Bromine-Enhanced Generation and Epoxidation of Ethylene in Tandem CO2 Electrolysis Towards Ethylene Oxide

The indirect electro-epoxidation of ethylene (C₂H₄), produced from CO₂ electroreduction (CO₂R), holds immense promise for CO₂ upcycling to valuable ethylene oxide (EO). However, this process currently has a mediocre Faradaic efficiency (FE) due to sluggish formation and rapid dissociation of active species, as well as reductive deactivation of Cu-based electrocatalysts during the conversion of C₂H₄ to EO and CO₂ to C₂H₄, respectively. Herein, we report a bromine-induced dual-enhancement strategy designed to concurrently promote both C₂H₄-to-EO and CO₂-to-C₂H₄ conversions, thereby improving EO generation, using single-atom Pt on N-doped CNTs (Pt₁/NCNT) and Br⁻-bearing porous Cu₂O as anode and cathode electrocatalysts, respectively. Physicochemical characterizations including synchrotron X-ray absorption, operando infrared spectroscopy, and quasi in situ Raman spectroscopy/electron paramagnetic resonance with theoretical calculations reveal that the favorable Br₂/HBrO generation over Pt₁/NCNT with optimal intermediate binding facilitates C₂H₄-to-EO conversion with a high FE of 92.2 %, and concomitantly, the Br⁻ with strong nucleophilicity protects active Cu⁺ species in Cu₂O effectively for improved CO₂-to-C₂H₄ conversion with a FE of 66.9 % at 800 mA cm⁻², superior to those in the traditional chloride-mediated case. Consequently, a single-pass FE as high as 41.1 % for CO₂-to-EO conversion can be achieved in a tandem system.