A High Pressure Operando Spectroscopy Examination of Bimetal Interactions in ‘Metal Efficient’ Palladium/In2O3/Al2O3 Catalysts for CO2 Hydrogenation

Abstract CO 2 hydrogenation to methanol has the potential to serve as a sustainable route to a wide variety of hydrocarbons, fuels and plastics in the quest for net zero. Synergistic Pd/In 2 O 3 (Palldium on Indium Oxide) catalysts show high CO 2 conversion and methanol selectivity, enhancing methanol yield. The identity of the optimal active site for this reaction is unclear, either as a Pd−In alloy, proximate metals, or distinct sites. In this work, we demonstrate that metal‐efficient Pd/In 2 O 3 species dispersed on Al 2 O 3 can match the performance of pure Pd/In 2 O 3 systems. Further, we follow the evolution of both Pd and In sites, and surface species, under operando reaction conditions using X‐ray Absorption Spectroscpy (XAS) and infrared (IR) spectroscopy. In doing so, we can determine both the nature of the active sites and the influence on the catalytic mechanism.