多孔Ti/SnO_2-Sb_2O_5/CNT-PbO_2电极的制备及其电催化氧化有机染料废水的研究
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摘要
采用电化学沉积法,利用多孔钛基体和碳纳米管(CNT)成功制备了一种新型的多孔Ti/Sn O2-Sb2O3/CNTPbO_2电极,并探讨了其对有机染料废水的降解效果。通过扫描电子显微镜(SEM)、能量色散谱(EDS)、X射线衍射(XRD)表征了电极的微观结构,与PbO_2电极相比,CNT-PbO_2表面更紧凑,PbO_2晶粒的尺寸更小。通过线性扫描伏安法(LSV),电化学活性表面积,电化学阻抗谱(EIS),电极加速寿命和计时电流曲线对CNT改性电极的电化学性能进行了表征。结果表明:与PbO_2电极相比,CNT-PbO_2可以使电化学反应体系具有更高的析氧电位、更长的寿命、更大的比表面积、更多的活性中心数量,以及更强的电化学氧化能力。与此同时,荧光能谱实验验证了CNT-PbO_2在电催化氧化过程中能产生更多的羟基自由基(·OH)。最后利用电极电催化氧化几种典型的有机染料污染物(罗丹明B,亚甲基蓝,酰胺黑10B),COD去除率表明CNT-PbO_2电极具有较好的电催化氧化能力。
A novel CNT-doped PbO_2 electrode with porous titanium as substrate(porous Ti/Sn O_2-Sb_2 O_3/CNT-Pb O_2)was successfully prepared by electrochemical deposition method,and the degradation of organic dye wastewaters were explored. The microstructure of modified electrodes was characterized by scanning electron microscopy(SEM), energy-dispersive spectroscopy(EDS), X-ray diffraction(XRD). In contrast with pure Pb O_2 electrode, CNT-doped Pb O_2 displayed a more compact surface with a smaller grain size of crystal. The electrochemical properties of modified electrodes were characterized linear sweep voltammetry(LSV), electrochemical active surface area, electrochemical impedance spectroscopy(EIS), accelerated life and chronoamperometry. Compared with pure Pb O_2,the results showed that CNT-Pb O_2 could provid higher oxygen evolution potential, longer life, larger surface area,more active sites, and stronger electrochemical oxidation ability for electrochemical reaction system. In addition, the fluorescence experimental indicated that CNT-doped Pb O_2 significantly increased the generation for hydroxyl radical(·OH) and further enhanced the ability of the electro-oxidation process. The results of COD removal rate of several typical organic dye pollutants(rhodamine B, methylene blue, amido black 10 B) demonstrated that CNT-doped Pb O_2 had a superior electro-catalytic oxidation ability.
A novel CNT-doped PbO_2 electrode with porous titanium as substrate(porous Ti/Sn O_2-Sb_2 O_3/CNT-Pb O_2)was successfully prepared by electrochemical deposition method,and the degradation of organic dye wastewaters were explored. The microstructure of modified electrodes was characterized by scanning electron microscopy(SEM), energy-dispersive spectroscopy(EDS), X-ray diffraction(XRD). In contrast with pure Pb O_2 electrode, CNT-doped Pb O_2 displayed a more compact surface with a smaller grain size of crystal. The electrochemical properties of modified electrodes were characterized linear sweep voltammetry(LSV), electrochemical active surface area, electrochemical impedance spectroscopy(EIS), accelerated life and chronoamperometry. Compared with pure Pb O_2,the results showed that CNT-Pb O_2 could provid higher oxygen evolution potential, longer life, larger surface area,more active sites, and stronger electrochemical oxidation ability for electrochemical reaction system. In addition, the fluorescence experimental indicated that CNT-doped Pb O_2 significantly increased the generation for hydroxyl radical(·OH) and further enhanced the ability of the electro-oxidation process. The results of COD removal rate of several typical organic dye pollutants(rhodamine B, methylene blue, amido black 10 B) demonstrated that CNT-doped Pb O_2 had a superior electro-catalytic oxidation ability.
引文
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[31]ISHIBASHI K,FUJISHIMA A,WATANABE T,et al.Detection of active oxidative species in TiO 2photocatalysis using the fluorescence technique[J].Electrochemistry Communications,2000,2(3):207-210.
[2]HUANG X,GAO B Y,YUE Q Y,et al.Compound bioflocculant used as a coagulation aid in synthetic dye wastewater treatment:the effect of solution p H[J].Separation and Purification Technology,2015,154:108-114.
[3]BONAN S,FEDRIZZI G,MENOTTAS,et al.Simultaneous determination of synthetic dyes in foodstuffs and beverages by high-performance liquid chromatography coupled with diode-array detector[J].Dyes and Pigments,2013,99(1):36-40.
[4]KHATRI A,PEERZADA M H,MOHSIN M,et al.A review on developments in dyeing cotton fabrics with reactive dyes for reducing effluent pollution[J].Journal of Cleaner Production,2015,87:50-57.
[5]VILAR V J P,BOTELHO C M S,BOAVENTURA R A R.Methylene blue adsorption by algal biomass based materials:biosorbents characterization and process behaviour[J].Journal of Hazardous Materials,2007,147(1/2):120-132.
[6]LACKEY L W,MINES R O,Jr,McC REANOR P T.Ozonation of acid yellow 17 dye in a semi-batch bubble column[J].Journal of Hazardous Materials,2006,138(2):357-362.
[7]LI Q,ZHANG Q,CUI H,et al.Fabrication of cerium-doped lead dioxide anode with improved electrocatalytic activity and its application for removal of Rhodamine B[J].Chemical Engineering Journal,2013,228:806-814.
[8]BRILLAS E,MARTINEZ-HUITLE C A.Decontamination of wastewaters containing synthetic organic dyes by electro-chemical methods.An updated review[J].Applied Catalysis B:Environmental,2015,166/167:603-643.
[9]CHEN J,XIE Z,TANG J,et al.Oxidation of toluene by dielectric barrier discharge with photo-catalytic electrode[J].Chemical Engineering Journal,2016,284:166-173.
[10]ABOU-SHADY A.Effect of separated cathode on the removal of dissolved organic carbon using anode oxidation,Fenton oxidation,and coagulation[J].Journal of Environmental Chemical Engineering,2016,4(1):704-710.
[11]ZHAO W,XING J T,CHEN DH,et al.Study on the performance of an improved Ti/Sn O2-Sb2O3/Pb O2based on porous titanium substrate compared with planar titanium substrate[J].RSC Advances,2015,5(34):26 530-26 539.
[12]VELICHENKO A B,AMADELLI R,BENEDETTI A,et al.Electrosynthesis and physicochemical properties of Pb O2films[J].Journal of The Electrochemical Society,2002,149(9):C445-C449.
[13]CHAPLIN B P.Critical review of electrochemical advanced oxidation processes for water treatment applications[J].Environmental Science:Processes&Impacts,2014,16(6):1182-1203.
[14]EL-GHENYMY A,RODRIGUEZ R M,BRILLAS E,et al.Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells.Kinetics,reaction intermediates,and toxicity assessment[J].Environmental Science and Pollution Research International,2014,21(14):8368-8378.
[15]WU X X,XU H F,LU L,et al.Pb O2-modified graphite felt as the positive electrode for an all-vanadium redox flow battery[J].Journal of Power Sources,2014,250:274-278.
[16]陈荣玲,黄卫民,何亚鹏,等.阴极脱氯协同多孔Ti/BDD电极阳极电催化氧化对氯苯酚[J].电化学,2017,4(6):126-130.
[17]KAUR R,KUSHWAHA J P,SINGH N.Electro-oxidation of Ofloxacin antibiotic by dimensionally stable Ti/Ru O2anode:evaluation and mechanistic approach[J].Chemosphere,2018,193:685-694.
[18]GAO J,YAN J,LIU Y,et al.A novel electro-catalyticdegradation method of phenol wastewater with Ti/IrO 2-Ta2O5anodes in high-gravity fields[J].Water Science and Technology:a Journal of the International Association on Water Pollution Research,2017,76(3):662.
[19]LIN H,NIU J F,DINGS Y,et al.Electrochimical degradation of perfluorooctanoic acid(PFOA)by Ti/Sn O2-Sb,Ti/Sn O2-Sb/Pb O2and Ti/Sn O2[J].Water Research,2012,46(7):2281-2289.
[20]李广忠,李纲,王辉,等.Sb掺杂纳米Sn O2/多孔Ti电极的制备及其降解甲基橙性能[J].稀有金属材料与工程,2015,44(6):1326-1330.
[21]HE Y P,HUANG W M,CHEN R L,et al.Enhanced electrochemical oxidation of organic pollutants by boron-doped diamond based on porous titanium[J].Separation and Purification Technology,2015,149:124-131.
[22]LI H,SUN Z,TIAN Y,et al.Facile and cost-effective synthesis of CNT@MCo2O4(M=Ni,Mn,Cu,Zn)core-shell hybrid nanostructures for organic dye removal[J].Rsc Advances,2015,5(97):79 765-79 773.
[23]吴根英,许双姐,王君翔,等.FR-CNTs-Pb O2/Sn O2-Sb/Ti电极性能及电催化降解罗丹明B[J].环境化学,2013,23(3):358-365.
[24]AN H,LI Q,TAO D J,et al.The synthesis and characterization of Ti/Sn O2-Sb2O3/Pb O2electrodes:The influence of morphology caused by different electrochemical deposition time[J].Applied Surface Science,2011,258:218-224.
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[26]MARTINEZ-HUITLE C A,FERRO S.Electrochemical oxidation of organic pollutants for the wastewater treatment:direct and indirect processes[J].Chemical Society Reviews,2006,35(12):1324-1340.
[27]DAN Y,LU H,LIU X,et al.Ti/Pb O2+nano-Co3O4composite electrode material for electrocatalysis of O2evolution in alkaline solution[J].International Journal of Hydrogen Energy,2011,36(3):1949-1954.
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[29]SHAO D,YAN W,LI X,et al.A highly stable Ti/TiHx/Sb-Sn O2anode:preparation,characterization and application[J].Industrial&Engineering Chemistry Research,2014,53(10):3898-3907.
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