在含[BMIM]PF_6的电解液中电沉积制备PbO_2电极的表征
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摘要
将离子液体[BMIM]PF_6(1-丁基-3-甲基-咪唑六氟磷酸盐)添加到250 g/L Pb(NO_3)_2的电解液中,通过阳极电沉积在预制SnO_2+Sb_2O_3中间层的钛网上制备了PbO_2电极(标记为PbO_2 Ⅰ),通过扫描电镜(SEM)、X射线衍射(XRD)、加速寿命试验、极化曲线测量、电催化降解试验等对其进行了表征,并与采用F~-为添加剂时制备的PbO_2电极(标记为PbO_2 Ⅱ)进行对比。结果显示:PbO_2 Ⅰ电极的晶面取向为β(110),晶粒大小均匀,棱角较多,表面平整致密;PbO_2 Ⅰ电极的加速寿命和电极性能稳定期分别为168.8 h和101.2 h。与PbO_2 Ⅱ电极相比,PbO_2 Ⅰ电极在20 g/L Na_2SO_4电解液中的析氧电位高0.12 V,对100 g/L苯酚模拟废水的电氧化降解率和化学需氧量(COD)去除率分别高8个百分点和25个百分点,而能耗低23%。离子液体改变了PbO_2的结晶过程,提高了电极的稳定性和对苯酚的电催化活性,抑制了析氧副反应。
1-Butyl-3-methylimidazolium hexafluorophosphate {[BMIM]PF_6}, an ionic liquid, was added to a 250 g/L Pb(NO_3)_2 electrolyte, in which PbO_2 electrode(coded as PbO_2-Ⅰ) was prepared by anodic electrodeposition on Ti mesh covered with an intermediate SnO_2–Sb_2O_3 layer. The properties of the PbO_2-I electrode were characterized and compared with the one prepared with F-as additive(coded as PbO_2-Ⅱ) by scanning electron microscopy(SEM), X-ray diffraction(XRD), accelerated life test, polarization curve measurement, and electrocatalytic degradation test. The results showed that the PbO_2-Ⅰ electrode is smooth and compact with an orientation of β(110), uniform crystal size, and many edges. The accelerated lifetime and stable performance period of the PbO_2-Ⅰelectrode are 168.8 h and 101.2 h, respectively. The PbO_2-Ⅰ electrode has an oxygen evolution potential 0.12 V higher than the PbO_2-Ⅱ electrode in a 20 g/L Na_2SO_4 electrolyte. The electrocatalytic degradation rate of phenol and the removal rate of COD(chemical demand of oxygen) by using the PbO_2-Ⅰ electrode are 8 and 25 percentage points higher and its energy consumption is 23% lower as compared to those by using the PbO_2-Ⅱ electrode. The ionic liquid changes the crystallization of PbO_2, improves its stability and electrocatalytic activity, and inhibits the side reaction of oxygen evolution.
1-Butyl-3-methylimidazolium hexafluorophosphate {[BMIM]PF_6}, an ionic liquid, was added to a 250 g/L Pb(NO_3)_2 electrolyte, in which PbO_2 electrode(coded as PbO_2-Ⅰ) was prepared by anodic electrodeposition on Ti mesh covered with an intermediate SnO_2–Sb_2O_3 layer. The properties of the PbO_2-I electrode were characterized and compared with the one prepared with F-as additive(coded as PbO_2-Ⅱ) by scanning electron microscopy(SEM), X-ray diffraction(XRD), accelerated life test, polarization curve measurement, and electrocatalytic degradation test. The results showed that the PbO_2-Ⅰ electrode is smooth and compact with an orientation of β(110), uniform crystal size, and many edges. The accelerated lifetime and stable performance period of the PbO_2-Ⅰelectrode are 168.8 h and 101.2 h, respectively. The PbO_2-Ⅰ electrode has an oxygen evolution potential 0.12 V higher than the PbO_2-Ⅱ electrode in a 20 g/L Na_2SO_4 electrolyte. The electrocatalytic degradation rate of phenol and the removal rate of COD(chemical demand of oxygen) by using the PbO_2-Ⅰ electrode are 8 and 25 percentage points higher and its energy consumption is 23% lower as compared to those by using the PbO_2-Ⅱ electrode. The ionic liquid changes the crystallization of PbO_2, improves its stability and electrocatalytic activity, and inhibits the side reaction of oxygen evolution.
引文
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[24]王雅琼,童宏扬,许文林.SnO2+Sb2O3中间层制备条件对Ti/SnO2+Sb2O3/PbO2阳极性能的影响[J].应用化学,2004,21(5):437-441.
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[26]CHAI S N,ZHAO G H,WANG Y J,et al.Fabrication and enhanced electrocatalytic activity of 3D highly ordered macroporous PbO2 electrode for recalcitrant pollutant incineration[J].Applied Catalysis B:Environmental,2014,147:275-286.
[27]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.
[28]SHMYCHKOVA O,LUK’YANENKO T,VELICHENKO A,et al.Bi-doped PbO2 anodes:electrodeposition and physico-chemical properties[J].Electrochimica Acta,2013,111:332-338.
[2]WU W Y,HUANG Z H LIN T T.Recent development of mixed metal oxide anodes for electrochemical oxidation of organic pollutants in water[J].Applied Catalysis A:General,2014,480:58-78.
[3]CHAPLIN B P.Critical review of electrochemical advanced oxidation processes for water treatment applications[J].Environmental Science:Processes and Impacts,2014,16(6):1182-1203.
[4]孔德生,吕文华,冯媛媛,等.DSA电极电催化性能研究及尚待深入探究的几个问题[J].化学进展,2009,21(6):1107-1117.
[5]徐浩,张倩,邵丹,等.钛基体二氧化铅电极制备改性方法研究进展[J].化工进展,2013,32(6):1307-1312,1371.
[6]PATEL P S,BANDER N,SARAF A,et al.Electrocatalytic materials(electrode materials)in electrochemical wastewater treatment[J].Procedia Engineering,2013,51:430-435.
[7]QUIROZ M A,REYNA S,MARTíNEZ-HUITLE C A,et al.Electrocatalytic oxidation of p-nitrophenol from aqueous solutions at Pb/PbO2 anodes[J].Applied Catalysis B:Environmental,2005,59(3/4):259-266.
[8]LI X H,PLETCHER D,WALSH F C.Electrodeposited lead dioxide coatings[J].Chemical Society Reviews,2011,40(7):3879-3894.
[9]HAN W Q,ZHONG C Q,LIANG L Y,et al.Electrochemical degradation of triazole fungicides in aqueous solution using TiO2-NTs/SnO2-Sn/PbO2 anode:experimental and DFT studies[J].Electrochimica Acta,2014,130:179-186.
[10]徐浩,延卫,常乐.Pb3O4层引入对钛基PbO2电极强化寿命的影响[J].稀有金属材料与工程,2012,41(3):462-466.
[11]XU H,SHAO D,ZHANG Q,et al.Preparation and characterization of PbO2 electrodes from electro-deposition solutions with deferent coper concentration[J].RSC Advances,2014,4(48):25011-25017.
[12]YAO Y W,ZHAO M M,ZHAO C M,et al.Preparation and properties of PbO2-ZrO2 nanocomposite electrodes by pulse electrodeposition[J].Electrochimica Acta,2014,117(7):453-459.
[13]乐长高.离子液体及其在有机合成反应中的应用[M].上海:华东理工大学出版社,2007:1-64.
[14]任俊毅,王少君,成卫国,等.负载型功能化离子液体的催化性能[J].化工学报,2009,60(6):1471-1476.
[15]Chen J,Xu B J,Ling G P.Amorphous Al-Mn coating on NdFeB magnets:electrodeposition from AlCl3-EMIC-MnCl2 ionic liquid and its corrosion behavior[J].Materials Chemistry and Physics,2012,134(2/3):1067-1071.
[16]孙珊珊,安茂忠,崔闻宇,等.锂离子电池用离子液体电解质的研究[J].电源技术,2010,34(1):55-58.
[17]马军德,李冰,颜灵光,等.乙二醇对ZnCl2-EMIC离子液体电沉积锌的影响[J].有色金属,2010,62(2):62-66.
[18]EL ABEDIN S Z,GIRIDHAR P,SCHWAB P,et al.Electrodeposition of nanocrystalline aluminium from a chloroaluminate ionic liquid[J].Electrochemistry Communications,2010,12(8):1084-1086.
[19]张跃宏,翟秀静,李亚琼,等.ZnCl2/TMAC离子液体中电镀锌的研究[J].有色金属(冶炼部分),2010(4):12-15.
[20]金炳勋,谢宏伟,顾惠敏,等.La3+离子在EMIMBF4离子液体中的电化学行为研究[J].稀有金属材料与工程,2012,41(4):599-602.
[21]AMADELLI R,ARMELAO L,VELICHENKO A B,et al.Oxygen and ozone evolution at fluoride modified lead dioxide electrodes[J].Electrochimica Acta,1999,45(4/5):713-720.
[22]GILROY D,STEVENS R.The electrodeposition of lead dioxide on titanium[J].Journal of Applied Electrochemistry,1980,10:511-525.
[23]常照荣,上官恩波,吴锋,等.钛基二氧化铅作为阳极电解制备羟基氧化镍的研究[J].功能材料,2007,38(5):816-818.
[24]王雅琼,童宏扬,许文林.SnO2+Sb2O3中间层制备条件对Ti/SnO2+Sb2O3/PbO2阳极性能的影响[J].应用化学,2004,21(5):437-441.
[25]孔海申.钛基二氧化铅电极(Ti/PbO2)稳定性的若干基础问题研究[D].长春:吉林大学,2013:4-6.
[26]CHAI S N,ZHAO G H,WANG Y J,et al.Fabrication and enhanced electrocatalytic activity of 3D highly ordered macroporous PbO2 electrode for recalcitrant pollutant incineration[J].Applied Catalysis B:Environmental,2014,147:275-286.
[27]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.
[28]SHMYCHKOVA O,LUK’YANENKO T,VELICHENKO A,et al.Bi-doped PbO2 anodes:electrodeposition and physico-chemical properties[J].Electrochimica Acta,2013,111:332-338.