Molecular-Fence Confinement Enabling Efficient Acidic CO 2 Electroreduction to Multi-carbon Products

Acidic CO2 electroreduction (CO2ER) enhances carbon utilization but faces significant challenges: intense hydrogen evolution reaction competition and poor multicarbon (C2+) product selectivity. We identify that this stems primarily from acid-induced destabilization of the critical *CO intermediate, exacerbated by adsorbed hydrogen. Here, we propose a dual-modification “molecular-fence” strategy to reconfigure the catalyst–electrolyte interface. We first engineer atomically dispersed Lewis acid Zr sites on Cu to electronically accelerate *CO formation. Subsequently, we anchor π-conjugated benzo-2,1,3-thiadiazole (BTD) molecules, which form a physical fence that spatially confines *CO intermediates and electrogenerated OH–. This synergy creates and sustains a localized, highly alkaline microenvironment in bulk acidic media, which concentrates *CO coverage and strengthens *CO binding to accelerate C–C coupling kinetics for acidic CO2ER. As a result, we achieve Faradaic efficiencies of 57.0% for ethylene (C2H4) and 74.9% for total C2+ products at 600 mA cm–2. Single-pass carbon efficiencies reach 64.2% for C2H4 and 79.9% for C2+. Remarkably, a high C2H4 selectivity (>52.0%) is sustained across a wide current density range of 400 to 700 mA cm–2. This work establishes the molecular-fence strategy as a broadly applicable paradigm for regulating interfacial microenvironments to enable efficient and selective CO2ER in challenging acidic media.