Molecular Enhancement of Direct Electrolysis of Dilute CO2

Producing chemicals and fuels via direct electrolysis of dilute CO 2 derived from industrial point sources can improve the economic feasibility of CO 2 electrolysis technology, yet it suffers from many challenges owing to unfavorable mass transport, reaction thermodynamics, and kinetics. Here we report a molecular enhancement strategy for direct electrolysis of a dilute CO 2 stream with a 10% concentration in typical flue gas, using a commercially available cobalt phthalocyanine (CoPc) catalyst. A poly(4-vinylpyridine) (P4VP)-modified CoPc electrode exhibits a remarkable CO partial current density of 252 mA cm –2 with a CO Faradaic efficiency of 90% under the dilute CO 2 feed, 2.24-fold higher than that of the bare CoPc electrode. The integration of the CoPc molecule and the P4VP modifier with abundant pyridine moieties creates a reaction microenvironment for sequentially capturing and activating CO 2, thus resulting in impressive electrocatalytic performance. The presented molecular enhancement strategy paves the way for direct utilization of a dilute CO 2 stream from industrial flue gas.