Triadic Sites Drive Tandem CO₂-to-Ethanol Conversion by Steering *CO Coverage and *COH Intermediate Formation

Single metal-coordinated nitrogen-doped carbon (M₁-NC) materials hold great promise for electrocatalytic CO₂ reduction, yet the precise modulation of their nitrogen configurations to steer ethanol selectivity remains a formidable challenge. Here, we designed Cu₁-NC anchored on a carbon support featured with a high pyrrolic-N to pyridinic-N ratio (CuN₄/pr-h-NC), which enables an exceptional Faradaic efficiency (FE) of 79.6% for ethanol. Experimental and theoretical studies reveal that pyrrolic-N and pyridinic-N synergize with Cu sites to form novel triadic sites, which regulate the potential-determining step (PDS) from the traditional C–C coupling step to the protonation step of *CO to *COH. Pyrrolic N boosts *CO surface coverage, after which *CO migrates to neighboring pyridinic N sites for hydrogenation to *COH. The resulting *COH readily couples with another *CO at the single Cu site, driving selective ethanol formation. Due to the single-metal-surface-independence of PDS, this mechanism extends to metals traditionally considered inactive for C–C coupling (M = Fe, Co, Ni, Zn). A positive correlation is observed between the ethanol FE and the pyrrolic N/pyridinic N ratio across the series, with ZnN₄/pr-h-NC reaching 71.8% at –0.5 V versus RHE. This work establishes an ensemble site engineering strategy to rationally steer CO₂ to ethanol pathways for M₁-NC electrocatalysts.