钛的阳极氧化过程与TiO_2纳米管的形成机理

阳极氧化法制备的TiO_2纳米管因其独特的结构和优异的性能在多个领域获得广泛应用。阳极氧化TiO_2的生长机理也成为本领域的研究热点,最近几年有关生长机理的文章屡见报端。本文从两种阳极氧化钛膜对比的角度,综述了阳极氧化钛纳米管生长机理的最新研究进展和研究意义。首先介绍了Ti的阳极氧化过程,综述了两种阳极氧化钛膜(致密膜和多孔膜)的区别和联系。随后阐述了TiO_2纳米管的形成过程,重点综述了TiO_2纳米管的几种生长机理。分析表明,传统的"场致溶解"理论在解释纳米管结构和形成过程时存在很多局限性,而黏性流动模型和两电流模型相结合能较全面地解释TiO_2纳米管的形成过程,但电子电流的产生机制和纳米孔道中的氧气气泡还有待进一步的实验验证。     

还原剂对多孔阳极氧化铝纳米孔道结构的影响

多孔阳极氧化铝(PAA)和多孔阳极氧化钛纳米管(PATNT)的结构调控近年来倍受关注. 在形成机理尚不清楚的情况下, 对PAA和PATNT的结构调控很难避免盲目性. 为验证“氧气气泡模具”可以形成纳米孔道这个新观点, 本文采用化学方法对PAA的结构进行调控, 成功地引入了一种还原剂来吸收纳米孔道中的氧气气泡. 在添加还原剂的草酸溶液中得到了一种特殊的阳极氧化铝膜. 研究了还原剂的含量对磷酸溶液中形成PAA孔道结构的影响, 结果表明随着还原剂含量的增加, PAA的孔道直径逐渐减小, 有序性降低. 对比了添加还原剂前后阳极氧化过程的电压-时间曲线的差异, 结果表明, 在含有还原剂溶液中制备的阳极氧化铝膜的导电性明显提高. 在密封的条件下, 还原剂能吸收掉孔道中的氧气, 使气泡模具效应消失, 得到完全的致密型氧化膜. 这些实验事实充分证明PAA中有序孔道的形成是氧气气泡模具效应的结果.     

L-胱氨酸在Pb/nanoTiO_2膜电极上的电催化还原

采用阳极氧化和恒电位沉积法制备Pb纳米粒子修饰的多孔Ti基TiO2(Pb/nanoTiO2)膜电极.通过对不同的电沉积电位和时间对比,找出了最佳电沉积条件.SEM分析显示该膜为均匀多孔结构,Pb纳米粒子均匀地分散在TiO2膜的表面.循环伏安和计时电流法研究了L-胱氨酸在Pb/nanoTiO2膜电极上的电催化还原活性,结果表明该电极对L-胱氨酸的还原具有高催化活性和稳定性.     

金纳米粒子和钼氧化物复合膜修饰电极的制备及应用

利用循环伏安法将金纳米粒子和钼氧化物共同电沉积在玻碳电极表面,制备了金纳米粒子和钼氧化物复合膜修饰电极,利用SEM和XPS研究了MoOx/AuNPs复合膜的表面形态,并研究其修饰电极对葡萄糖的电催化氧化过程. 首次提出了阳极扫描极化反向催化伏安法,即在反向扫描过程中纯的催化氧化电流通过扣减背景电流的方法被提取出来. 显著提高电流测量灵敏度改善了信噪比. 制备的MoOx/AuNPs复合膜修饰电极在0.01-4.0 mmol/L对葡萄糖具有线性响应,电流灵敏度为2.35 mA·L/（mmol·cm2）,检测限为9.01 μmol/L（信噪比为3）.     

Co(III)离子在二氧化铅电极上的阳极形成

文献上曾报导过Co(Ⅱ)离子具有加速PbO_2电极上氧阳极析出过程的作用,并表明当Co(Ⅱ)离子存在时,氧的析出过程有可能通过表面吸附的高价钴氧化物氧化水分子而形成.本文通过浓硫酸溶液中Co(Ⅱ)阳极氧化为Co(Ⅲ)以及O_2阳极析出动力学的研究,表明了O_2的析出和Co(Ⅲ)的形成是通过吸附在电极表面的高价钴(Ⅳ)的OH 基配合物分别氧化水分子和Co(Ⅱ)离子形成的,它与Cr(Ⅲ)、Mn(Ⅱ)离子的阳极氧化过程相类似,而不是通过Co(Ⅱ)离子直接放电形成的.本文利用文献所述的研究方法.在固定硫酸浓度(3.4mol·kg~(-1))下,研究CoSO_4浓度(0.05—0.35mol·drn~(-3))对于O_2和Co(Ⅲ)阳极形成过程分别的影响.在固定CoSO_4(0.2mol·     

二次阳极氧化技术的理论依据及其局限性

二次阳极氧化技术在多孔阳极氧化铝和氧化钛纳米管的制备过程中得到广泛应用,但其理论依据还不清楚。本文详细综述了二次阳极氧化和预压印技术的由来及其理论依据,阐明了二次阳极氧化过程中传统“场致助溶”理论无法解释的实验事实,分析了二次阳极氧化和预压印技术在多孔阳极氧化铝制备中的局限性和前提条件,并用氧气气泡模型对文献中报道的一些特殊孔道的形成机制进行了诠释,揭示了气泡模具和氧化物的黏性流动对圆柱形、规则有序孔道的形成的重要影响,展望了电子电流和氧气气泡模具对多孔氧化铝、氧化钛纳米管的制备和结构调控的指导作用。本综述对阳极氧化钛纳米管的制备和机理的深入研究,促进其在光催化和太阳能电池领域的应用有重要的意义。     

Ag(Ⅰ)与Co(Ⅱ)离子对阳极析氧过程的电催化作用

关于Co（Ⅱ）离子对PbO2和Pt电极上阳极析氧过程的催化作用，以及Ag（Ⅰ）离子对阳极氧化过程的催化作用，文献上已早有报导［1－4］，但大都是仅通过总的极化曲线进行对比研究得出的结果．由于在氧析出的同时往往有其它阳极氧化过程同时进行（例如，Co（Ⅱ）或Ag（Ⅰ）的阳极氧化），因此，很难从总的极化曲线得出正确的结论．本文用气体电量计法直接测量氧析出速度，并对Pt和PbO2电极进行了对比，得出了一些新的结果．1实验方法为了直接测量氧析出过程的分电流，实验时串联了一专收集O2的气体库仑计．电解槽和库仑计阳极均安装在各自…     

无锡钢电镀溶液中氟离子电化学行为的研究

采用交流伏安法、电化学阻抗谱(EIS)和Mott-Schottky 分析技术研究了无锡钢电镀液中氟离子电化学行为. 结果表明, 在氧化还原过程中氟离子抑制铬离子化学状态转变, 降低铅合金和铅氧化物阳极的氧化电流密度, 改变铅合金和铅氧化物阳极的氧化还原历程. EIS 结果表明电场作用下溶液中铬氧离子团发生聚合, 在铅合金阳极表面形成感抗现象. 含氟溶液中铬氧离子团在阳极表面的感抗现象消失, 溶液导电性提高. Mott-Schottky 曲线显示氟离子提高阳极材料的载流子密度, 铅合金阳极和铅氧化物阳极均为n 型半导体.     

阳极氧化/GCD新工艺法制备镍基超级电容器薄膜电极

采用磷酸阳极氧化法在金属镍表面形成阳极氧化复合膜,在1 mol·L^-1氢氧化钾溶液中进行大电流密度恒流充放电(GCD)处理, 使基体表面形成一层多孔纳米花瓣状膜. 采用扫描电镜(SEM), X射线光电子能谱(XPS), X射线衍射(XRD)仪, 对膜的形貌、组成和结构进行了表征, 使用电化学工作站、电池寿命测试仪对该膜的电容特性进行了测试. 结果表明, 所制氧化膜由三维多孔纳米花瓣状的NiO、α-Ni(OH)₂和β-Ni(OH)₂构成, 该膜具有优异的电容特性, 其在电流密度为6.7 A·g^-1时,比电容量达1509 F·g^-1, 而当电流密度为66.7 A·g^-1时,比电容量为1120 F·g^-1 (为6.7A·g^-1时的74%).在电流密度为66.7 A·g^-1时, 经过2000次循环测试后比电容量基本保持不变.     

几种稀土盐封闭的铝阳极氧化试样的腐蚀行为

为提高铝硫酸阳极氧化膜的抗污染和防腐蚀性能，分别采用环境友好的铈盐、钇盐和镧盐溶液对阳极氧化膜进行了封闭处理。采用动电位极化法比较了不同稀土盐封闭的铝阳极氧化试样在弱酸性NaCl腐蚀介质中的电化学行为，采用扫描电子显微镜（SEM）和能量色散谱（EDS）对封闭试样腐蚀前后的表面形貌、组成进行了表征。结果表明：在腐蚀介质的侵蚀及强电化学极化条件下，铈盐和镧盐封闭的阳极氧化膜对铝基体具有较好的保护作用，而钇盐封闭膜的保护作用则较差。这种差别的主要原因是不同稀土盐封闭过程中封闭产物的析出倾向及速率不同。     

The effect of anode surface area on nanoporous oxide formation during anodizing of low purity aluminum (AA1050 alloy)

Porous anodic alumina layers were obtained by a simple two-step anodization of low purity aluminum (99.5 % Al, AA1050 alloy) in a 0.3 M oxalic acid electrolyte at 45 V and 20 °C. The effect of anode surface area on structural features of nanoporous oxide and process of oxide formation was investigated. An ordered structure composed of nanostripes or nanopores was formed on the Al surface during electrochemical polishing in a mixture of perchloric acid and ethanol. This nanopattern is then replicated during the anodic oxide formation. It was found that the pore diameter, interpore distance, and porosity increase slightly with increasing surface area of the aluminum sample exposed to the anodizing electrolyte. On the other hand, a slight decrease in pore density and cell wall thickness was observed with increasing surface area of the sample. The detailed inspection of current density vs. time curves was also performed. The obtained results revealed that the higher surface area of the anode, the local current density minimum, was reached faster during first step of anodization and the increase in current density corresponding to the pore rearrangement process was observed earlier. Finally, a dense array of Pd nanowires (～90 nm in diameter) was synthesized by simple electrodeposition of metal inside the channels of through-hole nanoporous anodic alumina templates with relatively large surface areas (4 cm²).     

Simulation of anodizing current-time curves and morphology evolution of TiO2 nanotube arrays

Through introducing appropriate additives into the electrolytes, the morphology and growth efficiency of TiO₂ nanotube arrays (TNTAs) have been greatly influenced. The anodizing current transients and the corresponding morphology of TNTAs were investigated and compared in detail by SEM. To further understand the mechanism, the measured current-time curves obtained during the anodization of titanium in the electrolytes with different additives are simulated. Notably, in the total anodizing current, the ionic current is separated from the electronic current according to the present model, and that the electronic current and ionic current make different contributions to the growth of TNTAs. It is found that the initiation of nanopores may be caused by the rupture of the oxygen bubbles occluded in the growing oxide, and the opening of nanotubes is thought to be close related to the disturbance effect of the rising bubbles (caused by electronic current). The present results would be helpful for understanding the formation mechanism of TNTAs from the perspective of ionic and electronic current. And practically, the nanotube length can be predicted and deduced quantitatively via simulating and comparing electronic and ionic current.     

The first study on enhanced photoresponsivity of ZnO-TiO2 nanocomposite thin films by anodic polarization

The physical and photoelectrochemical properties of the anodized ZnO-TiO(2) thin films were investigated in this study. Impedance spectroscopy revealed a decrease in charge transfer resistance and Tafel plots determined enhancement of about 200 times in the exchange current (i(0)) after anodization at high positive potential. It was found from XPS analysis that after applying the potential of 5 V to the ZnO-TiO(2) photoelectrode, the lattice oxygen (O(2-)) in the thin film is oxidized to molecular oxygen and then, cations such as Zn(2+) can be solved in the basic electrolyte and passed to the solution. Moreover, according to AFM analysis it was observed that the surface of the samples has been grooved by applying anodic voltage resulting in an increase of effective surface of the film. A mechanism for describing the significant enhancement in the photoresponse of the anodized layer is proposed.     

Oxygen evolution: the mechanism of formation of porous anodic alumina

Abstract  Aluminium anodization behavior in ammonium sebacate solution (w = 4%) in ethylene glycol, and in several H₃PO₄-containing electrolytes, has been investigated. A new mechanism is proposed for the formation of porous anodic films. The model emphasizes the close relationship between pore generation and oxygen evolution. PO₄ ³⁻ ions incorporated in the anodic films behave as the primary source of avalanche electrons. It is the avalanche electronic current through the barrier film that causes oxygen evolution during anodization. When growth of anodic oxide and oxygen evolution occur simultaneously at the aluminium anode, cavities or pores are formed in the resulting films. Accordingly, the mechanisms of growth of barrier and porous films are not very different in nature. These findings are a decisive new step towards full understanding of the nature of anodic alumina films. Graphical abstract        

钛表面二氧化钛膜中氧空位点缺陷传输性能的电化学研究

"钛/TiO2氧化膜/溶液"界面电极体系的电化学性能主要决定于钛表面的TiO2氧化物膜.本文利用多种电化学技术,结合半导体物理的Mott-Schottky分析和Einstein方程,研究了金属钛在1.0mol·L-1HClO4溶液中表面半导体TiO2氧化膜的生长及氧化膜中氧空位点缺陷在外加电场作用下的传输性能,并根据离子性电荷传输与电子性电荷传输对电场变化响应时间之不同特点,确定氧化膜中点缺陷扩散系数.结果表明,电极电位或阳极析氧反应对稳态电流(iss)、氧化膜的阳极化常数(α)、膜中电场强度()、以及膜中氧空位点缺陷的扩散系数(D0)等重要物理化学参数,均有显著影响,并依据氧化膜中的结构变化进行分析.     

Oscillating oxygen evolution at Ta anodes

Anodic Ta oxide films are said to inhibit oxygen evolution. In industry, however, large amounts of gas are evolved during the anodization of tantalum anodes for electrolytic capacitor fabrication. We quantified the oxygen by fluorescence quenching in a flow-through cuvette and found that 4% of the anodic charge are consumed for oxygen evolution. In wires or sheets, this oxygen is removed by diffusion without bubble formation and, thus, not recognized. Due to the large inner area of the sintered Ta anodes, the oxygen evolution causes strong oscillations of the current density and bubble formation. The amount of oxygen is proportional to the oxide amount formed in parallel. This is explained by a model where mobile ions during oxide growth form interband states which allow electron tunneling. Accordingly, stationary no oxygen evolution is observed.     

多孔纳米氧化铝薄膜上荧光分子光谱特性研究

通过两步电化学阳极氧化技术制备了孔径为40nm的多孔纳米阳极氧化铝材料(AAO)，在AAO薄膜上分别填充了几种有机荧光分子使其形成高度有序的有机-无机复合体发光阵列，测定了此复合体的发射光谱．结果表明，AAO薄膜对有机分子具有较强的结合能力，其结合能力来源于物理和化学的协同作用．在AAO纳米薄膜上的有机荧光分子的最大发射波长均产生了明显的蓝移现象，初步探讨了此现象的机理．有机分子填充进入高度有序的AAO纳米孔阵列之中时，有机分子的聚集形式会发生改变并且也是高度有序的，同时由于极化作用使有机分子沿着纳米孔的轴向具有相对优势的分子取向，使有机分子在AAO纳米薄膜上形成了接近单分子层的高度有序的排列方式，增强了发光效率．     

铝阳极氧化膜纳米孔阵列结构的自组织过程分析

提出了在铝阳极氧化膜的生长过程中存在两种力的作用,一种是在阻挡层形成时就已经存在的由于基体铝与氧化铝之间晶格不匹配产生的内应力的作用,另一种是随着纳米孔的形成,存在于纳米孔内壁的表面张力的作用.铝阳极氧化膜纳米孔阵列的自组织过程是在这两种力的共同作用下进行的.这两种力的大小随着纳米孔形貌的变化而改变,当铝阳极氧化膜中的纳米孔呈规则的六角排列时,这两种力达到平衡,此时体系的能量也最低.     

Growth of Anodic Films on Compound Semiconductor Electrodes: InP in Aqueous (NH4)2S

 Film formation on compound semiconductors under anodic conditions is discussed. The surface properties of InP electrodes were examined following anodization in an (NH₄)₂S electrolyte. The observation of a current peak in the cyclic voltammetric curve was attributed to selective etching of the substrate and a film formation process. AFM images of samples anodized in the sulfide solution revealed surface pitting. Thicker films formed at higher potentials exhibited extensive cracking as observed by optical and electron microscopy, and this was explicitly demonstrated to occur ex situ rather than during the electrochemical treatment. The composition of the thick film was identified as In₂S₃ by EDX and XPS. The measured film thickness varies linearly with the charge passed, and comparison between experimental thickness measurements and theoretical estimates for the thickness indicate a porosity of over 70%. Cracking is attributed to shrinkage during drying of the highly porous film and does not necessarily imply stress in the wet film as grown. During the growth of the thick porous film, spontaneous current oscillations have been observed. The frequency of oscillation was found to be proportional to the current density, regardless of whether the measurements were carried out during a potential sweep or at constant potential. Thus, the charge passed per oscillation remained constant. A characteristic value of approximately 0.3 C · cm⁻² was measured under potential sweep conditions, and a similar value was obtained at constant potential.     

阳极氧化AZ91D镁合金在氯化钠稀溶液中的腐蚀行为

利用盐雾实验、极化曲线扫描、电化学阻抗谱和电化学噪声技术等电化学研究方法结合扫描电镜表面观测技术对AZ91D镁合金氧化膜在1%(w)氯化钠溶液中的耐蚀性能进行了评价. 结果表明, 氧化前后的镁合金腐蚀行为发生明显改变, 如未封孔的阳极氧化膜耐中性5%氯化钠盐雾试验时间超过200 h; 氧化后的镁合金自腐蚀电位明显正移, 点蚀诱导期延长; 阳极氧化膜的高频阻抗约为裸露镁合金的数千倍, 这些变化证明阳极氧化处理使镁合金获取了十分优异的耐蚀性能. 首次利用分形维数Df的变化规律初步描述氧化后AZ91D镁合金的腐蚀过程. 可以发现随着浸泡时间的延长, Df呈现出初期快速增长, 随后出现波动, 最后稍有降低的变化过程. 这种现象对应于氧化后AZ91D 镁合金在1%氯化钠溶液中腐蚀的三个阶段.