Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides

The effect of crystallizing solution chemistry on the subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In presence Mo ions, we find that varying oxidation state precursor from Fe(II) to Fe(III) causes a progressive loss atomic long-range order with stabilization 2–4 nm particles sample Fe(III). Fe also affects distribution and cations within spinel structure. Increasing gives decreased Fe-ion occupation increased Mo-ion tetrahedral sites, as revealed extended X-ray absorption fine sites appears be unexpected, considering octahedral preferred coordination number Mo(VI). analysis structure indicates local ordering vacancies induces contraction interatomic distances polyhedra compared atoms. Moreover, occupancy into thermodynamic site preference dopant in Fe2O3 assessed density functional theory calculations points stronger substitution at sites. Hence, suggest synthetized compound is thermodynamically metastable, is, kinetically trapped. Such suggested consequence ions. population these known reactive enabling particle growth, concomitant very small particles. We confirmed our hypothesis using blank experiment without further supporting impact ions growth oxide nanoparticles. Our findings provide new insights relationships between Fe-chemistry structural features Fe-oxide materials.