Abstract The electrochemical synthesis of propylene oxide is far from practical application due to the limited performance (including activity, stability, and selectivity). In this work, we spatially decouple the bromide-mediated process to avoid direct contact between the anode and propylene, where bromine is generated at the anode and then transferred into an independent reactor to react with propylene. This strategy effectively prevents the side reactions and eliminates the interference to stability caused by massive alkene input and vigorously stirred electrolytes. As expected, the selectivity for propylene oxide reaches above 99.9% with a remarkable Faradaic efficiency of 91% and stability of 750-h (>30 days). When the electrode area is scaled up to 25 cm2, 262 g of pure propylene oxide is obtained after 50-h continuous electrolysis at 6.25 A. These findings demonstrate that the electrochemical bromohydrin route represents a viable alternative for the manufacture of epoxides.
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