Nucleation and growth mechanism for the electropolymerization of aniline in trifluoroacetic acid/lithium perchlorate/propylene carbonate medium

In the present work, the nucleation and growth mechanism for the electropolymerization of aniline in propylene carbonate medium containing 0.06 M trifluoroacetic acid and 0.05 M lithium perchlorate was investigated at different potentials on highly oriented pyrolytic graphite (HOPG) by potentiostatic current-time transients (i-t) and atomic force microscopic (AFM) measurements. The electrochemical data fitted with the theoretical curves for nucleation and growth suggest that the electropolymerization of aniline consists of progressive nucleation followed by 3D growth at an early stage and layer-by-layer growth in subsequent periods. The results obtained from transient analysis were in good agreement with the results of the AFM analysis. In our previous studies with aqueous solutions, we observed only progressive nucleation followed by a 3D growth mechanism for the electropolymerization of aniline in a higher potential range, 1.5–2.0 V vs. Ag/AgCl. Hence, the results obtained from the present work indicate that the nucleation and growth mechanism depends on the medium.     

n-Alkanoic acid monolayers on 316L stainless steel promote the adhesion of electropolymerized polypyrrole films

The formation of a self-assembled monolayer significantly promotes the adhesion of electrodeposited polypyrrole on stainless steel. The monolayer affects the nucleation and growth mechanism of polypyrrole as a result of its hydrophobic nature. This was confirmed by analyzing current-time transients of the initial stages of electropolymerization and was in agreement with AFM images.     

Nucleation and Growth Mechanism of Electropolymerization of Methylene Blue: The Effect of Preparation Potential on Poly(methylene blue) Structure

Nucleation and growth mechanism of electropolymerization of methylene blue (MB) in a basic medium and the effect of preparation potential on poly(MB) film structure were investigated by using cyclic voltammetry, potentiostatic current‐time transient, scanning tunneling microscopy (STM), atomic force microscopy (AFM), and UV‐vis. absorption spectroscopy techniques. Electropolymerization of MB has been achieved by potentiodynamic (cyclic voltammetry) and potentiostatic (constant potential) techniques. The potentiostatic current‐time transients fitted with a theoretical model and morphological studies indicate that nucleation and growth mechanism of poly(MB) starts with a progressive layer‐by‐layer nucleation and growth besides random adsorption. Nucleation and growth of poly(MB) follows a process between progressive layer‐by‐layer and 3‐D instantaneous mechanism resulting in highly‐oriented poly(MB) nanofibers with increasing poly(MB) film thickness. Cyclic voltammetry and morphological studies exhibit that poly(MB) film structure changes depending on the preparation potential. Poly(MB) films prepared at the potential values of 900 and 950 mV show a well‐ordered, smooth surface but at the potential values higher than 1000 mV, rough polymer surface arises as overoxidation takes place. UV‐vis. absorption spectra of poly(MB) film and MB monomer show three peaks. The peak at 410 nm for poly(MB) shows 100 nm blue shift when compared to the MB monomer and is attributed to poly(MB) formation on the electrode.     

表面活性剂对苯胺电聚合的影响

利用胶束在电极一有面的定向及增溶作用研究了表面活性剂对苯胺电聚合的影响，结果表明：在阴离子表面活性剂十二烷基硫酸钠（ＳＤＳ）胶束体系中，胶束介质能催化苯胺的电聚合反应，使其氧化电位负移，减少膜的降解，提高膜的稳定性，同时，也使得聚合速率增大，在０．１ｍｏｌ／Ｌ的ＳＤＳ的胶束溶液中，其聚合效率提高到不含ＳＤＳ的纯体系的２５倍，在含有１０＾－４ｍｏｌ／ＬＳＤＳ的硫酸溶液中，聚苯胺（ＰＡＮ）的成核生长为     

Evaluation of Structure,Nucleation and Growth Mechanism of Electropolymerized Polypyrrole on Highly Oriented Pyrolytic Graphite Electrode

Chronoamperometry (i–t) and atomic force microscopy (AFM) were used to study the nucleation and growth mechanism of electropolymerized polypyrrole formed on highly oriented pyrolytic graphite (HOPG) substrate surface. From i–t measurements it was found that the nucleation and growth mechanism was a 3‐D progressive after nuclei overlapping. However, before nuclei overlapping, it was not clear whether the mechanism was 2‐D instantaneous or 3‐D progressive. This ambiguity in the nucleation and growth mechanism was confirmed as 3‐D progressive from the results of AFM measurements. In addition to nucleation and growth mechanism, possible models were proposed for different structures observed on the AFM image of polypyrrole, obtained from very early stages of polymerization.     

Redox mechanism and electrochemical behaviour or polyaniline deposits

Polyaniline (PANi) is prepared electrochemically by anodic oxidation of aniline in the eutectic mixture NH₄F, 2.35 HF (PANi-F), in aqueous sulfuric medium at different pH (PANi-S), or (PANi-N) if Na₂SO₄ is added. Thin deposits of PANi-F, prepared by potential step or sweeping, have a compact form at all aniline concentrations, with almost 100% polymerization yield and a strong adherence to the electrode. Thin deposits of PANi-N and PANi-S have identical characteristics, but only when prepared by potential sweeping at low aniline concentration. When the deposits are thick, only PANi-F displays these interesting properties, giving hard fibres, which adhere strongly to the electrode as the polymerization proceeds. Prepared with equal amounts of charge samples, a higher charge and discharge capacity is measured (coulombs) for PANi-F deposits than for PANi-N and PANi-S. Only PANi-F exhibits a faradaīc yield close to 1 after 2000 cycles.Observations on the electrochemical behaviour of PANi suggest a redox mechanism involving a proton + electron exchange and a doping process with ion insertion. The cyclic voltammograms obtained with PANi—coated electrodes show two or three rapid, reversible and clearly defined electrochemical systems. The second electrochemical system (2,2′) is obtained during the oxidation of aniline at higher potentials than those needed for the first (1,1′) and the third (3,3′) system. Therefore, a different structure of polymer may be associated with system 2,2′ than the para-coupling structure attributed to the systems 1,1′ and 3,3′. The polymerization of p-fluoraniline is possible (+0.72 V) at the same potential as aniline (+0.7 V). Hence, the participation of the ortho positions in the electropolymerization mechanism of aniline is a possibility to take into consideration. The cyclic voltammograms recorded during the electrodeposition of N-phenyl p-phenylenediamine, exhibit a similar form as those recorded for PANi-F. Therefore, it is confirmed that the polymerization of aniline proceeds through a head-to-tail coupling of cation radical.     

AFM studies of metal deposition: instantaneous nucleation and the growth of cobalt nanoparticles on boron-doped diamond electrodes.

In situ atomic force microscopy (AFM) is used to study the growth of cobalt nuclei on a boron doped diamond electrode under potentiostatic control. The rate of growth of the nuclei at the electrode surface is monitored using AFM as a function of time at different deposition potentials. The nucleation of cobalt nuclei is found to be "instantaneous" and the growth of the nuclei is shown to be kinetically rather than diffusionally controlled over periods of tens and hundreds of seconds. At very short times (<10 seconds) the kinetics of nucleation are apparent.     

苯胺在银和金电极上的表面增强拉曼光谱

聚苯胺作为性能较好的导电高聚物有很大的应用潜力,有关其聚合和导电机理的研究受到广泛重视。表面增强拉曼光谱(SERS)能现场(in situ)检测表面吸附分子、提     

Study of the growth process of in situ polyaniline deposited films

Polyaniline (PAni) thin films were deposited onto BK7 glass substrates using the in situ deposition technique. The control of the time and the aniline concentration in the PAni polymerization reaction on the film deposition allowed us to prepare films with different thickness, down to approximately 25 nm. The film growth process was monitored by measuring the UV-vis spectra and the AFM height profiles of the film surface. The curves of adsorption kinetics were analyzed with the Avrami's model, yielding an exponent n=3, thus indicating nucleation of spheroids at the initial stages of polymerization that grow through a diffusion process. AFM images of the surface height profiles corroborate this hypothesis, with spheroids growing with no preferred orientation during the in situ deposition.     

The adsorption and condensed film formation of cetyltrimethylammonium bromide at the mercury/electrolyte interface

The adsorption of cetyltrimethyammonium bromide (CTAB) on a hanging mercury electrode is studied in various electrolyte systems and temperatures. A condensed film is formed at negative potentials and at room temperature only in the presence of KBr. The decrease of the temperature favors the formation of the condensed film. Hysterisis phenomena are observed during the potential scans at both directions. Capacity time curves at the potentials where the film is formed show a nucleation and growth mechanism, with induction time depending on potential, which has been investigated using Avrami formulation and has been explained as a progressive one-dimensional nucleation with constant growth rate. The nucleation rate increases while moving toward more negative potentials. A linear decrease of the capacitance with time was observed in some cases independent of the measuring potential in a relative large potential range. The different types of micelles can affect the adsorption of CTAB on mercury. An unusual capacitance transient observed at a very narrow negative potential range is attributed to the formation of hemicylinders. The condensed film in the presence of the other electrolytes is observed only at high concentrations (1 M) and very low temperatures (5 degrees C).     

电聚合苯胺过程的在线紫外-可见光谱

用在线紫外-可见光谱电化学的方法对0.5mol/L硫酸水溶液中苯胺在ITO导电玻璃电极上的电化学聚的过程进行了研究.结果表明在循环伏安条件下苯胺发生了电聚合,聚合速率与苯胺浓度成正关系;而且在线紫外-可见电化学光谱表明,在0.01mol/L苯胺溶液的电聚合过程的诱导期较长.恒电位条件下的在线紫外-可见电化学光谱显示苯胺浓度为0.05mol/L,电位为0.8V时,在ITO电极上苯胺低聚合物中间体可能产生于聚苯胺形成之前;而0.01mol/L苯胺在0.8V电位下不发生聚合,但在线紫外-可见光谱又显示此时在电极上可能存在小的苯胺低聚物的中间体;在线紫外-可见光谱表明这种中间体是可能产生并存在电极表面上的.     

Specific features characterizing electrochemical synthesis of polyaniline conducted in the presence of poly(2-acrylamido-2-methyl-1-propanesulfonic acid) and the spectroelectrochemical characteristics of the obtained films

The electrochemical matrix polymerization of aniline in the presence of poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA) is performed in conditions that lead to the formation of an interpolymer complex comprising polyaniline and PAMPSA of the 1: 2 composition. The acceleration of the process of polymerization of aniline in the presence of PAMPSA as compared with traditional electropolymerization of aniline in hydrochloric acid is caused by the association of aniline molecules with the sulfo groups of PAMPSA and by a high concentration of hydrogen ions in the vicinity of a molecule of PAMPSA. It is established for the first time ever that, in the initial stages of synthesis for both polymeric and low-molecular-weight acids, the rate of polymerization is substantially greater at a smaller concentration of the acid. The distinguishing feature of the initial stage of electropolymerization of aniline at a low acidity of the environment is a non-autocatalytic character of the process, which may exert a discernible influence on a complex of physicochemical properties of polyaniline, including electric conduction. Studying spectroelectrochemical properties of the obtained films shows practical identity of their spectra with the spectra of standard polyaniline.     

Influence of the magnitude and direction of electric field on the transport and growth property of deposited polyaniline films

Polyaniline (PANI) films were deposited by electrochemical polymerization of aniline monomer on a fluorine-doped glass substrate at room temperature under different electric field directions. The as-synthesized PANI films obtained at different growth cycles were characterized by AC impedance spectroscopy and scanning electron microscopy (SEM). The results revealed that the film morphology, transport kinetics, and electrical properties are strongly dependent on the electric field direction and magnitude of the applied field during electropolymerization. The SEM morphology and AC impedance (modulus spectroscopy) indicate that a more homogeneous, high-porous, and conducting PANI film is induced by horizontal electric field direction (HEFD) electrodeposition, whereas the modulus spectroscopy of the PANI film deposited by vertical electric field direction (VEFD) reveals that VEFD deposition favours two-dimensional growth of PANI. The obtained polymer is more of dielectric in nature due to preferable dendritic growth which is supported by SEM analysis.     

In situ AFM study of electrochemical synthesis of polypyrrole/Au nanocomposite

In this work, in situ AFM measurements with simultaneously electrochemical characterization were developed to study the mechanisms of both polypyrrole (PPy) and PPy/Au composite deposition. The nanoscale information derived from the in situ AFM images associated with theoretical simulation from the measured current–time transient (i–t) reveals that Au nanoparticles with negatively charged carboxylic groups can be the nuclei by both adsorption on the electrode surface and doping on PPy for the polymerization, and thus has faster nucleation and growth rate than Py alone at the early polymerization stage. The PPy/Au deposition shows parallel nucleation processes of Au nanoparticle and Py, and an instantaneous 3D nucleation mode. The work not only provides fundamental insights for PPy/Au nanocomposite deposition process, but also optimization approaches to fabricate a superior PPy/Au film with favorable features for greater potential applications.     

ITO上电沉积Pd的成核机理及电催化性质

采用循环伏安技术和计时电流技术, 研究了ITO上电沉积Pd的过程, 发现Pd在ITO表面的电沉积是过电位成核且为不可逆的扩散控制过程; 根据Cottrell方程计算得到[PdCl₄]^2-的扩散系数为2.19×10^-5 cm²/s; 根据Scharifker的理论模型, 归一化处理电流-时间曲线, 与理论成核曲线对照, 判断Pd 的成核机理. 通过场发射扫描电子显微镜(FESEM)对Pd 的形貌进行分析, 讨论了沉积电位和沉积时间对Pd纳米粒子形貌的影响. 用X射线粉末衍射(XRD)对Pd纳米粒子进行结构分析, 并在0.5 mol/L H₂SO₄溶液中研究了其电化学性质及在碱性条件下乙醇分子的电催化性质.     

A Highly Sensitive Electrochemiluminescence Choline Biosensor Based on Poly(aniline‐luminol‐hemin) Nanocomposites

Poly(aniline‐luminol‐hemin) nanocomposites are prepared on an electrode surface through electropolymerization, and a highly sensitive electrochemiluminescence (ECL) biosensor for choline is developed based on the poly(aniline‐luminol‐hemin) nanocomposites and an enzyme catalyzed reaction of choline oxidase (CHOD). The obtained nanocomposites are characterized by scanning electron microscopy (SEM), atomic absorption spectrometry (AAS) and ECL. The results indicate that hemin can be incorporated into the poly(aniline‐luminol) nanocomposites using the facile electropolymerization method, and the poly(aniline‐luminol‐hemin) nanocomposites are rod shaped porous nanostructure. Moreover, the poly(aniline‐luminol‐hemin) nanocomposites exhibit higher ECL intensity than poly(aniline‐luminol) nanocomposites in alkaline media due to the catalytic effect of hemin on the ECL of the polymerized luminol and the electron transfer ability of hemin in the nanocomposites. CHOD is immobilized on the surface of the poly(aniline‐luminol‐hemin) nanocomposites modified electrode with glutaraldehyde, and the ECL biosensor based on poly(aniline‐luminol‐hemin)/CHOD exhibits a wider linear range for the choline detection. The enhanced ECL signals are linear with the logarithm of concentration of choline over the range of 1.0×10^?11～1.0×10^?7 mol L^?1 with a low detection limit of 1.2×10^?12 mol L^?1. Moreover, the proposed biosensor is successfully applied to the detection of choline in milk.     

Immobilization of phthalocyanines in conducting polymers. Polyaniline-copper tetrasulfophthalocyanine

Interaction between the anilinium cation and copper tetrasulfophthalocyanine anion (CuTSPc) was studied in an aqueous sulfuric acid solution using electronic absorption spectra. It was shown that up to 0.15 M aniline could be introduced into the solution at the dye concentration of 10⁻³ M, after which a solid deposit of a complex (salt) between the anilinium cation and copper tetrasulfophthalocyanine anion started precipitating rapidly. The effect of the dye on the kinetics of aniline polymerization on conducting glasses and on the properties of the polymer obtained was studied. It was found that phthalocyanine accelerates electropolymerization of aniline and is immobilized within the polymer matrix. It was shown that the self-catalytic synthesis mechanism characteristic of polyaniline is also preserved in the case of the composite of polyaniline-copper tetrasulfophthalocyanine.     

Palladium nanoparticles and nanowires deposited electrochemically: AFM and electrochemical characterization

Palladium nanoparticles and nanowires electrochemically deposited onto a carbon surface were studied using cyclic voltammetry, impedance spectroscopy and atomic force microscopy. The ex situ and in situ atomic force microscopy (AFM) topographic images showed that nanoparticles and nanowires of palladium were preferentially electrodeposited to surface defects on the highly oriented pyrolytic graphite surface and enabled the determination of the Pd nanostructure dimensions on the order of 50–150 nm. The palladium nanoparticles and nanowires electrochemically deposited onto a glassy carbon surface behave differently with respect to the pH of the electrolyte buffer solution. In acid or mild acid solutions under applied negative potential, hydrogen can be adsorbed/absorbed onto/into the palladium lattice. By controlling the applied negative potential, different quantities of hydrogen can be incorporated, and this process was followed, analysing the oxidation peak of hydrogen. It is also shown that the growth of the Pd oxide layer begins at negative potentials with the formation of a pre-monolayer oxide film, at a potential well before the hydrogen evolution region. At positive potentials, Pd(0) nanoparticles undergo oxidation, and the formation of a mixed oxide layer was observed, which can act as nucleation points for Pd metal growth, increasing the metal electrode surface coverage. Depending on thickness and composition, this oxide layer can be reversibly reduced. AFM images confirmed that the PdO and PdO₂ oxides formed on the surface may act as nucleation points for Pd metal growth, increasing the metal electrode surface coverage. Dedicated to Professor Dr. Algirdas Vaskelis on the occasion of his 70th birthday.     

Site selective micro-patterned rutile TiO2 film through a seed layer deposition

Micro-patterned films obtained from micro-contact printing (microCP) method are often challenged by site selectivity limitation. For applications site-selectivity requires improvements. In this paper a site-selective deposition of the rutile TiO2 thin films on patterned SnO2 film, which was formed on the patterned octadecyltrichlorosilane (OTS) SAMs through microCP is described. The depositions proceeded in an environmentally friendly aqueous solution (SnCl4 and peroxotitanium acidic solution) at a lower temperature (80 degrees C). It is shown that the OTS SAMs has a good selectivity deposition for SnO2 particles, which was mainly dominated by the heterogeneous nucleation mechanism. The SnO2 layer had a structure-directing effect for growth of the rutile TiO2, which was usually formed above 600 degrees C. The patterned films were characterized by a variety of techniques, including ellipsometry, optical microscopy, SEM, AFM, XPS, and DLS to determine the thicknesses, topologies, microstructures, chemical compositions of the films, particle sizes and zeta potentials of the titanium particles.     

Submicrometer intermediates in the citrate synthesis of gold nanoparticles: new insights into the nucleation and crystal growth mechanisms

The reduction of tetrachloroaurate by citrate ions in aqueous solutions yielding gold nanoparticles (GNPs) has been studied using in situ tapping mode atomic force microscopy (AFM), UV-vis absorption and dynamic light scattering (DLS) spectroscopies, small-angle X-ray scattering (SAXS) along with ex situ TEM, EDX and XPS. Special attention is given to mesoscale intermediates responsible for the intense coloring of the transient solutions and their role in nucleation and crystal growth. AFM detects liquid droplet-like domains, globules 30-50 nm in diameter arranged in submicrometer aggregates in the gray and blue solutions, and well separated individual particles in the final red sols. DLS shows abrupt appearance of species about 30 nm and larger but not growing Au nanoparticles, while SAXS reveals gradually increasing nanoparticles and no aggregates. The mesoscale structures observed in TEM become looser as the reaction proceeds; they contain signatures of oxidized Au and other solutes. The results are interpreted in terms of decomposition of supersaturated solutions to afford domains ("dense droplets") enriched by gold, and then, after nucleation and coalescence of Au nuclei inside them, rather slow growth of gold nanoparticles within the associated globules; the color changes of the transient solutions are due to increasing interparticle distances.