Electro-catalytic degradation properties of Ti/SnO<Subscript>2</Subscript>–Sb electrodes doped with different rare earths

Ti/SnO₂–Sb electrode has a good effect on the removal of organic pollutants. But its short service life limits its large-scale application in industry. Electro-catalytic degradation performances and service life of the electrode can be significantly improved by doping rare earth (RE) ions into the oxide coating of Ti/SnO₂–Sb electrode. Ti/SnO₂–Sb electrodes doped with different RE elements (Ce, Dy, La, and Eu) were prepared by the thermal decomposition method at 550 °C. Electro-catalytic degradation performances of electrodes doped with different RE elements were evaluated by linear sweep voltammetry (LSV) and Tafel curves. During the electrolysis, the conversion of p-nitrophenol was performed with these electrodes as anodes under galvanostatic control. The structures and morphologies of the surface coating of the electrodes were characterized by scanning electron microscope (SEM). The results demonstrate that the electro-catalytic degradation performances of Ti/SnO₂–Sb electrodes are improved to different levels by doping different RE ions. Improved Ti/SnO₂–Sb electrodes by the introduction of different RE have higher oxygen evolution potential, better electro-catalysis ability, better coverage, and longer electrode life.     

超声掺Bi二氧化铅电极电氧化降解2-氯苯酚研究

目的提高Pb O_2/Ti的使用寿命、对目标反应物的电氧化催化活性及选择性。方法以覆有Sn O_2+Sb_2O_3的Ti网为阳极,分别在Pb(NO_3)_2、Na F混合溶液及Pb(NO_3)_2、Na F、Bi(NO_3)_3组成的掺Bi混合溶液中,在电沉积液p H=2、60℃、电沉积电流密度为0.04 A/cm~2的条件下,进行常规电沉积及超声电沉积1 h,制备出Pb O_2/Sn O_2+Sb_2O_3/Ti,Bi-Pb O_2/Sn O_2+Sb_2O_3/Ti,Pb O_2(ultrasonic)/Sn O_2+Sb_2O_3/Ti,Bi-Pb O_2(ultrasonic)/Sn O_2+Sb_2O_3/Ti 4类二氧化铅电极。在硫酸溶液中测定其加速寿命,用稳态极化曲线分析电催化性及选择性,以2-氯苯酚的电氧化降解反应为模型反应,考察电解2-氯苯酚废水的处理效果,用X射线衍射仪和电子扫描电镜表征沉积层晶相和形貌。结果 Bi-Pb O_2(ultrasonic)/Sn O_2+Sb_2O_3/Ti的加速寿命比Pb O_2/Sn O_2+Sb_2O_3/Ti提高了54%。电氧化降解2-氯苯酚溶液4 h后,以掺Bi二氧化铅电极为阳极,相比于二氧化铅电极,对2-氯苯酚的脱除率提高了19%,槽压降低了7%,稳态极化曲线和电氧化降解2-氯苯酚溶液试验反映了相同的结论。结论超声波环境和Bi掺杂显著提升电极的性能,掺Bi的二氧化铅沉积层表现出较高的电催化性和电氧化2-氯苯酚的选择性,超声电沉积二氧化铅能增大电极比表面积,提高电极的表观催化活性和电极加速寿命。     

La掺杂的SnO2-Sb中间层对钛基IrO2+Ta2O5电极性能的影响

目的改善Ti/IrO_2+Ta_2O_5涂层电极的析氧电催化性能。方法用热分解法在钛基材上制备了La掺杂的SnO_2-Sb中间层,并以此作为基体涂覆IrO_2+Ta_2O_5活性层,制备了Ti/SnO_2-Sb-La/IrO_2+Ta_2O_5涂层电极。采用扫描电子显微镜(SEM)、能量散射能谱(EDS)及X-射线衍射光谱(XRD)技术分别分析了中间层和活性层的表面形貌、元素组成及晶相结构。采用线性扫描伏安曲线(LSV)和强化寿命测试方法在硫酸溶液中分别研究了Ti/SnO_2-Sb-La/IrO_2+Ta_2O_5涂层电极的析氧电催化活性和使用稳定性。同时,考察了La的掺杂比例对Ti/SnO_2-Sb-La/IrO_2+Ta_2O_5电极强化寿命的影响。结果相对未掺杂La的中间层,掺杂La后的中间层表面裂纹减少,有更高的析氧过电位和更低的析氧电流密度。La掺杂对活性层的表面形貌和晶相结构基本没有影响,但电极的析氧电流密度有所提高。通过测试不同La掺杂比例涂层电极的强化寿命,发现La最佳掺杂比例为nLa:nSn=0.5:100。和未掺杂La涂层相比,La最佳掺杂比例涂层电极的强化寿命提高了22.8%。结论相对于未掺杂的Ti/SnO_2-Sb/IrO_2+Ta_2O_5电极,La掺杂后的Ti/SnO_2-Sb-La/IrO_2+Ta_2O_5涂层电极析氧电催化活性和强化寿命都得到改善。     

新型二氧化铅电极的制备及其性能研究

用电沉积方法制备了Ti/SnO2+Sb2O3/PbO2,Ti/SnO2+Sb2O3/Bi-PbO2,Ti/PbO2三种二氧化铅电极,采用加速寿命试验对比了电极的寿命,采用扫描电镜表征了电极的表面形貌,并将所制备的电极用于处理苯酚溶液和含铜离子的溶液,分析了电解处理的效果.结果表明:未掺铋二氧化铅电极的加速寿命最长,且其处理的含铜废水可达国家排放标准,但掺铋电极的电催化性能更高.     

Photoelectrocatalytic activity of two antimony doped SnO2 films for oxidation of phenol pollutants

Two types of Sb-doped SnO2 films on titanium substrate were prepared by the combination of electro-deposition and dip-coating (Ti/SnO2-Sb2O4/SnO2-Sb2O4) and single dip-coating (Ti/SnO2-Sb2O4), respectively. The surface morphology and crystalline structure of both film electrodes were characterized using X-ray diffractometry(XRD) and scanning electron microscopy(SEM). XRD spectra indicate that the rutile SnO2 forms in two films and a TiO2 crystallite exists only in Ti/SnO2-Sb2O4 electrode. SEM images show that the surface morphology of two films is typically cracked-mud structure. The photooxidation experiment was proceeded to further confirm the two electrode activity. The results show that the photoelectrocatalytic degradation efficiency of Ti/SnO2-Sb2O4 electrode with sub-layer is higher than that of simple Ti/SnO2-Sb2O4 electrode using phenol as a model organic pollutant. The Ti/SnO2-Sb2O4/SnO2-Sb2O4 photoanode has a better photoelectrochemical performance than Ti/SnO2-Sb2O4 photoanode for the removal of organic pollutants from water.     

稀土Ce掺杂Ti/Sb-SnO2电极的电化学性能及应用

采用热分解法制备Ti/Sb-SnO2电极和Ti/Sb-SnO2/Ce电极,采用扫描电子显微镜(SEM)、X射线衍射(XRD)仪和电化学实验技术对电极的表面形貌、物相组成和电化学性能进行表征。结果表明:Ti/Sb-SnO2电极表面形成了SnO2晶胞,经稀土Ce改性后SnO2晶粒明显细化,SnO2衍射峰强度变强且峰形宽化。Ti/Sb-SnO2/Ce电极峰电流值最大、表面稳定性增强和催化活性明显提高。在最佳工艺条件下,Ti、Ti/Sb-SnO2和Ti/Sb-SnO2/Ce电极对橙黄G目标污染物的去除率分别为46.6%、61.9%和94.9%,且降解过程均符合一级反应动力学模型,速率常数分别为0.0289、0.0633、0.1971min-1,Ti/Sb-SnO2/Ce电极的速率常数分别是Ti/Sb-SnO2电极的3倍,Ti电极的7倍,表明在电极表面涂层中掺杂稀土元素Ce可有效提高电极的性能。     

溶胶凝胶法制备Sb掺杂Ti/SnO2 电极及其电催化性能

采用溶胶凝胶法制备了Sb掺杂Ti/SnO2电极,通过XRD,SEM,EDS及电化学测试、氧化物总量测试、加速寿命测试等技术手段,研究了Sb的掺杂对电极结构、形貌、电催化性能、使用寿命的影响。结果表明:Sb的掺入能有效改善电极的表面晶体结构和形貌,降低电极的苯酚氧化电位和液界电阻,提高电极的电催化效率;当制备的溶胶中锡锑比为9∶1时,制得的电极表面形貌平整、致密,稳定性和电催化效果最好。     

稀土Y掺杂Ti/SnO2+MnOx/PbO2电极的电化学性能研究

采用热分解和电沉积的方法制备了稀土元素Y掺杂Ti/SnO2+MnOx/PbO2耐酸阳极.用XRD、SEM表征了电极的物相和表面形貌,用CV、EIS测定了电极的电化学性能,并研究了Y掺杂对电极在强酸性溶液中使用寿命的影响.结果表明:Y以Y2O3的形式与SnO2形成半导体固溶体,使电极在高电流密度(4 A/cm2)下的预期使用寿命达到70 h;同时该电极的析氧电位高达2.1 V,且电极表面呈蘑菇状,电催化性较好,Ti/SnO2+Y2O3+MnOx/PbO2电极是一种较理想的耐酸阳极材料.     

不同阴离子铕盐掺杂Sb-SnO2/Ti电极的催化性能

利用热分解法制备了EuBr3、Eu(NO3)3、EuCl3、Eu(ClO4)3、Eu(AC)3掺杂Sb-SnO2/Ti电极,通过对乙醇氧化和对模拟废水（甲基橙、亚甲基蓝）的降解,研究电极的电催化性能。通过循环伏安法,X射线衍射（XRD）仪,扫描电子显微镜（SEM）,X射线光电子能谱（XPS）等对电极进行了表征。结果表明,不同Eu盐掺杂Sb-SnO2/Ti电极对不同体系表现出不同催化性能。Eu(ClO4)3掺杂电极对降解甲基橙有最好的效果,EuCl3掺杂对降解亚甲基蓝表现最佳,而对于电催化氧化乙醇体系,Eu(NO3)3掺杂电极表现出了最高的催化活性     

钛基PbO2电极上苯酚的电化学氧化

以Ti为基体，通过热分解Pb（NO3）2水溶液制备了Ti／PbO2电极以及含有SnO2＋Sb2O3中间层的Ti／SnO2＋Sb2O3／PbO2电极，并将所制备的电极应用于模拟苯酚废水的电化学氧化降解。结果表明：含有SnO2＋Sb2O3中间层的Ti／SnO2＋Sb2O3／PbO2电极在相同的操作电流密度下，槽电压低于未加中间层的Ti／PbO2电极。以聚合前驱体制得的Ti／SnO2＋Sb2O3／PbO2电极为阳极时，在25℃，电流密度15mA／cm^2下，恒电流电解浓度为2．13×10^-3mol／L的模拟苯酚废水，电解3．0h后，苯酚浓度降为1．67×10^-5mol／L，苯酚去除率达99．2％；电解6．5h后，COD下降率为84.3％。阳极寿命快速检测实验结果表明，添加锡锑中间层后的Ti／SnO2＋Sb2O3／PbO2电极，其寿命显著提高。     

CdS修饰TiO2纳米管阵列的制备及光催化性能研究

首先通过恒压阳极氧化法在纯钛箔表面制备TiO2纳米管阵列,其次运用电化学沉积法在TiO2纳米管阵列表面修饰CdS颗粒,最后表征其对甲基橙的光催化降解性能.研究表明,通过电化学沉积可以在管阵列表面获得均匀分布的CdS纳米颗粒.TiO2纳米管阵列在经过CdS修饰后,对可见光的吸收范围明显增大;光照2 h后,对甲基橙的降解效率由修饰前的57.1%提高到修饰后的76.4%,COD的去除率也从49%提高到70.6%.     

热丝化学气相沉积法制备钛基 BDD 电极及苯酚降解性能研究

目的研究硼掺杂对改善金刚石膜的电阻率的影响,制备掺硼金刚石膜。方法采用热丝化学气相沉积系统,以CH4,H2,(CH3O)3B混合气体为反应气,在钛片衬底上沉积制备掺硼金刚石膜电极。对不同生长阶段沉积出的电极进行扫描电镜、EDX光电子能谱、激光Raman光谱、X射线衍射、电化学性能表征及废水降解应用研究。结果制备出的掺硼金刚石膜呈现出均匀的(111)晶面,Raman光谱图中金刚石特征峰与硼原子特征峰峰型显著,具有较低的背景电流和更宽的电位窗口(3.5 V),对苯酚废水COD降解效果显著。结论有机污染物的吸附量与电极表面的粗糙度正相关,实验室制备的BDD/Ti电极表面粗糙度小,不利于析氢和析氧等副反应的发生,能降低直接电化学氧化作用,从而得到更宽的电势窗口。     

Characterization of RuO2＋SnO2／Ti anodes with high SnO2-concentrations

Two SnO2 RuO2/Ti anodes with high SnO2-concentrations were prepared by painting, sintering and annealing through a sol-gel technique. The microstructure, morphology and grain size of coatings and the electrochemical properties of the anodes were investigated by XRD, DTA, SEM, TEM and CV. It is demonstrated that the anodic coatings consist of solid solution (Sn, X)O2 (X represents Ru or Ti) phases. The average grain size of the coatings is about less than 30 nm. When the annealing temperature increases from 450℃ to 600℃, the solid solutions decompose. The crystal of the coating is equiaxial. The morphology of TiO2 SnO2/Ti coatings is a mixture of mud-flat cracking with a kind of agglomerated structure.     

不同前驱体制备的锡锑中间层对Ti／SnO2＋Sb2O3／PbO2电极性能的影响

研究了以乙二醇与柠檬酸反应制得的乙二醇柠檬酸酯溶液、乙二醇、乙醇、正丁醇为前驱体溶剂制备的锡锑中间层对Ti/SnO2 Sb2O3/PbO2电极性能的影响,用XRD、ESEM对不同前驱体制备的锡锑中间层和对应的二氧化铅活性层进行了表征,并用极化曲线法和阳极寿命快速检测法比较了不同前驱体对Ti/SnO2 Sb2O3/PbO2电极的阳极寿命和在1．0mol/L硫酸溶液中的电催化活性的影响。结果表明,不同前驱体溶剂对锡锑中间层的结构和形貌有着显著的影响;以乙二醇与柠檬酸反应制得的聚合前驱体为溶剂制备的锡锑中间层表面致密,锡锑含量相对较高,该中间层的均匀度和平整度明显好于其它3种前驱体。由聚合前驱体中间层制得的Ti/SnO2 Sb2O3/PbO2电极的使用寿命明显提高,但不同中间层前驱体对电极的电催化活性影响不大。     

耐酸非贵金属Ti／MO2阳极SnO2＋Sb2O4中间层研究

采用热分解法制备了非贵金属Sn02＋Sb204中间层Ti基MO2活性层电极，利用SEM，XRD和XPS方法对中间层进行了表征。测定了Ti／SnO2＋Sb2Od／MnO2和Ti／SnO2＋Sb2O4／PbO2电极在硫酸溶液中的析氧极化曲线，二者起始析氧过电位均比贵金属小；考察了在高电流密度（4A／cm^2）下的加速寿命，二者依次分别达到18h和86h。实验表明，SnO2＋Sb2O4是一种具有良好导电性和结合力的耐酸Ti基MO2电极中间层材料。     

钛基亚氧化钛电极强化电解失效行为研究

亚氧化钛具电化学窗口宽、耐蚀性好等诸多优点,是非常有应用潜力的污水处理用阳极材料。但目前关于其在污水处理方面的研究主要集中在其电化学性能,还未对其用于污水处理的强化电解性能进行过评价。本研究采用强化电解方法测试钛基亚氧化钛电极的寿命和失效前后的形貌和结构变化,分析其电化学性能和表面反应的机理。结果表明,亚氧化钛电极的强化电解寿命是320 h左右,每12 h反置电流可延长电解池整体寿命至840 h(电极寿命420 h),失效前后的亚氧化钛组成变化不大,涂层出现裂纹和脱落,导致基体钝化,使得槽压迅速升高而发生失效。     

高能球磨辅助固相法制备Zr掺杂的钛酸锂

采用改进的高温固相法合成Zr4+掺杂的Li4Ti5O12,研究了原位包覆技术、高能球磨和金属元素掺杂对其晶型、相结构、颗粒形貌以及电化学性能的影响。结果表明:改进后的高温固相法能有效阻止颗粒团聚、提升颗粒的均匀分散度;Zr4+掺杂能降低电极极化、提升锂离子扩散系数,从而改善电化学性能。所得Li4Ti4.95Zr0.05O12在0.5 C倍率下首次放电比容量达176 mAh·g-1,在40 C高倍率下仍达52 mAh·g-1。另探讨了不同离子半径的Zr4+和Ce4+对掺杂效果的影响,结果表明较小离子半径的元素掺杂效果较好。     

TiO2／Ti电极上外加阳极偏压对亚甲基蓝光催化降解的影响

主要研究了在纳米多孔TiO2／Ti电极上外加阳极偏压对亚甲基蓝光催化降解的影响。另外还讨论了在TiO2／Ti中掺杂过渡族金属离子对亚甲基蓝降解情况的影响。降解程度通过亚甲基蓝的褪色情况来表征。实验结果表明，降解效率随着所加阳极偏压的增大而增大，直到阳极偏压达到3．5V，增大速率开始减小。掺杂Mn^2＋和Cr^3＋可以促进光电催化效率，而掺杂Ni^2＋却会降低光电催化效率。离子半径和各离子的功函数可以解释这种现象。     

EFFECT OF SnO_2 ADDITION ON THE SERVICE LIFE AND ELECTROCHEMICAL PROPERTIES OF Ti/IrO_2,+Ta_2O_5 ANODES IN PHENOLSULFONIC ACID SOLUTION

1. IntroductionSince the discovery more than 30 years ago[1] t Ti based oxide anodes with various mixtures have been applied in different electrochemical fields. Amollg that, RllOZ TiOZ hasbeen successfully used in chlor-alkali indllstry[2] 9 and Ti/IrOZ TaZOS allode was generallyverified as the best binary mixture for oxygen evolution in acid media due to its goodelectrocatalytic activity and high durability[3--5]. However, in an extreme electrolyte, thesuitability of this anode is doub…     

Visible Light Photocatalysis of Ni-Deposited TiO_2 Nanotubes for Methyl Orange Degradation in Alkaline Medium

The photocatalysis of Ti O2nanotubes(Ti/TNT) and Ni-deposited Ti O2nanotubes(Ti/TNT–Ni) for methyl orange degradation was investigated.Methyl orange was selected as the model pollutant,and its photocatalytic degradation was determined in 1 mol/L KOH solution.Ti/TNT was produced by anodizing method,and the electrodeposition of nickel on TNT was performed galvanostatically.The characterization of electrodes was performed by scanning electron microscopy,energy-dispersive X-ray spectroscopy and X-ray diffraction analysis.The electrochemical behavior of the electrodes was determined by cyclic voltammetry and electrochemical impedance spectroscopy.The irradiation was applied by visible light source(k = 635 nm) for 48 h.UV/vis spectroscopy was used for determination of the concentration of methyl orange.Furthermore,after 48-h irradiation,the solutions were analyzed by Fourier transform infrared spectroscopy.Results showed that the concentration of methyl orange decreased from 100 ppm(10-6) to 16 ppm,after48-h irradiation with the photocatalysis of Ti/TNT–Ni.