Novel Denitrification Fuel Cell for Energy Recovery of Nitrate-N and TN Removal Based on NH4+ Generation on a CNW@CF Cathode.

NO3- is an undesirable environmental pollutant that causes eutrophication in aquatic ecosystems, and its pollution is difficult to eliminate because it is easily converted into NH4+ instead of N2. Additionally, it is a high-energy substance. Herein, we propose a novel denitrification fuel cell to realize the chemical energy recovery of NO3- and simultaneous conversion of total nitrogen (TN) into N2 based on the outstanding ability of NH4+ generation on a three-dimensional copper nanowire (CNW)-modified copper foam (CF) cathode (CNW@CF). The basic steps are as follows: direct and highly selective reduction of NO3- to NH4+ rather than to N2 on the CNW@CF cathode, on which negative NO3- ions can be easily adsorbed due to their double-electron layer structure and active hydrogen ([H]) can be generated due to a large number of catalytic active sites exposed on CNWs. Then, NH4+ is selectively oxidized to N2 by the strong oxidation of chlorine free radicals (Cl•), which originate from the reaction of chlorine ions (Cl-) by photogenerated holes (h+) and hydroxyl radicals (OH•) under irradiation. Then, the electrons from the oxidation on the photoanode is transferred to the cathode to form a closed loop for external power generation. Owing to the continuous redox loop, NO3- completely reduces to N2, and the released chemical energy is converted into electrical energy. The results indicate that 99.9% of NO3- can be removed in 90 min, and the highest yield of electrical power density reaches 0.973 mW cm-2, of which the nitrate reduction rates on the CNW@CF cathode is 79 and 71 times higher than those on the Pt and CF cathodes, respectively. This study presents a novel and robust energy recycling concept for treating nitrate-rich wastewater.