Highly selective transformation of ammonia nitrogen to N₂ based on a novel solar-driven...

A highly selective method for transforming ammonia nitrogen to N₂ was proposed, based on a novel solar-driven photoelectrocatalytic-chlorine radical reactions (PEC-chlorine) system. The PEC-chlorine system was facilitated by a visible light response WO₃ nanoplate array (NPA) electrode in an ammonia solution containing chloride ions (Cl^-). Under illumination, photoholes from WO₃ promote the oxidation of Cl^- to chlorine radical (Cl). This radical can selectively transform ammonia nitrogen to N₂ (79.9%) and NO₃^- (19.2%), similar to the breakpoint chlorination reaction. The ammonia nitrogen removal efficiency increased from 10.6% (PEC without Cl^-) to 99.9% with the PEC-chlorine system within 90 min operation, which can be attributed to the cyclic reactions between Cl^-/Cl and the reaction intermediates (NH₂, NHCl, etc.) that expand the degradation reactions from the surface of the electrodes to the whole solution system. Moreover, Cl is the main radical species contributing to the transformation of ammonia nitrogen to N₂, which is confirmed by the tBuOH capture experiment. Compared to conventional breakpoint chlorination, the PEC-chlorine system is a more economical and efficient means for ammonia nitrogen degradation because of the fast removal rate, no additional chlorine cost, and its use of clean energy (since it is solar-driven).