Abstract：A NF/CNTs/Cu-Pd bimetallic composite electrode was effectively synthesized using the cathodic electrodeposition technique. The objective was to achieve efficient electrocatalytic reduction of nitrate in wastewater. SEM-EDS, XRD, and XPS analysis confirmed the successful deposition of Cu-Pd nanoparticles onto the nickel foam (NF) substrate. The efficacy of NO3--N and TN removal in simulated water was investigated by manipulating various factors, including current density, initial pH value, initial nitrate concentration, and Cl- concentration. The approach was also applied to actual saline wastewater to validate its feasibility. The results showed that NF/CNTs/Cu-Pd exhibited effective NO3--N removal capabilities without Cl-, while TN removal efficiency was relatively modest, with NO3--N primarily converted into NH4+-N. However, in the presence of Cl-, both NO3--N and TN were efficiently removed. The optimal reaction conditions were determined to be a current density of 30mA/cm2, an initial pH value of 7, an initial concentration of 50mg/L, and a chloride ion concentration of 2.0g/L. Under optimal conditions, the removal efficiencies of NO3--N and TN reached 100% and 97.2%, respectively. The presence of dissolved organic matter (DOM) in actual wastewater could impede NO3--N removal. After removing the DOM, the removal efficiency of NO3--N decreased to 95.5%, and the TN removal efficiency declined to 85.6%.
王畅, 刘吉明, 王永恒, 逯新宇. 改性Cu-Pd双金属电极电化学还原硝酸盐性能研究[J]. 中国环境科学, 2023, 43(10): 5196-5207.
WANG Chang, LIU Ji-ming, WANG Yong-heng, LU Xin-yu. Study on the electrochemical reduction of nitrate using a modified Cu-Pd bimetallic electrode. CHINA ENVIRONMENTAL SCIENCECE, 2023, 43(10): 5196-5207.
Yao F B, Jia M C, Yang Q, et al. Highly selective electrochemical nitrate reduction using copper phosphide self-supported copper foam electrode:Performance, mechanism, and application[J]. Water Research, 2021,193:116881.
[2]
蓝梅,董萌,吴宏举.地下水硝酸盐氮污染原位修复研究进展[J]. 工业水处理, 2015,35(8):15-17. Lan M, Dong M, Wu H J. Research progress in-situ remediation technology of groundwater nitrate nitrogen pollution[J]. Industrial Water Treatment, 2015,35(8):15-17.
[3]
Song W, Gao B Y, Xu X, et al. Adsorption of nitrate from aqueous solution by magnetic amine-crosslinked biopolymer based corn stalk and its chemical regeneration property[J]. Journal of Hazardous Materials. 2016,304(0):280-290.
[4]
Belkada F D, Kitous O, Drouiche N, et al. Electrodialysis for fluoride and nitrate removal from synthesized photovoltaic industry wastewater[J]. Separation and Purification Technology, 2018,204(0):108-115.
[5]
张鹏程,李晓玲,王晓婷,等.活性污泥体系中C/N/S对硝酸盐还原过程的影响[J]. 中国环境科学, 2021,41(5):2117-2122. Zhang P C, Li X L, Wang X T, et al. Effect of C/N/S on nitrate reduction process in activated sludge system[J]. China Environmental Science, 2021,41(5):2117-2122.
[6]
刘霞,石会龙,李成帅,等.g-C3N4/BiVO4光催化还原水中硝酸盐氮性能研究[J]. 现代化工, 2022,42(12):215-220. Liu X, Shi H L, Li C S, et al. Study on photocatalytic reduction of nitrates-based nitrogen in water by g-C3N4/BiVO4[J]. Modern Chemical Industry, 2022,42(12):215-220.
[7]
Brian P C, John R S, Charles J W. The Selectivity and Sustainability of a Pd-In/gamma-Al2O3 Catalyst in a Packed-Bed Reactor:The Effect of Solution Composition[J]. Catalysis Letters, 2009,130(1/2):56-62.
[8]
Martinez J, Ortiz A, Ortiz I, State-of-the-art and perspectives of the catalytic and electrocatalytic reduction of aqueous nitrates[J]. Applied Catalysis B:Environmental, 2017,207:42-59.
[9]
Xu H, Ma Y Y, Chen J, et al. Electrocatalytic reduction of nitrate-a step towards a sustainable nitrogen cycle[J]. Chemical Society Reviews, 2022,51(7):2710-2758.
[10]
Yang J, Sebastian P, Duca M, et al. pH dependence of the electroreduction of nitrate on Rh and Pt polycrystalline electrodes[J]. Chemical Communications, 2014,50(17):2148-2151.
[11]
Wang X, Zhu M, Zeng G, et al. A three-dimensional Cu nanobelt cathode for highly efficient electrocatalytic nitrate reduction[J]. Nanoscale, 2020,12(17):9385-9391.
[12]
Li W, Xiao C W, Zhao Y, et al. Electrochemical Reduction of High-Concentrated Nitrate Using Ti/TiO2 Nanotube Array Anode and Fe Cathode in Dual-Chamber Cell[J]. Catalysis Letters, 2016,146(12):2585-2595.
[13]
Li M, Feng C, Zhang Z, et al. Efficient electrochemical reduction of nitrate to nitrogen using Ti/IrO2-Pt anode and different cathodes[J]. Electrochimica Acta, 2009,54(20):4600-4606.
[14]
Dortsiou M, Katsounaros I, Polatides C, et al. Influence of the electrode and the pH on the rate and the product distribution of the electrochemical removal of nitrate[J]. Environmental Technology, 2013,34(3):373-381.
[15]
Peel J W, Reddy K J, Sullivan B P, et al. Electrocatalytic reduction of nitrate in water[J]. Water Research, 2003,37(10):2512-2519.
[16]
Su L H, Li K, Zhang H B, et al. Electrochemical nitrate reduction by using a novel Co3O4/Ti cathode[J]. Water Research, 2017,120:1-11.
[17]
Kerkeni S, Lamy-Pitara E, Barbier J, Copper-platinum catalysts prepared and characterized by electrochemical methods for the reduction of nitrate and nitrite[J]. Catalysis Today, 2002,75(1-4):35-42.
[18]
Vooys D, Arnoud C A, Van S, et al. Electrocatalytic reduction of NO3− on palladium/copper electrodes[J]. Journal of Molecular Catalysis. A, 2000,154(1):203-215.
[19]
Gootzen J F E, Lefferts L,Veen J A R, et al. Electrocatalytic nitrate reduction on palladium based catalysts activated with germanium[J]. Applied Catalysis A:General, 1999,188(1):127-136.
[20]
Tenne R, Patel K, Hashimoto K, et al. Efficient electrochemical reduction of nitrate to ammonia using conductive diamond film electrodes[J]. Journal of Electroanalytical Chemistry, 1993,347(1):409-415.
[21]
查晓松,冯智梁,金苏雯.铁-铜双金属还原去除水中硝酸盐研究[J]. 水处理技术, 2020,46(8):44-48. Cha X S, Feng Z L, Jin S W. Removal of nitrate in water by reduction of iron-based bimetal[J]. Technology of Water Treatment, 2020, 46(8):44-48.
[22]
Zhang Z Q, Xu Y P, Shi W X, et al. Electrochemical-catalytic reduction of nitrate over Pd-Cu/γAl2O3 catalyst in cathode chamber:Enhanced removal efficiency and N2 selectivity[J]. Chemical Engineering Journal, 2016,290(0):201-208.
[23]
Su J F, Ruzybayev I, Shah I, Huang C P, The electrochemical reduction of nitrate over micro-architectured metal electrodes with stainless steel scaffold[J]. Applied Catalysis B:Environmental, 2016,180:199-209.
[24]
Li Q, Zhang Q, Ding L, et al. Synthesis of silver/multi-walled carbon nanotubes composite and its application for electrocatalytic reduction of bromate[J]. Chemical Engineering Journal, 2013,217(0):28-33.
[25]
Gu Y J, Wong W T, Nanostructure PtRu/MWNTs as anode catalysts prepared in a vacuum for direct methanol oxidation[J]. Langmuir 2006,22(26):11447-11452.
[26]
Ding L, Li Q, Zhou D D, et al. Modification of glassy carbon electrode with polyaniline/multi-walled carbon nanotubes composite:Application to electro-reduction of bromate[J]. Journal of Electroanalytical Chemistry, 2012,668:44-50.
[27]
Zhang Q, Ding L, Cui H, et al. Electrodeposition of Cu-Pd alloys onto electrophoretic deposited carbon nanotubes for nitrate electroreduction[J]. Applied Surface Science, 2014,308(1):113-120.
[28]
Zhang Y M, Zhao Y L, Chen Z, et al. Electrochemical reduction of nitrate via Cu/Ni composite cathode paired with Ir-Ru/Ti anode:High efficiency and N2 selectivity[J]. Electrochimica Acta, 2018,291:151-160.
[29]
Vanlangendonck Y, Corbisier D, Van Lierde A, Influence of operating conditions on the ammonia electro-oxidation rate in wastewaters from power plants (ELONITA™ technique)[J]. Water Research, 2005, 39(13):3028-3034.
[30]
Lüdtke K, Peinemann K V, Kasche V, et al. Nitrate removal of drinking water by means of catalytically active membranes[J]. Journal of Membrane Science, 1998,151(1):3-11.
[31]
Chen Z, Wang Y,Wang J, et al. Enhanced activity and selectivity of electrocatalytic denitrification by highly dispersed CuPd bimetals on reduced graphene oxide[J]. Chemical Engineering Journal, 2021, 416(0):129074.
[32]
Duan W, Li G, Lei Z, et al. Highly active and durable carbon electrocatalyst for nitrate reduction reaction[J]. Water Research, 2019,161:126-135.
[33]
Kong X J, W Z H, Ren Z R, et al. Degradation of lipid regulators by the UV/chlorine process:Radical mechanisms, chlorine oxide radical (ClO•)-mediated transformation pathways and toxicity changes[J]. Water Research, 2018,137:242-250.
