Catalytic carbon monoxide oxidation over strontium, cerium and copper-substituted lanthanum manganates and cobaltates
Chan, K.S. ; Ma, J. ; Jaenicke, S. ; Chuah, G.K. ; Lee, J.Y.
Chan, K.S.
Ma, J.
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Abstract
The influence of either A or B-site substitution in perovskite-type mixed oxides on the catalytic oxidation of carbon monoxide has been studied. The following systems were investigated: (La,Sr) MnO3, La(Mn,Cu)O3, (La,Sr)CoO3 and (La,Ce)CoO3. Cobaltates are generally more active than the manganates. Substitution in the A or B-site improved the catalytic activity with oxidation starting from 75 °C. A volcano plot of activity versus composition was obtained for each series with up to a 10-fold increase in catalytic activity for the substituted compounds. Lattice oxygen participates in the reaction even under stoichiometric conditions. The catalysts show a positive rate dependence on the carbon monoxide partial pressure so that under reducing conditions, the reaction is not inhibited. A bistability in the rate of catalytic oxidation at high carbon monoxide concentration was observed over La1-xSrxMnO3 and LaMn1-xCuxO3 (0≤x≤0.2). This bistability has been attributed to a carbon monoxide-driven reconstruction of the reduced surface, leading to pairs of Mn2 ions with a Mn-Mn distance comparable to the spacing in the metal. These pairs provide reactive sites for carbon monoxide oxidation and oxygen chemisorption. Such metal-metal pairs are not found in the perovskite lattice but are a structural feature of the closely related hexagonal 4-layered packing which is the normal crystal structure of SrMnO3. The change back to the less active state is due to reoxidation of the surface. It was confirmed that a low mobility of lattice oxygen is a necessary condition for hysteresis in these oxides. © 1994.
Keywords
(La,Sr)MnO3, (La/Sr)CoO3 and (La/Ce)CoO3, carbon monoxide oxidation, La(Mn/Cu)O3, oxygen mobility, perovskites, steady-state multiplicity
Source Title
Applied Catalysis A, General
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Date
1994-01-06
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Article