Electrochemical coupling reactions of benzyl halides on a powder cathode and cavity cell

Benzyl halides adsorbed on a cathode made of pure or silver-doped graphite powder were reduced in an undivided cell using an aqueous electrolyte and an inert anode, in the absence or presence of benzaldehyde. The product ratio is influenced by the applied potential, the leaving halide group and presence/absence of silver electrocatalyst. The highest yield of bibenzyl was obtained from the electrolysis of benzyl bromide on silver-doped graphite at a constant potential equal to −1.0 V vs Ag/AgCl (sat. KCl). Benzyl chloride is less prone to dimerization, but undergoes efficient carbonyl addition to benzaldehyde, especially in the presence of silver. The results can be interpreted as a competition of radical and anionic processes.     

Electrocarboxylation of benzyl chlorides at silver cathode at the preparative scale level

The electrocarboxylation of benzyl chlorides to the corresponding carboxylic acids performed at silver cathodes was investigated both theoretically and experimentally in order to find the influence of the operative parameters on the selectivity and on the Faradic efficiency of the process. Theoretical considerations were confirmed by the electrocarboxylation of 1-phenyl-1-chloroethane performed in undivided cells equipped with sacrificial anodes both in a bench-scale electrochemical batch reactor and in a continuous batch recirculation reaction system equipped with a parallel plate electrochemical cell. Selectivity and Faradic yields higher than 80% and 70%, respectively, were obtained by working under anhydrous conditions both under amperostatic and potentiostatic alimentation at appropriate values of either current density or applied potential.     

Cavity microelectrodes for the voltammetric investigation of electrocatalysts: the electroreduction of volatile organic halides on micro-sized silver powders

In this work the use of cavity-microelectrodes is described for the study of the electrocatalytic properties of silver powders in the electroreduction of trichloromethane, taken as model compound. The key role played by the Ag surface status has driven the research towards the use of micro- and nanosized materials, whose exploitation requires the full understanding of the complex behaviour of multiphasial interfaces, and the development of the appropriate investigation methodologies. Moreover, comparison with electrodeposited silver macroelectrodes demonstrates the advantages of using cavity-microelectrodes, especially in terms of improvement of the electrocatalytic activity, insignificance of ohmic drop and double layer capacitance in the voltammetric response, and simplicity offered by the experimental procedure for renovating the electrode material and surface.     

Electrochemical oxidation of alcoholamines at gold

Gold is a good electrocatalyst for alcoholamine oxidation in basic media. In this work the effect of alcoholamine concentration, electrolyte pH and potential scan rate on electrooxidation was studied. The adsorption of alcoholamines on a layer plays a significant role in the oxidation mechanism. The rate determining step of the process was found to be heterogeneous dehydrogenation of the alcoholamine molecule, involving electron transfer to the gold electrode and the formation of water molecule. The catalytic effect of the gold electrode on alcoholamine oxidation is higher than that observed both for aliphatic alcohol and amines.     

Electrochemical behaviour of phenylethanolamine at gold in aqueous solution

The electrooxidation of phenylethanolamine (2-amino-1-phenylethanol) at a gold electrode in alkaline electrolyte has been studied. Measurement of the differential capacitance of the electric double layer versus the electrode potential has shown that the adsorption of phenylethanolamine at the gold-solution interface plays a significant role in the oxidation mechanism. The effect of amine concentration, electrolyte pH and potential scan rate on the electrooxidation is analysed.     

Electrochemical behaviour of benzylamine, 2-phenylethylamine and 4-hydroxyphenylethylamine at gold. A comparative study

The electrooxidation of benzylamine, 2-phenylethylamine and 4-hydroxyphenylethylamine (tyramine) at a gold electrode in contact with an alkaline electrolyte solution was studied. The effect of amine concentration, electrolyte pH and potential scan rate on the electrooxidation was analysed. The adsorption of amines on the gold-solution interface was found to play a significant role in the oxidation mechanism. The rate determining step was the heterogeneous dehydrogenation of the amine molecule, involving electron transfer to the gold electrode and the formation of a water molecule. The catalytic effect of the gold electrode on both benzylamine and 2-phenylethylamine oxidation is higher than that for tyramine.     

Use of silver nanoparticles as an electron transfer facilitator in electrochemical ligand-binding of haemoglobin

Silver nanoparticles have an activity for high intensity electron transfer. They can facilitate the electron transfer from the redox centre of a protein, as a high volume molecule, to the electrode surface. In this study, silver nanoparticles were deposited on the surface of a graphite carbon electrode in the 1 V potential region. Deposition of silver nanoparticles, with a diameter between 70 and 150 nm, was observed on the graphite electrode by transmission electron microscopy (TEM). The results demonstrated that the fine redox waves of haemoglobin could be achieved after modification of the graphite electrode by silver nanoparticles. The cathodic and anodic peaks of haemoglobin were at −135 and +375 mV vs. Ag/AgCl, respectively. The effect of guanosine 3′,5′-triphosphate (GTP), guanosine diphosphate (GDP) and guanosine monophosphate (GMP) on the structure of haemoglobin was investigated. It was observed that GTP shifts the cathodic and anodic peaks positively, indicating the transfer of the haem group to the surface of protein as a reflex of easier oxidation and reduction, while GDP and GMP do not show this behaviour. GTP binds with haemoglobin, while GDP and GMP do not.     

Electrochemical oxidation of glucose on silver nanoparticle-modified composite electrodes

Silver nanoparticle-modified composite electrodes were prepared by electroless forming silver nanoparticles in carbon black dispersed electroless silver plating solution, and then incorporating the silver nanoparticle/carbon black mixture in a polystyrene matrix. The electrooxidation of glucose in 0.1 M NaOH was studied by using cyclic voltammetry. The electrode has surface-confined nanoparicles showing effective catalytic behavior in the studies of glucose oxidation. It showed stepwise electrocatalytic oxidation behavior clearly without suppression by high background redox current caused by inner layer silver of disk-type silver electrodes. Initially the glucose was catalytically oxidized by AgO, and then the reaction glucose oxidation intermediates with Ag₂O were followed stepwisely. Based on the cyclic voltammetric results, pulsed amperometric detection parameters for flow injection analysis were optimized for sensitive detection of glucose.     

Electrochemical oxidation of benzene at a glassy carbon electrode

Benzene oxidation in sulfuric acid at a glassy carbon electrode was investigated using voltammetric, chronoamperometric, and spectroscopic methods. The results are compared with those at a Pt electrode. Benzene was observed to be oxidized to benzoquinone presumably by active oxygen that was adsorbed on the GC electrode in the oxygen evolution region. It is concluded that oxidation at glassy carbon can produce benzoquinone or quinone-like compounds from an aqueous benzene solution. The applied potential for benzene oxidation should be less than 2.1 V vs RHE in order to prevent glassy carbon electrode damage by oxidation during long operation.     

Adsorption of thiourea on monocrystalline silver electrodes in neutral solution

Impedance spectroscopy and radiometric method have been used in the study of thiourea (TU) adsorption on monocrystalline silver electrodes of basal indices: (1 1 1), (1 0 0) and (1 1 0) in neutral solution. The dependence of the surface concentration of TU on the electrode potential and on the bulk concentration was determined for each studied surface. From radiometric measurements it follows that adsorption of TU on silver electrodes takes place in the entire range of applied potentials. The process of adsorption is practically reversible with respect to the electrode potential (in the range of the double layer) and the bulk concentration of TU. Differential capacity of silver electrodes in 0.01 M NaClO₄ solution containing TU of concentrations from 10⁻⁶ to 5 × 10⁻⁴ M has been measured. The isotherms of TU adsorption, determined from the capacitance and radiometric measurements have been compared and the Gibbs energy of adsorption was calculated. The values of limiting surface concentration of adsorbed TU as well as the Gibbs energy of adsorption depend on the plane of Ag electrode and follow the sequence: Ag(1 1 1) > Ag(1 0 0) > Ag(1 1 0) which is in agreement with the surface density of Ag atoms.     

Electrocatalytic carboxylation of chloroacetonitrile at a silver cathode for the synthesis of cyanoacetic acid

The electrocatalytic carboxylation of chloroacetonitrile to cyanoacetic acid performed at silver cathodes was investigated both theoretically and experimentally. Silver exhibits powerful electrocatalytic activities towards the reduction of chloroacetonitrile. In CO₂-saturated CH₃CN, reduction of NCCH₂Cl occurs at potentials that are about 0.7 V more positive than those observed at glassy carbon and gives cyanoacetic acid in good yields. Theoretical considerations on the effect of operative parameters on the performances of the process were confirmed by electrocarboxylation experiments performed in undivided cells equipped with sacrificial anodes both in a bench-scale electrochemical batch reactor and in a continuous batch recirculation reaction system equipped with a parallel plate electrochemical cell. Selectivities and Faradic efficiencies higher than 80% were obtained by working under anhydrous conditions both under amperostatic and potentiostatic alimentation at proper values of either current density or applied potential.     

Electrocatalytic reduction of hydrogen peroxide at nanostructured copper modified electrode

The electrocatalytic reduction of hydrogen peroxide (H₂O₂) has been studied at nanostructured copper (Cu_nano) modified glassy carbon (GC/Cu_nano) electrode in phosphate buffer (pH 7.2). The electrical properties of GC/Cu_nano modified electrodes were studied by electrochemical impedance spectroscopy (EIS). Surface and electrochemical characterization were carried out by using atomic force microscopy (AFM) and cyclic voltammetry. A well-defined H₂O₂ reduction signal, which is due to mediation of a surface active site redox transition exhibits at the GC/Cu_nano electrode. The Cu_nano is acting as a bridge without the aid of any other electron mediator, which enables the direct electron transfer between the modified electrode and the substrate. The results are compared with bulk copper macroelectrode and emphasized the efficiency of the Cu_nano modified electrode. Systematic investigations were made to optimize the experimental parameter, such as applied potential (E_app) for copper electrodeposition. The calibration curve obtained from chronoamperometric studies was found to be linear in the range 0.5 to 8.0 μM H₂O₂ with a detection limit of ca.10 nM (S/N = 3) at the GC/Cu_nano electrode. The modified electrode is stable for 1 week in phosphate buffer after repetitive measurements.     

Electrochemical hydrodehalogenation of polychloromethanes at silver and carbon electrodes

The reductive dehalogenation of CCl₄, CHCl₃, CH₂Cl₂ and CH₃Cl has been investigated by cyclic voltammetry and controlled-potential electrolysis at Ag, glassy carbon (GC) and graphite electrodes in dimethylformamide (DMF) + 0.1 M Et₄NClO₄ in the absence and presence of a proton donor. In particular, the study was focused in the evaluation of the intermediates and final products of the reduction process and how their distribution could be affected by tuning relevant chemical and electrochemical parameters. In general, depending on the value of the applied potential, all polychloromethanes (PCMs) can be partially or completely dechlorinated, methane being exclusively formed in the latter case. The nature of the electrode material and the proton availability of the medium affect drastically the distribution of reduction products. The results point out that at both types of electrode, reduction of PCMs takes place through two competing reaction pathways both leading to methane. One reaction route involves a sequence of reductive dehalogenation steps, with the removal of one chlorine atom at a time, whereas the other is based on hydrogenolysis of carbenes and bypasses the intermediacy of partially dechlorinated PCMs. The presence of a proton source affects substantially the hydrodehalogenation efficiency, enhancing the concentration of intermediate PCMs and the final yield of methane. The silver electrode exhibits an extraordinary electrocatalytic effect resulting in remarkable positive shifts of the reduction potentials of all PCMs with respect to GC. The Ag surface strongly affects the kinetics of the dissociative electron transfer to CH_nCl_(4−n) (n = 0–3) as well as the reactivity of the intermediate radicals, carbanions and carbenes.     

On minimum mass transfer at a sintered metal electrode

Limiting diffusion currents were measured at the inner surface of sintered nickel electrodes sheets and a model adapted from heterogeneous catalysis was used to quantify the minimum mass transfer within the porous material. External mass transport from the bulk electrolyte was induced by rotating a disc facing the sintered nickel disc electrode located at the bottom of a cylinder. Values of the volumetric mass transfer coefficient at two sintered materials were thus obtained. The method and its limitations are discussed.     

Electrochemical behavior of folic acid on mercury meniscus modified silver solid amalgam electrode

Voltammetric behavior of folic acid and folates has been investigated using direct current voltammetry, differential pulse voltammetry and adsorptive stripping differential pulse voltammetry at a mercury meniscus modified silver solid amalgam electrode (m-AgSAE). The optimum conditions have been found for their determination in a 1:9 mixture of methanol and aqueous acetate buffer, with the limit of detection about 0.5 nmol L⁻¹. RSD at this concentration level amounted to less than 4%. Practical applicability of the newly developed method was verified by analysis of three vitamin preparations and of two multivitamin juices.     

Synthesis, characterization and electrocatalytic activity of silver nanorods towards the reduction of benzyl chloride

This paper describes a simple method of synthesizing silver nanorods using the polyol process, where propylene glycol serves both as a reducing agent and as a solvent in the presence of a capping reagent such as polyvinylpyrrolidone (PVP). The diameter and length of silver nanorods could be controlled by changing the AgNO₃/PVP ratio. The end-to-end assembly of the silver nanorods was found. The silver nanorods were characterized by using scanning electron microscopy, transmission electron microscopy, X-ray diffraction and absorption spectroscopy. The catalytic activity of a glassy carbon electrode with Ag nanorods exhibits extraordinary electrocatalytic activities towards the electro-reduction of benzyl chloride.     

Electrochemical synthesis of hydrogen peroxide: Rotating disk electrode and fuel cell studies

The electrochemical reduction of oxygen on various catalysts was studied using the thin-layer rotating disk electrode (RDE) method. High-surface-area carbon was modified with an anthraquinone derivative and gold nanoparticles. Polytetrafluoroethylene (PTFE) and cationic polyelectrolyte (FAA) were used as binders in the preparation of thin-film electrodes. Our primary goal was to find a good electrocatalyst for the two-electron reduction of oxygen to hydrogen peroxide. All electrochemical measurements were carried out in 0.1 M KOH. Cyclic voltammetry was used in order to characterise the surface processes of the modified electrodes in O₂-free electrolyte. The RDE results revealed that the carbon-supported gold nanoparticles are active catalysts for the four-electron reduction of oxygen in alkaline solution. Anthraquinone-modified high-area carbon catalyses the two-electron reduction at low overpotentials, which is advantageous for hydrogen peroxide production.In addition, the polymer electrolyte fuel cell technology was used for the generation of hydrogen peroxide. The cell was equipped with a bipolar membrane which consisted of commercial Nafion 117 as a cation-exchange layer and FT-FAA as an anion-exchange layer. The bipolar membranes were prepared by a hot pressing method. Use of the FAA ionomer as a binder for the anthraquinone-modified carbon catalyst resulted in production of hydrogen peroxide.     

Electrochemical reduction of chromate ions from dilute artificial solutions in a GBC-reactor

Reduction of chromate in very low concentration (20 ppm) has been carried out in a GBC reactor. Final concentrations below 0.5 ppm have been achieved at reasonable reaction rates. Spontaneous reduction of chromate by hydrogen in a GBC reactor without an external power source requires careful selection of cathode material. Chemically stable materials such as titanium and RVC tend to passivate when in contact with chromate solution and are unsuitable for use as cathode materials. Graphite, active carbon and graphite felt show no obvious passivation. Reduction of oxidized groups and oxygen are the major side reactions. These occur significantly, especially when using an activated carbon bed as a cathode.     

相转移催化合成肉桂酸苄酯的研究

探索了以十六烷基三甲基溴化铵为相转移催化剂催化合成肉桂酸苄酯的方法,考察了催化剂、温度、时间和物料配比等因素对反应的影响。实验结果表明：十六烷基三甲基溴化铵是一种有效的催化剂,在最适宜的条件下,产率可达91.7％。最适宜的条件是：肉桂酸钠与氯化苄摩尔比为1：1．3,催化剂的质量为0．6g,反应时间3．0h,反应温度为95℃。产物的结构经IR,^1H NMR和MS表征。     

Using an electrode with renewable surface for study of silver reduction from acid thiourea solutions

Sulfur-containing thiourea (TU) decomposition products exert a considerable effect on the silver electroreduction rate in TU solutions. The technique of removing a thin layer from a metal electrode in-situ at a fixed electrode potential makes it possible to minimize the influence of adsorbed impurities on the rate of the process under study. The values of the exchange current and transfer coefficient for silver reduction from TU solutions have been determined using this technique. Impurities in acid TU solution substantially increase the reduction rate for potentials more positive than about −0.5 V vs. Ag/AgCl.