Modification of the gold electrode for the electrochemical study of cytochrome c

The modification of the gold electrode by some nitrogen hetero-cycles is used for electrochemically studying cytochrome c. Fifteen molecules are tested, but only six are active. The prominent characteristics of the active molecules are defined, and the competition between cytochrome c, 4,4′-bipyridine, 1,2-bis(4-puridyl)ethylene and aldrithiol-4 for the adsorption at the gold electrode has been studied in particular.     

Effect of cobalt bis(dicarbollides) on electrochemical oxygen reduction on Pt electrode in methanol-acid solution

Electrochemical oxygen reduction on a platinum electrode has been investigated in methanol-0.05 M H₂SO₄ aqueous solutions in the presence of acids of cobalt bis(dicarbollide) (H⁺B⁻, H⁺[(1,2-C₂B₉H₁₁)₂-3-Co]⁽⁻⁾) or its hexachlorinated derivative (H⁺BCl⁻, H⁺ [(8,8′,9,9′,12,12′-Cl₆-(1,2-C₂B₉H₈)₂-3-Co)]⁽⁻⁾). Methanol oxidation was suppressed with H⁺BCl⁻ significantly, and selective oxygen reduction was achieved on a platinum electrode. The efficiency of oxygen reduction to H₂O, which depended on the electrode potential, was lower by 2% to 20% than that without H⁺BCl⁻. The mechanism was investigated by surface-enhanced infrared absorption spectroscopy (SEIRAS). H⁺BCl⁻ suppresses formation of both the catalytic poison, linear CO (ads.), from methanol and the formate, the intermediate of the non-CO path of methanol oxidation.     

Electropolymerization of chlorinated phenols on a Pt electrode in alkaline solution. Part II: An electrochemical quartz crystal microbalance study

Electropolymerization of phenol and mono-, di-, tri-, pentachlorophenols was studied using EQCM on a Pt electrode at 0.78 V (SHE) in 1 M NaOH solution containing 0.1 M of the corresponding phenol. The highest electropolymerization rate was found for ortho-substituted chlorophenols indicating a weak fouling of the electrode. Low electropolymerization rates for para-substituted chlorophenols suggest a low permeability of the polymer film, resulting in rapid electrode fouling. The EQCM data suggest that electropolymerization of chlorophenols occurs without Cl-elimination for the monomers with unsubstituted ortho and para positions. Dechlorination is most pronounced for electropolymerization of para-substituted isomers. The mechanism of electropolymerization of chlorophenols is discussed.     

SFG study on potential-dependent structure of water at Pt electrode/electrolyte solution interface

Structure of water at Pt/electrolyte solution interface was investigated by sum frequency generation (SFG) spectroscopy. Two broad peaks were observed in OH stretching region at ca. 3200 cm⁻¹ and ca. 3400 cm⁻¹, which are known to be due to the symmetric OH stretching (υ₁) of tetrahedrally coordinated, i.e., strongly hydrogen bonded “ice-like” water, and the asymmetric OH stretching (υ₃) of water molecules in a more random arrangement, i.e., weakly hydrogen bonded “liquid-like” water, respectively. The SFG intensity strongly depended on electrode potential. Several possibilities are suggested for the potential dependence of the SFG intensity.     

The influence of electrochemical annealing in CO saturated solution on the catalytic activity of Pt nanoparticles

Combining non-destructive, identical location—transmission electron microscopy (IL-TEM) with rotating disk electrode (RDE) measurements, the influence of different treatment procedures on the catalytic activity of carbon supported Pt nanoparticles is probed. IL-TEM shows that the treatment of the catalyst has only minor influence on its structure or the particle shape and size; in particular no treatment induced particle agglomeration is observed. At the same time, both CO stripping and CO bulk measurements are significantly influenced by the electrochemical treatment. In consistence with previous studies this can be explained by the removal of defects in the CO adlayer structure while cycling in CO saturated solution. In contrast, however, it is demonstrated that CO annealing has no impact on the oxygen reduction reaction in the mixed kinetic-diffusion control potential region.     

The influence of chemical passivation on the PZT/Pt electrode interface

It has been recognized that the interdiffusion of atomic species between a PZT film and the Pt bottom electrode leads to the gradual degradation of a PZT capacitor. In order to prevent this interdiffusion, experimental studies on chemical passivation to the bottom electrode surface were carried out by the sulfurization method. It was observed that a sulfur layer was built up on the Pt substrate with small grains, which resulted in a structural change at the Pt surface. Atomic force microscopy (AFM) showed that the film roughness of the Pt surface was increased by sulfur treatment. Pb(Zr_0.5Ti_0.5)O₃(PZT) thin films were prepared on a Pt/Ti/SiO₂Si bottom electrode by spin-coating techniques. The microstructure and the preferred orientation of the PZT films were shown to depend on the sulfur-treated electrode. The PZT capacitor on a clean Pt electrode was confirmed to be ferroelectric with Pr=17.7 μC/cm² and Ec=65 kV/cm from the P-E hysteresis curves. The fatigue behavior of a PZT film capacitor prepared on a sulfur-treated one was observed to be relaxed, but the absolute value of Pr was paid off.     

Structure of detonation waves in nitromethane and a nitromethane/methanol mixture

The results of experimental studies of the structure of the reaction zone for steady-state detonation of nitromethane and its mixtures with methanol. For pure nitromethane, the characteristic reaction time and detonation parameters were determined. For a nitromethane/methanol mixture, a dependence of the detonation parameters of the mixtures on methanol concentration is presented. It is shown that in pure nitromethane and with small additions of methanol, the detonation front is stable, or the size of the inhomogeneities of the front is less than 1 m. At a methanol concentration of 10% or higher, instability of the front is observed.     

The electrochemical behavior of erythromycin A on a gold electrode

The reactivity of erythromycin (pure) was investigated on a gold electrode in neutral electrolyte by cyclic voltammetry. The resulting structural changes were observed with HPLC and FTIR spectroscopy by analyzing the bulk electrolyte after the electrochemical reactions. The results were compared with those previously obtained for azithromycin and clarithromycin under the same experimental conditions. It was found that the electrochemical behavior of erythromycin A differs from that of azithromycin dihydrate. Comparison with the electrochemical activity of basic clarithromycin suggests that the electrochemical activity of erythromycin is similar but more pronounced than that of clarithromycin.HPLC analysis confirmed these observations and showed that during the electrochemical oxidation of erythromycin A, the amount of starting macrolide decreased while the amount of starting impurities increased. Also some new products were observed. FTIR spectroscopy confirmed that erythromycin A is more reactive than clarithromycin, although similar changes in their molecular structures were observed.     

Role of chloronium complex in the electrochemical chlorination of c-hexene in nitromethane

The anodic chlorination of c-hexene in NM solution having 150 ppm water content involves three charge-transfer reactions. The effect of potential on change in product distribution is more effective at the beginning of electrolysis. A mechanism for the process is suggested.     

Unfolding of cytochrome c immobilized on self-assembled monolayers. An electrochemical study

The electron transfer (ET) process of progressively unfolded bovine cytochrome c immobilized on different self-assembled monolayers (SAMs) was investigated. Insight is gained on the role of the SAM surface on the functionality of the partially unfolded and non-native forms of the adsorbed protein. Direct electrochemical measurements were performed on cytochrome c adsorbed on mercaptopyridine (MP) and mixed 11-mercapto-1-undecanoic acid/11-mercapto-1-undecanol (MUA/MU) at varying temperature, in the presence of urea as unfolding agent. Under strongly unfolding conditions, a non-native form of cytochrome c, in which the methionine ligand is replaced by a histidine, was observed on both MP and MUA/MU SAMs. The E°′ of the native form, in which the haem is axially coordinated by methionine and histidine, slightly shifts to negative values upon increasing urea concentration. However, the non-native bis-histidinate species shows a much lower E°′ value (by approximately 0.4 V) which is by far enthalpic in origin and largely determined by axial ligand swapping. Analysis of the reduction enthalpies and entropies and of the ET rate constants indicate that the nature of the SAM (hydrophilic or anionic) results in changes in the conformational rearrangement of the cytochrome c under unfolding conditions.     

Regioselective bromination of toluene by electrochemical method

A simple, regioselective, environmentally cleaner and economical method for the electrochemical preparation of benzyl bromide from toluene by two-phase electrolysis is reported. Electrochemical bromination of toluene is carried out in an undivided cell at 0 °C and the process parameters are studied and optimized. In this method 94% yield and 98% conversion is achieved.     

An electrochemical methanol sensor based on a Pd-Ni/SiNWs catalytic electrode

A novel electrochemical methanol sensor based on a catalytic electrode of palladium-nickel/silicon nanowires (Pd-Ni/SiNWs) is presented in this paper. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and electrochemical methods are employed to investigate the Pd-Ni/SiNWs electrode materials. These nanocomposite materials exhibit a highly ordered, wire-like structure with a wire length of ∼50 μm and a wire diameter ranging from 100 to 300 nm. The substrate has good electrocatalytic activity towards the oxidation of methanol in alkaline solutions. The performances of the prototype sensor are characterized by cyclic voltammetry and fixed potential amperometry techniques. In a 1 mol L⁻¹ KOH solution containing different methanol concentrations, the sensor exhibits a good sensitivity of 1.96 mA mmol⁻¹ L cm⁻² with R² = 0.99 and the corresponding detection limit of 18 μmol L⁻¹ (signal-to-noise ratio = 3, S/N = 3) for cyclic voltammetry. Meanwhile, the electrode also displays a sensitivity of 0.48 mA mmol⁻¹ L cm⁻² with R² = 0.98 and the corresponding detection limit of 25 μmol L⁻¹ (S/N = 3) for a fixed potential amperometry at −0.3 V versus an Ag/AgCl reference electrode. The results demonstrate that the Pd-Ni/SiNWs catalytic electrode has potential as an efficient and integrated sensor for methanol detection.     

镉试剂在汞电极上的伏安行为

三氮烯试剂是一类性能优良的金属显色剂,镉试剂是最早应用于分析目的和研究报道的三氮烯试剂[1],镉试剂化学结构式如下： 在光度方面镉试剂有着广泛的应用,可用于检测Cd2+、Hg2+、pd2+、Cu2+、Ag+、Au3+及CN-、S2-等离子[2,3],但在电化学分析方面的应用还未见报道。     

镉试剂在汞电极上的伏安行为

通过固液相模板反应合成了2,36,71114,15-四苯并-1,4,9,12-四氮[16]轮烯稀土金属配合物,通过测定红外、紫外-可见、核磁、元素分析及摩尔电导等数据,确定了配合物的组成及结构。     

Influence of water content on the product distribution in the electrochemical chlorination of c-hexene in nitromethane

Effect of water content on product distribution in electrochemical chlorination of c-hexene in nitromethane solution was studied. Formation of 1-chloro, c-hexanone which occurs at the beginning of electrolysis is more effective at lower water content.     

二氧化碳在银电极上发生电还原反应时的电极失活原因

在KHCO3水溶液中,利用线性扫描、塔菲尔曲线、恒电位电解、电化学阻抗谱方法,研究了CO2在银电极上发生电还原反应的动力学特征,发现当电解反应进行一段时间后,阴极表面生成了一层棕黑色物质附着在电极表面,导致生成CO的平衡电位负移,交换电流密度变小,电荷转移电阻增大,电流效率和电流密度迅速降低。用X射线光电子能谱(XPS)分析了有害物质的主要成分,证明阴极表面附着物主要为石墨碳和微量Zn,这些物质附着在阴极表面,导致电极失活,阻碍CO2电还原反应继续进行。     

Electropolymerization of chlorinated phenols on a Pt electrode in alkaline solution Part III: A Fourier transformed infrared spectroscopy study

FTIR spectroscopy was employed to investigate high molecular weight substances formed on a platinum electrode surface during the electrochemical oxidation of phenol and its chlorinated derivatives. Potentiodynamic (potential range from –0.80 V to 0.85 V vs SHE; scan rate 200 mV s^–1) and potentiostatic (at 0.78 V vs SHE) electropolymerization was used in alkaline solutions (1 M NaOH) containing 0.1 M of phenol, monochlorophenols, dichlorophenols, trichlorophenols and pentachlorophenol. The IR spectra of the corresponding monomers were recorded for the comparison. The FTIR spectroscopy studies revealed that the polymers formed under potentiodynamic and potentiostatic conditions are of aromatic nature (–C=C– stretching vibrations at 1450–1600 cm^–1), they have ether-linkages (=C—O—C= stretching vibrations at 1100–1300 cm^–1) and quinone groups (–C=O stretching vibrations at 1630–1800 cm^–1 and –C—H out-of-plane bending at 760 cm^–1). The intensities of the hydroxyl group bands in most of the polymers are rather weak compared to those in the corresponding monomers. Vibrations at 2850–2960 cm^–1, which are present in most of the IR spectra of polymers formed under cyclic voltammetry conditions, correspond to the stretching vibrations of the sp³ hybridized C—H bond and suggest that the cleavage of the benzene ring occurs to some extent during electrooxidation–electropolymerization of phenol and its chlorinated derivatives when reaching the potential of oxygen evolution (0.85 V vs SHE).     

Electrodepositing Pt on a Nafion-bonded carbon electrode as a catalyzed electrode for oxygen reduction reaction

The research aims to increase the utilization of platinum (Pt) catalysts and thus to lower the catalyst loadings in the electrode for oxygen reduction reaction (ORR). The electrodeposition of Pt was performed on a rotation disk electrode (RDE) of glass carbon (GC), on which a layer of Nafion-bonded carbon of Vulcan XC 72R was dispersed in advance. The behaviors of Pt RDE and GC RDE in an aqueous solution containing HCl and H₂PtCl₆ were firstly studied. It was found that Pt deposition could be achieved if the electrode potential is controlled below −0.20 V versus (saturated-potassium-chloride silver chloride electrode) SSCE. However, quite a high overpotential is necessary if a quick and apparent deposition were required. Unfortunately, at a high overpotential, the hydrogen evolution would be unavoidable and even accelerated by the formation of nanometer size of Pt particles on the RDE. It was found that it is futile to increase platinum deposits just through extending the deposition time. It was also found that too large deposition current is not helpful for increase of platinum deposition because most of the current was consumed on hydrogen evolution in this case. It has been confirmed that it is conducive to richen Pt ions, present in the form of anionic complex in solution, onto the working electrode to be deposited. It is also helpful to eliminate the hydrogen bubbles formed on the working electrode, i.e., uncatalyzed carbon electrode (UCE), by imposing a positive current on the UCE for a length of time in advance of each cathodic deposition. The potential changes during deposition were recorded. Cyclic voltammograms (CV) of electrodes in 0.5 M H₂SO₄ before and after the deposition were used to assess loading of metal catalysts in a wide range of potential from −0.20 to 1.1 V versus SSCE. The results have shown that the performance of such an electrode with loadings estimated to be 50 μg Pt/cm² is much better than those of a conventional electrode with loadings of 100 μg Pt/cm².     

Effect of microstructure on the electrochemical behavior of Pt/YSZ electrodes

Two types of O₂,Pt/YSZ electrode preparation (Pt/YSZ cermet and sputtered platinum film) have been characterized by SEM and by cyclic voltammetry and chronoamperometry at 450 °C in 20 kPa oxygen. Cyclic voltammetry on the cermet and on the as-sputtered non-porous film electrode evidenced the characteristics of the PtO _x /Pt couple. The corresponding redox reaction occurs at the metal/electrolyte interface and it manifests itself by an anodic wave and one of more cathodic peaks in the voltammogram. Heat treatment of the sputtered electrode at 700 °C in oxygen atmosphere resulted in a porous structure by coalescence of the film. Cyclic voltammetry of the porous film electrode featured the characteristics of the O₂/O²⁻ couple, i.e. the redox reaction of gaseous oxygen occurring at the tpb. Chronoamperometry at anodic potentials showed similar features for both electrode preparations: an initial inhibition, a current peak and a slow activation, the latter being related to the phenomenon of electrochemical promotion of catalysis.