Modulation Excitation Spectroscopy: A Powerful Tool to Elucidate Active Species and Sites in Catalytic Reactions.

ConspectusA rational design of catalysts requires a knowledge of the active species and sites. Often, catalyst surfaces are dominated by spectators, which do not participate in the reaction, while the catalytically active species and sites are hidden. Modulation-excitation spectroscopy (MES) allows discrimination between active and spectator species by applying a concentration modulation, which is translated into the active (that is, actively responding) species by phase-sensitive detection (PSD).While MES has been known for a while, its combination with infrared spectroscopy (IR-MES) has been applied to the detailed mechanistic analysis of a wide range of supported metal and metal oxide catalysts only recently, used for catalytic reactions such as CO2 hydrogenation, water-gas shift, and CO and selective oxidation. The applicability of IR-MES is not limited to catalysis but has started to expand into other areas of research (e.g., gas sensing).In the context of renewable energy, CO2 hydrogenation has been a matter of intense mechanistic debate, despite its great importance for synthesis gas production and further processing to fuels and chemicals. Applying IR-MES to supported Cu and Au catalysts enabled us to discriminate between redox and associative mechanisms. While CO2 hydrogenation to CO and water follows an associative pathway with sequential H2 activation via hydrides and formation of carbon- and oxygen-containing intermediates, such as carbonates and formates, the reverse reaction, that is, the water-gas shift reaction, was shown to proceed via a redox mechanism including oxygen vacancy formation followed by reoxidation of the catalyst by CO2.Recent IR-MES studies on (supported) metal oxides have provided direct spectroscopic insight into the catalytically active sites during the selective oxidation of alkanes and alcohols. By further expanding the potential of IR-MES by transient isotopic exchange experiments, we were able to resolve the nuclearity-dependent vanadium and adsorbate dynamics of supported vanadia catalysts during oxidative dehydrogenation, highlighting the intimate interplay between the surface vanadia species and the support. The strong influence of the support material (ceria and titania) on the sequence of reaction steps provides an explanation for the different catalytic performance. Based on these mechanistic insights, the rational design of improved catalysts has been possible.Expanding the application of IR-MES to the area of gas sensing, as recently demonstrated for doped SnO2, provides access to enhanced mechanistic insight, including previously undetected surface species. Methodical challenges arising from background features associated with semiconductor metal oxides have been successfully tackled, supporting further expansion of IR-MES in the gas sensing community. Mechanistically, the application of IR-MES allows identification of the actively participating OH groups and adsorbed species (e.g., alkoxy, CO, carbonate) and monitoring of reaction sequences based on their temporal behavior, providing a level of understanding typically not accessible by steady-state methods.As outlined above, the combination of MES/PSD with IR spectroscopy constitutes a powerful approach for the identification of catalytically active species and sites, which is essential for a profound mechanistic understanding of surface reactions, greatly facilitating the rational design of catalysts and other functional materials.

Importance of Metal-Support Interactions for CO2 Hydrogenation: An Operando Near-Ambient Pressure X-ray Photoelectron Spectroscopy Study on Gold-Loaded In2O3 and CeO2 Catalysts.

Metal-support interactions, which are essential for the design of supported metal catalysts, used, e.g., for CO2 activation, are still only partially understood. In this study of gold-loaded In2O3 and CeO2 catalysts during CO2 hydrogenation using near-ambient pressure X-ray photoelectron spectroscopy, supported by near edge X-ray absorption fine structure, we demonstrate that the role of the noble metal strongly depends upon the choice of the support material. Temperature-dependent analyses of X-ray photoelectron spectra under reaction conditions reveal that gold is reduced on CeO2, enabling direct H2 activation, but oxidized on In2O3, leading to decreased activity of Au/In2O3 compared to bare In2O3. At elevated temperatures, the catalytic activity of the In2O3 catalysts strongly increases as a result of facilitated CO2 and (In2O3-based) H2 activation, while the catalytic activity of Au/CeO2 is limited by reoxidation by CO2. Our results underline the importance of operando studies for understanding metal-support interactions to enable a rational support selection in the future.

Refining the mechanism of CO2 and H2 activation over gold-ceria catalysts by IR modulation excitation spectroscopy.

The activation and utilization of the greenhouse gas CO2 is of great interest for the energy transition as a fossil-free carbon source for mitigating climate change. CO2 hydrogenation via the reverse water-gas shift reaction (RWGSR) converts CO2 to CO, a crucial component of syngas, enabling further transformation by means of the Fischer-Tropsch process. In this study, we unravel the detailed mechanism of the RWGSR on low-loaded Au/CeO2 catalysts using IR modulation excitation spectroscopy (MES), by periodically modulating the concentration of the reactants, followed by phase-sensitive detection (PSD). Applying such a MES-PSD approach to Au/CeO2 catalysts during RWGSR gives direct spectroscopic evidence for the active role of gold hydride, bidentate carbonate and hydroxyl species in the reaction mechanism, while disproving the participation of other species such as formate. Our results highlight the potential of modulation excitation spectroscopy combined with phase-sensitive detection to provide new mechanistic insight into catalytic reactions not accessible by steady-state techniques, including a profound understanding of the sequence of reaction steps.

Unraveling the Active Vanadium Sites and Adsorbate Dynamics in VOx/CeO2 Oxidation Catalysts Using Transient IR Spectroscopy.

The oxidative dehydrogenation (ODH) of propane over supported vanadia catalysts is an attractive route toward propene (propylene) with the potential of industrial application and has been extensively studied over decades. Despite numerous mechanistic studies, the active vanadyl site of the reaction has not been elucidated. In this work, we unravel the ODH reaction mechanism, including the nuclearity-dependent vanadyl and surface dynamics, over ceria-supported vanadia (VOx/CeO2) catalysts by applying (isotopic) modulation excitation IR spectroscopy supported by operando Raman and UV-vis spectroscopies. Based on our loading-dependent analysis, we were able to identify two different mechanisms leading to propylene, which are characterized by isopropyl- and acrylate-like intermediates. The modulation excitation IR approach also allows for the determination of the time evolution of the vanadia, hydroxyl, and adsorbate dynamics, underlining the intimate interplay between the surface vanadia species and the ceria support. Our results highlight the potential of transient IR spectroscopy to provide a detailed understanding of reaction mechanisms in oxidation catalysis and the dynamics of surface catalytic processes in general.