铁表面自组装缓蚀功能膜的电化学阻抗谱研究

在铁表面自组装十四烷基胺膜.研究该膜在0.5 mol/LH2SO4溶液中对铁的缓蚀性能.电化学阻抗谱测试表明,随着组装时间的延长,缓蚀性能也随之增强,最大缓蚀效率为68.7%.而以十二烷基硫醇和十四烷基胺修饰的混合膜则更为致密、稳定,对铁的缓蚀能力也明显优于仅以十二烷基硫醇或十四烷基胺修饰的单一膜,其缓蚀效率可提高至78.2%.     

铁表面银纳米粒子自组装膜及其缓蚀性能研究

应用化学还原法于水溶液中制备银纳米粒子.在十二烷基硫醇的保护下,将银纳米粒子从水相转移到甲苯相,并将处理好的铁电极浸泡在含有十二烷基硫醇保护的银纳米粒子/甲苯溶液中,制得十二烷基硫醇/银纳米粒子自组装混合膜.电化学方法如交流阻抗谱(EIS)、极化曲线等研究该自组装膜在0.5 mol.L-1H2SO4溶液中的缓蚀作用.XPS测试证实该自组装膜十二烷基硫醇和银纳米粒子之存在.     

硫醇自组装膜对金电极上吡咯电化学聚合的影响

用电化学聚合法在多种烷基硫醇自组装膜修饰金电极上制备了聚吡咯.通过计时安培法、循环伏安法和交流阻抗技术研究了自组装膜的烷基链长和端基功能团对吡咯聚合过程和性质的影响.当自组装膜较完美时,聚吡咯沉积在自组装膜表面;而当自组装膜有一定缺陷时,吡咯在针孔处成核,然后继续生长并完全覆盖在自组装膜表面.研究结果表明,烷基硫醇的链越短,吡咯聚合越容易;疏水的烷基硫醇自组装膜有利于聚吡咯在电极表面的生长.     

图案化自组装膜导向的电沉积

通过图案化自组装膜导向的电沉积制备了聚吡咯(PPy)微结构. 由微接触印刷方法制备图案化自组装膜并作为电沉积的模板. 研究发现, 自组装膜在导向电沉积中在不同的基底上具有不同的作用: 在十二烷基硫醇(DDT)、十八烷基硫醇(ODT)修饰的金基底上和十八烷基三氯硅烷(OTS)修饰的铟锡氧化物玻璃上(ITO), 电沉积主要发生在自组装膜未修饰区, 而在半导体单晶硅表面, PPy沉积在OTS修饰区, 是基底表面的导电性及PPy与基底表面基团相容性共同作用的结果.     

二茂铁硫醇自组装膜的电化学行为及其离子对效应

详细了研究１０－二基铁－１－癸硫醇（ＨＳＣ１０Ｆｃ）在金基底上形成的自组装单分子膜的电化学行为,发现ＨＳＣ１０Ｆｃ在金基底上形成稳定的自组装膜,并且在０．１ｍｏｌ／Ｌ的ＨＣｌＯ４溶液中表现出可逆的氧化还原行为,但其氧化还原峰的峰形和峰位极易溶液中阴离子种类和浓度的影响,考察了二茂铁自组装膜及通过后置换形成的二茂铁硫醇／十二烷基硫醇混合膜在混合电解液中的电化学行为,直接比较了两种不同阴离子与二茂铁阳     

不同链长直链烷基硫醇自组装的吸附动力学

本文利用电化学方法,并结合接触角和原子力显微镜表征手段对直链烷基硫醇自组装的吸附动力学进行了研究。分别考察了短链正六烷基硫醇、中链正十二烷基硫醇和长链正十八烷基硫醇三种链长硫醇分子的组装动力学,每种链长考察了四个浓度。实验结果表明:硫醇自组装由快速吸附和缓慢重组两个过程组成,其组装过程符合扩散控制的Langmuir模型。表观吸附动力学常数kobs与吸附动力学常数ka都显示了浓度相关性,由此估算出烷基硫醇链每增加一个CH2单元,吸附自由能变化约0.09kJ/mol。     

烯丙基硫脲和十二烷基硫醇对铜的缓蚀作用

用自组装技术在铜电极表面上制备了纯烯丙基硫服自组装膜，并以十二烷基硫 醇进一步修饰得到混合自组装膜。最后，将混合膜覆盖的铜电极浸入NaCl溶液中， 进行交流电处理，电化学交流阻抗谱和极化曲线测定表明，经过交流电处理后，在 0．5mol·dm^-3 NaCl溶液中，电荷传递电阻增大，腐蚀电流密度下降，膜的最大 覆盖度为98．6％，对金属铜腐蚀的续蚀效率为98．5％。而且，不论交流电处理与 否，混合自组装膜在较宽的电极电位范围内均表现出很强的稳定性。     

由烷基硫醇组成的三元混合膜结构与性质研究

本文采用共吸附法制备了由戊硫醇(PT),癸硫醇(DT)和十六烷基硫醇(HDT)组成的三元混合膜,通过循环伏安,X-射线光电子能谱,扫描隧道显微镜(STM)和导电原子力对其结构及性质进行了表征。研究表明硫醇分子通过Au-S键在金电极上形成了一层致密的单分子膜,组装膜表面组成与其在组装液中的摩尔浓度有关。混合膜中各组分形成独立的相区,具有不同的电子传递能力。该研究为未来纳米器件的开发提供更多样化的表面以及更加详实的理论依据。     

金电极上L-半胱氨酸短链分子自组装单层的电化学性能和拉曼光谱研究

用循环伏安法分别测定了金电极表面L-半胱氨酸(L-Cys)和十二硫醇自组装单分子层的电化学行为, 实验发现虽然单层结构排列致密, 但并不能有效地阻碍铁氰化钾与电极间异相电子转移过程, 同时观察到十二烷基硫醇自组装层能较好地阻碍电子转移作用. 运用表面增强拉曼散射光谱技术, 以十二烷基硫醇作为缺陷探针, 从分子水平上证实了L-半胱氨酸自组装单层的稳定性和致密性.     

硫醇分子链长对氧化还原自组装多层膜电化学行为影响的初步研究(英文)

以烷基硫醇和二茂铁衍生物构建的氧化-还原自组装多层膜为模型体系,研究烷基硫醇分子链长对多层膜电化学行为的影响.实验表明,二茂铁基团和电极之间的电子传递反应速率随两者距离的增加呈现指数级下降的趋势;烷基硫醇分子链长对自组装膜电化学行为的影响于不同情况下表现不同.本实验条件下,当多层膜上的电活性基团与电极比较接近时,长链分子自组装膜呈现较强的电化学响应.而当电极与电活性基团之间的距离较远时,短链烷基硫醇分子自组装膜呈现较强的电化学响应.     

The electrochemical characterisation of benzyl mercaptan-modified Au(111): structure and copper deposition

The behaviour of benzyl mercaptan self-assembled monolayers on Au(111) in sulfuric acid solution was studied using cyclic voltammetry and in situ scanning tunnelling microscopy. Modification of the Au(111) surface in an ethanolic solution of benzyl mercaptan leads to a disordered monolayer. However, by partial reductive desorption a striped c (15 x sqrt [3]) and a (2 x sqrt [3]) structure were obtained. The disordered benzyl mercaptan film was also used for the study of copper deposition. At -0.02 V versus SCE, that is in the underpotential deposition region, monoatomic high islands appear on the surface. Bulk deposition of copper starts at -0.08 V versus SCE with the growth of dendrites underneath the thiol film. At higher overpotentials, the growth of three-dimensional copper clusters commences.     

铜电极表面硅烷膜的自组装及其性能研究

应用自组装技术在铜电极表面上制备3巯基丙基三甲氧基硅烷自组装膜.红外光谱研究该自组装膜结构,电化学方法考察3-巯基丙基三甲氧基硅烷膜在5%NaCl溶液中对铜电极的缓蚀性能.结果表明,于不同浓度的3-巯基丙基三甲氧基硅烷乙醇溶液中自组装的硅烷膜表现出较好的抗腐蚀性.     

铜表面二硫代氨基甲酸改性葡萄糖自组装膜的缓蚀作用

合成了一种环境友好型的缓蚀剂--二硫代氨基甲酸改性葡萄糖（DTCG）。 采用该缓蚀剂在铜表面制备了自组装膜,并运用电化学阻抗谱、极化曲线方法研究了该膜在3%NaCl溶液中对铜的缓蚀性能。 研究结果表明,DTCG自组装膜对铜有良好的缓蚀效果,在自组装时间为4 h、自组装浓度为120 mg/L的缓蚀效率接近于97%。 量子化学计算结果也证明了DTCG具有优异的缓蚀性能。     

表面硅烷化铜箔的电化学腐蚀与防护研究

用γ-氨丙基三甲氧基硅烷(γ-APS)溶液对铜箔表面硅烷化处理,采用动电位极化和电化学交流阻抗研究不同pH的γ-氨丙基三甲氧基硅烷溶液自组装铜箔电极在0.1 mol.L^-1NaCl溶液的腐蚀防护效果,采用扫描电子显微镜观察γ-氨丙基三甲氧基硅烷自组装膜的表面形貌.结果表明,γ-氨丙基三甲氧基硅烷自组装铜箔有较好的腐蚀防护效果,其中pH=7的γ-氨丙基三甲氧基硅烷溶液自组装膜的抗腐蚀效果最佳.     

A study of copper corrosion inhibition by self-assembled films of 3-mercapto-1<Emphasis Type="Italic">H</Emphasis>-1,2,4-triazole

Self-assembled monolayers of 3-mercapto-1H-1,2,4-triazole (MTA) was formed over a copper surface at various immersion periods. Fourier transform infrared spectroscopy and cyclic voltammetry were used to characterize the films. Atomic force microscopy and scanning electron microscopy were employed for the characterization of surface morphology. The wettability of the film was examined using contact angle measurements. The corrosion protection ability of the films was assessed in a chloride solution using electrochemical impedance spectroscopy and polarization measurements. The results of the study clearly ascertained the protection ability of self-assembled films of the MTA over copper. The theoretical studies also vouched for the experimental results.     

吡咯烷二硫代氨基甲酸铵自组装膜对铜的缓蚀作用

吡咯烷二硫代氨基甲酸铵(APDTC)是一种环境友好型金属缓蚀剂, 以其在铜表面制备了自组装单分子膜(SAMs), 用电化学方法研究在0.5 mol·L-1 HCl介质中APDTC SAMs对铜的缓蚀作用及其吸附行为. 结果表明, APDTC分子易在铜表面形成稳定的APDTC SAMs, 改变了电极表面的双电层结构, SAMs同时抑制了铜的阳极氧化过程和阴极还原过程, 铜电极的电荷转移电阻明显提高, 双电层电容明显降低. 电化学阻抗和极化曲线测试结果显示, 在0.5 mol·L-1 HCl介质中, 铜表面APDTC SAMs表现出良好的缓蚀效果. 研究结果还表明, APDTC的吸附行为符合Langmuir吸附等温式, 吸附机理是介于化学吸附和物理吸附之间的一种吸附.     

Preconcentration of trace elements on oxine cellulose

Summary X-ray Diffraction Analysis of Corrosion Products on Electrochemically Polarized Copper Surface An investigation was undertaken to examine the feasibility of X-ray diffractometry for the identification and characterization of corrosion products formed, electrochemically, on copper surface in various aqueous media. The removal of the products from the metal surface was useful in overcoming serious interferences from the intense diffraction lines of copper and was most satisfactory for the identification of common film components such as cuprous oxide, cuprous chloride and cupric oxide. In addition, the results obtained for the surface film components by slow scan linear (or potentiodynamic) polarization agreed favourably with the X-ray diffraction analysis. The influence of the solution pH and temperature on the nature of the corrosion products was evident on the results obtained by both techniques. The dominance of cuprous oxide as the major film component at the low solution pH and of cupric oxide as the predominant species at the higher solution pH and higher temperature were also confirmed by both results.Work undertaken while at the School of Applied Chemistry, Western Australian Institute of Technology, W. A. 6102 (Australia).     

覆铜板在NaCl溶液中的腐蚀电化学行为

应用线性极化、循环伏安(CV)及电化学阻抗谱(EIS)等电化学方法对覆铜板(CCL)和纯铜的腐蚀电化学行为进行了研究和比较. 结果表明, 覆铜板的耐蚀性弱于纯铜, 其阳极溶解过程与纯铜有所不同; 在较低电位下, CCL 以铜的氯化络合物的形式溶解, CuCl-2的扩散为该过程的控制步骤; 随着电位的升高, 腐蚀产物CuCl在电极表面形成疏松多孔的膜, Cl-在膜中的传输成为溶解过程的控制步骤. 电极表面CuCl 膜的消长过程是产生感抗弧的主要原因.     

Fabrication and anti‐corrosion property of superhydrophobic hybrid film on copper surface and its formation mechanism

Compact and uniform superhydrophobic films were prepared on copper substrates using one‐step solution‐immersion process, and the appropriate preparation conditions were selected for mixed solutions. SEM shows that the hybrid film of 1‐dodecanethiol and tetradecanoic acid on copper substrate is more compact with the contact angle of 160°. The electrochemical impedance spectroscopy and polarization test demonstrate that the anti‐corrosion property of surface‐modified copper substrate is greatly improved, especially for the hybrid film. Moreover, the competitive adsorption process and adsorptive geometry of hybrid film were well explained based on the results of quantum chemistry calculations, SEM, and energy dispersive X‐ray analysis. Copyright © 2009 John Wiley & Sons, Ltd.