Insights into the Role of Defects in Fe2(MoO4)3 Catalysts

The catalytic activity and selectivity of Fe2(MoO4)3 obtained from solidstate synthesis protocols is investigated for the oxidative dehydrogenation (ODH) of ethanol to acetaldehyde. While Fe2(MoO4)3 annealed in a MoO3 atmosphere is found to be inactive, ball-milling of such solid-state synthesis precursors leads to an increase in activity, which cannot be attributed purely to the change in the specific surface area nor to a geometric effect of smaller particles. In a systematic study of the synthesis of Fe2O3-free Fe2(MoO4)3 samples, the correlation of ball-milling time, defect concentration, and catalytic activity is presented. In-depth X-ray diffraction studies, magnetic susceptibility, and 57Fe-Mo''ssbauer spectroscopic measurements disclose characteristic signatures of the defect sites in the solid materials introduced by ball-milling and indicate: (i) MoO3- enriched amorphous layers of variable thickness (shell-like) and (ii) crystalline bulk defects corresponding to a reduction in the molar volume of the solid. The onset of recrystallization processes sets in around 300 degrees C and is accompanied by an enhanced MoO3 mobility in the particles, which adds to an increase in activity and a decreasing selectivity under catalytic conditions. Accordingly, the defects associated with the decreasing amorphous fraction are converted to crystalline bulk defects, which are monitored by the magnetic hyperfine field distribution of the respective Fe sites. Overall, this study shows the importance of the amorphous layer thickness with a sufficient defect concentration and of the bulk defects' contribution to the chemical gradients, important for the MoO3 mobility and reduction of the MoO3 loss as a volatile species at the solid/gas phase boundary in ODH catalysis.