Multislice frozen phonon high angle annular dark-field image simulation study of Mo–V–Nb–Te–O complex oxidation catalyst “M1”

Multislice frozen phonon calculations were performed on a model structure of a complex oxide which has potential use as an ammoxidation catalyst. The structure has 11 cation sites in the framework, several of which exhibit mixed Mo/V substitution. In this paper the sensitivity of high-angle annular dark-field (HAADF) imaging to partial substitution of V for Mo in this structure is reported. While the relationship between the average V content in an atom column and the HAADF image intensity is not independent of thickness, it is a fairly weak function of thickness suggesting that HAADF STEM imaging in certain cases can provide a useful starting point for Rietveld refinements of mixed occupancy in complex materials. The thermal parameters of the various cations and oxygen anions in the model affect the amount of thermal diffuse scattering and therefore the intensity in the HAADF images. For complex materials where the structure has been derived via powder Rietveld refinement, the uncertainty in the thermal parameters may limit the accuracy of HAADF image simulations. With the current interest in quantitative microscopy, simulations need to accurately describe the electron scattering to the very high angles often subtended by a HAADF detector. For this system approximately 15% of the scattering occurs above 200 mrad at 200 kV. To simulate scattering to such high angles, very fine sampling of the projected potential is necessary which increases the computational cost of the simulation.

► HAADF image simulations for complex oxidation catalyst with mixed Mo/V occupancy.
► Quantitative comparison with HAADF images requires many calculations to high angles.
► High angle electron scattering from atoms changes with Debye-Waller thermal parameters.
► Uncertainty in thermal parameters limits accuracy of simulations.
► Mixed cation site occupancy and thickness affect relative HAADF image intensities.