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Abstract 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 (NO₃⁻) and chloride (Cl⁻) to ammonia (NH₃) and chlorine (Cl₂) 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 NH₃and Cl₂and 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 (NH₄)₂SO₄(83.8 mM) and NaClO (243.4 mM) at an electrical cost of 7.1 kWh per kilogram of solid products, while residual NH₃/NH₄⁺(0.3 mM), NO₂⁻(0.2 mM), and Cl₂/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. 

Abstract Electrochemical upcycling of nitrate into ammonia at ambient conditions offers a sustainable synthesis pathway that can complement the current industrial NH₃production from the Haber–Bosch process. One of the key rate‐limiting steps is the effective desorption of gaseous or interfacial bubble products, mainly NH₃with some minor side products of nitrogen and hydrogen, from the electrode surfaces to sustain available sites for the NO₃⁻reduction reaction. To facilitate the gaseous product desorption from the catalytic sites, hydrophobic polytetrafluoroethylene (PTFE) nanoparticles are blended within a CuO catalyst layer, which is shown to eliminate the undesirable accumulation and blockage of electrode surfaces and largely decouples the electron‐ and phase‐transfer processes. The NH₃partial current density normalized by the electrochemically active surface area (ECSA) increases by nearly a factor of 17.8 from 11.4 ± 0.1 to 203.3 ± 1.8 mA cm⁻²_ECSA. The DFT and ab‐initio molecular dynamics simulations suggest that the hydrophobic PTFE nanoparticles may serve as segregated islands to enhance the spillover and transport the gaseous products from electrocatalysts to the PTFE. Thus, a higher ammonia transfer is achieved for the mixed PTFE/CuO electrocatalyst. This new and simple strategy is expected to act as inspiration for future electrochemical gas‐evolving electrode design.