Reaction-Induced Metal-Metal Oxide Interactions in Pd In2O3/ZrO2 Catalysts Drive Selective and Stable CO2 Hydrogenation to Methanol

<p>Ternary Pd-In₂O₃/ZrO₂ systems hold promise as industrial catalysts for CO₂-based methanol synthesis, but maximization of their productivity requires appropriate structuring of the active phase, promoter, and carrier. Here, we report that Pd-In₂O₃/ZrO₂ systems prepared by impregnation evolve into a unique catalyst architecture under CO₂ hydrogenation conditions, leading to selective and stable behavior. Detailed space and time-resolved <em>operando</em> characterization and simulations reveal that the restructuring process, completed within the first 30&nbsp;min under reaction conditions, is governed by the energetics of metal-metal oxide interactions. The resulting architecture comprises InPd<em>_x</em> alloy particles decorated by InO<em>_x</em> layers, whose proximity is crucial to avoiding performance losses typically observed when palladium agglomerates. The findings highlight the potential beneficial role of reaction-induced restructuring in advancing catalyst design.</p>