Substituent tuning of Cu coordination polymers enables carbon-efficient CO2 electroreduction to multi-carbon products

CO 2 electroreduction is a potential pathway to achieve net-zero emissions in the chemical industry. Yet, CO 2 loss, resulting from (bi)carbonate formation, renders the process energy-intensive. Acidic environments can address the issue but at the expense of compromised product Faradaic efficiencies (FEs), particularly for multi-carbon (C 2+ ) products, as rapid diffusion and migration of protons (H + ) favors competing H 2 and CO production. Here, we present a strategy of tuning the 2-position substituent length on benzimidazole (BIM)-based copper (Cu) coordination polymer (CuCP) precatalyst – to enhance CO 2 reduction to C 2+ products in acidic environments. Lengthening the substituent from H to nonyl enhances H + diffusion retardation and decreases Cu-Cu coordination numbers (CNs), favoring further reduction of CO. This leads to a nearly 24× enhancement of selectivity towards CO hydrogenation and C-C coupling at 60 mA cm −2 . We report the highest C 2+ product FE of more than 70% at 260 mA cm −2 on pentyl-CuCP and demonstrate a CO 2 -to-C 2+ single-pass conversion (SPC) of ~54% at 180 mA cm −2 using pentyl-CuCP in zero-gap electrolyzers. Acidic CO 2 electroreduction suffers poor selectivity for multi-carbon products. Here, the authors report that lengthening the 2-position substituents of benzimidazole-based copper coordination polymer precatalysts retards H + diffusion, reduces Cu-Cu coordination numbers, and promotes C-C coupling.