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The research of steady-state electrochemical kinetics of effective and selective conversion of total nitrogen to N2

  • Zhiping Ye
  • Ruxue Shen
  • Xule Zhou
  • Jachao Yao
  • Jade WangEmail author
Research Article
  • 30 Downloads

Abstract

The electrochemical conversion of inorganic nitrogen forms (i.e., NO3-N, NO2-N, and NH4+-N) to N2 was studied using Ti as cathode and Ti/PbO2 as anode in the simulated wastewater. According to linear sweep voltammetry, nitric nitrogen was effectively converted to N2 on Ti cathode at the working potential more negative than − 1.1 V (vs. SCE). Ti/PbO2 anode had the working potential of + 0.8 V (vs. SCE) for NH4+-N converted to N2. The apparent rate constants of NO3-N to NO2-N and NO2-N to N2 were 2.46 × 10−2 min−1 and 4.03 × 10−2 min−1, respectively. The kinetic analyses revealed that the reduction of NO3-N was a two-step process, and NO2-N was an unstable intermediate, which could be easily oxidized to NO3-N or reduced to NH4+-N. The majority of NH4+-N could be effectively converted to N2 on Ti/PbO2 anode with the apparent rate constants of 5.12 × 10−2 min−1. The dual-chamber (DC) reactor with circulation was used in the batch electrolysis of simulated and actual wastewater. The results verified the pathways of NH4+-N oxidation and NO3-N reduction and achieved high conversion rate of total nitrogen (TN) to N2.

Keywords

Reaction kinetics Electrochemical conversion Nitric nitrogen Ammonia Ti cathode Ti/PbO2 anode 

Notes

Funding information

The authors thank the National Natural Science Foundation of China (No. 51878614) for the financial support of this work.

References

  1. Ansari A, Nematollahi D (2018) A comprehensive study on the electrocatalytic degradation, electrochemical behavior and degradation mechanism of malachite green using electrodeposited nanostructured β-PbO2 electrodes. Water Res 144:462–473CrossRefGoogle Scholar
  2. Aouina N, Cachet H, Debiemme-Chouvy C, Tran TTM (2010) Insight into the electroreduction of nitrate ions at a copper electrode, in neutral solution, after determination of their diffusion coefficient by electrochemical impedance spectroscopy. Electrochim Acta 55:7341–7345CrossRefGoogle Scholar
  3. Bouzek K, Paidar M, Sadílková A, Bergmann H (2001) Electrochemical reduction of nitrate in weakly alkaline solutions. J Appl Electrochem 31:1185–1193Google Scholar
  4. Bunce NJ, Bejan D (2011) Mechanism of electrochemical oxidation of ammonia. Electrochim Acta 56:8085–8093CrossRefGoogle Scholar
  5. Camargo JA, Alonso A, Salamanca A (2005) Nitrate toxicity to aquatic animals: a review with new data for freshwater invertebrates. Chemosphere 58:1255–1267CrossRefGoogle Scholar
  6. Candido L, Gomes JACP (2011) Evaluation of anode materials for the electro-oxidation of ammonia and ammonium ions. Mater Chem Phys 129:1146–1151CrossRefGoogle Scholar
  7. Cao J, Zhao H, Cao F, Zhang J, Cao C (2009) Electrocatalytic degradation of 4-chlorophenol on F-doped PbO2 anodes. Electrochim Acta 54:2595–2602CrossRefGoogle Scholar
  8. Cremasco A, Osório WR, Freire CMA, Garcia A, Caram R (2008) Electrochemical corrosion behavior of a Ti-35Nb alloy for medical prostheses. Electrochim Acta 53:4867–4874CrossRefGoogle Scholar
  9. Dash BP, Chaudhari S (2005) Electrochemical denitrification of simulated ground water. Water Res 39:4065–4072CrossRefGoogle Scholar
  10. Ding J, Zhao Q, Jiang J, Wei L, Wang K, Zhang Y, Hou W, Yu H (2016) Electrochemical disinfection and removal of ammonia nitrogen for the reclamation of wastewater treatment plant effluent. Environ Sci Pollut R 24:1–7Google Scholar
  11. Dortsiou M, Kyriacou G (2009) Electrochemical reduction of nitrate on bismuth cathodes. J Electroanal Chem 630:69–74CrossRefGoogle Scholar
  12. Fernandes A, Santos D, Pacheco MJ, Ciríaco L, Lopes A (2014) Nitrogen and organic load removal from sanitary landfill leachates by anodic oxidation at Ti/Pt/PbO2, Ti/Pt/SnO2 -Sb2O4, and Si/BDD. Appl Catal B-Environ 148-149:288–294CrossRefGoogle Scholar
  13. Fernandes A, Santos D, Pacheco MJ, Ciríaco L, Lopes A (2016) Electrochemical oxidation of humic acid and sanitary landfill leachate: influence of anode material, chloride concentration and current density. Sci Total Environ 541:282–291CrossRefGoogle Scholar
  14. Fernandez YN, Maranon E, Soons J, Castrillon L (2008) Denitrification of wastewater containing high nitrate and calcium concentrations. Bioresour Technol 99:7976–7981CrossRefGoogle Scholar
  15. Garcia-Segura S, Lanzarini-Lopes M, Hristovski K, Westerhoff P (2018) Electrocatalytic reduction of nitrate: fundamentals to full-scale watertreatment applications. Appl Catal B-Environ 236:546–568CrossRefGoogle Scholar
  16. Hasnat MA, Alam MS, Karim MU, Rashed MA, Machida M (2011) Divergent catalytic behaviors of Pt and Pd films in the cathode of a sandwiched type membrane reactor. Appl Catal B-Environ 107:294–301CrossRefGoogle Scholar
  17. He D, Li Y, Ooka H, Go YK, Jin F, Kim SH, Nakamura R (2018) Selective Electrocatalytic reduction of nitrite to dinitrogen based on decoupled proton-electron transfer. J Am Chem Soc 140:2012–2015CrossRefGoogle Scholar
  18. Horányi G, Rizmayer EM (1982) Role of adsorption phenomena in the electrocatalytic reduction of nitric acid at a platinized platinum electrode. J Electroanal Chem 140:347–366CrossRefGoogle Scholar
  19. Hossain MM, Kou N, Kawaguchi T, Shimazu K (2013) Reduction of nitrate on electrochemically pre-reduced tin-modified palladium electrodes. J Electroanal Chem 707:59–65CrossRefGoogle Scholar
  20. Islam M, Patel R (2010) Synthesis and physicochemical characterization of Zn/Al chloride layered double hydroxide and evaluation of its nitrate removal efficiency. Desalination 256:120–128CrossRefGoogle Scholar
  21. Katsounaros I, Dortsiou M, Kyriacou G (2009) Electrochemical reduction of nitrate and nitrite in simulated liquid nuclear wastes. J Hazard Mater 171:323–327CrossRefGoogle Scholar
  22. Katsounaros I, Ipsakis D, Polatides C, Kyriacou G (2006) Efficient electrochemical reduction of nitrate to nitrogen on tin cathode at very high cathodic potentials. Electrochim Acta 52:1329–1338CrossRefGoogle Scholar
  23. Katsounaros I, Kyriacou G (2008) Influence of nitrate concentration on its electrochemical reduction on tin cathode: identification of reaction intermediates. Electrochim Acta 53:5477–5484CrossRefGoogle Scholar
  24. Kim KW, Kim YJ, Kim IT, Park GI, Lee EH (2005) The electrolytic decomposition mechanism of ammonia to nitrogen at an IrO2 anode. Electrochim Acta 50:4356–4364CrossRefGoogle Scholar
  25. Lacasa E, Cañizares P, Llanos J, Rodrigo MA (2012) Effect of the cathode material on the removal of nitrates by electrolysis in non-chloride media. J Hazard Mater 213-214:478–484CrossRefGoogle Scholar
  26. Lan H, Liu X, Liu H, Liu R, Hu C, Qu J (2016) Efficient nitrate reduction in a fluidized electrochemical reactor promoted by Pd-Sn/AC particles. Catal Lett 146:91–99CrossRefGoogle Scholar
  27. Li M, Feng C, Zhang Z, Lei X, Chen R, Yang Y, Sugiura N (2009a) Simultaneous reduction of nitrate and oxidation of by-products using electrochemical method. J Hazard Mater 171:724–730CrossRefGoogle Scholar
  28. Li M, Feng C, Zhang Z, Shen Z, Sugiura N (2009b) Electrochemical reduction of nitrate using various anodes and a Cu/Zn cathode. Electrochem Commun 11:1853–1856CrossRefGoogle Scholar
  29. Li M, Feng C, Zhang Z, Sugiura N (2009c) Efficient electrochemical reduction of nitrate to nitrogen using Ti/IrO2–Pt anode and different cathodes. Electrochim Acta 54:4600–4606CrossRefGoogle Scholar
  30. Lin S, Wu C (1996) Electrochemical removal of nitrite and ammonia for aquaculture. Water Res 30:715–721CrossRefGoogle Scholar
  31. Liu H, Wu B, Liu S, Shao P, Liu X, Zhu C, Wang Y, Wu Y, Xue Y, Gao J, Hao Y, Tian H (2018) A regional high-resolution emission inventory of primary air pollutants in 2012 for Beijing and the surrounding five provinces of North China. Atmos Environ 181:20–33CrossRefGoogle Scholar
  32. Mácová Z, Bouzek K, Šerák J (2007) Electrocatalytic activity of copper alloys for NO3 reduction in a weakly alkaline solution. J Appl Electrochem 37:557–566CrossRefGoogle Scholar
  33. Mattarozzi L, Cattarin S, Comisso N, Guerriero P, Musiani M, Vázquez-Gómez L, Verlato E (2013) Electrochemical reduction of nitrate and nitrite in alkaline media at CuNi alloy electrodes. Electrochim Acta 89:488–496CrossRefGoogle Scholar
  34. Mukimin A, Vistanty H, Zen N (2015) Oxidation of textile wastewater using cylinder Ti/β-PbO2, electrode in electrocatalytic tube reactor. Chem Eng J 259:430–437CrossRefGoogle Scholar
  35. Pérez-Gallent E, Figueiredo MC, Katsounaros I, Koper MTM (2017) Electrocatalytic reduction of nitrate on copper single crystals in acidic and alkaline solutions. Electrochim Acta 227:77–84CrossRefGoogle Scholar
  36. Pérez G, Ibáñez R, Urtiaga AM, Ortiz I (2012) Kinetic study of the simultaneous electrochemical removal of aqueous nitrogen compounds using BDD electrodes. Chem Eng J 197:475–482CrossRefGoogle Scholar
  37. Reyter D, Bélanger D, Roué L (2011) Optimization of the cathode material for nitrate removal by a paired electrolysis process. J Hazard Mater 192:507–513CrossRefGoogle Scholar
  38. Simsek H, Kasi M, Wadhawan T, Bye C, Blonigen M, Khan E (2012) Fate of dissolved organic nitrogen in two stage trickling filter process. Water Res 46:5115–5126CrossRefGoogle Scholar
  39. Song S, Fan J, He Z, Zhan L, Liu Z, Chen J, Xu X (2010) Electrochemical degradation of azo dye C.I. Reactive Red 195 by anodic oxidation on Ti/SnO2–Sb/PbO2 electrodes. Electrochim Acta 55:3606–3613CrossRefGoogle Scholar
  40. Szpyrkowicz L, Daniele S, Radaelli M, Specchia S (2006) Removal of NO3 from water by electrochemical reduction in different reactor configurations. Appl Catal B-Environ 66:40–50CrossRefGoogle Scholar
  41. Talhi B, Monette F, Azzouz A (2011) Effective and selective nitrate electroreduction into nitrogen through synergistic parameter interactions. Electrochim Acta 58:276–284CrossRefGoogle Scholar
  42. Verlato E, Cattarin S, Comisso N, Mattarozzi L, Musiani M, Vázquez-Gómez L (2013) Reduction of nitrate ions at Rh-modified ni foam electrodes. Electrocatalysis 4:203–211CrossRefGoogle Scholar
  43. Wang L, Li M, Liu X, Feng C, Chen N, Ma X, Ding G (2017) Electrochemical behavior of Ti-based nano-electrode for highly efficient denitrification in Synthetic Groundwater. J Electrochem Soc 164:E326–E331CrossRefGoogle Scholar
  44. Wang W, Chen D, Chu J, Li J, Xue T, Wang L, Wang D, Qi T (2013) Influence and hydrolysis kinetics in titanyl sulfate solution from the sodium hydroxide molten salt method. J Cryst Growth 381:153–159CrossRefGoogle Scholar
  45. Xia Y, Dai Q (2018) Electrochemical degradation of antibiotic levofloxacin by PbO2 electrode: kinetics, energy demands and reaction pathways. Chemosphere 205:215–222CrossRefGoogle Scholar
  46. Xu H, Su J, Xian X, Huang W, Lin H (2008) A kinetics of indirect electro-oxidation reaction of NH3-N with chloride ion in a filter-press type electrochemical cell. Chem J Chinese U 29:1416–1419Google Scholar
  47. Yang S, Wang L, Jiao X, Li P (2017) Electrochemical reduction of nitrate on Different Cu-Zn Oxide Composite Cathodes. Int J Electrochem Sci 12:4370–4383CrossRefGoogle Scholar
  48. Yao J, Zhou M, Wen D, Xue Q, Wang J (2016) Electrochemical conversion of ammonia to nitrogen in non-chlorinated aqueous solution by controlling pH value. J Electroanal Chem 776:53–58CrossRefGoogle Scholar
  49. Zhao H, Xu X, Ke F, Li W, Feng M, Zhang H (2013) Nitrogen removal from wastewater plant secondary effluent in a compound natural treatment system. Ecol Eng 57:361–365CrossRefGoogle Scholar
  50. Zhou M, Wang W, Chi M (2009) Enhancement on the simultaneous removal of nitrate and organic pollutants from groundwater by a three-dimensional bio-electrochemical reactor. Bioresour Technol 100:4662–4668CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Environment, Zhejiang University of TechnologyHangzhouChina

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