Unusual valences and fast electron exchange in MoFe2O4

The distribution of d electrons over the cations in MoFe2O4, which is represented by the formal valence assignment, is shown to be complicated by the equilibrium reactions Fe2+B+Fe3+A+Mo3+⇌Fe3+B+Fe2+A+Mo4+ We have used thermal treatment to confirm that the Mo are primarily on octahedral sites; FeA[MoBFeB]O4. K-shell absorption and Mössbauer data at T = 423 K > Tc demonstrate that the iron has an average valence near 2.5+ with fast electron transfer (τh < 10−8 sec) on both octahedral and tetrahedral sites. Paramagnetic susceptibility data give a Curie constant CM = 7.95 ± 0.2 emu/mole and a Weiss constant θp = −445 K; magnetometer measurements confirm a compensation point near 160 K. Transport data give a surprisingly high electronic conductivity, but also give an activated mobility similar to that found in AlFe2O4 and CrFe2O4 where mixed Fe3+2+ valences on both A and B sites have been demonstrated. However, a positive Seebeck coefficient and a preexponential factor one order of magnitude higher in MoFe2O4 point to involvement of a fraction of the Mo atoms in electronic transport, which would be consistent with the observation of a τh < 10−8 sec on the A sites of a spinel. An energy diagram consistent with these data and other information about the relative redox potentials of these ions in oxides are proposed for this system.