Abstract

Electrochemical CO2 conversion into valuable products provides a promising solution for achieving a carbon-neutral energy cycle. Herein, an active and stable Bi/Nafion interface is fabricated over Bi nanosheets with the modification of Nafion, which exhibits superior CO2 conversion with formate selectivity of above 95% in a wide potential range, partial current density of 72.12 mA cm−2 at − 1.07 V vs. RHE in H-type cell. The extraordinary CO2 reduction performance could be ascribed to a high CO2 permeability and enhanced local proton activity at the Bi/Nafion interface, which leads to promoted CO2 adsorption and feasible proton-coupled electron transfer during the CO2 reduction process. Computational investigations reveal the modification of Nafion offers a comfortable platform to enable the key intermediate *OCHO to be stable. This work offers a valuable insight into interfacial manipulation of electrodes to convert CO2 to valuable products.

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