Upcycling wastewater nitrate into ammonia fertilizer via concurrent electrocatalysis and membrane extraction

Electrocatalytic upcycling of nitrate (NO₃⁻) in wastewater into the valuable ammonium-based fertilizer has been considered as a green and appealing alternative to biological nitrogen removal or the industrial ammonia (NH₃) production processes. This work investigated an innovative and energy-efficient electrolysis flow-through cell consisting of a porous activated iron nickel (FeNi) alloy cathode and a hollow polypropylene fiber membrane extraction unit to realize the electrochemical NO₃⁻ reduction and simultaneous upcycling to ammonium sulphate salts ((NH₄)₂SO₄). Cathodic and anodic electrochemical half-reactions were coupled to enable NO₃⁻ reduction to ammonia and in-situ acid/base productions to promote the membrane stripping of NH₃. Our results show that after electrolysis operation for 14 h for a synthetic wastewater containing 150 mM NO₃⁻ under a cathodic current density of 30 mA·cm⁻², 99 % of NO₃⁻ removal efficiency, 98 % of ammonia selectivity, 93 % of Faradic efficiency and 97 % of total ammonia nitrogen (TAN) recovery were achieved respectively. A NH₃ recovery flux and a specific energy consumption reached 2050 g-(NH₄)₂SO₄·m⁻²·d⁻¹ and 11 kWh·kg⁻¹-(NH₄)₂SO₄, respectively, which outcompetes many reported processes. Direct electron transfer was the main mechanisms of electrochemical NO₃⁻ reduction to ammonia. Interfacial reaction thermodynamics and kinetics analysis of key intermediates (e.g., *NO₃, *NO₂, and *NO) shows that the NiFe₂O₄ (3 1 1)-Ni site on the thermally activated FeNi alloy surface exhibited higher reactivity and specificity toward electrochemical NO₃⁻ reduction to ammonia over nitrogen (N₂) or hydrogen (H₂) generation. Ultimately, this study aims to promote sustainable nitrogen nutrient recovery and ammonia fertilizer synthesis from wastewater treatment.