Operando Spectroscopic Insights into CO2 Reduction at Electrode/Polyelectrolyte Interfaces

The electrode/polyelectrolyte interface is a notable feature in modern electrochemical technologies that utilize membrane electrode assembly (MEA) configurations. However, its interfacial structure and catalytic behavior remain poorly understood. Here we developed an integrated operando Raman spectroscopy and mass spectrometry (MS) method, to directly investigate the CO2 reduction mechanism at the electrode/polyelectrolyte interface within a practical MEA electrolyzer operating at high current densities. Combined with isotope labeling experiments and ab initio molecular dynamics (AIMD) simulations, we provide, for the first time, the direct spectroscopic evidence of *CCO, a crucial intermediate for C2 product formation, which has been frequently hypothesized but rarely detected in previous studies. By contrast, the linearly adsorbed *COL intermediate, typically observed in conventional liquid electrolytes, was absent. These distinct behaviors arise from the unique structure of the electrode/polyelectrolyte interface, which shifts the rate‐determining step from the usual C‐C coupling to the *CCO hydrogenation in the conversion of CO2 to C2 products. This study not only deepens our understanding of electrode/polyelectrolyte interfacial characteristics, but also offers valuable insights for advancing the performance of CO2 MEA electrolyzers.