RESUMEN
Nitrate-containing wastewaters have been recognized as an important source for recovering valuable ammonia. This work targets integrating a series of transition metals (M = Fe, Co, Ni, and Zn) onto Cu crystallites through a layered-plating method. The strategy to promote the nitrate reduction reaction (NO3-RR) involves tuning M surfaces in specific ratios for the hydrogenation of nitrogenous species on MxCu1-x electrodes. Electrochemical analysis and operando Raman spectra identified that a solid-state Cu2O-to-Cu0 transition acted as the primary mediator, while its high corrosion resistance protected the M metals or metal oxides from inactivation in nitrate-to-ammonia pathways. Among bimetals, FeCu was the best combination, with the order of performance in constant potential electrolysis, Fe0.36Cu0.64 > Ni0.73Cu0.27 > Co0.34Cu0.66 > Zn0.64Cu0.36. The collaboration of Cu and M in deoxygenating nitrate and subsequently hydrogenating NOx at respective overpotentials is key to enhancing ammonia yield. Nitrate removal (96 %), NH3 selectivity (93 %), and Faradaic efficiency (92 %) were optimized on Fe0.36Cu0.64 electrode at -0.6 V (vs. RHE). A steady yield as high as 14,080 µg h-1 mg-1 was achieved at 30 mA cm-2 using a real water sample (NO3- â¼ 500 mg-N L-1, pH 4) as the input stream, continuously operated for 96 h.
RESUMEN
The composite electrode of NiCo oxide supported by porous carbon was synthesized for nitrite oxidation and nitrate electro-sorption. The crystal structure and chemical state of the Co and Ni oxyhydroxides which were precipitated on loofah-derived activated carbon (AC) using hypochlorite were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and BET surface area. The voltammetry showed that the redox couple of Co(II)/Co(III) and Ni(II)/Ni(III) as the mediator catalytically transferred the electrons of NO2-/NO3-; the Ni site had a relatively high transfer coefficient and diffusive current, while the Co site was better in the capacitive removal of the nitrite and nitrate compounds. A batch electrolysis of nitrite ions was operated under constant anodic potential mode (0 to + 1.5 V vs. Ag/AgCl) to assess the performance of the composite electrodes. The adsorption capacity of NiCo/AC (Ni = 5% and Co = 5% on AC by weight) was 23.5 mg-N g-1, which was twice that of AC substrate (7.5 mg-N g-1), based on a multilayer adsorption model. The steady-state kinetics of the consecutive reaction were derived to determine the rate steps of the electrochemical oxidation of NO2- and adsorption of NO3-.