Multivalent Cu sites synergistically adjust carbonaceous intermediates adsorption for electrocatalytic ethanol production

Copper (Cu)-based catalysts show promise for electrocatalytic CO₂ reduction (CO₂RR) to multi-carbon alcohols, but thermodynamic constraints lead to competitive hydrocarbon (e.g., ethylene) production. Achieving selective ethanol production with high Faradaic efficiency (FE) and current density is still challenging. Here we show a multivalent Cu-based catalyst, Cu-2,3,7,8-tetraaminophenazine-1,4,6,9-tetraone (Cu-TAPT) with Cu²⁺ and Cu⁺ atomic ratio of about 1:2 for CO₂RR. Cu-TAPT exhibits an ethanol FE of 54.3 ± 3% at an industrial-scale current density of 429 mA cm⁻², with the ethanol-to-ethylene ratio reaching 3.14:1. Experimental and theoretical calculations collectively unveil that the catalyst is stable during CO₂RR, resulting from suitable coordination of the Cu²⁺ and Cu⁺ with the functional groups in TAPT. Additionally, mechanism studies show that the increased ethanol selectivity originates from synergy of multivalent Cu sites, which can promote asymmetric C–C coupling and adjust the adsorption strength of different carbonaceous intermediates, favoring hydroxy-containing C₂ intermediate (*HCCHOH) formation and formation of ethanol.