A Stable and Conductive Covalent Organic Framework with Isolated Active Sites for Highly Selective Electroreduction...

Electroreduction of CO₂ to acetate provides a promising strategy to reduce CO₂ emissions and store renewable energy, but acetate is usually a by-product. Here, we show a stable and conductive two-dimensional phthalocyanine-based covalent-organic framework (COF) as an electrocatalyst for reduction of CO₂ to acetate with a single-product Faradaic efficiency (FE) of 90.3(2)% at -0.8 V (vs. RHE) and a current density of 12.5 mA cm^-2 in 0.1 M KHCO₃ solution. No obvious degradation was observed over 80 hours of continuous operation. Combined with the comparison of the properties of other catalysts with isolated metal active sites, theoretical calculations and in situ infrared spectroscopy revealed that the isolated copper-phthalocyanine active site with high electron density is conducive to the key step of C-C coupling of *CH₃ with CO₂ to produce acetate, and can avoid the coupling of *CO with *CO or *CHO to produce ethylene and ethanol.