Spin Polarized Chiral Co₃O₄ Boosts High-Pressure CO₂ Electroreduction to Ethanol With 90% Selectivity

Electrocatalytic CO₂ reduction (CO₂RR) to value-added multicarbon products using non-copper-based catalysts remains a major challenge, especially for selective ethanol production. Herein, we report that chiral Co₃O₄ featuring strong electron spin polarization achieves a maximum ethanol Faradaic efficiency of 90% at -0.9 V versus NHE in KHCO₃ electrolytes under a 30 bar CO₂ pressure, substantially outperforming both racemic Co₃O₄ and previously reported non-copper-based catalysts. The enhanced spin polarization in chiral Co₃O₄ facilitates electron transfer and promotes the activation of the adsorbed CO₂, while also lowering the free energy change for C-C coupling to form *COCHO intermediate, thereby promoting ethanol production. Our work establishes spin polarization as a key determinant for efficient C-C coupling on non-copper-based catalysts and provides mechanistic principles for the rational design of CO₂RR electrocatalyst.