电芬顿技术隶属于电化学高级氧化技术,在环境废水处理方面,其核心和关键是电极材料的元素掺杂改性。本文就电芬顿技术中阴极材料和阳极材料的研究进展以及电化学氧化效率的影响因素几个方面做了介绍,并对其发展趋势进行了展望。 Electro-Fenton technology is subordinate to advanced electrochemical oxidation technology. In the treatment of environmental wastewater, it is important to modify electrode material by element doping. In this paper, we investigated the research and development of cathode and anode materials and influence factors for the treatment of wastewater in electro-Fenton process, and its development tendency is forecast.
电芬顿技术,电极材料,环境废水, The Electro-Fenton Process Electrode Materials Environmental Wastewater元素掺杂改性电极材料在环境废水处理中的 应用
由于Ce3+和Ce4+之间的氧化还原,使其具有较强的储氧能力,并且Ce3+和H2O2可发生类芬顿反应产生强氧化性的∙OH [10] ,所以Ce元素得到了国内外的广泛关注。Assumpcão M.H.等人制备了炭黑和纳米CeO2复合材料,并通过圆盘电极测试比较了炭黑材料与添加二氧化铈的复合材料的电化学行为。结果表明,在转移电子数相同的电化学体系中,当只有炭黑时过氧化氢的量为41%;而当添加的CeO2含量为4%时,产生过氧化氢的量为44%。这一研究结果证明了掺杂适量的二氧化铈有利于促进体系中的氧气发生两电子反应。刘勇等人将过渡金属氧化物CeO2负载到石墨毡上,制备出复合石墨毡阴极材料,修饰后的石墨毡电荷传输阻力变小,氧化还原电流强度显著增强,活性表面积增大8倍,电流密度是未改性前的8.5倍,20 min时甲基橙脱色率达到96.8%。与未改性石墨毡相比,去除率提高133.2倍,显著提高了其电催化氧化性能。由于纯的CeO2较差的热稳定性,可掺杂过渡金属对其进行改性,形成CexA1-xO2 (A = 过渡金属)复合材料。当掺杂过渡金属后,铈离子会被过渡金属离子所取代,从而产生一些晶格缺陷,这使得晶格中氧离子的迁移通道变得比较大,从而有效地降低了晶格中氧的扩散阻力,提高了氧活度。并且过渡金属离子不同价态之间的转化也有助于形成氧空位,从而提高CeO2的电催化活性。我们课题组采用3D Ce0.75Zr0.25O2/RGO复合材料作为阴极材料降解环丙沙星,在5 h和6.5 h时其降解效率和矿化效率分别达到100%和96.38%。除此之外,我们对CexA1-xO2/CF (A = Zr, Cu and Ni)三种阴极材料进行了对比,发现复合材料Ce0.75Zr0.25O2/CF作为阴极材料时,在1 h后环丙沙星被降解完全,在6 h时其矿化效率达到97.45%。
刘义刚,韩晶晶,孟祥海,李 轶,赵 鹏,张素鸽,李亚楠. 元素掺杂改性电极材料在环境废水处理中的应用Application of Element Doping Modified Electrode Materials for Treatment of the Wastewater in Environment[J]. 环境保护前沿, 2017, 07(06): 518-526. http://dx.doi.org/10.12677/AEP.2017.76066
参考文献 (References)ReferencesKolpin, D.W., Furlong, E.T., Meyer. M.T., Thurman, E.M., Zaugg, S.D., Barber, L.B. and Buxton, H.T. (2002) Pharmaceuticals, Hormones, and Other Organic Wastewater Contaminants in U.S. Streams, 1999-2000: A National Reconnaissance. Environmental Science & Technology, 36, 1202-1211. <br>https://doi.org/10.1021/es011055jMezyk, S.P., Landsman, N.A., Swancutt, K.L., Bradford, C.N., Cox, C.R., Kiddle, J.J. and Mezyk, S.P. (2007) Free Radical Chemistry of Advanced Oxidation Process Removal of Nitrosamines in Water. Environmental Science & Technology, 41, 5818-5823.Shukla, S. and Oturan, M.A. (2015) Dye Removal Using Electrochemistry and Semiconductor Oxide Nanotubes. Environmental Chemistry Letters, 13, 157-172. <br>https://doi.org/10.1007/s10311-015-0501-ySopaj, F., Oturan, N., Pinson, J., Podvorica, F. and Oturan, M.A. (2016) Effect of the Anode Materials on the Efficiency of the Electro-Fenton Process for the Mineralization of the Antibiotic Sulfamethazine. Applied Catalysis B: Environmental, 199, 331-341. <br>https://doi.org/10.1016/j.apcatb.2016.06.035Brillas, E., Sires, I. and Oturan, M.A. (2009) Electro-Fenton Process and Related Electrochemical Technologies Based on Fenton’s Reaction Chemistry. Chemical Reviews, 9, 6570-6631. <br>https://doi.org/10.1021/cr900136gOturan, N., Ganiyu, S.O., Raffy, S. and Oturan, M.A. (2017) Sub-Stoichiometric Titanium Oxide as a New Anode Material for Electro-Fenton Process: Application to Electrocatalytic Destruction of Antibiotic Amoxicillin. Applied Catalysis B: Environmental, 217, 214-223. <br>https://doi.org/10.1016/j.apcatb.2017.05.062Gonzalez, Z., Sanchez, A., Blanco, C., Granda, M., Menendez, R. and San-tamaría, R. (2011) Enhanced Performance of a Bi-Modified Graphite Felt as the Positive Electrode of a Vanadium Redox Flow Battery. Electrochemistry Communications, 13, 1379-1382.Garcia-Segura, S., Garrido, J.A., Rodriguez, R.M., Cabot, P.L., Centellas, F., Arias, C. and Brillas, E. (2012) Mineralization of Flumequine in Acidic Medium by Electro-Fenton and Photoelectro-Fenton Processes. Water Research, 46, 2067-2076. <br>https://doi.org/10.1016/j.watres.2012.01.019Ding, X., Wang, S., Shen, W., Mu, Y., Wang, L., Chen, H. and Zhang, L. (2017) Fe@Fe2O3 Promoted Electrochemical Mineralization of Atrazine via a Triazinon Ring Opening Mechanism. Water Research, 112, 9-18.
<br>https://doi.org/10.1016/j.watres.2017.01.024Heckert, E.G., Seal, S. and Self, W.T. (2008) Fenton-Like Reaction Catalyzed by the Rare Earth Inner Transition Metal Cerium. Environmental Science & Technology, 42, 5014-5019. <br>https://doi.org/10.1021/es8001508Zhao H, Qian L, Guan X, Wu D, Zhao G. (2016) Continuous Bulk FeCuC Aerogel with Ultradispersed Metal Nanoparticles: An Efficient 3D Heterogeneous Electro-Fenton Cathode over a Wide Range of pH 3-9. Envi-ronmental Science & Technology, 50, 5225-5233. <br>https://doi.org/10.1021/acs.est.6b00265Babaei-Sati, R., Parsa, J.B. (2017) Electrogeneration of H2O2 Using Graphite Cathode Modified with Electrochemically Synthesized Polypyrrole/MWCNT Na-nocomposite for Electro-Fenton Process. Journal of Industrial and Engineering Chemistry, 52, 270-276. <br>https://doi.org/10.1016/j.jiec.2017.03.056王爱民, 曲久辉, 史红星, 茹加, 刘会娟, 雷鹏举. 活性碳纤维阴极电芬顿反应降解微囊藻毒素研究[J]. 高等学校化学学报, 2005, 26(9): 1669-1672.Sun, Y. and Pignatello, J.J. (1993) Photochemical Reactions Involved in the Total Mineralization of 2,4-D by Iron(3+)/Hydrogen Peroxide/UV. Environmental Science & Technology, 27, 304-310.
<br>https://doi.org/10.1021/es00039a010Li, Y., Han, J.J., Xie, B.R., Li, Y.N., Zhan, S.H. and Tian, Y. (2017) Synergistic Degradation of Antimicrobial Agent Ciprofloxacin in Water by Using 3D CeO2/RGO Composite as Cathode in Electro-Fenton System. Journal of Electroanalytical Chemistry, 784, 6-12. <br>https://doi.org/10.1016/j.jelechem.2016.11.057