Anna Zabilska

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Origin of the Activity Trend in the Oxidative Dehydrogenation of Ethanol over VOx/CeO2

Olga Safonova, Anna Zabilska

Supported vanadia (VOx) is a versatile catalyst for various redox processes where ceria-supported VOx 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 VOx/CeOx 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 Ce4+/Ce3+ 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(-2) surface loading (ca. 30 % of VOx monolayer coverage), is related to the formation of spectator V4+ and Ce3+ species, which were identified here for the first time. These results might prove to be helpful for the rational optimization of VOx/CeO2 catalysts and the refinement of the theoretical models.

WILEY-V C H VERLAG GMBH2023

Beware of beam damage under reaction conditions: X-ray induced photochemical reduction of supported VOx catalysts during in situ XAS experiments

Davide Ferri, Olga Safonova, Anna Zabilska

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 of the investigated chemical processes, thereby sometimes omitting the fact that intense X-ray irradiation may induce additional transformations in metal speciation and, thus, in the corresponding XAS spectra. In this work, we report on X-ray induced photochemical reduction of vanadium in supported vanadia (VOx) catalysts under reaction conditions, detected at a synchrotron beamline. While this process was not observed in an inert atmosphere and in the presence of water vapor, it occurred at room temperature in the presence of a reducing agent (ethanol or hydrogen) alone or mixed with oxygen. Temperature programmed experiments have shown that X-ray induced reduction of VOx species appeared very clear at 30-100 degrees C but was not detected at higher temperatures, where the thermocatalytic ethanol oxidative hydrogenation (ODH) takes place. Similar to other studies on X-ray induced effects, we suggest approaches, which can help to mitigate vanadium photoreduction, including defocusing of the X-ray beam and attenuation of the X-ray beam intensity by filters. To recognize beam damage under in situ/operando conditions, we suggest performing X-ray beam switching (on and off) tests at different beam intensities under in situ conditions.

ROYAL SOC CHEMISTRY2022

Supported vanadia (VOx) belongs to some of the most versatile selective oxidation and reduction catalysts applied for many reactions in the chemical industry and pollution control. Among them, the oxidative dehydrogenation (ODH) of alcohols is particularly attractive since it is one of the main industrial methods of formaldehyde production and a possible route for the transformation of renewable bioethanol to value-added products, such as acetaldehyde and acetic acid. Despite many spectroscopic methods used to investigate the mechanism of this reaction, the details about the redox involvement of VOx species and promoting supports (CeO2 and TiO2) remain debated. In this study, we used an element-specific operando X-ray absorption spectroscopy (XAS) to probe the redox transformations of active sites in vanadia-titania and vanadia-ceria catalysts during ethanol and methanol ODH. By carefully designing the steady-state and transient operando XAS experiments and by applying advanced chemometric methods, we could discriminate specifically and often quantitatively, which role plays each redox couple during the alcohol ODH cycle and uncover hidden structure activity-relationships.Chapter 1 introduces the relevant literature and summarizes the goals and the scope of the thesis.In Chapter 2, we investigate the redox dynamics of active sites in a bilayered VOx/TiOx/SiO2 catalyst (an analog of a widely used VOx/TiO2 catalyst with comparable activity) during ODH of ethanol. Operando time-resolved V and Ti K-edge XAS coupled with a transient experimental strategy quantitatively showed that the formation of acetaldehyde over VOx/TiOx/SiO2 catalyst is kinetically coupled to the formation of a V4+ intermediate, while the formation of V3+ is delayed and its rate is 10-70 times lower. The only very weak redox activity of the Ti4+/Ti3+ couple was detected, which suggests that TiOx species promote the redox activity of VOx indirectly, either via the fast electron transport between VOx species or by changing the electronic structure of VOx species.In Chapter 3, we report on possible difficulties, which can occur during in situ XAS studies of supported vanadia (VOx) catalysts at synchrotron beamlines related to X-ray-induced photochemical reduction of vanadium. We rigorously tested this phenomenon and suggest approaches, which can help to identify and mitigate vanadium photoreduction interfering chemical speciation.In Chapter 4, we focused on the structure-activity relationships in VOx/CeO2 system. We prepared a series of VOx/CeO2 catalysts using high-surface-area CeO2 Using time-resolved operando quick XAS at V K- and Ce L3-edges, we demonstrated that during oxygen cut-off experiments vanadium and cerium change their oxidation states in concert with each other and with the production of acetaldehyde. It suggests that both reducible vanadium and cerium are parts of the same active sites. The maximum VOx/CeO2 activity per mass of catalyst observed at ca. 3 V/nm2 coincides with the maximal amount of cerium atoms, which reversibly change their oxidation state during oxygen cut-off experiments.In Chapter 5, we prove that the mechanistic findings described in Chapter 4 for ethanol ODH over VOx/CeO2 catalysts are also valid for methanol ODH. Moreover, we confirm that the VOx surface density is the main descriptor of the activity for VOx/CeO2 catalysts in alcohol ODH.

EPFL2022