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It is challenging to develop a competent catalyst achieving both high current thickness and large Faradaic effectiveness (FE) for CO2RR. Herein, we synthesized fluorine-doped cagelike permeable carbon (F-CPC) by purposely tailoring its structural properties. The optimized F-CPC possesses big surface with modest mesopore and abundant micropores in addition to large electrical conductivity. When used as catalyst for CO2RR, F-CPC exhibits FE of 88.3per cent for CO at -1.0 V vs RHE with a cu