Alkanethiol monolayers at reduced and oxidized zinc surfaces with corrosion protection: a sum frequency generation and electrochemistry investigation

In this work, octadecanethiol (ODT) was demonstrated to form ordered monolayers at either electrochemically reduced or oxidized Zn surfaces, by means of sum frequency generation (SFG) spectroscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The SFG spectra of ODT-modified Zn electrodes featured three methyl group resonances in the C-H vibrational region (2800-3100 cm(-1)). A significant decrease in interfacial capacitance and an increase in charge-transfer resistance were observed in EIS measurement after ODT modification. The alkane chain tilt angle of ODT within a monolayer at the Zn surface was estimated as 0 degrees with respect to the surface normal by interfacial capacitance measurement via EIS. CV and SFG investigation revealed that ODT monolayers undergo reductive desorption from the Zn electrode in 0.5 M NaOH at -1.66 V (vs SCE) and in 0.5 M NaClO4 at -1.62 V. The integrated charge consumed to the desorption of ODT is determined as 87 mC/cm2 from the reductive peak on CV curve, resulting in a coverage of 9.0 x 10(-10) mol/cm2 (5.4 x 10(14) molecules/cm2) if assuming the reduction follows a one-electron process. ODT monolayers show corrosion protection to underlying zinc at the early immersion stage in base, salt, and acid media. However, the protection efficiency was reduced with immersion time due to the presence of defects within the monolayers.     

Electrochemical sensing of membrane potential and enzyme function using gallium arsenide electrodes functionalized with supported membranes

We deposit phospholipid monolayers on highly doped p-GaAs electrodes that are precoated with methyl-mercaptobiphenyl monolayers and operate such a biofunctional electrolyte-insulator-semiconductor (EIS) setup as an analogue of a metal-oxide-semiconductor setup. Electrochemical impedance spectra measured over a wide frequency range demonstrate that the presence of a lipid monolayer remarkably slows down the diffusion of ions so that the membrane-functionalized GaAs can be subjected to electrochemical investigations for more than 3 days with no sign of degradation. The biofunctional EIS setup enables us to translate changes in the surface charge density Q and bias potentials Ubias into the change in the interface capacitance Cp. Since Cp is governed by the capacitance of semiconductor space charge region CSC, the linear relationships obtained for 1/Cp2 vs Q and 1/Cp2 vs Ubias suggests that Cp can be used to detect the surface charges with a high sensitivity (1 charge per 18 nm2). Furthermore, the kinetics of phospholipids degradation by phospholipase A2 can also be monitored by a significant decrease in diffusion coefficients through the membrane by a factor of 104. Thus, the operation of GaAs membrane composites established here allows for electrochemical sensing of surface potential and barrier capability of biological membranes in a quantitative manner.     

Redox mediation at 11-mercaptoundecanoic acid self-assembled monolayers on gold

Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and digital simulation techniques were used to investigate quantitatively the mechanism of electron transfer (ET) through densely packed and well-ordered self-assembled monolayers (SAMs) of 11-mercaptoundecanoic acid on gold, either pristine or modified by physically adsorbed glucose oxidase (GOx). In the presence of ferrocenylmethanol (FcMeOH) as a redox mediator, ET kinetics involving either solution-phase hydrophilic redox probes such as [Fe(CN)6]3-/4- or surface-immobilized GOx is greatly accelerated: [Fe(CN)6]3-/4- undergoes diffusion-controlled ET, while the enzymatic electrochemical conversion of glucose to gluconolactone is efficiently sustained by FcMeOH. Analysis of the results, also including the digital simulation of CV and EIS data, showed the prevalence of an ET mechanism according to the so-called membrane model that comprises the permeation of the redox mediator within the SAM and the intermolecular ET to the redox probe located outside the monolayer. The analysis of the catalytic current generated at the GOx/SAM electrode in the presence of glucose and FcMeOH allowed the high surface protein coverage suggested by X-ray photoelectron spectroscopy (XPS) measurements to be confirmed.     

In situ electrodeposition of Pt nanoclusters on glassy carbon surface modified by monolayer choline film and their electrochemical applications

Pt nanoclusters attached to the monolayer choline (Ch) modified glassy carbon surface were successfully synthesized by use of in situ cyclic voltammetry (CV) method. Field emission scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electrochemical impedance spectroscopy (EIS) were used to characterize the properties of this modified electrode. It was demonstrated that Ch was immobilized onto the carbon surface forming a covalently planted Ch monolayer, which could induce the formation of Pt nanoclusters. The preliminary study found that the homogeneous nanostructured Pt/Ch film exhibited remarkable electrocatalytic activity towards the oxidation of methanol and nitrite.     

Studies of protection of iron corrosion by rosin imidazoline self‐assembled monolayers

A type of rosin imidazoline (IM) has been synthesized using rosin acid and diethylenetriamine (DETA) as raw materials. The monolayers of IM were assembled on the surface of iron. The monolayers of the IM inhibitor were characterized by electrochemical impedance spectroscopy (EIS), electrochemical polarization curves and double‐layer capacitance. Surface analysis was carried out to establish the mechanism of corrosion inhibition of iron by X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy. The IM inhibitor showed good inhibition efficiency for iron in 0.1 M H₂SO₄. The inhibition mechanism of IM inhibitor was interpreted using molecular simulation. Copyright © 2006 John Wiley & Sons, Ltd.     

胆碱与谷氨酸共价单层混合修饰玻碳电极的制作与表征及其测定亚硝酸根的分析应用

A choline and L-glutamic acid mixed monolayer covalently modified glassy carbon electrode (Ch-Glu/GCE) was fabricated and characterized by X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). It provided an excellent example of mixed covalent monolayer modification of carbon electrodes with alkanol and amino acid, and also a facile means for altering the interfacial architecture. The Ch-Glu/GCE displayed good catalytic activity toward the oxidation of nitrite anions. Differential pulse voltammetry was used for determination of nitrite at the Ch-Glu/GCE. The Ch-Glu/GCE showed higher capability for restraint of pollutions than a simple Ch modified electrode or a simple Glu modified electrode.     

Oxidative acetylenic coupling reactions as a surface chemistry tool

A novel method to prepare redox monolayers on silicon electrodes has been developed that employs Cu(I)-catalyzed oxidative acetylenic coupling reactions for molecular electronic type applications. As the first case study, ethynylferrocene was covalently immobilized onto an acetylene-terminated monolayer on a Si(100) surface to give a 1,3-diyne (C≡C-C≡C-) linked redox assembly. The derivatization process requires no protection/de-protection steps, nor activation procedures. The effect of the conjugated diyne linkage on the rate of electron transfer between tethered ferrocenyl units and the silicon electrode is benchmarked against well-established "click" products (i.e. 1,2,3-triazole linkage). The surfaces, after each step, are characterized thoroughly using X-ray reflectivity (XRR), X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The coupling chemistry provides a useful strategy for functionalizing silicon surfaces and contributes to an expanding repertoire of wet chemistry routes for the functionalization of solid substrates.     

Tyrosine derivatives assembled on gold

Two different tyrosine derivatives, one with the OH group free and one with the OH group phosphorylated, linked to 3-mercaptopropionic acid through an amide bond are adsorbed to gold surfaces. The adsorbates are studied by means of X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IRAS). The techniques are used to investigate the coordination to the surface and the molecular orientation of adsorbates relative to the surface. Molecular surface interactions, causing chemical shifts in the core level XPS spectra of the adsorbates on gold, are investigated using multilayer films as references. Angle-dependent XPS, XPS(theta), and IRAS are used to estimate molecular orientation relative to the surface. The tyrosine derivatives adsorb chemically to the surface through the sulfur atoms and highly organized monolayers are formed with the OH and the PO(2-)(3) exposed to the air/vacuum interface.     

1-Dodecanethiol self-assembled monolayers on cobalt

Cobalt and its alloys are used in a broad range of application fields. However, the use of this metal is especially limited by its strongly oxidizable nature. The use of alkanethiol self-assembled monolayers (SAMs) is a very efficient way to protect against such oxidation and/or to inhibit corrosion. This surface modification method has been particularly applied to oxidizable metals such as copper or nickel, yet the modification of cobalt surfaces by alkanethiol SAMs received limited attention up to now. In this work, we study the influence of parameters by which to control the self-assembly process of 1-dodecanethiol monolayers on cobalt: nature of the surface pretreatment, solvent, immersion time, and concentration. Each of these parameters has been optimized to obtain a densely packed and stable monolayer able to efficiently prevent the reoxidation of the modified cobalt substrates. The obtained monolayers were characterized by X-ray photoelectron spectroscopy (XPS), polarization modulation infrared reflection-absorption spectroscopy, and contact angle measurements. The stability of the optimized 1-dodecanethiol monolayer upon air exposure for 28 days has been confirmed by XPS.     

Electron transport through a self-assembled monolayer of thiol-end-functionalized tetraphenylporphines and metal tetraphenylporphines

The monolayers of several thiol-end-functionalized tetraphenylphophines (SH-TPP) and metal tetraphenylporphines (SH-MTPP) were self-assembled on gold surfaces and identified by cyclic voltammetry (CV), electrochemical impedance spectroscopy, scanning electrochemical microscopy, and the contact angle. The CV peaks of the [Fe(CN)6]3-/ [Fe(CN)6]4- couple were used to identify the efficiency of electrons transferring through the self-assembled monolayer (SAM). The results suggested that SH-TPP and SH-MTPP could form high-quality SAMs on gold surfaces. The SAMs blocked electron transport from the gold electrode to solution. When the length of the thiol-end-link spacer (alkyl group) increased, the electron transport ability of the SAM decreased because of the increased insulator properties of the alkyl chain. With the insertion of metallic ions, the electron transport ability of the SAM of SH-MTPP increased compared to that of the SAM of SH-TPP, which was probably due to the fact that (i) the insertion of metallic ions changed the molecular structure and the molecular structure of SH-MTPP played an important role in electron transport through the SAM and (ii) the insertion of metallic ions increased the electron tunneling probability through the monolayer.     

Microwave Pyrolysis and Electrochemical Supercapacitor of S-doped g-C_3N_4 Nanoparticles

In this study, S-doped g-C_3N_4 nanoparticles were successfully prepared by one-step solid-state microwave synthesis. The detailed characterizations through XRD, FT-IR, SEM and XPS were studied. In addition, the electrochemical properties as supercapacitor of the sample were tested by cyclic voltammetry(CV), galvanostatic charge-discharge(GCD) and electrochemical impedance spectroscopy(EIS) techniques. The results showed a high specific capacitance of 691 F/g at current density of 4 A/g in 2 M KOH + 0.15 M K_3[Fe(CN)_6] electrolyte. This study shows that the microwave synthesis is a promising way to design carbon-based electrodes for supercapacitor.     

Transition Metal Salt Doping on Polypyrrole/MWCNT Composites for Supercapacitor Applications

Polypyrrole doped by Zn²⁺ ions was synthesized as nanocomposites with MWCNT by in-situ oxidative polymerization and investigated as electrode material for supercapacitors. The uniform coating of polypyrrole on MWCNT was characterized by field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). The effect of Zn²⁺ ions were characterized by Fourier transform infrared (FTIR) spectroscopy. The electrochemical performances were investigated by cyclic voltammetry (CV), constant current charging/discharging cyclic test (CC) and electrochemical impedance spectroscopy (EIS) using a three-electrode system. The doped polypyrrole composites show higher specific capacitance and better cyclic stability.     

Electrochemical investigations on stability and protonation behavior of pyridine-terminated aromatic self-assembled monolayers

Based on electrochemical methods such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), Au(111) electrodes modified by self-assembled monolayers (SAMs) of a homologous series of pyridine-terminated thiols with aromatic backbones have been investigated. An important correlation between the chain structure and film integrity in electrolytic media was found. Monolayers with odd numbers of methylene spacers in the molecular chain showed superior barrier properties compared to even numbered counterparts. A positive influence of an increase in the number of attached phenyl rings on the integrity of SAMs was observed. Furthermore, cathodic desorption of the investigated SAMs is characterized by multiwave desorption peaks and extraordinarily large cathodic charges indicating an unusual desorption process. Moreover, protonation behavior of the SAMs has been investigated by X-ray photoelectron spectroscopy (XPS) and electrochemical methods. Protonation has been found to be reversible and surface pK(a) values have been determined to be around 5 for all investigated monolayers.     

金属锂在含(亚)硫酰基添加剂电解液中电化学可逆性研究

分别以亚硫酰氯(SOCl2)、硫酰氯(SO2Cl2)、二甲亚砜(DMSO)、苯磺酰氯(BSC)和苯基乙烯基亚砜(PVSO)作为添加剂, 加入至1 mol•L－1 LiPF6/碳酸乙烯酯(EC)＋碳酸二甲酯(DMC)(体积比为1∶1)电解液中, 采用恒电流沉积-溶出法、循环伏安法(CV)、电化学阻抗谱(EIS)、X射线光电子能谱(XPS)测试技术, 研究了添加剂对电化学金属锂沉积-溶出可逆性以及金属锂负极/电解液界面性质的影响. 电化学测试结果表明, 添加SO2Cl2和BSC能显著改善金属锂电极的循环性能, 100% DOD(锂全溶出)条件下, 循环效率稳定在90%左右. 电化学测试、添加剂分子电子亲和能计算并结合XPS测试结果表明, 较早反应成膜的SO2Cl2和BSC添加剂可以在一定程度上抑制电解液溶剂的分解, 使锂电极循环效率和寿命得以提高. 洞察和比较添加剂的结构揭示, 含磺酰基的化合物明显优于含亚磺酰基的化合物.     

Electrochemical Study of Schiff Bases by Means of Self‐Assembled Monolayers

In this paper, Schiffbases were investigated using cyclic voltammetry (CV) and impedance electrochemical spectroscopy (EIS) techniques by means of self‐assembled monolayers for the first time, where a 0.1 M KCl solution and the redox couple of Fe(CN)₆^3?/Fe(CN)₆^4?were used as the electrolyte and probing‐pin, respectively. The monolayers formed by the employed Schiff base were proved to be relatively stable, and its electrochemical response in the studied system with different pH values was also de scribed clearly with CV and EIS plots. The results show that the monolayer of Schiff bases could exist in the solution with pH value from 2 to 10. In the EIS measurement in the concentration range from 10^?5 M to 5× 10^?4 M, a nearly linear relation ship between the charge transfer resistance (R_ct) and the logarithm concentration of Cu²+was observed, suggesting that Cu²+ could be titrated with the EIS method quasi‐quantitatively. The phenomenon agreed with the former report very well. Using the self‐assembled monolayers to study Schiff bases with the electrochemical method is the major contribution of our work.     

用于超级电容器电极材料的聚苯胺基碳(英文)

在不同温度下碳化硫酸掺杂的聚苯胺制备了含杂原子(氮和氧原子)的新型碳材料.分别通过扫描电镜、元素分析仪、X射线光电子能谱仪和比表面积测试仪对这些碳材料的形貌特征、元素组成、表面化学组成和比表面积进行了表征.用循环伏安法、恒电流充放电法和交流阻抗法对其进行了电化学性能的研究.研究结果表明,在温度为800℃下碳化聚苯胺得到的碳有很好的电化学性能,尽管它的比表面积很小(325m·2g-1),但在0.5A·g-1电流密度下其比电容高达153F·g-1.它的高比电容可能与其含有合适比例的杂原子(氮和氧原子)有关,因为合适比例的氮和氧杂原子能够产生最大的赝电容.这些结果表明这种碳材料是一种很有发展前景的超级电容器电极材料.     

Ce掺杂Mn3O4及其电化学电容行为

用溶胶-凝胶方法合成了Mn₃O₄和Ce掺杂Mn₃O₄. 采用X射线衍射(XRD)、傅里叶变换红外(FT-IR)光谱、场发射扫描电镜(FESEM)和透射电子显微镜(TEM)对其结构和形貌进行了表征. 采用循环伏安、电化学交流阻抗和恒流充放电技术对其电化学性能进行了测试. 研究结果表明, Ce掺杂对Mn₃O₄的形貌和电化学性能均有显著影响. 当Ce离子占金属离子总量的3%时, 掺杂Mn₃O₄的单电极比电容高达477 F·g^-1, 比未掺杂的提高了43.7%, 并且表现出更好的循环稳定性.     

LiBOB基电解液成膜性及其循环性能

通过循环伏安(CV)、电化学阻抗谱(EIS)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和傅立叶变换红外(FTIR)光谱研究了双乙二酸硼酸锂(LiBOB)基电解液在石墨表面的成膜性及其在常温(25 ℃)和高温(70 ℃)下对石墨循环性能的影响. 结果表明, LiBOB基电解液的成膜电位在1.7 V, 其中BOB-离子还原形成的草酸盐是固体电解质相界面(SEI)膜的有效成分之一. 电化学阻抗谱显示, 膜阻抗在循环过程中呈现减小趋势, 这有利于提高循环稳定性. 在常温和高温条件下, 石墨在该电解液体系中均表现出优于其在LiPF6基电解液体系中的循环性能.     

Ti, F复合掺杂改进LiNi1/3Co1/3Mn1/3O2正极材料的电化学性能

采用复合离子掺杂技术对LiNi1/3Co1/3Mn1/3O2进行改性, 并对材料的结构及电化学性能进行了考察.