Direct electrosynthesis and separation of ammonia and chlorine from waste streams via a stacked membrane-free electrolyzer.

Electrosynthesis, a viable path to decarbonize the chemical industry, has been harnessed to generate valuable chemicals under ambient conditions. Here, we present a membrane-free flow electrolyzer for paired electrocatalytic upcycling of nitrate (NO) and chloride (Cl) to ammonia (NH) and chlorine (Cl) gases by utilizing waste streams as substitutes for traditional electrolytes. The electrolyzer concurrently couples electrosynthesis and gaseous-product separation, which minimizes the undesired redox reaction between NH and Cl and thus prevents products loss. Using a three-stacked-modules electrolyzer system, we efficiently processed a reverse osmosis retentate waste stream. This yielded high concentrations of (NH)SO (83.8 mM) and NaClO (243.4 mM) at an electrical cost of 7.1 kWh per kilogram of solid products, while residual NH/NH (0.3 mM), NO (0.2 mM), and Cl/HClO/ClO (0.1 mM) pollutants in the waste stream could meet the wastewater discharge regulations for nitrogen- and chlorine-species. This study underscores the value of pairing appropriate half-reactions, utilizing waste streams to replace traditional electrolytes, and merging product synthesis with separation to refine electrosynthesis platforms.