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• W2235320605 abstract "The electrochemical treatment of water contaminated by nitrate is receiving more and more attention due to its convenience, low investment cost and environmental friendliness, particularly if the resulting product is harmless nitrogen. In this context, the most efficient electrochemical process for converting nitrate to nitrogen is based on a paired electrolysis where nitrate is reduced to ammonia at the cathode and chlorine is generated at the anode and immediately transformed to hypochlorite, which reacts with ammonia to produce N2 according to the reaction: 2ClO + 2NH3 + 2OH ↔ N2 + 2Cl + 4H2O. At a pure copper cathode, the electroreduction of nitrate produces ammonia and nitrite depending on the electrode potential. In that case, nitrite ions are subsequently oxidized to nitrate at the anode, which strongly decreases the efficiency of the paired electrolysis. A way to avoid this problem is to use a cation exchange membrane (between the anode and the cathode) preventing nitrite to reach the anode. However, during wastewater treatment, the pores of the membrane would be blocked with organic and inorganic compounds (e.g., carbonates) making it ineffective. Another limitation of copper is its poor corrosion resistance in presence of chloride, nitrate and ammonia. The aim of this study was thus to optimize the nitrate removal by a paired electrolysis process by finding a new cathode material with a better corrosion resistance than copper and a good activity and selectivity for the electroconversion of nitrate to ammonia. The corrosion resistance of Ni, Cu, Cu90Ni10 and Cu70Ni30 (wt.%) electrodes was studied in presence of chloride, nitrate and ammonia and their activity and selectivity toward ammonia generation during nitrate electroreduction was evaluated. Then, the most promising Cu-Ni alloy was tested as cathode material in an unseparated muti-electrode electrolyzer in semi batch mode. Lastly, the effect of chloride concentration on the efficiency of the electrochemical process was investigated. The electrochemical corrosion investigation revealed that nickel and cupro-nickel electrodes have corrosion rates four to ten times slower than pure copper in presence of nitrate and ammonia, respectively. This corrosion resistance of Ni-containing materials is attributed to the formation of a NiO/Ni(OH)2 stable and protective layer on the electrode surface. Moreover, the pitting potential of cupro-nickel alloys in presence of chloride remains 100 to 200 mV higher that of pure copper and nickel. This higher resistance to localized corrosion was confirmed by 72h immersion tests. According to this electrochemical corrosion study, the order of the corrosion resistance of these materials is Ni ~ Cu70Ni30 > Cu90Ni10 >> Cu. The next step of this study was to evaluate the electrochemical behavior of the Cu, Ni, Cu90Ni10 and Cu70Ni30 materials toward nitrate electroreduction. The linear sweep voltammograms (LSV) (Fig. 1) of copper in presence of 0.01 M nitrate shows two reduction waves. The first one at ca. −1.0 VSCE is attributed to the reduction of nitrate to nitrite, and the second one at ca. −1.3 VSCE is assigned to the reduction of nitrite to ammonia. LSVs recorded in presence of nitrate of pure nickel and cupronickel electrodes show only one peak at -1.1 VSCE. Prolonged electrolyses demonstrates that this wave corresponds to the direct reduction of nitrate to ammonia. As conclusion, Cu70Ni30 electrode shows the best activity for the electroreduction of nitrate to ammonia and a good corrosion resistance in presence of chloride, ammonia or nitrate in alkaline solution. It was thus selected as cathode material for paired electrolyses. Paired electrolyses were carried by using an undivided (i.e., without membrane) multi-cell electrolyzer with Cu70Ni30 as cathode material and Ti/IrO2 as anode material. For comparison, pure Ni and Cu were also tested as cathode materials. During these electrolyses, ammonia was never detected, suggesting that it was immediately oxidized to nitrogen at the anode. Results revealed that Cu70Ni30 is the best cathode for the conversion of nitrate to nitrogen by paired electrolysis, the nitrate concentration decreasing from 620 to less than 50 ppm in 3 hours (Fig. 2), with an energy consumption as low as 20 kWh/kg NO3." @default.
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• W2235320605 date "2011-01-01" @default.
• W2235320605 modified "2023-09-25" @default.
• W2235320605 title "Nitrate Removal by a Paired Electrolysis Process" @default.
• W2235320605 doi "https://doi.org/10.1149/ma2011-01/28/1605" @default.
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