Hydrophobic, Ultrastable Cu δ+ for Robust CO 2 Electroreduction to C 2 Products at Ampere-Current Levels.

Copper (Cu) is the only known material that can efficiently electrocatalyze CO 2 to value-added multicarbon products. Owing to the instability of the Cu δ+ state and microscopic structure in reactions, Cu catalysts are still facing big challenges with low selectivity and poor durability, particularly at high current densities. Herein, we report a rational one-step surface coordination approach for the synthesis of Cu dendrites with an ultrastable Cu δ+ state and hydrophobicity (Cu CF), even after exposure to air for over 6 months. As a result, Cu CF exhibited a C 2 FE of 90.6% at a partial current density of 453.3 mA cm -2 in a flow cell. A 400 h stable electrolysis at 800 mA and even a ground-breaking stable operation at a large industrial current of 10 A were achieved in the membrane electrode assembly (MEA) form. We further demonstrated a continuous production of C 2 H 5 OH solution with 90% relative purity at 600 mA over 50 h in a solid-electrolyte reactor. Spectroscopy and computation results suggested that Cu(II) carboxylate coordination species formed on the surface of Cu CF, which ensured the stability of the Cu δ+ state and hydrophobicity. As a result, rich active sites and a stable three-phase interface on the catalyst surface were achieved, along with the optimized *CO adsorption strength and adsorption configuration. The mixed *CO adsorption configurations on Cu CF made the *CO dimerization process easier, which promoted the conversion of CO 2 to C 2 products. This work provides a promising paradigm for the design and development of Cu-based catalysts with ultrahigh stability under industrial current densities.