Abstract
Different mixed cobalt—iron molybdates Co 1 − x Fe x MoO 4 (0 ≤ x ≤ 1) have been prepared by means of a ceramic process. The oxidation of pulverulent samples leads to ferric molybdate Fe 2(MoO 4) 3, spinelle Co 3O 4 and cobalt molybdate CoMoO 4. After a strong grinding which reduces the grain size (about 0.1 μm) and induces crystallographic defects in the grains, the cobalt—iron molybdates can be partially oxidized into cation-deficient phases. This oxidation corresponds to an isostructural substitution of part of the Fe 2+ and Co 2+ ions by Fe 3+ and Co 3+ ions and the creation of cation vacancies. The concomitant presence of trivalent cations and associated cation vacancies in the lattice stabilizes the highest-temperature variety of the cobalt or iron molybdates, i.e., the a variety.
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