Oxidation State and Surface Reconstruction of Cu under CO₂ Reduction Conditions from In Situ X‑ray Characterization

The electrochemical CO₂ reduction reaction (CO₂RR) using Cu-based catalysts holds great potential for producing valuable multi-carbon products from renewable energy. However, the chemical and structural state of Cu catalyst surfaces during the CO₂RR remains a matter of debate. Here, we show the structural evolution of the near-surface region of polycrystalline Cu electrodes under in situ conditions through a combination of grazing incidence X-ray absorption spectroscopy (GIXAS) and X-ray diffraction (GIXRD). The in situ GIXAS reveals that the surface oxide layer is fully reduced to metallic Cu before the onset potential for CO₂RR, and the catalyst maintains the metallic state across the potentials relevant to the CO₂RR. We also find a preferential surface reconstruction of the polycrystalline Cu surface toward (100) facets in the presence of CO₂. Quantitative analysis of the reconstruction profiles reveals that the degree of reconstruction increases with increasingly negative applied potentials, and it persists when the applied potential returns to more positive values. These findings show that the surface of Cu electrocatalysts is dynamic during the CO₂RR, and emphasize the importance of in situ characterization to understand the surface structure and its role in electrocatalysis.