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

A 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.