Ti/RuO_2-ZrO_2-SnO_2电极的研制及处理有机废水的研究
|
摘要
通过涂覆热分解法制备了Ti/RuO_2-ZrO_2-SnO_2、Ti/RuO_2电极材料,采用X射线衍射(XRD)、扫描电镜(SEM)和循环伏安(CV)对电极材料进行表征,考察了电流密度、Na Cl质量浓度、p H值及电极间距对废水COD降解率的影响。结果表明,Ti/RuO_2-ZrO_2-SnO_2电极对COD具有更高的降解率,对其进行工艺优化。电极材料对废水降解的最佳工艺条件为电流密度40 m A/cm2,Na Cl质量浓度4 g/L,p H=5. 0,电极间距10 mm,COD的降解率达到90. 5%。Ti/RuO_2-ZrO_2-SnO_2电极中SnO_2与RuO_2生成固溶体,有利于增强涂层与基体之间的结合力,提高电极的稳定性; ZrO_2起到细化晶粒的作用,致使电极表面粗糙度增加,增强了电极的电催化性能,且降解过程符合一级动力学模型。
The paper intends to introduce a novel approach to preparing Ti/RuO_2-SnO_2-ZrO_2 and Ti/RuO_2 electrodes at the high temperature of 450 ℃ via the thermal decomposition method,in which titanium plate has been used as the support and isopropyl alcohol with Ru Cl3· n H2 O, Sn Cl4· 5 H2 O and Zr O( NO3)2 and that with Ru Cl3·n H2 O only as the masking liquid,respectively. The electrodes have been characterized by a number of approaches,including the scanning electron microscope( SEM),the X-ray diffractometer( XRD) and the cyclic voltammetry( CV). Then,the above mentioned methods have been further adopted for degrading the chemical oxygen demand( COD) in the sewage purification. The corresponding results of the above mentioned experiments and researches demonstrate that the degrading rate of COD in the case for Ti/RuO_2-SnO_2-ZrO_2 tends to be higher than that in the condition of Ti/RuO_2. Fur-thermore,we have also investigated the effects of the current density,the NaC l concentration,the pH value and the electrode spacing distribution through a series of single-factor and orthogonal tests in detail. The afforementioned analyses indicate that the said single-factor and orthogonal tests tend to produce their main effects for degrading the COD in the sewage by using Ti/RuO 2-SnO 2-ZrO 2,the pH value and the degradation rate of COD in it at a high rate of 90. 5% under the the optimum condition for degradation,that is to say,the current density of 40 mA/cm2,the concentration of NaC l of 4 g/L,pH value of 5. 0 with the electrode spacing of 10 mm. Besides,the characterization results also disclose that the formation of the solid solution of SnO 2 and RuO 2 in the Ti/RuO 2-ZrO 2-SnO 2 electrode proves to be beneficial for enhancing the bonding between coating and substrate.Besides,it can also help to improve the stability of the electrode,for ZrO 2 can refine the grain size,increase the surface roughness of the electrode and further enhance the electro-catalytic performance. In addition,the experimental data of the COD degradation has been found fitted by the pseudo-first-order model,and the reaction kinetic of COD degradation in the sewage in the condition of Ti/RuO 2-SnO 2-ZrO 2 tends to be well in accord with the model prediction.
The paper intends to introduce a novel approach to preparing Ti/RuO_2-SnO_2-ZrO_2 and Ti/RuO_2 electrodes at the high temperature of 450 ℃ via the thermal decomposition method,in which titanium plate has been used as the support and isopropyl alcohol with Ru Cl3· n H2 O, Sn Cl4· 5 H2 O and Zr O( NO3)2 and that with Ru Cl3·n H2 O only as the masking liquid,respectively. The electrodes have been characterized by a number of approaches,including the scanning electron microscope( SEM),the X-ray diffractometer( XRD) and the cyclic voltammetry( CV). Then,the above mentioned methods have been further adopted for degrading the chemical oxygen demand( COD) in the sewage purification. The corresponding results of the above mentioned experiments and researches demonstrate that the degrading rate of COD in the case for Ti/RuO_2-SnO_2-ZrO_2 tends to be higher than that in the condition of Ti/RuO_2. Fur-thermore,we have also investigated the effects of the current density,the NaC l concentration,the pH value and the electrode spacing distribution through a series of single-factor and orthogonal tests in detail. The afforementioned analyses indicate that the said single-factor and orthogonal tests tend to produce their main effects for degrading the COD in the sewage by using Ti/RuO 2-SnO 2-ZrO 2,the pH value and the degradation rate of COD in it at a high rate of 90. 5% under the the optimum condition for degradation,that is to say,the current density of 40 mA/cm2,the concentration of NaC l of 4 g/L,pH value of 5. 0 with the electrode spacing of 10 mm. Besides,the characterization results also disclose that the formation of the solid solution of SnO 2 and RuO 2 in the Ti/RuO 2-ZrO 2-SnO 2 electrode proves to be beneficial for enhancing the bonding between coating and substrate.Besides,it can also help to improve the stability of the electrode,for ZrO 2 can refine the grain size,increase the surface roughness of the electrode and further enhance the electro-catalytic performance. In addition,the experimental data of the COD degradation has been found fitted by the pseudo-first-order model,and the reaction kinetic of COD degradation in the sewage in the condition of Ti/RuO 2-SnO 2-ZrO 2 tends to be well in accord with the model prediction.
引文
[1] ZHAO Xiaomei(赵晓梅),XIE Zhengwei(谢正伟),HEPing(何平),et al. Progress in electrochemical degrada-tion of organic wastewater[J]. Journal of Wuhan Universi-ty of Technology(武汉理工大学学报),2013,35(5):127-133.
[2] LI Mei(李媚),WANG Kezhi(王克之),LI Xuelian(李雪莲),et al. Treatment of P chlorophenol wastewater byadsorption electrochemical oxidation process and its kinet-ics[J]. Journal of Environmental Engineering(环境工程学报),2013,7(9):3427-3432.
[3] GUINEA E,GARRIDO J A,RODRIGUEZ R M,et al.Degradation of the fluoroquinolone enrofloxacin by electro-chemical advanced oxidation processes based on hydrogenperoxide electrogeneration[J]. Electrochimica Acta,2010,55(6):2101-2115.
[4] GRUBB W T. Catalysis,electrocatalysis,and hy-drocarbon fuel cells[J]. Nature, 1963, 198(4883):883-884.
[5] LIU Yucheng(刘宇程),LIANG Qingling(梁庆玲),YANG Bing(杨冰),et al. Electrocatalytic oxidation ofphenol wastewater by Ti/Ru O2-Sn O2-Ti O2coating elec-trode[J]. Journal of Safety and Environment(安全与环境学报),2018,18(2):683-690
[6] LI Huiyuan(李慧媛),GAO Ding(高丁),SHI Jiang-hong(史江红),et al. Electrochemical degradation ofTBBPA in solution by Ti/Ru O2-Ir O2electrode and its deg-radation mechanism[J]. Journal of Environmental Science(环境科学学报),2017,37(2):642-650.
[7] VAHIDHABANU S,STEPHEN A J. Effect of rutheniumoxide/titanium mesh anode microstructure on electrooxida-tion of pharmaceutical effluent[J]. International Journalof Waste Resources,2015,5(4):1000191.
[8] KONG Desheng(孔德生),LWenhua(吕文华),FENGYuanyuan(冯媛媛),et al. Research on electrocatalyticproperties of DSA electrode and some problems to be fur-ther explored[J]. Progress in Chemistry(化学进展),2009,21(6):1107-1117.
[9] YAN He(闫鹤),YU Xiujuan(于秀娟),WANG Hui(王辉),et al. Electrocatalytic removal of rhodamine Bchromaticity by Ti/Ru O2electrodes[J]. EnvironmentalProtection Science(环境保护科学),2004,30(3):13-16.
[10] CHEN Yuwu(陈裕武),HAN Weiqing(韩卫清),SUNXiuyun(孙秀云),et al. Advanced treatment of pharma-ceutical intermediate biochemical effluent by Ti/Ru O2anodization[J]. Environmental Science&Technology(环境科技),2010,23(1):24-29.
[11] ASMUSSEN R M,TIAN M,CHEN A. A new approachto wastewater remediation based on bifunctional elec-trodes[J]. Environmental Science&Technology,2009,43(13):5100-5105.
[12] FENG Jianjun(冯建俊),LI Xueming(黎学明),SUDeshui(苏德水),et al. Pretreatment of toluene twoamine wastewater by Pb O2composite electrode[J]. En-vironmental Protection and Environmental Protection(化工环保),2017,39(2):673-678.
[13] TSUJI E,IMANISHI A,FUKUI K I,et al. Electrocata-lytic activity of amorphous Ru O2,electrode for oxygenevolution in an aqueous solution[J]. Electrochimica Ac-ta,2011,56(5):2009-2016.
[14] YADAV A A,PAWAR S C,PATIL D H,et al. Proper-ties of(200)oriented,highly conductive Sn O2thin filmsby chemical spray pyrolysis from non-aqueous medium:effect of antimony doping[J]. Journal of Alloys&Com-pounds,2015,652:145-152.
[15] BAI H,HE P,CHEN J,et al. Electrocatalytic degrada-tion of bromocresol green wastewater on Ti/Sn O2-Ru O2electrode[J]. Water Science&Technology,2017,75(1):220-227.
[16] RODRIGUEZ F A,RIVERO E P,LARTUNDO R L,etal. Preparation and characterization of Sb2O5-doped Ti/Ru O2-Zr O2,for dye decolorization by means of activechlorine[J]. Journal of Solid State Electrochemistry,2014,18(11):3153-3162.
[17] CHELLAMMAL S,KALAISELVI P,GANAPATHY P,et al. Anodic incineration of phthalic anhydride usingRu O2-Ir O2-Sn O2-Ti O2coated on Ti anode[J]. ArabianJournal of Chemistry,2016,9:S1690-S1699.
[18] LU Qiang(卢强). Preparation of coated titanium elec-trode and degradation of nitrobenzene in wastewater(涂层钛电极的制备及其降解废水中硝基苯的研究)[D]. Nanjing:Nanjing University of Science andTechnology,2011.
[19] WANG Lixuan(王立璇),MA Hongrui(马宏瑞),MENGGaofei(孟高飞),et al. Study on the treatment of pharma-ceutical wastewater by DSA electrode catalytic oxidationprocess[J]. Industrial Water Treatment(工业水处理),2017,37(7):35-38.
[20] XU H,LI J,YAN W,et al. Preparation and character-ization of titanium based Pb O2,electrodes doped withsome common elements[J]. Rare Metal Materials&En-gineering,2013,42(5):885-890.
[21] XU Lili(徐丽丽),SHI Hanchang(施汉昌),CHENJinluan(陈金銮). Electrochemical oxidation of ammonianitrogen wastewater by Ti/Ru O2-Ti O2-Ir O2-Sn O2electrode[J]. Environmental Science(环境科学),2007,28(9):2009-2013.
[22] CUI Li(崔丽),HUANG Kaituo(黄开拓),LI Dan(李丹),et al. Experimental study on treatment of antibioticpharmaceutical wastewater by electro catalytic oxidation[J]. Environmental Protection and Circular Economy(环境保护与循环经济),2017,37(1):36-40.
[23] XIAO Hongkang(肖宏康),XIAO Shuhu(肖书虎),ZHANG Guofang(张国芳),et al. Treatment of simula-ted berberine pharmaceutical wastewater by electrochemi-cal oxidation process[J]. Journal of Environmental En-gineering(环境工程学报),2011,5(5):987-991.
[2] LI Mei(李媚),WANG Kezhi(王克之),LI Xuelian(李雪莲),et al. Treatment of P chlorophenol wastewater byadsorption electrochemical oxidation process and its kinet-ics[J]. Journal of Environmental Engineering(环境工程学报),2013,7(9):3427-3432.
[3] GUINEA E,GARRIDO J A,RODRIGUEZ R M,et al.Degradation of the fluoroquinolone enrofloxacin by electro-chemical advanced oxidation processes based on hydrogenperoxide electrogeneration[J]. Electrochimica Acta,2010,55(6):2101-2115.
[4] GRUBB W T. Catalysis,electrocatalysis,and hy-drocarbon fuel cells[J]. Nature, 1963, 198(4883):883-884.
[5] LIU Yucheng(刘宇程),LIANG Qingling(梁庆玲),YANG Bing(杨冰),et al. Electrocatalytic oxidation ofphenol wastewater by Ti/Ru O2-Sn O2-Ti O2coating elec-trode[J]. Journal of Safety and Environment(安全与环境学报),2018,18(2):683-690
[6] LI Huiyuan(李慧媛),GAO Ding(高丁),SHI Jiang-hong(史江红),et al. Electrochemical degradation ofTBBPA in solution by Ti/Ru O2-Ir O2electrode and its deg-radation mechanism[J]. Journal of Environmental Science(环境科学学报),2017,37(2):642-650.
[7] VAHIDHABANU S,STEPHEN A J. Effect of rutheniumoxide/titanium mesh anode microstructure on electrooxida-tion of pharmaceutical effluent[J]. International Journalof Waste Resources,2015,5(4):1000191.
[8] KONG Desheng(孔德生),LWenhua(吕文华),FENGYuanyuan(冯媛媛),et al. Research on electrocatalyticproperties of DSA electrode and some problems to be fur-ther explored[J]. Progress in Chemistry(化学进展),2009,21(6):1107-1117.
[9] YAN He(闫鹤),YU Xiujuan(于秀娟),WANG Hui(王辉),et al. Electrocatalytic removal of rhodamine Bchromaticity by Ti/Ru O2electrodes[J]. EnvironmentalProtection Science(环境保护科学),2004,30(3):13-16.
[10] CHEN Yuwu(陈裕武),HAN Weiqing(韩卫清),SUNXiuyun(孙秀云),et al. Advanced treatment of pharma-ceutical intermediate biochemical effluent by Ti/Ru O2anodization[J]. Environmental Science&Technology(环境科技),2010,23(1):24-29.
[11] ASMUSSEN R M,TIAN M,CHEN A. A new approachto wastewater remediation based on bifunctional elec-trodes[J]. Environmental Science&Technology,2009,43(13):5100-5105.
[12] FENG Jianjun(冯建俊),LI Xueming(黎学明),SUDeshui(苏德水),et al. Pretreatment of toluene twoamine wastewater by Pb O2composite electrode[J]. En-vironmental Protection and Environmental Protection(化工环保),2017,39(2):673-678.
[13] TSUJI E,IMANISHI A,FUKUI K I,et al. Electrocata-lytic activity of amorphous Ru O2,electrode for oxygenevolution in an aqueous solution[J]. Electrochimica Ac-ta,2011,56(5):2009-2016.
[14] YADAV A A,PAWAR S C,PATIL D H,et al. Proper-ties of(200)oriented,highly conductive Sn O2thin filmsby chemical spray pyrolysis from non-aqueous medium:effect of antimony doping[J]. Journal of Alloys&Com-pounds,2015,652:145-152.
[15] BAI H,HE P,CHEN J,et al. Electrocatalytic degrada-tion of bromocresol green wastewater on Ti/Sn O2-Ru O2electrode[J]. Water Science&Technology,2017,75(1):220-227.
[16] RODRIGUEZ F A,RIVERO E P,LARTUNDO R L,etal. Preparation and characterization of Sb2O5-doped Ti/Ru O2-Zr O2,for dye decolorization by means of activechlorine[J]. Journal of Solid State Electrochemistry,2014,18(11):3153-3162.
[17] CHELLAMMAL S,KALAISELVI P,GANAPATHY P,et al. Anodic incineration of phthalic anhydride usingRu O2-Ir O2-Sn O2-Ti O2coated on Ti anode[J]. ArabianJournal of Chemistry,2016,9:S1690-S1699.
[18] LU Qiang(卢强). Preparation of coated titanium elec-trode and degradation of nitrobenzene in wastewater(涂层钛电极的制备及其降解废水中硝基苯的研究)[D]. Nanjing:Nanjing University of Science andTechnology,2011.
[19] WANG Lixuan(王立璇),MA Hongrui(马宏瑞),MENGGaofei(孟高飞),et al. Study on the treatment of pharma-ceutical wastewater by DSA electrode catalytic oxidationprocess[J]. Industrial Water Treatment(工业水处理),2017,37(7):35-38.
[20] XU H,LI J,YAN W,et al. Preparation and character-ization of titanium based Pb O2,electrodes doped withsome common elements[J]. Rare Metal Materials&En-gineering,2013,42(5):885-890.
[21] XU Lili(徐丽丽),SHI Hanchang(施汉昌),CHENJinluan(陈金銮). Electrochemical oxidation of ammonianitrogen wastewater by Ti/Ru O2-Ti O2-Ir O2-Sn O2electrode[J]. Environmental Science(环境科学),2007,28(9):2009-2013.
[22] CUI Li(崔丽),HUANG Kaituo(黄开拓),LI Dan(李丹),et al. Experimental study on treatment of antibioticpharmaceutical wastewater by electro catalytic oxidation[J]. Environmental Protection and Circular Economy(环境保护与循环经济),2017,37(1):36-40.
[23] XIAO Hongkang(肖宏康),XIAO Shuhu(肖书虎),ZHANG Guofang(张国芳),et al. Treatment of simula-ted berberine pharmaceutical wastewater by electrochemi-cal oxidation process[J]. Journal of Environmental En-gineering(环境工程学报),2011,5(5):987-991.