Dry reforming of methane (DRM) is an attractive reaction for synthesis gas production, since it converts two greenhouse gases into valuable chemical feedstock. Silica supported bimetallic catalysts with constant metal loading but varying Ni/Co ratios (x_Ni=1, 0.8, 0.6, 0.5, 0.4, 0.2, 0) were produced via spray‐drying for the application in DRM, aiming at the identification of compositions with superior activity. In this study, building block particles refer to an inert framework, supporting the catalyst. The elemental distribution of Si, Ni, and Co within such building block particles was evaluated using scanning transmission electron microscopy. Additionally, X‐ray diffraction and temperature‐programmed reduction experiments confirmed that Ni and Co initially exist in an oxidic state within the SiO₂ framework after production and later transform into an alloyed metallic state upon reduction with hydrogen, as confirmed by X‐ray photoelectron spectroscopy. A systematic comparison of the activity over a temperature range (323–1150 K) was performed using temperature scanning measurements. The highest intrinsic activity was found with the bimetallic Ni₄₀Co₆₀ particles.

The activity and stability of Ni-based catalysts for CO₂ methanation strongly depend on the morphology and chemical composition of the support. In this work, Ni catalysts with four oxidic supports (SiO₂, Al₂O₃, CeO₂, ZrO₂) were synthesized via a one-step spray pyrolysis approach. Comprehensive characterization by STEM-EDS, XRD, and N₂ adsorption was used to resolve support morphology, Ni particle size, and nanoparticle incorporation into the support matrix. Beyond steady-state activity and reaction mechanism, the support material also affects the activation period and initial stability of the catalysts. By combining temperature-programmed methanation scans on fresh and spent samples with long-term stability tests, we clearly identify support-dependent changes in initial activity and their correlation with Ni–support interactions. Enhanced physical embedding and stronger chemical binding of Ni nanoparticles significantly reduce activity changes during the first hours on stream. Overall, this study demonstrates that the support and the corresponding metal–support interactions not only affect reaction pathways and activity, but also the pretreatment and activation required to reach a stable operating point, which is of crucial importance in kinetic catalysis research.