Bifunctional Gas Diffusion Electrode Enables In Situ Separation and Conversion of CO₂ to Ethylene from Dilute Stream

Abstract The requirement of concentrated carbon dioxide (CO₂) feedstock significantly limits the economic feasibility of electrochemical CO₂ reduction (eCO₂R) which often involves multiple intermediate processes, including CO₂ capture, energy‐intensive regeneration, compression, and transportation. Herein, a bifunctional gas diffusion electrode (BGDE) for separation and eCO₂R from a low‐concentration CO₂ stream is reported. The BGDE is demonstrated for the selective production of ethylene (C₂H₄) by combining high‐density‐polyethylene‐derived porous carbon (HPC) as a physisorbent with polycrystalline copper as a conversion catalyst. The BGDE shows substantial tolerance to 10 vol% CO₂ exhibiting a Faradaic efficiency of ≈45% toward C₂H₄ at a current density of 80 mA cm⁻², outperforming previous reports that utilized such partial pressure (P_CO2 = 0.1 atm and above) and unaltered polycrystalline copper. Molecular dynamics simulation and mixed gas permeability assessment reveal that such selective performance is ensured by high CO₂ uptake of the microporous HPC as well as continuous desorption owing to the molecular diffusion and concentration gradient created by the binary flow of CO₂ and nitrogen (CO₂|N₂) within the sorbent boundary. Based on detailed techno‐economic analysis, it is concluded that this in situ process can be economically compelling by precluding the C₂H₄ production cost associated with the energy‐intensive intermediate steps of the conventional decoupled process.