海水温度对金属氧化物阳极强化电解失效行为影响

采用热分解法在钛基体上制备钌铱锡金属氧化物阳极,通过SEM、EDX、循环伏安、电化学阻抗谱及强化电解寿命试验等测试方法,探求不同海水温度对于钌铱锡金属氧化物阳极强化电解失效行为的影响规律。结果表明：在5~20 ℃海水温度条件下,阳极寿命短,失效阳极的中心区域存在少量残余涂层,呈现龟裂状形貌,而边缘地带Ti基体基本暴露,涂层发生局部电化学溶解或剥落;当海水电解温度为40 ℃时,阳极寿命较长,阳极涂层发生均匀电化学溶解。另外,随着海水温度的升高,阳极电化学活性表面积增大,稳定性逐渐提高。5~20 ℃条件下阳极失效主要是由于Ru组元的选择性溶解和涂层局部剥落导致,而40 ℃条件下涂层也发生电化学溶解,但TiO2钝化膜的形成是引起阳极失效的主要原因     

烧结温度对Ti/IrO2-Ta2O5纳米氧化物阳极微观结构和电催化性能的影响

采用Pechini法制备Ti/IrO2-Ta2O5纳米氧化物阳极,通过SEM、EDX、XRD、极化曲线、循环伏安、电化学阻抗谱及强化电解寿命试验等测试手段,研究了烧结温度对Ti/IrO2-Ta2O5阳极微观结构和电催化性能的影响。结果表明,阳极涂层成分分布均匀,IrO2晶粒偏析不明显;Ta在铱钽固溶体中的固溶度随烧结温度升高而增大,涂层晶粒逐渐细化。随着烧结温度的升高,阳极析氧电催化活性降低,电化学活性表面积减小;500 ℃下所得Ti/IrO2-Ta2O5阳极表现出最高的强化电解寿命。     

Ti基RuO2-CeO2-SnO2涂层阳极的电催化性能

利用热分解法制备了不同CeO2含量的Ti基RuO2-CeO2-SnO2涂层阳极, 通过循环伏安曲线和电化学阻抗谱测试了所制备的涂层阳极的电催化性能, 并用扫描电镜对涂层阳极的表面形貌进行了观察. 结果表明 制备温度对涂层阳极的性能有很大影响, 在涂层阳极中引入CeO2可以增加RuO2-CeO2- SnO2涂层的有效活性表面积, 从而提高涂层阳极的电催化活性, 且CeO2含量的最佳摩尔分数为0.4.     

Stability and morphology of (Ti0·1Ru0·2Sn0·7)O2 coating on Ti in chloralkali medium

Abstract

Today's mixed metal oxide anodes are widely used in the chloralkali industry. Stability is one of the main properties of these anodes because of their high cost. Morphology of mixed metal oxide coating is a determining factor in electrochemical stability of mentioned anodes. In this article the effect of temperature and times of heat treatment on the morphology and electrochemical stability of Ti/(Ti_0·1Ru_0·2Sn_0·7)O₂ anode has been investigated. The anodes were prepared by brushing and thermal decomposition method. Mud cracked morphology appeared on the sample by this process. Increasing the temperature of calcination causes the density of cracks on the surface and electrochemical stability of coating to decrease. Increasing the time had different effects in the first and final calcination times. The anode which was prepared at 450°C, for 10 min in the first calcination time and 1 h in the final calcination time had the highest stability and optimum morphology.     

含氟电解液中钛基铱钽氧化物电极的稳定性

目的 分析钛基铱钽氧化物电极在含氟电解液中的应用前景。方法 采用热分解法制备出钛基铱钽氧化物电极,借助扫描电镜分析了氟元素对钛基铱钽氧化物电极表面形貌的影响。应用循环伏安、稳态极化和电化学阻抗等方法,研究了氟元素对铱钽氧化物电极在硫酸溶液中电催化性能的影响。结果 当溶液中的氟含量高于5 mg/L时,铱钽氧化物电极在2 A/cm2下强化电解72 h后,表面开始出现裂纹,且裂纹尺寸和数量随溶液中氟含量的增加而增加。强化电解72 h下,氟含量低于10 mg/L时,氟对钛基铱钽氧化物电极循环伏安特性的影响较小,但氟含量高于10 mg/L时,电极伏安面积可增大24%。强化电解过程中,氟元素可增加电极的电荷转移电阻,增大电极的析氧电位,降低电极的双电层电容。结论 电解液中的氟元素可加速钛基铱钽氧化物电极的失效。氟元素虽可提高电极表面的粗糙度,改善电催化性能,但活性成分氧化铱的溶解损失更大,导致电极的析氧电催化性能降低。钛基铱钽氧化物电极在氟含量低于5 mg/L的酸性电解液中具有应用前景。     

Ti/IrO2-Ta2O5-SnO2纳米氧化物阳极的研究

采用Pechini方法制备不同Sn含量的Ti/IrO2-Ta2O5-SnO2纳米氧化物阳极,并运用SEM、EDX、XRD等分析手段和析氧电位、循环伏安、强化电解等方法对阳极的表面形貌、微观结构和电化学性能进行研究。结果表明,制备的氧化物涂层由(IrSn)O2固溶体和非晶态的Ta2O5构成,组成与名义成分基本一致。随着Sn含量的增加,氧化物涂层表面裂纹增多。Sn的加入使Ti/IrO2-Ta2O5-SnO2氧化物阳极的析氧电位升高,稳定性降低。     

Improvement of stability of trivalent chromium electroplating of Ti based IrO2+Ta2O5 coating anodes

The preparation process and properties of the thermally prepared Ti anodes coated with IrO2+Ta2O5 was studied. The structure and morphologies of the IrO2+Ta2O5 coatings were determined by XRD and SEM. Their electrochemical properties were studied by polarization curve and cyclic voltammetry. Trivalent chromium electroplating using Ti/IrO2+Ta2O5 anodes is carried out and the results were analyzed. Results show that this anode exhibits excellentelectrochemical activity and stability in sulfate electrolysis. The electrocatalytic activity is determined not only by the content of IrO2 but also the structure and morphology of the anode coatings. The electroplating results indicats that Ti/IrO2+Ta2O5 anodes have excellent capabilities and merits in improving the stability of trivalent chromium electroplating in sulfate system.     

Fe-30Ni-5NiO alloy as inert anode for low-temperature aluminum electrolysis

Fe-30Ni-5NiO alloy anodes were prepared by a spark plasma sintering process for aluminum electrolysis. NiO nano-particles with the size of ∼20 nm were dispersed in the anodes. The oxidation behaviors of the anodes were investigated at 800°C and 850°C, respectively. The electrolysis corrosion behaviors were tested in a cryolite-alumina electrolyte at a low temperature of 800°C with anodic current densities of ∼0.5 A/cm². The results indicated that the oxidation kinetic of the anodes followed a parabolic law. A continuous Fe₂O₃ film selectively formed on the surface of the anode during the electrolysis process. A semi-continuous Al₂O₃ layer was observed at oxide film/alloy interface, probably caused by an in-situ chemical dissolution process.     

溶胶凝胶法制备Ru-Ir-Sn-Ti阳极涂层及其电化学性能研究

采用溶胶凝胶法制备Ru-Ir-Sn-Ti阳极涂层,对涂层进行析氯电位、析氧电位、极化曲线、循环伏安曲线、电化学交流阻抗等电化学测试以及强化电解寿命测试,并与热分解法制备的阳极涂层进行对比。结果表明:与热分解法制备的阳极涂层相比,溶胶凝胶法制备的Ru-Ir-Sn-Ti阳极涂层具有较低的析氯电位、较高的析氧电位、良好的电催化活性和较长的强化电解寿命。     

A study on the deactivation of an IrO2–Ta2O5 coated titanium anode

The deactivation of an IrO₂–Ta₂O₅ coated titanium anode was studied during an accelerated life test at 2 A cm⁻² in 1 mol dm⁻³ H₂SO₄ solution using CV, EIS, SEM and EDX. The changes of voltammetric charge, double layer capacitance, oxide film resistance and charge transfer resistance of oxygen evolution with time during the electrolysis were monitored. The morphology and surface composition of the oxide anode before and after electrolysis test were analysed. A comprehensive process of deactivation of the oxide anode was proposed based on the test results and analysis.     

钛基钌镧氧化物涂层结构对电化学活性的影响

以RuCl33H2O和LaCl37H2O为前驱物,通过热分解方法制备Ti基Ru-La氧化物涂层,用循环伏安法(CV)、热分析(DSC-TG)法、X射线衍射(XRD)仪及原子力显微镜(AFM)等测试手段对涂层电化学活性、结构和形貌进行表征。结果表明,加入La使钌基氧化物涂层晶粒细化,扩大了活性表面积,从而使电化学活性得到提高。另外,La提高了RuCl3热分解温度,并抑制了RuO2和RuOx(x>2)结晶和长大,其混合氧化物主要以非晶态形式存在。当La含量达到30%(摩尔分数)时,晶粒尺寸达到最小值,其电化学活性最好。     

ELECTROCHEMICAL PROPERTIES AND MICROSTRUCTURE OF Ir-Ta-Ti METAL OXIDE COATED TITANIUM ANODES

1. IntroductionSince the discovery of dimensionally stable anodes (DSAs)l1], they have been wide1yused in industrial production, particularly in the chlor-alkali industry because of theirexcellent stability and low overvoltage for chlorine reaction. Presently, mixed metal oxidecoated titanium anodes have also been used in cathodic protection fOr their corrosionresistance, low consumption rate and high electrochemical perfOrmance[2l3]. In recent years,there is an increasing interest in the re…     

熔盐电脱氧法制备ZrMn2储氢合金

采用熔盐电脱氧法,由MnO2和ZrO2混合氧化物直接合成ZrMn2合金。研究烧结温度、电解电压及电解时间等工艺参数对产物组成的影响。在900°C的CaCl2熔盐中,经900°C烧结的混合氧化物阴极在3.1 V恒电压下电解12 h,可制备出纯相的ZrMn2合金。XRD和循环伏安结果表明,在电解过程中,Mn-O化合物首先还原成单质Mn,ZrO2和CaZrO3再在单质Mn表面还原,并与其合金化,形成ZrMn2合金。以粉末微电极为工作电极,循环伏安测试结果表明,所制备的ZrMn2合金表现出良好的电化学储氢性能。     

不同方法制备的Ru-Ti-Ir-Ta/Ti四元涂层钛阳极的比较

采用热分解法和Sol-gel法,制备了具有三明治涂层结构的Ru-Ti-Ir-Ta/Ti四元金属氧化物钛阳极.采用XRD和SEM方法分析了涂层的相组织结构特征,通过Tafel曲线和循环伏安曲线的测试研究并比较了涂层的电催化活性.结果表明,两种方法制备的阳极涂层相成分都以 (Ir, Ta)O2和(Ti, Ru)O2金红石固溶体相为主.在热分解法制备的涂层中还存在单质金属钌.采用Sol-gel法制备涂层,其晶粒更为细小.采用热分解法和Sol-gel法制备的钛阳极涂层表面形貌有明显的不同,前者可见明显的"泥裂状"裂纹,后者呈碎石状.采用Sol-gel制备的钛阳极比热分解法制备的钛阳极具有更好的电催化活性和耐蚀性.     

钛基Ru-La-Sn涂层阳极的电催化性能

利用热分解法制备了不同La含量的钛基Ru-La-Sn涂层阳极，通过开路电位测试、循环伏安测试、阳极极化曲线测试和电化学交流阻抗谱测试研究了所制备涂层的电催化活性，并用扫描电镜对涂层阳极的表面形貌进行了观察。测试结果表明，制备温度对涂层阳极的表面形貌有很大影响，在涂层阳极中引入La可以提高涂层阳极的电催化活性，且La引入的最佳值为0．2(摩尔分数)。Ru-La-Sn涂层阳极电催化性能提高的原因在于La的引入可以增加涂层的有效活性表面积。     

Effect of heat treatment of titanium substrates on the properties of IrO<Subscript>2</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> coated anodes

The Ti substrates of IrO 2 -Ta 2 O 5 coated anodes were treated by solid-solution and aging, stress relieving annealing, and recrystallization annealing, and the coatings were prepared by thermal decomposition of a mixture of H 2 IrCl 6·6H 2 O dissolved in hydrochloric acid and TaCl 5 dissolved in alcohol. Scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and accelerated life test (ALT) were employed to study the microstructure and electrochemical properties of the anodes. Compared with the anode without heat treatment, the anodes with heat treatment are of higher electrochemical activity and longer accelerated life; especially, the anode with recrystallization annealing treatment has the best electrochemical properties and the longest accelerated life.     

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。     

析氯析氧组合涂层钛阳极的研究

采用溶胶-凝胶法,制各具有三明治结构的钛阳极,即在钛基材上先被覆Ti70%-Ru30%(摩尔分数,下同)氧化物底层,然后被覆Ir70%-Ta30%中间层,最后被覆Ti70%-Ru30%氧化物表层.通过XRD、电极电位、极化曲线、循环伏安、强化电解寿命等试验方法研究具有三明治结构的钛阳极的物理性能和电化学性能.结果表明,三明治结构阳极涂层主要组成物相为(Ti,Ru)O2金红石相固溶体、IrO2金红石相和非晶态的氧化钽,三明治结构的钛阳极具有优越的析氯和析氧的电催化活性,在析氯和析氧环境中能更好地保持电位稳定性,在高电流密度和高酸度下,有更强的耐蚀性,是较好的析氯析氧合一的钛阳极.     

酸蚀刻剂对钛基体及其IrO2-PbO2涂层表面形貌及电化学性能的影响研究

采用热分解法制备Ti/IrO₂-PbO₂阳极,深入研究硫酸、硝酸、盐酸、草酸、盐酸/草酸蚀刻顺序对Ti/IrO₂-PbO₂阳极性能的影响规律,借助场发射扫描电子显微镜、X射线衍射、循环伏安法、线性扫描伏安法、电化学交流阻抗谱、加速寿命试验等考察钛基体及氧化物涂层的形貌、结构及电化学行为。结果表明：钛基体在双酸中的腐蚀效果优于单酸,获得更致密更均匀的表面结构。双酸腐蚀使钛表面拥有完整的TiH_x晶型,有助于提高涂层负载量,增强活性层与基体的结合力。改变双酸蚀刻顺序对阳极电化学性能有一定的影响。草酸/盐酸蚀刻剂处理Ti/IrO₂-PbO₂阳极具有最佳的电催化活性与最长的加速寿命。     

The durability of different elements doped manganese dioxide-coated anodes for oxygen evolution in seawater electrolysis

Manganese-molybdenum (Mn-Mo), manganese-molybdenum-vanadium (Mn-Mo-V), manganese-molybdenum-iron (Mn-Mo-Fe) and manganese-iron-vanadium (Mn-Fe-V) anodes were prepared by anodic electrodeposition on iridium oxide-coated titanium substrates for oxygen evolution in seawater electrolysis. XRD, FESEM, EDX and oxygen evolution efficient analysis revealed that the prepared anodes had a γ-MnO₂ structure and show a unique mesh-like nanostructure. Oxygen evolution efficiencies were all measured to be more than 99%. The durability tests were performed at 1000 A·m^− 2 in 3.5 wt% NaCl solution at pH 12 and 90 °C. The Mn-Fe-V anode was the most stable electrode during the sea water electrolysis, and maintained an oxygen evolution efficiency of 87.96% even after 500 h. It has been found that the main reason for the eventual decrease in oxygen evolution efficiency was partly because of the peeling and electrochemical dissolution of the oxide layer after electrolysis. Also, it was found that the addition of iron and vanadium would maintain a high level of oxygen evolution efficiency during electrolysis.