Catalytic reactions are associated with dynamical changes in the catalyst that include the oxidation state and local structural variations. The understanding of such dynamics, particularly at the atomic-scale, is of great importance for revealing the activity and selectivity of the catalyst in numerous reactions. Combining in situ X-ray absorption spectroscopy with in situ diffuse reflectance infrared Fourier transform spectroscopy, we studied the redox-induced dynamical changes for a VOX monolayer catalyst supported on a α-Fe2O3 powder. The results show that several co-existing VOX species reversibly change their V oxidation states between +5 and +4, in concurrence with a structural change from two-dimensional chains to well connected V–O–V networks. These changes are also associated with the breaking and formation of the V
O vanadyl group. This combined study provides new insight into how VOX species change during catalytic reactions, which leads to proposed atomic-scale models for the redox-induced dynamics of the catalyst.
