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Abstract In‐situ infrared spectroscopy is one of the most effective methods to study the surface species on solid catalysts. Still, it is sometimes difficult to identify the reactive intermediates because spectator species, the catalyst support, and experimental noise also contribute to the total spectra. In this study, we prepared three archetypical Ni/Al 2 O 3 catalysts that showed significantly different catalytic activity and selectivity for CO 2 hydrogenation, depending on the calcination and reduction temperature. After detailed characterization, we used a combination of Modulation Excitation‐Phase Sensitive Detection‐Diffuse Reflectance Infrared Fourier Transform Spectroscopy (ME‐PSD‐DRIFTS) and Steady State Isotopic Kinetic Analysis (SSITKA) to show that bicarbonates and formates are key reactive intermediates. Furthermore, we also observe carbonyls on the catalyst with the most metallic character and highest selectivity towards CH 4 . These results confirm that the hydrogenation of CO 2 occurs in an associative and consecutive reaction pathway that is highly structure‐sensitive. In this way, we also demonstrate how the simultaneous collection of spectroscopic and kinetic data during modulated or transient experiments is a powerful tool for investigating solid catalysts under realistic operation conditions.
Kock et al. (Sat,) studied this question.