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

Ternary Pd‐In₂O₃/ZrO₂ catalysts exhibit technological potential for CO₂‐based methanol synthesis, but developing scalable systems and comprehending complex dynamic behaviors of the active phase, promoter, and carrier are key for achieving high productivity. Here, we show that the structure of Pd‐In₂O₃/ZrO₂ systems prepared by wet impregnation evolves under CO₂ hydrogenation conditions into a selective and stable architecture, independent of the order of addition of Pd and In phases on the zirconia carrier. Detailed operando characterization and simulations reveal a rapid restructuring driven by the metal‐metal oxide interaction energetics. The proximity of InPd_x alloy particles decorated by InO_x layers in the resulting architecture prevents performance losses associated with Pd sintering. The findings highlight the crucial role of reaction‐induced restructuring in complex CO₂ hydrogenation catalysts and offer insights into the optimal integration of acid‐base and redox functions for practical implementation.