Exhaustive denitrification via chlorine oxide radical reactions for urea based on a novel photoelectrochemical cell

Urea is a major source of nitrogen pollution in domestic sewage and its denitrification is difficult since it is very likely to be converted into ammonia or nitrate instead of expected N₂. Herein, we propose an exhaustive denitrification method for urea via the oxidation of amine/ammonia-N with chlorine oxide radical, which induced from a bi-functional RuO₂//WO₃ anode, and the highly selective reduction of nitrate-N on cathode in photoelectrochemical cell (PEC). Under illumination, the WO₃ photoanode side promotes the quantities hydroxyl and reactive chlorine radical, and these radicals are immediately combined to stronger chlorine oxide radical by RuO₂ side, which obviously enhances the efficiency and speed of the urea oxidation. Synchronously, the over-oxidized nitrate can be selectively reduced by Pd and Au nanoparticles on the surface of cathode. Eventually, exhaustive denitrification is realized by the circulative reaction. Experimental observations and theoretical calculation revealed that chlorine oxide radical promoted significant denitrification of urea with an efficiency of 99.74% in 60 min under the optimum condition. The removal rate constant of the RuO₂//WO₃ anode was 3.08 times than that of single WO₃ anode and 2.64 times than that of single RuO₂ anode, confirming the chlorine oxide radical had stronger ability on denitrification than reactive chlorine radical. Also, the bi-functional anode contributed to best current efficiencies, utilizing the energy availably. This work proposes a promising method of exhaustive denitrification for urea.