Nucleation and growth mechanisms during electropolymerization of substituted 3-alkylthiophenes

In the present work the electrochemical study of compounds based on 3-((ω-bromoalkyloxy) methyl) thiophene, varying the length of the alkyl chain between 6 and 12 carbon atoms, is reported. Electropolymerization of the monomers was achieved by potentiodynamic (cyclic voltammetry, CV) and potentiostatic (constant potential) techniques. Voltammograms obtained by CV show that all monomers can be electrochemically oxidized at potentials about 1800 mV to synthesize the respective polymer. Besides, the potential shifts to more anodic potentials on successive scans, increasing thus the resistivity of the material. Nucleation and growth mechanism (NGM) of electropolymerization was investigated by a potentiostatic technique (j-t). Deconvolution of the current-time transient data fitted with a theoretical model suggests that at short times the instantaneous nucleation with two-dimensional growth (IN2D) contribution prevails, followed by an instantaneous nucleation with three-dimensional growth controlled by the charge transfer (IN3Dct) contribution and, finally at longer times, the instantaneous nucleation with three-dimensional growth controlled by diffusion (IN3Ddif) contribution becomes important. The predominance of each contribution to the NGM depends on the monomer being electropolymerized, and the electrolysis time. The morphology predicted from these NGMs fully correlates with that determined by SEM.     

FTIR reflectance studies of electrochemically prepared polypyrrole films

-1 . The effects of some relevant electrochemical parameters (the electrolyte, the polymerization current density, and the deposition time) on the reflectance spectra of polypyrrole are reported. The optical constants for polypyrrole films were calculated from the reflectance spectra by Kramers–Kronig technique. The decrease of the electropolymerization current density and film thickness results in an increase of the reflectance and dc conductivity values for PPY(TSO). Received: 6 November 1997/Accepted: 17 December 1997     

Investigation of dodecylammonium adsorption on mica,albite and quartz surfaces by QM/MM simulation

The absorption mechanisms of collector and mineral surface structures play important roles in studies of lepidolite flotation. In this work, quantum mechanics (QM) and hybrid quantum mechanics/molecular mechanics (MM) methods were implemented to investigate the flotation mechanisms of lepidolite from muscovite, quartz and albite. The crystal structures, electron density distributions, bonds and the densities of states of lepidolite were calculated and compared with those of muscovite. The adsorption structures and energies of monomer dodecylammonium (DDA) on the three different minerals were also calculated. The headgroup of the DDA cation was found to adsorb on the surface of minerals, with its hydrophobic tail stretching into the vacuum slab, approximately perpendicular to the surface. Simulation results indicate that the purity of fine lepidolite is limited by the existence of muscovite, due to their similarities in surficial structure and properties. Other gangues were found to be removed efficiently with the use of acidic conditions. The results are in good agreement with other experiments. Compared with simple MM simulations, the use of the QM/MM methods to investigate the adsorption on minerals without specific forcefield parameters was concluded to be a more accurate method to attain monomer surfactant–mineral adsorption energies.     

H2O在Al(111)表面吸附的量子化学研究

用量子化学从头算方法，以原子族Ａｌ１０模拟表面，研究了水在Ａｌ（１１１）表面上不同吸附拉的吸附情况，计算得到了稳定的吸附构型和结合能，结果表明：顶位是其最佳吸附位，而且水在表面能以两种取向被吸附，距表面较远时，Ｈ端靠近表面，然后跨过一能垒到达最佳吸附位，此时氧端靠近表面。在吸附过程中，水向表面转移电荷，导致表面功函降低，在氧原子不加极化函数进，水分子的二次轴垂直于表面时能量最低；当考虑中氧的ｄ轨道     

Dynamics of Pd monomers and dimers adsorbed on the (001) surfaces of strongly correlated nickel oxides

The adsorption and diffusion of Pd monomers and dimers on the (001) surfaces of strongly correlated nickel oxides were investigated using density functional theory combined with the on-site Coulomb repulsion U. The results were compared with those of Pd on nonmagnetic MgO(001). For the Pd monomer, the most stable adsorption site was found to be near the surface O atom. The surface diffusion of the Pd monomer occurred by a hopping process over surface hollow sites. The diffusion energy barrier was 0.21 eV, which was lower than that for Pd on MgO(001). In the case of the Pd dimer, the smallest and stable cluster, the most stable adsorption structure had a flat geometry, with both Pd atoms sitting above the neighboring surface O atoms. The surface diffusion of the Pd dimer occurred by rotational and sliding processes, in contrast to that of the Pd dimer on MgO(001). The diffusion energy barriers ranged from 0.33 to 0.36 eV. The values for the surface diffusion of Pd dimers on NiO(001) were lower than those of Pd on MgO(001). This suggests that Pd dimers move more rapidly on NiO(001) than on MgO(001), and that the sintering of Pd clusters closely related to catalytic activities can occur more easily compared to that of Pd on MgO(001).     

A contact angle and ToF-SIMS study of SAM-thiol interactions on polycrystalline gold

A process of chemical differentiation of neighboring Au features on a substrate (for biosensing applications) involves a step, where after electrochemical removal of a self-assembled monolayer (SAM) from one feature, another SAM is deposited onto it by incubation with a different thiol. During this incubation step, other undesorbed features are also exposed to this thiol which may lead to a partial SAM-thiol exhange, the extent of which is a function of time. Here, such surface reactions were followed on polystalline Au in both directions using contact angle measurements and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The thiols involved were dodecanethiol (DDT) which forms SAM promoting adsorption of proteins and 11-mercaptoundecyl)tri(ethylene glycol) (TPEG) whose SAM prevents such adsorption. The surface reactions in both directions cannot be described by a simple pseudo-first-order kinetics. It was found that while the DDT SAM interaction with a TPEG solution leads eventually to a total replacement, the reverse process, TPEG SAM interaction with DDT, leads to no noticeable exchange over the first 3 h and then asymptotically approaches ∼50% replacement.     

分子印迹-碳纳米管修饰电极检测扑热息痛

以扑热息痛为模板,邻苯二胺为单体,采用电聚合法制备了分子印迹-多壁碳纳米管复合膜修饰电极,研究了扑热息痛在该修饰电极上的电化学行为。结果表明,该修饰电极对扑热息痛的电极反应具有明显的电催化活性。该修饰电极对扑热息痛的方波伏安检测线性范围为2.0×10-6—8.0×10-5mol/L,检出限为1.0×10-8mol/L。该修饰电极显示了良好的稳定性和重现性。     

Electrochemical formation and properties of thin polyaniline films on Au(111) and p-Si(111)

The specific aspects of phase formation phenomena involved in electrodeposition of conducting polymer layers are critically discussed. The mechanism of formation and the properties of electrodeposited thin polyaniline (PANI) films on Au(111) and p-Si(111) are investigated by means of transient measurements, cyclic voltammetry, electrochemical impedance spectroscopy and atomic force microscopy (AFM). Experimental results show that the initial stages of PANI electrodeposition on Au(111) can be described by a model including progressive appearance and preferential 2D growth of polymer islands. The electropolymerization process on p-Si(111) substrates is preceded by anodic formation of an inhomogeneous thin SiO₂ layer giving rise to a progressive appearance and growth of 3D PANI islands. The electrochemical redox properties of electrodeposited PANI films on p-Si(111) are influenced strongly by the electronic band structure of silicon. PACS 81.10.Aj; 82.45.Wx; 82.45.Vp     

Investigations on the invalidated process and related mechanism of PEG during copper via-filling process

The invalidated process and related mechanism of PEG during copper via-filling process were investigated by means of electrochemical polarization and electrochemical impedance (EIS) measurements, and infra-red spectrum (IR) measurement was employed to analyses the invalidated products of PEG. The results suggest that the adsorption strength of PEG on cathode surface and its inhibition to copper reduction decrease gradually with the increase of passed charges (PC). Both the anodic and the cathodic electrifying process can cause the invalidation of PEG, but their invalidated courses are different. PEG will further polymerize to form new PEG with bigger MW on the anode surface, which causes the dispersive ability of plating solution to decrease. As a result, super-filling behavior cannot be obtained and many small wales formed on the specimen surface during copper via-filling process. Inversely, PEG will decompose to form new PEG with smaller MW on the cathode surface, which results in the decrease of PEG adsorption ability and inhibition. As a result, super-filling behavior cannot be obtained and the brightness of the specimen surface decreases during copper via-filling process. The decomposition of PEG is easily to happen than its polymerization when the anodic and cathodic reactions happen in the same plating solution simultaneously. So the main invalidated product of PEG during copper via-filling process is PEG with smaller MW.     

Étude de l'adsorption électrochimique de l'oxygène sur des lames minces d'or par la mesure de leur résistance électrique

The electrical resistance changes of thin gold film electrodes of preferential orientation [111] with film thickness and potential have been studied. The applicability of the Fuchs-Sondheimer (FS) relation to the decrease of resistance observed at the first negative polarization and the first few potential sweeps for different thicknesses have shown that this phenomenon is due to a surface process, interpreted as a cleaning of the electrodes. The resistance changes observed during the electrochemical adsorption and desorption of oxygen also obey the FS relation. The analysis of the resistance variation with the charge exchanged during these reactions has allowed us to show that the electrochemical adsorption of oxygen, on these gold films occurs by a two-dimensional island mechanism with formation of different structures of the surface layer. The values of the resistivity change caused by the adsorption of 1% oxygen atoms (with respect to the total number of metal atoms in the films) at low coverage have been compared with those observed in other systems (metal-gas, metal-metal).     

Characterization of iron surface modified by 2-mercaptobenzothiazole self-assembled monolayers

A self-assembled monolayer of 2-mercaptobenzothiazole (MBT) adsorbed on the iron surface was prepared. The films were characterized by electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared reflection spectroscopy (FT-IR) and scanning electron microscopy (SEM). Besides, the microcalorimetry method was utilized to study the self-assembled process on iron surface and the adsorption mechanism was discussed from the power-time curve. The results indicated that MBT was able to form a film spontaneously on iron surface and the presence of it could protect iron from corrosion effectively. However, the assembling time and the concentration influence the protection efficiency. Quantum chemical calculations, according to which adsorption mechanism was discussed, could explain the experimental results to some extent.     

Interaction of water with stepped Co(0001): how is it different from flat Co(0001)?

The adsorption and dissociation of water monomer and dimer on stepped Co(0001) surface were studied by means of first-principles calculations. Present results indicate that the adsorption strength of water is greatly enhanced by the presence of step, while the activity of water monomer dissociation does not exhibit a noticeable improvement. Nevertheless, water dimer partial dissociation on stepped Co(0001) is more active than on flat Co(0001), and the promotion of oxygen atom on O–H bond cleavage of H₂O is more prominent on stepped surface than on flat Co(0001). The findings reveal the importance of low coordinated surface atoms on metallic catalysts and the vital role of surface rippling on water dissociation. Together with previous reports, the activity of water dissociation on cobalt-based catalytic surfaces depends dominantly on O-containing species like oxygen atom, H₂O or hydroxyl.     

Imaging of dynamic processes on surfaces by light

This work focuses on imaging of dynamic processes on surfaces, using light to illuminate the area of interest. The methods discussed here are those in which the photoelectrons emitted from or the light reflected off the surface are measured. While the first approach is well-known since electron microscopy was invented and has been used in surface science applications for a decade, genuine optical microscope methods using polarized light were first developed in 1995 for imaging surface reactions.

The results discussed here are from different fields of surface research. These include the imaging of adsorption phenomena, surface diffusion and growth processes. The main emphasis will be on pattern formation of surface reactions under strictly controlled parameters. The most recent techniques expand the range of observable pressure conditions by many orders of magnitude, thus bridging the pressure gap in imaging surface reactions.     

Adsorption of 2‐amino‐5‐cyanopyridine on a gold surface as probed by surface‐enhanced Raman spectroscopy

The adsorption of 2‐amino‐5‐cyanopyridine (2‐ACP) was investigated in solution at different pH values by i n situ surface‐enhanced Raman scattering (SERS) spectroscopy combined with the electrochemical method. The assignments of the main bands were first performed on the basis of the spectral features of similar compounds and with the help of density functional theory calculations. The results revealed that the adsorption and the interfacial structure of 2‐ACP on the Au electrode depended on the applied potential and the pH values of the solution. In the natural solution, 2‐ACP was adsorbed on the surface with a vertical orientation by the CN group from − 0.4 to − 1.0 V, whereas in the − 0.4 to 0.8 V range, the N atom of the pyridine ring was bound to the surface. A transition region for the reorientation of the two adsorption modes was observed from − 0.8 to − 0.4 V. A flat configuration was preferred at an extremely negative potential. A similar surface adsorption behavior was observed in the alkali environment, while the Stark effect slope decreased because of the adsorption of OH⁻. Due to the protonation of N atom in the acidic solution, the potential region for the coexistence of two configurations ranged from − 0.4 to 0.2 V. Additionally, a similar adsorption configuration was proposed on the Au colloids at various pH values. The results revealed that the adsorption behavior became more complex on colloidal surfaces than that on a rigid electrode surface. Copyright © 2010 John Wiley & Sons, Ltd.     

含咔唑与偶氮分散红共聚物的表面增强共振拉曼光谱研究

借助于表面增强共振拉曼光谱散射(SERRS)技术,研究了一种新型的偶氮聚合物材料侧链含咔唑与偶氮分散红共聚物(CAP)在化学沉积法制备的银膜表面的拉曼峰增强和吸附行为。实验结果显示,CAP在银表面的状态为: 聚合物通过咔唑单体中咔唑基团和偶氮单体中硝基与银膜衬底发生物理吸附,而聚合物的主链与衬底相距较远没有相互作用。可以推测,聚合物在衬底表面的这种状态将对偶氮光存储器件的稳定性和工作效率产生不良影响。     

Development of GaAs Epitaxy from Bulk to Ultrathin Films. Growth for Nanostructure Devices

The effects of stoichiometry on various features of III–V compounds are investigated. It is shown experimentally that the optimum vapor pressure of V elements minimizes the deviation from the stoichiometric composition. Vapor pressure control technology is applied not only to the liquid phase epitaxy and bulk crystal growth but also to the surface reaction in molecular-layer epitaxy. The surface reactions of monomolecular layer growth by using chemical adsorption of precursors were investigated for GaAs, InP, Si, etc. The atomic scale controlled epitaxy of these materials has been studied with the study of surface reaction mechanism. The self-limiting growth in atomic or molecular layer was achieved with doping technology in each materials developed by choosing precursor materials.     

Elementary processes at semiconductor/electrolyte interfaces: perspectives and limits of electron spectroscopy

Semiconductor device properties based on electrolyte contacts or modified by electrochemical reactions are dominated by the electronic structure of the interface. Electron spectroscopy as e.g. photoemission is the most appropriate surface science techniques to investigate elementary processes at semiconductor/electrolyte interfaces. For such investigations a specific experimental set-up (SoLiAS) has been built-up which allows performing model experiments as well as surface analysis after emersion under different experimental conditions. The experimental approach is presented by a number of experiments performed during the last years with GaAs as substrate material. Model experiments by adsorption and coadsorption of electrolyte species give information on fundamental aspects of semiconductor/electrolyte interactions. Emersion experiments give information on a final composition and the related electronic structure of electrodes after electrochemical reactions. The use of frozen electrolytes will help to bridge the gap between these two approaches. With the combination of the experimental procedures one may expect a detailed analysis of electrolyte (modified) interfaces covering chemical composition, electronic structure of surfaces/interfaces as well as surface/interface potentials.     

Electrochemical reactions with participation of excitons at anthracene electrodes

The specificity of electrochemical reactions with participation of excitons occuring at an anthracene electrode is discussed. The solutions of the diffusion equations for excitons in the presence of an electrochemical reaction at the interface are given for semi-infinite and finite crystals. The possibility of the occurrence of electrochemical reactions at both interfaces is considered. Depending on the energy of the exciting light photons, apart from excitons, either electrons of the free zone, or the excited particles of the electrolytic contact can participate in the reaction. In accordance with this, the influence of the interfacial potential drop caused by adsorption manifests itself in a different manner at different optical excitation frequencies. Special consideration is given to the effect of the dielectric constant of the solvent on the kinetics of electrochemical reactions with participation of excitons.     

Chemical and electrochemical investigations of high carbon steel corrosion inhibition in 10 % HCl medium by quinoline chalcones

The corrosion inhibitive effect of 3-(3-oxo-3-phenyl-propenyl)-1H-quinolin-2-one (PPQ) and 3-(3-oxo-3-phenyl-propenyl)-1H-benzoquinolin-2-one (PPBQ) on high carbon steel (HCS) in 10 % HCl media was evaluated by chemical (weight loss) and electrochemical (electrochemical impedance spectroscopy and potentiodynamic polarization technique) measurements. The inhibition efficiencies obtained from weight loss and electrochemical measurements were in good agreement. The inhibition efficiency was found to increase with the increase in inhibitor concentration but decreased with rise in temperature. Potentiodynamic polarization studies revealed the mixed mode inhibition of inhibitors. The adsorption behavior of these inhibitors on the HCS surface was found to obey the Langmuir adsorption isotherm. The thermodynamic parameter values of free energy of adsorption (?G _ads) and enthalpy of adsorption (?H _ads) revealed that the inhibitor was adsorbed on the HCS surface via both chemisorption and physisorption mechanisms. The adsorption mechanism of inhibition was supported by spectroscopic techniques (UV–visible, FT-IR, and wide-angle X-ray diffraction), surface analysis (SEM–EDS), and adsorption isotherms.