shell structured composite metal oxide, the morphology of the core MgO has to be nanocrystalline, and also the nanocrystalline domains has to be sustained until the core was exhausted into MgCl2.

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