Titania-supported vanadia (VO x /TiO 2 ) catalysts exhibit outstanding catalytic in a number of selective oxidation and reduction processes. In spite of numerous investigations, the nature of redox transformations of vanadium and titanium involved in various catalytic processes remains difficult to detect and correlate to the rate of products formation. In this work, we studied the redox dynamics of active sites in a bilayered 5% V 2 O 5 /15% TiO 2 /SiO 2 catalyst (consisting of submonolayer VO x species anchored onto a TiO x monolayer, which in turn is supported on SiO 2 ) during the oxidative dehydrogenation of ethanol. The VO x species in 5% V 2 O 5 /15% TiO 2 /SiO 2 show high selectivity to acetaldehyde and an ca. 40 times higher acetaldehyde formation rate in comparison to VO x species supported on SiO 2 with a similar density. Operando time-resolved V and Ti K-edge X-ray absorption near-edge spectroscopy, coupled with a transient experimental strategy, quantitatively showed that the formation of acetaldehyde over 5% V 2 O 5 /15% TiO 2 /SiO 2 is kinetically coupled to the formation of a V 4+ intermediate, while the formation of V 3+ is delayed and 10–70 times slower. The low-coordinated nature of various redox states of VO x species (V 5+ , V 4+ , and V 3+ ) in the 5% V 2 O 5 /15% TiO 2 /SiO 2 catalyst is confirmed using the extensive database of V K-edge XANES spectra of standards and specially synthesized molecular crystals. Much weaker redox activity of the Ti 4+ /Ti 3+ couple was also detected; however, it was found to not be kinetically coupled to the rate-determining step of ethanol oxidation. Thus, the promoter effect of TiO x is rather complex. TiO x species might be involved in a fast electron transport between VO x species and might affect the electronic structure of VO x , thereby promoting their reducibility. This study demonstrates the high potential of element-specific operando X-ray absorption spectroscopy for uncovering complex catalytic mechanisms involving the redox kinetics of various metal oxides.

In situ X-ray absorption spectroscopy (XAS) is a powerful technique for the investigation of heterogeneous catalysts and electrocatalysts. The obtained XAS spectra are usually interpreted from the point of view...

Supported vanadia (VO x ) is a versatile catalyst for various redox processes where ceria-supported VO x have shown to be particularly active in the oxidative dehydrogenation (ODH) of alcohols. In this work, we clarify the origin of the volcano-shaped ethanol ODH activity trend for VO x /CeO x catalysts using operando quick V K-and Ce L 3 -edge XAS experiments performed under transient conditions. We quantitatively demonstrate that both vanadium and cerium are synergistically involved in alcohol ODH. The concentration of reversible Ce 4 + /Ce 3 + species was identified as the main descriptor of the alcohol ODH activity. The activity drop in the volcano plot, observed at above ca. 3 V nm À 2 surface loading (ca. 30 % of VO x monolayer coverage), is related to the formation of spectator V 4 + and Ce 3 + species, which were identified here for the first time. These results might prove to be helpful for the rational optimization of VO x /CeO 2 catalysts and the refinement of the theoretical models.