Electrocatalytic Upcycling of Nitrate Wastewater into an Ammonia Fertilizer via an Electrified Membrane

Electrochemically upcycling wastewater nitrogen such as nitrate (NO₃^-) and nitrite (NO₂^-) into an ammonia fertilizer is a promising yet challenging research topic in resource recovery and wastewater treatment. This study presents an electrified membrane made of a CuO@Cu foam and a polytetrafluoroethylene (PTFE) membrane for reducing NO₃^- to ammonia (NH₃) and upcycling NH₃ into (NH₄)₂SO₄, a liquid fertilizer for ready-use. A paired electrolysis process without external acid/base consumption was achieved under a partial current density of 63.8 ± 4.4 mA·cm^-2 on the cathodic membrane, which removed 99.9% NO₃^- in the feed (150 mM NO₃^-) after a 5 h operation with an NH₃ recovery rate of 99.5%. A recovery rate and energy consumption of 3100 ± 91 g-(NH₄)₂SO₄·m^-2·d^-1 and 21.8 ± 3.8 kWh·kg^-1-(NH₄)₂SO₄, respectively, almost outcompete the industrial ammonia production cost in the Haber-Bosch process. Density functional theory (DFT) calculations unraveled that the in situ electrochemical conversion of Cu²⁺ into Cu¹⁺ provides highly dynamic active species for NO₃^- reduction to NH₃. This electrified membrane process was demonstrated to achieve synergistic nitrate decontamination and nutrient recovery with durable catalytic activity and stability.