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Solid oxide cell technologies play a pivotal role in the realm of renewable energy storage, guiding us through the journey toward decarbonization. Understanding how electrocatalytic materials behave under high‐temperature conditions is an absolute necessity to push these technologies forward. Operando spectroscopic investigations, such as near‐ambient pressure X‐ray photoelectron spectroscopy (NAP–XPS), offer insights into the chemical nature of active working electrodes, including the dynamic response of redox states and adsorbate chemistry to changing electrochemical conditions. Mixed ceramic–metallic electrodes exhibit a limited region with electrochemically active triple‐phase‐boundary (TPB) sites, which are located close to the electrolyte/electrode interface. To monitor this specific region spectroscopically, metallic (Ni) and bimetallic (NiCu) network‐like structures are synthesized on a yttria‐stabilized zirconia electrolyte and the electrochemical state and performance are studied by using operando NAP–XPS. In the experiments, the surface oxidation states under different polarizations are revealed, the gas composition dependent Nernst shift is confirmed, electrocatalytic activities are unraveled, and hydrogen evolution is correlated with the applied potential. The findings demonstrate, the effectiveness of thin‐film model cells with spectroscopically accessible TPB regions for probing interfacial states and electrochemical processes. The obtained fundamental knowledge can provide valuable insights for the advancement of renewable energy storage technologies.

The reactive metal-support interaction in the Cu-In2O3 system and its implications on the CO2 selectivity in methanol steam reforming (MSR) have been assessed using nanosized Cu particles on a powdered cubic In2O3 support. Reduction in hydrogen at 300 °C resulted in the formation of metallic Cu particles on In2O3. This system already represents a highly CO2-selective MSR catalyst with ~93% selectivity, but only 56% methanol conversion and a maximum H2 formation rate of 1.3 µmol gCu−1 s−1. After reduction at 400 °C, the system enters an In2O3-supported intermetallic compound state with Cu2In as the majority phase. Cu2In exhibits markedly different self-activating properties at equally pronounced CO2 selectivities between 92% and 94%. A methanol conversion improvement from roughly 64% to 84% accompanied by an increase in the maximum hydrogen formation rate from 1.8 to 3.8 µmol gCu−1 s−1 has been observed from the first to the fourth consecutive runs. The presented results directly show the prospective properties of a new class of Cu-based intermetallic materials, beneficially combining the MSR properties of the catalyst’s constituents Cu and In2O3. In essence, the results also open up the pathway to in-depth development of potentially CO2-selective bulk intermetallic Cu-In compounds with well-defined stoichiometry in MSR.