Environment Matters: CO₂RR Electrocatalyst Performance Testing in a Gas-Fed Zero-Gap Electrolyzer

Among the electrolyzers under development for CO₂ electroreduction at practical reaction rates, gas-fed approaches that use gas diffusion electrodes (GDEs) as cathodes are the most promising. However, the insufficient long-term stability of these technologies precludes their commercial deployment. The structural deterioration of the catalyst material is one possible source of device durability issues. Unfortunately, this issue has been insufficiently studied in systems using actual technical electrodes. Herein, we make use of a morphologically tailored Ag-based model nanocatalyst [Ag nanocubes (NCs)] assembled on a zero-gap GDE electrolyzer to establish correlations between catalyst structures, experimental environments, electrocatalytic performances, and morphological degradation mechanisms in highly alkaline media. The morphological evolution of the Ag–NCs on the GDEs induced by the CO₂ electrochemical reduction reaction (CO₂RR), as well as the direct mechanical contact between the catalyst layer and anion-exchange membrane, is analyzed by identical location and post-electrolysis scanning electron microscopy investigations. We find that at low and mild potentials positive of −1.8 V versus Ag/AgCl, the Ag–NCs undergo no apparent morphological alteration induced by the CO₂RR, and the device performance remains stable. At more stringent cathodic conditions, device failure commences within minutes, and catalyst corrosion leads to slightly truncated cube morphologies and the appearance of smaller Ag nanoparticles. However, comparison with complementary CO₂RR experiments performed in H-cell configurations in a neutral environment clearly proves that the system failure typically encountered in the gas-fed approaches does not stem solely from the catalyst morphological degradation. Instead, the observed CO₂RR performance deterioration is mainly due to the local high alkalinity that inevitably develops at high current densities in the zero-gap approach and leads to the massive precipitation of carbonates which is not observed in the aqueous environment (H-cell configuration).