均匀设计RuIrSnLa/Ti氧化物涂层的回归与灰色关联分析

对RuIrSnLa四元金属氧化物涂层的组成进行了研究. 采用均匀设计、偏最小二乘回归(PLS)与灰色关联度分析相结合的方法, 以使用寿命、伏安电量、析氯电位、析氧电位及析氧析氯电位差为考察指标, 对电化学性能的影响因素进行了主次分析, 并对涂层配方进行了优选. 结果表明: Ir对提高阳极的使用寿命影响最大, 其次是Ru, Sn是提高析氧电位的主要元素, 而La对提高阳极电催化活性, 降低析氯电位及增大析氧析氯电位差起着主要作用, PLS分析认为, La对阳极稳定性呈负效应. 采用偏最小二乘回归与灰色关联度相结合的分析方法, 可以优势互补, 为多元金属氧化物涂层的成分设计和理论研究提供依据.     

均匀设计RulrSnLa/Ti氧化物涂层的回归与灰色关联分析

对RuIrSnLa四元金属氧化物涂层的组成进行了研究.采用均匀设计、偏最小二乘回归(PLS)与灰色关联度分析相结合的方法,以使用寿命、伏安电量、析氯电位、析氧电位及析氧析氯电位差为考察指标,对电化学性能的影响因素进行了主次分析,并对涂层配方进行了优选.结果表明:Ir对提高阳极的使用寿命影响最大.其次是Ru,Sn是提高析氧电位的主要元素,而La对提高阳极电催化活性,降低析氯电位及增大析氧析氯电位差起着主要作用,PLS分析认为,La对阳极稳定性呈负效应.采用偏最小二乘回归与灰色关联度相结合的分析方法,可以优势互补,为多元金属氧化物涂层的成分设计和理论研究提供依据.     

添加碳纳米管对钌铱锡氧化物阳极性能的影响

本文采用热分解法制备Ti/Ru-Ir-Sn氧化物阳极,运用TGA、SEM、EDS、循环伏安、电化学交流阻抗、极化曲线以及强化电解寿命测试方法,探讨添加不同含量碳纳米管（CNTs）对Ti/Ru-Ir-Sn氧化物阳极的影响规律. 热重分析和阳极能谱数据表明,在烧结温度470 ^oC条件下CNTs未发生高温氧化分解,仍以单质形式存在阳极涂层中. 与对比样品相比,涂层表面裂纹增多,但仍保持典型形貌. 添加CNTs显著改善了Ti/Ru-Ir-Sn氧化物阳极的电化学性能,增大了阳极的活性表面积,减小了涂层内部电阻,提高了阳极析氯电催化活性,析氯电位增加缓慢,阳极强化电解寿命也得到明显延长. 其中,添加0.1 g·L^-1 CNTs的Ti/Ru-Ir-Sn氧化物阳极电催化活性和稳定性最优.     

钌锡比对Ru-Ir-Sn氧化物阳极涂层性能的影响

应用溶胶凝胶法制备了不同钌锡摩尔比氧化物阳极涂层.SEM,EDX,强化电解寿命,循环伏安和电化学阻抗等测试表明,钌锡摩尔比对阳极涂层的表面形貌以及电化学性能有很大影响.随着钌含量的增加涂层的强化电解寿命呈先增加后降低变化,析氯电位呈先降低后增加;电流效率呈先增加后降低,与其对应的循环伏安电量以及双电层电容值亦呈先增加后减小变化.     

烧结温度对Ru-Ir-Sn氧化物阳极涂层性能的影响

应用溶胶凝胶法制备不同焙烧温度的氧化物阳极涂层,SEM,EDX,XRD、强化电解寿命、循环伏安和电化学阻抗等测试表明,烧结温度对阳极涂层的表面形貌以及电化学性能有着很大的影响.随着烧结温度的升高,析氯电位相应增加,寿命相对较长,循环伏安电量与双电层电容值有所下降.     

高温析氯电催化剂用稀土氧化物的性能

采用热分解工艺制备稀土氧化物电极 ,研究了涂液组分、热分解温度及涂刷次数等对涂层电极性能的影响。对多种稀土化合物电极在70 0℃高温NaCl KCl( 1∶1 ,摩尔比 )熔体中的阳极析氯极化曲线测定结果表明 ,0 6A·cm- 2 的电流密度下 ,一些稀土氧化物可降低析氯过电位50～ 1 1 0mV。多次重复试验的误差小于 3 0mV。另外还从稀土氧化物能带结构的角度对其高温析氯电催化活性进行了解释。     

海水电解Ru-Ti-Ir-Sn氧化物阳极涂层研究

应用热分解法制备不同组分的Ru-Ti-Ir-Sn氧化物阳极涂层,并由SEM、EDX、强化电解寿命、电流效率、抗Mn2+污染、极化曲线和循环伏安等实验方法研究该Ru-Ti-Ir-Sn氧化物阳极涂层的物理性能和电化学性能.结果表明,优化配方的Ru-Ti-Ir-Sn氧化物阳极涂层对电解海水具有较好的综合性能.     

涂液浓度对Ru-Ti-Ir氧化物阳极涂层性能的影响

应用热分解法制备了由不同浓度涂液形成的Ru-Ti-Ir氧化物阳极涂层,SEM,EDX,XRD、强化电解寿命、极化曲线、循环伏安和电化学阻抗等测试表明,涂液浓度对阳极涂层的表面形貌有着很大的影响,但不甚影响其析氯极化过程.随着涂液浓度的增加,阳极涂层的伏安电量和双电层电容都出现先降低后增加的变化趋势.     

析氯钛基RuO_2－Co_3O_4－TiO_2（60）涂层的研究

用稳定极化、Ｘ射线衍射、透射电镜和扫描电镜的方法研究了钛基ＲｕＯ_２－Ｃｏ_３Ｏ_４－ＴｉＯ_２（６０）涂层的析氯活性、导电性、使用寿命、微观结构和表面形貌。并对其活性表面积进行了评价。详细讨论了涂层成份、微观结构和表面形貌对涂层析氯活性和活性表面积的影响。发现在０～１０ｍ／ｏＣｏ_３Ｏ_４和６０ｍ／ｏＴｉＯ_２成份范围内ＲｕＯ_２、Ｃｏ_３Ｏ_４和ＴｉＯ_２可形成单一金红石型固溶体,且有优异的析氯活性、电导率和使用寿命。以此研究为基础可改进氯碱工业广泛使用的传统ＲｕＯ_２－ＴｉＯ_２阳极,降低阳极涂层中贵金属含量,提高阳极的电化学性能．     

稀土元素镧对锌阳极带电化学性能的影响

研究了镧的加入对牺牲锌阳极带电化学性能的影响。结果表明，稀土元素镧对锌阳极带的电位和电流效率影响很小，实验结果符合相关标准。证明在纯锌中添加微量稀土元素镧改善锌阳极带机械性能，同时保持必要的电化学性能的工艺方法是有效、可行的。     

An alternative approach to selective sea water oxidation for hydrogen production

Sea water electrolysis is one of the promising ways to produce hydrogen since it is available in plentiful supply on the earth. However, in sea water electrolysis toxic chlorine evolution is the preferred reaction over oxygen evolution at the anode. In this work, research has been focused on the development of electrode materials with a high selectivity for oxygen evolution over chlorine evolution. Selective oxidation in sea water electrolysis has been demonstrated by using a cation-selective polymer. We have used a perm-selective membrane (Nafion^®), which electrostatically repels chloride ions (Cl⁻) to the electrode surface and thereby enhances oxygen evolution at the anode. The efficiency and behaviour of the electrode have been characterized by means of anode current efficiency and polarization studies. The surface morphology of the electrode has been characterized by using a scanning electron microscope (SEM). The results suggest that nearly 100% oxygen evolution efficiency could be achieved when using an IrO₂/Ti electrode surface-modified by a perm-selective polymer.     

Studying the Link between the Potential of a Metal-Oxide Anode, the Current Efficiency for Chlorate, and the Current Losses for the Oxygen and Chlorine Evolution in a Wide Range of the Chlorate Electrolysis Conditions

Dependences of the current efficiency for chlorate and current losses for the oxygen evolution on the anode potential are studied. The study is performed in a cell without directed electrolyte circulation during the electrolysis of chloride–chlorate solutions of various compositions at the ORTA and ORTA-I1 anodes, at different current densities, temperatures, and solution pH. At identical temperatures, the dependences have extremums. The anode potentials corresponding to extremums coincide with critical potentials (found in a polarization study) for anodes covered with coatings containing ruthenium dioxide. The current efficiency for chlorate at ORTA-I1 is higher than that at ORTA, while the extremum region is less pronounced. The problem of how to substantially decrease the specific power consumption in the chlorate production by simultaneously increasing the anodic current density and the electrolysis temperature is considered.     

Corrosion and electrochemical behavior of metal-oxide anodes during electrolysis with an ion-exchange membrane

The reasons for a specific behavior of anodes in chlorine electrolysis with an ion-exchange membrane are considered. The corrosion rate in modeling conditions and the predicted lifetime of anodes of different compositions are studied. The anodes’ coatings contain mixed oxides of Ir, Ru, Sn, or Ti. The effect of the anode’s position relative to the membrane and a relative stability of the anode coatings are examined in conditions simulating a heavy alkalization of the anolyte caused by a membrane rupture. A considerable advantage of using the anode with a coating containing 15, 15, and 70 mol % of RuO₂, IrO₂, and TiO₂ is demonstrated     

钌镧氧化物涂层在NaCl 溶液中的电化学阻抗谱(EIS)研究

测量了钌镧氧化物涂层的电化学阻抗谱(EIS), 结合循环伏安(CV)及扫描电子显微镜形貌分析, 研究了钌镧氧化物涂层阳极在3.5% NaCl 溶液中电化学表面结构及电化学行为. 在非析氯反应区间, 该涂层EIS 数据的最佳拟合等效电路是R_s(R_ctQ_dl), 在析氯反应区间, 其等效电路为R_s(R_fQ_f)(R_ctWQ_dl). 高频段阻抗行为对应涂层的物理阻抗, 低频段对应涂层与溶液界面的电化学反应阻抗. 实验结果表明, 随着La 浓度增加, 氧化膜及双电层的伪电容增大, 且在La 含量30mol%时达到最大值, 与CV实验结果一致, 证明了加入La 能提高RuO₂涂层的电催化活性. 但在析氯反应区间, 涂层氧化膜的导电性在含La 大于30 mol%之后迅速下降, 在低频段产生Warburg 阻抗, 与其表面钝化和特性吸附现象有关,这是导致含La 70 mol%时电催化活性急剧下降的原因.     

Ti/RuO2-IrO2-SnO2-Sb2O5阳极在农村饮用水消毒中的应用

采用热分解法制备了一种新型高效析氯阳极Ti/RuO₂-IrO₂-SnO₂-Sb₂O₅,将其应用于农村饮用水消毒频繁停开、低电解液浓度的特殊工况下,并与Ti/RuO₂-SnO₂-Sb₂O₅、Ti/RuO₂-TiO₂、Ti/RuO₂-TiO₂-IrO₂三种析氯阳极进行性能对比。通过SEM、EDS、XRD等方法表征测试阳极表面形貌、元素及组成,考察了氯化钠浓度、电流密度、停开频率对阳极析氯效果和寿命的影响。研究发现,Ti/RuO₂-IrO₂-SnO₂-Sb₂O₅阳极活性强、稳定性高;阳极涂层各组分高度融合为固溶体,结构致密,稳定性强;在15 g·L^-1 NaCl、400 A·m^-2电流密度、20℃条件下,Ti/RuO₂-IrO₂-SnO₂-Sb₂O₅阳极电解的电流效率达到91.55%;频繁停开、强化电解条件下寿命达到231 h,是Ti/RuO₂-TiO₂阳极的77倍,预估在400 A·m^-2电流密度下能够使用20年。     

Anodic oxide-film of the Co—Sn—O composition

Properties and electrocatalytic activity of thin-film (∼2 μm) oxide coatings on aTi support are considered by the example of the anodic chlorine evolution reaction. The coatings are obtained by thermally decomposing Co and Sn chloride solutions of different compositions on a Ti plate. The Co and Sn oxides are present in all studied compositions as individual phases and form no compounds or solid solutions. The oxide coating containing 70 at. % Co and 30 at. % Sn reveals a maximum electrocatalytic activity. The existence of the optimum composition is attributed to a favorable effect tin dioxide has on the formation of a transition layer between the Ti support and oxide coating. Tin dioxide hampers the Ti diffusion in the main coating and its subsequent oxidation, thus diminishing the negative impact titanium oxides have on the coating