Oxygen-vacancy-induced Raman softening in the catalyst Fe$_2$(MoO$_4$)$_3$

Abstract

Iron molybdate (Fe$_2$(MoO$_4$)$_3$) is a widely used commercial catalyst for oxidative dehydrogenation. Recently, the possibility that bulk oxygen atoms participate in catalytic reactions has been proposed based on the experimentally observed significant reduction in Raman intensity during the catalytic process, which implies the formation of oxygen defects. In this work, we performed density functional theory (DFT) calculations to elucidate the microscopic mechanism of the experimentally observed Raman intensity variation. Our phonon analysis reveals that oxygen-dominated vibrational modes, with a small contribution from Mo, occur near 782cm$^{-1}$-- the same frequency region where the Raman intensity reduction was measured. To make the calculations computationally feasible for this large system, we introduced an effective frozen-phonon approach to mimic defect effects into the Raman intensity. Our results suggest that oxygen vibrations are primarily responsible for the decrease in the calculated Raman intensity. Moreover, structural relaxation of Fe$_2$(MoO$_4$)$_3$ containing an oxygen vacancy indicates that oxygen diffusion from the bulk to the surface may occur very rapidly, such that the local symmetry remains effectively unchanged. This interpretation is in line with the absence of measurable peak shifts or broadening in the experimental Raman spectra.