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Sample records for aqueous electrochemical mechanisms

  1. NEW INSIGTHS ON THE KINETICS AND MECHANISM OF THE ELECTROCHEMICAL OXIDATION OF DICLOFENAC IN NEUTRAL AQUEOUS MEDIUM

    International Nuclear Information System (INIS)

    Cid-Cerón, M.M.; Guzmán-Hernández, D.S.; Ramírez-Silva, M.T.; Galano, A.; Romero-Romo, M.; Palomar-Pardavé, M.

    2016-01-01

    Highlights: • DCF electrochemical oxidation was studied from aqueous solution with a CPE. • Both stagnant and forced convection conditions were considered. • We found DCF electrochemical oxidation is a mass transfer-controlled process. • An EC mechanism was found where the electrodic is quasi-reversible. • C reaction provokes the breaking up the DCF through the nitrogen atom. • DCF diffusion coefficient was experimental and theoretically calculated. - Abstract: The diclofenac (DCF) electrochemical oxidation mechanism was studied through: linear voltammetry (LV), chronoamperometry (CA) sampled-current voltammetry (SCV), potentiostatic coulometry (PC) cyclic voltammetry (CV) under stagnant conditions and linear voltammetry under forced convection conditions (FCLV) over a carbon paste electrode (CPE) from an aqueous medium containing 0.1 M phosphate buffer at pH 7. It was found that the DCF electrochemical oxidation involves an EC mechanism, where the electrochemical reaction is carried out through a one electron-exchange while the chemical reaction involves breaking up the DCF through the nitrogen atom, thereby generating the fragments 2,6 dichloroaniline and 2-(2hydroxyprop-2-enyl)phenol. Reverting the potential scan in the cathodic direction at different scan rates and regardless of its rate, after the oxidation peak, it was found that it was possible to reduce only 38% of the DCF oxidized. The spectrophotometric study carried out during different macro-electrolysis periods allowed observing that the current decrease of the oxidation peak coupled to the DCF absorption (at 270 nm), together with the development of a new spectrophotometric absorption maximum (450 nm), all confirm the EC mechanism proposed. With the use of several experimental techniques (CA, LV and FCLV) and theoretical ones using the Stokes–Einstein approach, the DCF diffusion coefficient was determined, this being in average 8.1 × 10"−"6 cm"2 s"−"1.

  2. Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization

    Science.gov (United States)

    Sulyma, Christopher Michael

    This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used. The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses. For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu

  3. Electrochemical oxidation of 4-morpholinoaniline in aqueous solutions: Synthesis of a new trimer of 4-morpholinoaniline

    International Nuclear Information System (INIS)

    Esmaili, Roya; Nematollahi, Davood

    2011-01-01

    Research highlights: → Electrochemical study of 4-morpholinoaniline in various pHs. → Electrochemical trimerization of 4-morpholinoaniline in aqueous solution. → Green method for the synthesis of '4-morpholinoaniline-trimer'. → Potential-pH diagram for 4-morpholinoaniline. - Abstract: Electrochemical oxidation of 4-morpholinoaniline has been studied in various pHs using cyclic voltammetry and controlled-potential coulometry. The electrochemical trimerization of 4-morpholinoaniline is described and its mechanism has been studied in aqueous solution. This method provides a green, reagent-less, and environmentally friendly procedure with high atom economy, for the synthesis of '4-morpholinoaniline-trimer' using a carbon electrode in an undivided cell in good yield and purity.

  4. Tailoring the Electrochemical and Mechanical Properties of PEDOT:PSS Films for Bioelectronics

    KAUST Repository

    Elmahmoudy, Mohammed

    2017-02-21

    The effect of 3-glycidoxypropyltrimethoxysilane (GOPS) content in poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) dispersions on the properties of films spun cast from these formulations is investigated. It has been found out that the concentration of GOPS has a tremendous, yet gradual impact on the electrical, electrochemical, and mechanical properties of the PEDOT:PSS/GOPS films and that there is an optimum concentration which maximizes a particular feature of the film such as its water uptake or elasticity. The benefits of aqueous stability and mechanical strength with GOPS are to be compensated by an increase in the electrochemical impedance. GOPS aids obtaining excellent mechanical integrity in aqueous media with still highly conducting properties. Moreover, active devices like organic electrochemical transistors that contain 1 wt% GOPS, which is a concentration that leads to film with high electrical conductivity with sufficient mechanical stability and softness, exhibit steady performance over three weeks. These results suggest that variations in the concentration of such an additive like GOPS can enable a facile co-optimization of electrical and mechanical properties of a conducting polymer film for in vivo bioelectronics application.

  5. Technetium electrodeposition from aqueous formate solutions at graphite electrode: electrochemical study

    International Nuclear Information System (INIS)

    Maslennikov, A.; Peretroukhine, V.; Masson, M.; Lecomte, M.

    1999-01-01

    Recovery of technetium from aqueous formate buffer solutions of ionic strength μ = 1.0 was studied in the pH interval from 1.6 to 7.5 at graphite cathode in an electrolytic cell with separated compartments was studied, using cyclic voltammetry (CV) and inverse stripping voltammetry (ISV) techniques. It has been shown that Tc electrodeposition process becomes possible at the potentials of graphite cathode E cath. 1/2 = -0.72±0.02 V/SCE and was pH independent in the interval pH = 3.46-7.32. Mechanism of electrodeposition, including Tc(VII)/Tc(IV) reduction in the solution followed by Tc(IV) hydrolysis at the electrode surface with formation of hydrated Tc oxide cathodic deposit has been proposed. The further precision of the Tc(VII) electrochemical reduction mechanism in formate buffer media and optimization of the electrodeposition process seems to be possible using additional analytical facilities except electrochemical methods. (orig.)

  6. ELECTROCHEMICAL BEHAVIOUR OF METHYLENE BLUE IN NON-AQUEOUS SOLVENTS

    International Nuclear Information System (INIS)

    Caram, J.A.; Suárez, J.F. Martínez; Gennaro, A.M.; Mirífico, M.V.

    2015-01-01

    Graphical abstract: Display Omitted - Highlights: • The dye is electro-reduced in two separated monoelectronic charge transfers. • Solvent/supporting electrolyte/acid/base modifies the electrochemical parameters. • A dissociation equilibrium of the dye in non-aqueous solvent is proposed. • The electro-generated and stable dye-radical is also chemically produced in EDA or KOH/DMF. • A new species is reversibly formed in KOH/EtOH or ACN. - Abstract: The electrochemical behaviour of methylene blue in solution of non-aqueous solvents with different supporting electrolytes was studied by cyclic voltammetry. Dye electro-reduction presents two well-defined processes of monoelectronic charge transfer yielding a free radical in the first process and an anion in the second electron transfer. Free radical and anion are long living species in some of the studied media. Effects of supporting electrolyte and solvent on the peak potentials, the peak current functions and the reversibility of the charge transfer processes are reported. A dissociation equilibrium of the dye in solution of non-aqueous solvents and the acid or base added determine markedly the electrochemical responses. In the particular cases of KOH/DMF or EDA basic media the chemical formation of the stable methylene blue radical was detected and it was characterized by EPR spectroscopy. A general reaction scheme is proposed

  7. Opto-electrochemical spectroscopy of metals in aqueous solutions

    International Nuclear Information System (INIS)

    Habib, K.

    2016-01-01

    In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the electrical resistance of aluminium samples during the initial stage of anodisation processes in aqueous solution. In fact, because the resistance values in this investigation were obtained by holographic interferometry, electromagnetic method rather than electronic method, the abrupt rate change of the resistance was called electrical resistance–emission spectroscopy. The anodisation process of the aluminium samples was carried out by electrochemical impedance spectroscopy (EIS) in different sulphuric acid concentrations (1.0%–2.5% H 2 SO 4 ) at room temperature. In the meantime, the real time holographic interferometry was used to determine the difference between the electrical resistance of two subsequent values, dR, as a function of the elapsed time of the EIS experiment for the aluminium samples in 1.0%, 1.5%, 2.0%, and 2.5% H 2 SO 4 solutions. The electrical resistance–emission spectra of the present investigation represent a detailed picture of not only the rate change of the electrical resistance throughout the anodisation processes but also the spectra represent the rate change of the growth of the oxide films on the aluminium samples in different solutions. As a result, a new spectrometer was developed based on the combination of the holographic interferometry and electrochemical impedance spectroscopy for studying in situ the electrochemical behavior of metals in aqueous solutions.

  8. Electrosynthesis of Clozapine Drug Derivative via an EC Electrochemical Mechanism

    Directory of Open Access Journals (Sweden)

    Esmail Tammari

    2017-12-01

    Full Text Available The fact that oxidation, as one of the main routes of phase I metabolism of drugs, follows by conjugation reactions, and also formation of nitrenium ion as one of the clozapine oxidation products, directed us to investigate the oxidation of clozapine (CLZ in the presence of nucleophile. The oxidation of clozapine (CLZ has been studied on a glassy carbon electrode in the absence and presence of 2-thiobarbituric acid (TBA as nucleophile in aqueous medium by means of cyclic voltammetry and on the graphite rods in controlled-potential coulometry. Cyclic voltammetry studies were realized for CLZ in the pHs 1.0 to 8.0. Results indicate that the electrochemical behavior of CLZ depends on the pH. Based on the obtained electrochemical results, an ECE mechanism was proposed to explain the electrochemical oxidation of CLZ. The results revealed that oxidized CLZ participates in Michael type addition reaction with TBA and via an EC mechanism converts to the corresponding new dibenzodiazepin derivatives. The product has been characterized by IR, 1H NMR, 13C NMR and MS.

  9. Electrochemical deposition of coatings of highly entropic alloys from non-aqueous solutions

    Directory of Open Access Journals (Sweden)

    Jeníček V.

    2016-03-01

    Full Text Available The paper deals with electrochemical deposition of coatings of highly entropic alloys. These relatively new materials have been recently intensively studied. The paper describes the first results of electrochemical coating with highly entropic alloys by deposition from non-aqueous solutions. An electrochemical device was designed and coatings were deposited. The coatings were characterised with electronic microscopy scanning, atomic absorption spectrometry and X-ray diffraction methods and the combination of methods of thermic analysis of differential scanning calorimetry and thermogravimetry.

  10. Electrochemical mechanism of uranium mononitride dissolution in aqueous solutions of nitric acid

    Energy Technology Data Exchange (ETDEWEB)

    Ershov, Boris G. [Russian Academy of Sciences, Moscow (Russian Federation). Frumkin Inst. of Physical Chemistry and Electrochemistry

    2017-09-01

    It was shown that the dissolution of UN with metallic conduction follows an electrochemical mechanism when it proceeds in contact with an electrically conductive medium (HNO{sub 3} solution). According to this mechanism, the oxidation of UN (at the anode) passes an electron into the UN matrix, which is a conductor, and can then reduce nitric acid in a parallel reaction a short distance away at another exposed surface of the UN (at the cathode). As a result, the reduction of HNO{sub 3} affords NO and NO{sub 2}, while oxidation of uranium mononitride affords NH{sub 3}, N{sub 2}, and N{sub 2}O. The occurrence of these two separate processes accounts for the composition and yields of the products formed from UN and HNO{sub 3} as well as for the nitrogen isotope distribution between them when UN and HNO{sub 3} were labeled with {sup 14} N or {sup 15}N. A mathematical equation describing the dependence of N{sub 2} and N{sub 2}O yields on HNO{sub 3} concentration was derived. It was also shown that the calculated value of standard electromotive force of the galvanic pair formed on the UN surface during its dissolution in HNO{sub 3} is high enough to initiate and support the electrochemical mechanism of its dissolution in nitric acid.

  11. Electrochemical polymerization of furfural on a platinum electrode in aqueous solutions of potassium biphthalate

    Directory of Open Access Journals (Sweden)

    Jorge Luiz Joaquim Hallal

    2005-03-01

    Full Text Available Three different electrochemical methods confirm the growth processes of polyfurfural on platinum electrodes in aqueous solutions. The electrochemical oxidative polymerization of furfural occurs only with 0.10 mol L-1 potassium biphthalate as the supporting electrolyte. Electrochemical and spectroscopic methods are employed to characterize the polymeric film produced. Based on spectroscopic data, a polymeric structure involving furfural and biphthalate anions is discussed.

  12. Conductivity and electrochemical stability of concentrated aqueous choline chloride solutions

    Science.gov (United States)

    Grishina, E. P.; Kudryakova, N. O.

    2017-10-01

    The conductivity and electrochemical stability of choline chloride (ChCl) solutions with water contents ranging from 20 to 39 wt % are studied. Exposing ChCl to moist ambient air yields a highly concentrated aqueous solution that, as an electrolyte, exhibits the properties and variations in conductivity with temperature and concentration characteristic of other similar systems. Its electrochemical stability window, determined by cyclic voltammetry, is comparable to that of ChCl-based deep eutectic solvents (DESs). Products of the electrolysis of ChCl‒H2O mixtures seem to be less toxic than those of Reline, Ethaline, and Maline.

  13. Electrochemical studies on nanometal oxide-activated carbon composite electrodes for aqueous supercapacitors

    Science.gov (United States)

    Ho, Mui Yen; Khiew, Poi Sim; Isa, Dino; Chiu, Wee Siong

    2014-11-01

    In present study, the electrochemical performance of eco-friendly and cost-effective titanium oxide (TiO2)-based and zinc oxide-based nanocomposite electrodes were studied in neutral aqueous Na2SO3 electrolyte, respectively. The electrochemical properties of these composite electrodes were studied using cyclic voltammetry (CV), galvanostatic charge-discharge (CD) and electrochemical impedance spectroscopy (EIS). The experimental results reveal that these two nanocomposite electrodes achieve the highest specific capacitance at fairly low oxide loading onto activated carbon (AC) electrodes, respectively. Considerable enhancement of the electrochemical properties of TiO2/AC and ZnO/AC nanocomposite electrodes is achieved via synergistic effects contributed from the nanostructured metal oxides and the high surface area mesoporous AC. Cations and anions from metal oxides and aqueous electrolyte such as Ti4+, Zn2+, Na+ and SO32- can occupy some pores within the high-surface-area AC electrodes, forming the electric double layer at the electrode-electrolyte interface. Additionally, both TiO2 and ZnO nanoparticles can provide favourable surface adsorption sites for SO32- anions which subsequently facilitate the faradaic processes for pseudocapacitive effect. These two systems provide the low cost material electrodes and the low environmental impact electrolyte which offer the increased charge storage without compromising charge storage kinetics.

  14. CEC mechanism in electrochemical oxidation of nitrocatechol-boric acid complexes

    International Nuclear Information System (INIS)

    Rafiee, Mohammad; Nematollahi, Davood; Salehzadeh, Hamid

    2011-01-01

    Graphical abstract: Display Omitted Highlights: → Nitrochetechol and its anionic form undergo complex reaction with boric acid. → The electron transfer of complex is coupled with both proceeding and following chemical reactions. → Electrochemical behavior of complex is resolved by diagnostic criteria and digital simulation. - Abstract: The electrochemical behavior of nitrocatechols-boric acid complexes in aqueous solution has been studied using cyclic voltammetry. The results indicate that nitrocatechol-boric acid complex derivatives are involved in the CEC mechanism. In this work, the impact of empirical parameters on the shape of the voltammograms is examined based on a CEC mechanism. In addition, homogeneous rate constants of both the preceding and the following reactions were estimated by comparing the experimental cyclic voltammograms with the digitally simulated results. The calculated dissociation constants for the complexes (K d ) and for ring cleavage of nitroquinone (k f2 ) were found to vary in the following order: 4-nitrocatechol > 3-methylnitrocatechol > 3-metoxynitrocatechol.

  15. A Review for Aqueous Electrochemical Supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Cuimei [Key Laboratory of Preparation and Applications of Environmental Friendly Materials, Ministry of Education, College of Chemistry, Jilin Normal University, Siping (China); Zheng, Weitao, E-mail: wtzheng@jlu.edu.cn [Department of Materials Science, Key Laboratory of Mobile Materials, Ministry of Education and State Key Laboratory of Superhard Materials, Jilin University, Changchun (China)

    2015-05-08

    Electrochemical capacitor is the most promising energy-storage device that can meet the demands of high-power supply and long cycle life; however, low-energy density and high-fabrication cost limit its further development. Researchers have paid more attention to the development of electrode material in the past, and very few people attach importance to the research of the electrolyte, especially the redox electrolyte, which is important for improving specific capacitance greatly. This paper presents a review of the research in not only electrode material but also redox aqueous electrolyte and together with an important part of supercapacitor device. The advantages and disadvantages for different electrode material and electrolyte are discussed. And the new trends in supercapacitor development are also summarized.

  16. A Review for Aqueous Electrochemical Supercapacitors

    International Nuclear Information System (INIS)

    Zhao, Cuimei; Zheng, Weitao

    2015-01-01

    Electrochemical capacitor is the most promising energy-storage device that can meet the demands of high-power supply and long cycle life; however, low-energy density and high-fabrication cost limit its further development. Researchers have paid more attention to the development of electrode material in the past, and very few people attach importance to the research of the electrolyte, especially the redox electrolyte, which is important for improving specific capacitance greatly. This paper presents a review of the research in not only electrode material but also redox aqueous electrolyte and together with an important part of supercapacitor device. The advantages and disadvantages for different electrode material and electrolyte are discussed. And the new trends in supercapacitor development are also summarized.

  17. A review for aqueous electrochemical supercapacitors

    Directory of Open Access Journals (Sweden)

    Cuimei eZhao

    2015-05-01

    Full Text Available Electrochemical capacitor is the most promising energy storage device that can meet the demands of high power supply and long cycle life, however low energy density and high fabrication cost limit its further development. Researchers have paid more attention to the development of electrode material in the past, and very few people attach importance to the research of the electrolyte, especially the redox electrolyte, which is important for improving specific capacitance greatly. This paper presents a review of the research in not only electrode material but also redox aqueous electrolyte and together with an important part of supercapacitor device. The advantages and disadvantages for different electrode material and electrolyte are discussed. And the new trends in supercapacitor development are also summarized.

  18. Electrochemical reactions of uranyl(VI) complexes in aqueous solution, non-aqueous solvents, and ionic liquids

    International Nuclear Information System (INIS)

    Ikeda, Yasuhisa

    2006-01-01

    Author's recent experimental results on the chemistry of U(V) in aqueous solution, non-aqueous solvents, and ionic solvents by cyclic voltametry are described. The U(V) was produced by electrochemical reduction of uranyl U(VI) ions or complexes such as carbonates, DMF(N, N-dimethylformamide), DMSO(dimethylsulfoxide), acetylacetonato, and other organic polydental ligands. The produced U(V) complexes were studied by spectrophotometry using optical-transmission thin-layer electrode. The U(V) complexes in non-aqueous solvents were found to be rather stable, they undergo ligand-dissociation reaction but not disproportionation reaction. The structure and electronic spectra as well as IR spectra of the complexes were studied. The present method was further developed to study the behavior of U(V) complexes in ionic liquids as molten salts, e.g., alkaline metals chlorides. Thus, the present research contributes to understanding the chemistry of 5fl system. Application to such nuclear technology as spent fuel reprocessing is discussed. (S. Ohno)

  19. A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO2to CO

    KAUST Repository

    Rasul, Shahid; Anjum, Dalaver H.; Jedidi, Abdesslem; Minenkov, Yury; Cavallo, Luigi; Takanabe, Kazuhiro

    2014-01-01

    The challenge in the electrochemical reduction of aqueous carbon dioxide is in designing a highly selective, energy-efficient, and non-precious-metal electrocatalyst that minimizes the competitive reduction of proton to form hydrogen during aqueous

  20. Self-discharge of AC/AC electrochemical capacitors in salt aqueous electrolyte

    International Nuclear Information System (INIS)

    García-Cruz, L.; Ratajczak, P.; Iniesta, J.; Montiel, V.; Béguin, F.

    2016-01-01

    The self-discharge (SD) of electrochemical capacitors based on activated carbon electrodes (AC/AC capacitors) in aqueous lithium sulfate was examined after applying a three-hour cell potential hold at U i values from 1.0 to 1.6 V. The leakage current measured during the potentiostatic period as well as the amplitude of self-discharge increased with U i ; the cell potential drop was approximately doubled by 10 °C increase of temperature. The potential decay of both negative and positive electrodes was explored separately, by introducing a reference electrode and it was found that the negative electrode contributes essentially to the capacitor self-discharge. A diffusion-controlled mechanism was found at U i ≤ 1.4 V and U i ≤ 1.2 V for the positive and negative electrodes, respectively. At higher U i of 1.6 V, both electrodes display an activation-controlled mechanism due to water oxidation and subsequent carbon oxidation at the positive electrode and water or oxygen reduction at the negative electrode.

  1. Electrochemical characterization of single-walled carbon nanotubes for electrochemical double layer capacitors using non-aqueous electrolyte

    International Nuclear Information System (INIS)

    Ruch, P.W.; Koetz, R.; Wokaun, A.

    2009-01-01

    Single-walled carbon nanotubes (SWCNTs) were investigated by cyclic voltammetry and electrochemical impedance spectroscopy in a non-aqueous electrolyte, 1 M Et 4 NBF 4 in acetonitrile, suitable for supercapacitors. Further, in situ dilatometry and in situ conductance measurements were performed on single electrodes and the results compared to an activated carbon, YP17. Both materials show capacitive behavior characteristic of high surface area electrodes for supercapacitors, with the maximum full cell gravimetric capacitance being 34 F/g for YP17 and 20 F/g for SWCNTs at 2.5 V with respect to the total active electrode mass. The electronic resistance of SWCNTs and activated carbon decreases significantly during charging, showing similarities of the two materials during electrochemical doping. The SWCNT electrode expands irreversibly during the first electrochemical potential sweep as verified by in situ dilatometry, indicative of at least partial debundling of the SWCNTs. A reversible periodic swelling and shrinking during cycling is observed for both materials, with the magnitude of expansion depending on the type of ions forming the double layer.

  2. Optimisation and application of electrochemical techniques for high temperature aqueous environments

    International Nuclear Information System (INIS)

    Bojinov, M.; Laitinen, B. T.; Maekelae, K.; Maekelae, M; Saario, T.; Sirkiae, P.; Beverskog, B.

    1999-01-01

    Different localised corrosion phenomena may pose a serious hazard to construction materials employed in high-temperature aqueous environments. The operating temperatures in electric power production have been increased to improve plant efficiencies. This has lead to the demand for new, further improved engineering materials. The applicability of these materials in the operating power plant environments largely depends on the existence of a protective surface oxide film. Extensive rupture of these films can lead to increased reaction of the underlying metal with environment. Therefore by modifying the composition of the base metal the properties of the surface oxides can be optimised to withstand the new operational environments of interest. To mitigate the risk of detrimental corrosion phenomena of structural materials, mechanistic understanding of the contributing processes is required. This calls for more experimental information and necessitates the development of new experimental techniques and procedures capable of operating in situ in high temperature aqueous environments. The low conductivity of the aqueous medium complicates electrochemical studies on construction and fuel cladding materials carried out in simulated LWR coolant conditions or in actual plant conditions, especially in typical BWR environments. To obtain useful information of reactions and transport processes occurring on and within oxide films on different materials, an electrochemical arrangement based on a thin-layer electrode (TLEC) concept was developed. In this presentation the main results are shown from work carried out to optimise further the geometry of the TLEC arrangement and to propose recommendations for how to use this arrangement in different low-conductivity environments. Results will be also given from the test in which the TLEC arrangement was equipped with a detector electrode. The detector electrode allows detecting soluble products and reaction intermediates at

  3. Electrochemical behavior of nanostructured MnO2/C (Vulcan® composite in aqueous electrolyte LiNO3

    Directory of Open Access Journals (Sweden)

    Vujković Milica

    2011-01-01

    Full Text Available The electrolytic solutions of contemporary Li-ion batteries are made exclusively with the organic solvents since anodic materials of these batteries have potentials with greater negativity than the potential of the water reduction, thus the organic electrolytes can withstand the voltages of 3-5 V that are characteristic for these batteries. Ever since it was discovered that some materials can electrochemically intercalate and deintercalate Li+ ions in aqueous solutions, numerous studies have been conducted with the aim of extending operational time of the aqueous Li-ion batteries. Manganese oxide has been studied as the electrode material in rechargeable lithium-ion batteries with organic electrolytes. In this paper its electrochemical behavior as an anode material in aqueous electrolyte solutions was examined. MnO2 as a component of nanodispersed MnO2/C (Vulcan® composite was successfully synthesized hydrothermally. Electrochemical properties of this material were investigated in aqueous saturated LiNO3 solution by both cyclic voltammetry and galvanostatic charging/discharging (LiMn2O4 as cathode material techniques. The obtained composite shows a relatively good initial discharge capacity of 96.5 mAh/g which, after 50th charging/discharging cycles, drops to the value of 57mAh/g. MnO2/C (Vulcan® composite, in combination with LiMn2O4 as a cathode material, shows better discharge capacity compared to other anodic materials used in aqueous Li-ion batteries according to certain studies that have been conducted. Its good reversibility and cyclability, and the fact that hydrothermal method is simple and effective, makes MnO2/C(Vulcan® composite a promising anodic material for aqueous Li-ion batteries.

  4. Study of the aqueous synthesis, optical and electrochemical characterization of alloyed Zn{sub x}Cd{sub 1-x}Te nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Matos, Charlene Regina Santos [Postgraduate Program in Materials Science and Engineering, Federal University of Sergipe, São Cristóvão, SE (Brazil); Candido, Luan P.M.; Souza, Helio Oliveira [Department of Chemistry, Federal University of Sergipe, São Cristóvão, SE (Brazil); Pereira da Costa, Luiz [Institute of Technology and Research (ITP), Tiradentes University, Aracaju, SE (Brazil); Sussuchi, Eliana Midori [Department of Chemistry, Federal University of Sergipe, São Cristóvão, SE (Brazil); Gimenez, Iara F., E-mail: gimenez@ufs.br [Postgraduate Program in Materials Science and Engineering, Federal University of Sergipe, São Cristóvão, SE (Brazil); Department of Chemistry, Federal University of Sergipe, São Cristóvão, SE (Brazil); Postgraduate Program in Chemistry, Federal University of Sergipe, São Cristóvão, SE (Brazil)

    2016-08-01

    The effects of experimental factors such as initial reaction pH, capping ligand, and heating method on the optical and electrochemical properties of aqueous alloyed Zn{sub x}Cd{sub 1-x}Te nanocrystals were evaluated. Here the type of capping ligand (glutathione GSH and 3-mercaptopropionic acid MPA) was found to be the most significant factor in controlling the range of photoluminescence emission. Also a pronounced pH effect on the emission wavelength has been verified in the presence of GSH, in contrast to MPA for which only a minor pH effect was observed. The heating method (microwave or hydrothermal) was found to be irrelevant for the emission wavelength at the conditions studied. The electrochemical characterization in aqueous medium (cyclic voltammetry and differential pulse voltammetry) evidenced a good correlation between electrochemical and optical band gap values and allowed estimation of band edge positions. - Highlights: • ZnCdTe quantum dots were obtained by aqueous synthesis. • Nature of capping ligand was the most relevant factor. • Optical and electrochemical band gaps were well correlated.

  5. Kinetic mechanism for modeling of electrochemical reactions.

    Science.gov (United States)

    Cervenka, Petr; Hrdlička, Jiří; Přibyl, Michal; Snita, Dalimil

    2012-04-01

    We propose a kinetic mechanism of electrochemical interactions. We assume fast formation and recombination of electron donors D- and acceptors A+ on electrode surfaces. These mediators are continuously formed in the electrode matter by thermal fluctuations. The mediators D- and A+, chemically equivalent to the electrode metal, enter electrochemical interactions on the electrode surfaces. Electrochemical dynamics and current-voltage characteristics of a selected electrochemical system are studied. Our results are in good qualitative agreement with those given by the classical Butler-Volmer kinetics. The proposed model can be used to study fast electrochemical processes in microsystems and nanosystems that are often out of the thermal equilibrium. Moreover, the kinetic mechanism operates only with the surface concentrations of chemical reactants and local electric potentials, which facilitates the study of electrochemical systems with indefinable bulk.

  6. Electrochemically induced transformation of NiS nanoparticles into Ni(OH)2 in KOH aqueous solution toward electrochemical capacitors

    International Nuclear Information System (INIS)

    Hou Linrui; Yuan Changzhou; Li Diankai; Yang Long; Shen Laifa; Zhang Fang; Zhang Xiaogang

    2011-01-01

    Highlights: → NiS is synthesized by means of the H 2 O/CS 2 interface under hydrothermal treatment. → NiS itself owns poor electrochemical capacitance in 2 M KOH solution. → NiS is electrochemically induced and transformed into electroactive Ni(OH) 2 . → Ni(OH) 2 is responsible for good energy storage of the NiS in the KOH solution. → The new formed Ni(OH) 2 delivers large energy density at high rates. - Abstract: Nickel sulfide nanoparticles (NPs) are first synthesized by virtue of a unique H 2 O/CS 2 interface under mild hydrothermal treatment. Electrochemical data reveals that the as-synthesized NiS NPs themselves own poor supercapacitive behavior at initial cyclic voltammetry (CV) cycles in 2 M KOH solution, while a specific capacitance of 893 F g -1 can be surprisingly obtained at a current density of 5 A g -1 just after continuous 320 CV cycles. X-ray diffraction and Fourier transform infrared techniques demonstrate that what is really responsible for the good electrochemical capacitance in the KOH aqueous solution is the new electrochemically formed Ni(OH) 2 phase, rather than NiS NPs themselves. The Ni(OH) 2 is slowly formed during the continuous CV cycling process, in which the electrochemically induced phase transformation from NiS to Ni(OH) 2 phase takes place. Furthermore, the new Ni(OH) 2 phase demonstrates the great ability of delivering large specific capacitance at high rates.

  7. Relationship between structural properties and electrochemical characteristics of monolithic carbon xerogel-based electrochemical double-layer electrodes in aqueous and organic electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Zeller, Mario [Bavarian Center for Applied Energy Research e.V. (ZAE Bayern), Wuerzburg (Germany); Institute of Radiology, University Clinic, University of Wuerzburg (Germany); Lorrmann, Volker; Reichenauer, Gudrun; Wiener, Matthias [Bavarian Center for Applied Energy Research e.V. (ZAE Bayern), Wuerzburg (Germany); Pflaum, Jens [Bavarian Center for Applied Energy Research e.V. (ZAE Bayern), Wuerzburg (Germany); Department of Experimental Physics VI, Julius-Maximilians-University of Wuerzburg (Germany)

    2012-05-15

    The impact of the micropore width, external surface area, and meso-/macropore size on the charging performance of electrochemical double-layer capacitor (EDLC) electrodes is systematically investigated. Nonactivated carbon xerogels are used as model electrodes in aqueous and organic electrolytes. Monolithic porous model carbons with different structural parameters are prepared using a resorcinol-formaldehyde-based sol-gel process and subsequent pyrolysis of the organic precursors. Electrochemical properties are characterized by utilizing them as EDLC half-cells operated in aqueous and organic electrolytes, respectively. Experimental data derived for organic electrolytes reveals that the respective ions cannot enter the micropores within the skeleton of the meso- and macroporous carbons. Therefore the total capacitance is limited by the external surface formed by the interface between the meso-/macropores and the microporous carbon particles forming the xerogel skeleton. In contrast, for aqueous electrolytes the total capacitance solely depends on the total surface area, including interfaces at the micropore scale. For both types of electrolytes the charging rate of the electrodes is systematically enhanced when increasing the diameter of the carbon xerogel particles from 10 to 75 nm and the meso-/macropore size from 10 to 121 nm. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Electrochemical corrosion study of Mg–Al–Zn–Mn alloy in aqueous ethylene glycol containing chloride ions

    Directory of Open Access Journals (Sweden)

    Harish Medhashree

    2017-01-01

    Full Text Available Nowadays most of the automobiles use magnesium alloys in the components of the engine coolant systems. These engine coolants used are mainly composed of aqueous ethylene glycol along with some inhibitors. Generally the engine coolants are contaminated by environmental anions like chlorides, which would enhance the rate of corrosion of the alloys used in the coolant system. In the present study, the corrosion behavior of Mg–Al–Zn–Mn alloy in 30% (v/v aqueous ethylene glycol containing chloride anions at neutral pH was investigated. Electrochemical techniques, such as potentiodynamic polarization method, cyclic polarization and electrochemical impedance spectroscopy (EIS were used to study the corrosion behavior of Mg–Al–Zn–Mn alloy. The surface morphology, microstructure and surface composition of the alloy were studied by using the scanning electron microscopy (SEM, optical microscopy and energy dispersion X-ray (EDX analysis, respectively. Electrochemical investigations show that the rate of corrosion increases with the increase in chloride ion concentration and also with the increase in medium temperature.

  9. Material removal mechanisms in electrochemical-mechanical polishing of tantalum

    International Nuclear Information System (INIS)

    Gao, F.; Liang, H.

    2009-01-01

    Material removal mechanisms in tantalum chemical-mechanical polishing (CMP) and electrochemical-mechanical polishing (ECMP) were investigated using the single frequency electrochemical impedance spectroscopy (EIS). Through measuring the impedance of the tantalum surface, the single frequency EIS scan made it possible to observe the CMP and ECMP processes in situ. The impedance results presented competing mechanisms of removal and formation of a surface oxide layer of tantalum. Analysis indicated that the thickness of the oxide layer formed during polishing was related to the mechanical power correlated to the friction force and the rotating speed. Furthermore, the rate of growth and removal of the oxide film was a function of the mechanical power. This understanding is beneficial for optimization of CMP and ECMP processes.

  10. Electrochemical oxidation of loop diuretic furosemide in aqueous acid medium and its analytical application

    Directory of Open Access Journals (Sweden)

    Shikandar D. Bukkitgar

    2016-12-01

    Full Text Available An investigation of oxidative–reductive mechanisms of pharmaceutically important molecules gives us information about the metabolic fact of targeted drug. As compared to recent ongoing, time-consuming and costly techniques, there is an urgent needing for development of a sensitive technique, which can help easy understanding of these pathways. Therefore, in the present work, an effective, low-cost and time-saving technique to investigate the reaction mechanism of furosemide in aqueous acid medium is attempted. Furosemide undergoes two-proton and two-electron transfer reaction. The product obtained was analysed by UV spectra. It was found that the chemical oxidation and electrochemical oxidation of furosemide follows two different pathways. In addition, an effective technique has been developed to determine furosemide in its trace level. Good recoveries and low detection limit accomplished the magnitude of the proposed method. The proposed method was adopted for furosemide determination in human urine and pharmaceutical samples.

  11. High Energy Density Aqueous Electrochemical Capacitors with a KI-KOH Electrolyte.

    Science.gov (United States)

    Wang, Xingfeng; Chandrabose, Raghu S; Chun, Sang-Eun; Zhang, Tianqi; Evanko, Brian; Jian, Zelang; Boettcher, Shannon W; Stucky, Galen D; Ji, Xiulei

    2015-09-16

    We report a new electrochemical capacitor with an aqueous KI-KOH electrolyte that exhibits a higher specific energy and power than the state-of-the-art nonaqueous electrochemical capacitors. In addition to electrical double layer capacitance, redox reactions in this device contribute to charge storage at both positive and negative electrodes via a catholyte of IOx-/I- couple and a redox couple of H2O/Had, respectively. Here, we, for the first time, report utilizing IOx-/I- redox couple for the positive electrode, which pins the positive electrode potential to be 0.4-0.5 V vs Ag/AgCl. With the positive electrode potential pinned, we can polarize the cell to 1.6 V without breaking down the aqueous electrolyte so that the negative electrode potential could reach -1.1 V vs Ag/AgCl in the basic electrolyte, greatly enhancing energy storage. Both mass spectroscopy and Raman spectrometry confirm the formation of IO3- ions (+5) from I- (-1) after charging. Based on the total mass of electrodes and electrolyte in a practically relevant cell configuration, the device exhibits a maximum specific energy of 7.1 Wh/kg, operates between -20 and 50 °C, provides a maximum specific power of 6222 W/kg, and has a stable cycling life with 93% retention of the peak specific energy after 14,000 cycles.

  12. Understanding of electrochemical and structural changes of polypyrrole/polyethylene glycol composite films in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Pirvu, Cristian, E-mail: c_pirvu@chim.pub.ro [University Polytechnic of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7 Polizu, 011061 Bucharest (Romania); Manole, Claudiu Constantin; Stoian, Andrei Bogdan; Demetrescu, Ioana [University Polytechnic of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7 Polizu, 011061 Bucharest (Romania)

    2011-11-30

    Highlights: > Electrochemical monitoring of PPy and PPy-PEG films over immersion time. > Electrochemical and surface analysis showed that PEG improves the stability of PPy films. > Mott-Schottky analysis reveals p-type conductance for both films. > In situ AFM analysis sustains electrochemical behaviour. > A model of PPy and PPy-PEG films behaviour during immersion was elaborated. - Abstract: Electrochemical monitoring of electrical and structural changes of both PPy and PPy-PEG films electrochemical deposited, in order to highlight if the structural stability offered by PEG has an influence on electrical properties and stability in aqueous solution over immersion time was investigated. Electrochemical analysis suggests that PPy-PEG film inserts cations easier than PPy film for a short immersion time probably due to ability of PEG to form complexes with metal cations. The FTIR spectra showed that the PEG incorporation decreases the rate of PPy overoxidation probably by restraining the electron release and by rendering O{sub 2} inaccessible to PPy. Mott-Schottky analysis based on capacitance measurement reveal p-type conductance for both films. The in situ AFM analysis sustains electrochemical behaviour and has permitted elaboration of a model of PPy and PPy-PEG films behaviour during immersion in testing solution.

  13. Influence of aqueous phase on electrochemical biocorrosion tests in diesel/water systems

    Energy Technology Data Exchange (ETDEWEB)

    Bento, F.M. [Dept. of Soils, Faculty of Agronomy, UFRGS, 7712 Bento Goncalves Avenue, CEP: 91540-001, POA, RS (Brazil); Englert, G.E.; Muller, I.L. [Dept. of Metallurgy, Biocorrosion and Biofilms Lab, UFRGS, 99 Osvaldo Aranha Avenue s.615D, CEP: 90035-190, POA, RS (Brazil); Gaylarde, C.C. [Dept. of Biophisics, UFRGS POA, RS (Brazil)

    2004-08-01

    Storage tanks containing microbially contaminated diesel oil are susceptible to corrosion. This process may be evaluated electrochemically in the laboratory using simulated storage systems containing diesel oil and an aqueous phase. The simulated aqueous phase must supply mineral nutrients for microbial growth, together with adequate electrical conductivity, without, however, being too corrosive, so as to allow the aggressive nature of the microbial metabolites to be detected. In this investigation, microbial growth was measured in six electrically conductive media overlaid with metropolitan diesel oil containing an additive package. The microorganisms were the filamentous fungi, Hormoconis resinae, Paecilomyces variotii and Aspergillus fumigatus, the bacterium Bacillus subtilis and the yeast Candida silvicola, all previously isolated from contaminated diesel oil. After 60 days incubation with pure or mixed inocula of these microorganisms, pH, conductivity and viable microorganisms were measured. The electrochemical behaviour of carbon steel ASTM 283-93-C was determined in each of the six media (uninoculated) and in selected inoculated medium via measurements of open circuit potential and potentiostatic polarization curves. The uptake of phosphate (corrosion inhibitor), microbial growth, pH, conductivity and anodic and cathodic polarization curves were assessed in the water phase after 30 and 60 days of incubation with each single species Aspergillus fumigatus and Hormoconis resinae and with the consortium. The medium which proved most appropriate was Bushnell-Haas medium modified by the omission of chlorides, which allowed satisfactory microbial growth and had low aggressivity towards the steel. The performance of electrochemical tests in aerated, rather than deaerated, electrolyte solutions is suggested to be important to allow the detection of microbial influence on passive film formation and stability. (Abstract Copyright [2004], Wiley Periodicals, Inc.)

  14. How Solid-Electrolyte Interphase Forms in Aqueous Electrolytes.

    Science.gov (United States)

    Suo, Liumin; Oh, Dahyun; Lin, Yuxiao; Zhuo, Zengqing; Borodin, Oleg; Gao, Tao; Wang, Fei; Kushima, Akihiro; Wang, Ziqiang; Kim, Ho-Cheol; Qi, Yue; Yang, Wanli; Pan, Feng; Li, Ju; Xu, Kang; Wang, Chunsheng

    2017-12-27

    Solid-electrolyte interphase (SEI) is the key component that enables all advanced electrochemical devices, the best representative of which is Li-ion battery (LIB). It kinetically stabilizes electrolytes at potentials far beyond their thermodynamic stability limits, so that cell reactions could proceed reversibly. Its ad hoc chemistry and formation mechanism has been a topic under intensive investigation since the first commercialization of LIB 25 years ago. Traditionally SEI can only be formed in nonaqueous electrolytes. However, recent efforts successfully transplanted this concept into aqueous media, leading to significant expansion in the electrochemical stability window of aqueous electrolytes from 1.23 V to beyond 4.0 V. This not only made it possible to construct a series of high voltage/energy density aqueous LIBs with unprecedented safety, but also brought high flexibility and even "open configurations" that have been hitherto unavailable for any LIB chemistries. While this new class of aqueous electrolytes has been successfully demonstrated to support diversified battery chemistries, the chemistry and formation mechanism of the key component, an aqueous SEI, has remained virtually unknown. In this work, combining various spectroscopic, electrochemical and computational techniques, we rigorously examined this new interphase, and comprehensively characterized its chemical composition, microstructure and stability in battery environment. A dynamic picture obtained reveals how a dense and protective interphase forms on anode surface under competitive decompositions of salt anion, dissolved ambient gases and water molecule. By establishing basic laws governing the successful formation of an aqueous SEI, the in-depth understanding presented in this work will assist the efforts in tailor-designing better interphases that enable more energetic chemistries operating farther away from equilibria in aqueous media.

  15. The mechanism and kinetics of the electrochemical cleavage of azo bond of 2-hydroxy-5-sulfophenyl-azo-benzoic acids

    International Nuclear Information System (INIS)

    Mandic, Zoran; Nigovic, Biljana; Simunic, Branimir

    2004-01-01

    The electrochemical reduction of 2-hydroxy-5-[(4-sulfophenyl)azo]benzoic acid, 2-hydroxy-5-[(3-sulfophenyl)azo]benzoic acid, 2-hydroxy-5-[(2-sulfophenyl)azo]benzoic acid and 2-hydroxy-5-azo-benzoic acid has been carried out in aqueous solutions at glassy carbon electrode using cyclic voltammetry and chronoamperometry. The position of sulfo substituent relative to azo bridge as well as pH of the solution have significant impact on the electrochemical behavior of these compounds. It has been proposed that these compounds are reduced predominantly as hydrazone tautomers resulting in corresponding hydrazo compounds. The overall electrochemical reduction follows DISP2 mechanism, ultimately leading to the 5-amino salicylic acid and sulfanilic acid. The rate determining step is the homogenous redox reaction between intermediate hydrazo compound and 5-amino salicylic acid quinoneimine. The mechanism is proposed in which activated complex of 5-amino salicylic acid quinoneimine and intermediate hydrazo compound is formed with the simultaneous loss of one proton

  16. Treatment of aqueous wastes contaminated with Congo Red dye by electrochemical oxidation and ozonation processes

    International Nuclear Information System (INIS)

    Faouzi Elahmadi, Mohammed; Bensalah, Nasr; Gadri, Abdellatif

    2009-01-01

    Synthetic aqueous wastes polluted with Congo Red (CR) have been treated by two advanced oxidation processes: electrochemical oxidation on boron doped diamond anodes (BDD-EO) and ozonation under alkaline conditions. For same concentrations, galvanostatic electrolyses have led to total COD and TOC removals but ozonation process can reach only 85% and 81% of COD and TOC removals, respectively. UV-vis qualitative analyses have shown different behaviors of CR molecules towards ozonation and electrochemical oxidation. Rapid discoloration has been observed during ozonation, whereas color persistence till the end of galvanostatic electrolyses has been seen during BDD-EO process. It seems that the oxidation mechanisms involved in the two processes are different: simultaneous destruction of azoic groups is suggested during ozonation process but consecutive destruction of these groups is proposed during BDD-EO. However, energetic study has evidenced that BDD-EO appears more efficient and more economic than ozonation in terms of TOC removals. These results have been explained by the fact that during BDD-EO, other strong oxidants electrogenerated from the electrolyte oxidation such as persulfates and direct-oxidation of CR and its byproducts on BDD anodes complement the hydroxyl radicals mediated oxidation to accomplish the total mineralization of organics.

  17. Spectro-electrochemical and DFT study of tenoxicam metabolites formed by electrochemical oxidation

    International Nuclear Information System (INIS)

    Ramírez-Silva, M.T.; Guzmán-Hernández, D.S.; Galano, A.; Rojas-Hernández, A.; Corona-Avendaño, S.; Romero-Romo, M.; Palomar-Pardavé, M.

    2013-01-01

    Highlights: • Tenoxicam deprotonation and electrochemical oxidation were studied. • Both spectro-electrochemical and theoretical DFT studies were considered. • It was found that the ampholitic species of tenoxicam is a zwitterion. • Electrochemical oxidation of tenoxicam yields two non-electroactive products. • The nature of these fragments was further confirmed by a chromatography study. -- Abstract: From experimental (spectro-electrochemical) and theoretical (DFT) studies, the mechanisms of tenoxicam deprotonation and electrochemical oxidation were assessed. From these studies, new insights on the nature of the ampholitic species involved during tenoxicam's deprotonation in aqueous solution are presented; see scheme A. Moreover, it is shown that, after the analysis of two different reaction schemes that involve up to 10 different molecules and 12 reaction paths, the electrochemical oxidation of tenoxicam, yields two non-electroactive products that are predominately formed by its fragmentation, after the loss of two electrons. The nature of these fragments was further confirmed by a chromatography study

  18. Ion Movement in Polypyrrole/Dodecylbenzenesulphonate Films in aqueous and non-aqueous electrolytes

    DEFF Research Database (Denmark)

    Vidanapathirana, K.; Careem, M.A.; Skaarup, Steen

    2002-01-01

    The electrochemical characteristics during the redox process of polypyrrole (PPy) films, prepared using dodecylbenzenesulphonate (DBS-) dopant species, have been investigated using a combination of cyclic voltammetry and Electrochemical Quartz Crystal Microbalance (EQCM) measurements. Investigati......The electrochemical characteristics during the redox process of polypyrrole (PPy) films, prepared using dodecylbenzenesulphonate (DBS-) dopant species, have been investigated using a combination of cyclic voltammetry and Electrochemical Quartz Crystal Microbalance (EQCM) measurements....... Investigations were carried out using aqueous and non-aqueous electrolytes to study the effect of solvent on the ion movement during redox processes. When PPy films are cycled in aqueous electrolytes transport of both anion and cation occurs during oxidation and reduction. However, when cycled in the nonaqueous...

  19. Understanding of electrochemical and structural changes of polypyrrole/polyethylene glycol composite films in aqueous solution

    International Nuclear Information System (INIS)

    Pirvu, Cristian; Manole, Claudiu Constantin; Stoian, Andrei Bogdan; Demetrescu, Ioana

    2011-01-01

    Highlights: → Electrochemical monitoring of PPy and PPy-PEG films over immersion time. → Electrochemical and surface analysis showed that PEG improves the stability of PPy films. → Mott-Schottky analysis reveals p-type conductance for both films. → In situ AFM analysis sustains electrochemical behaviour. → A model of PPy and PPy-PEG films behaviour during immersion was elaborated. - Abstract: Electrochemical monitoring of electrical and structural changes of both PPy and PPy-PEG films electrochemical deposited, in order to highlight if the structural stability offered by PEG has an influence on electrical properties and stability in aqueous solution over immersion time was investigated. Electrochemical analysis suggests that PPy-PEG film inserts cations easier than PPy film for a short immersion time probably due to ability of PEG to form complexes with metal cations. The FTIR spectra showed that the PEG incorporation decreases the rate of PPy overoxidation probably by restraining the electron release and by rendering O 2 inaccessible to PPy. Mott-Schottky analysis based on capacitance measurement reveal p-type conductance for both films. The in situ AFM analysis sustains electrochemical behaviour and has permitted elaboration of a model of PPy and PPy-PEG films behaviour during immersion in testing solution.

  20. Highly Quantitative Electrochemical Characterization of Non-Aqueous Electrolytes & Solid Electrolyte Interphases

    Energy Technology Data Exchange (ETDEWEB)

    Sergiy V. Sazhin; Kevin L. Gering; Mason K. Harrup; Harry W. Rollins

    2012-10-01

    The methods to measure solid electrolyte interphase (SEI) electrochemical properties and SEI formation capability of non-aqueous electrolyte solutions are not adequately addressed in the literature. And yet, there is a strong demand in new electrolyte generations that promote stabilized SEIs and have an influence to resolve safety, calendar life and other limitations of Li-ion batteries. To fill this gap, in situ electrochemical approach with new descriptive criteria for highly quantitative characterization of SEI and electrolytes is proposed. These criteria are: SEI formation capacity, SEI corrosion rate, SEI maintenance rate, and SEI kinetic stability. These criteria are associated with battery parameters like irreversible capacity, self-discharge, shelf-life, power, etc. Therefore, they are especially useful for electrolyte development and standard fast screening, allowing a skillful approach to narrow down the search for the best electrolyte. The characterization protocol also allows retrieving information on interfacial resistance for SEI layers and the electrochemical window of electrolytes, the other important metrics of characterization. The method validation was done on electrolyte blends containing phosphazenes, developed at Idaho National Laboratory, as 1.2M LiPF6 [80 % EC-MEC (2:8) (v/v) + 20% Phosphazene variety] (v/v), which were targeted for safer electrolyte variations.

  1. Rapid and molecular selective electrochemical sensing of phthalates in aqueous solution

    KAUST Repository

    Zia, Asif I.

    2015-05-01

    Reported research work presents real time non-invasive detection of phthalates in spiked aqueous samples by employing electrochemical impedance spectroscopy (EIS) technique incorporating a novel interdigital capacitive sensor with multiple sensing thin film gold micro-electrodes fabricated on native silicon dioxide layer grown on semiconducting single crystal silicon wafer. The sensing surface was functionalized by a self-assembled monolayer of 3-aminopropyltrietoxysilane (APTES) with embedded molecular imprinted polymer (MIP) to introduce selectivity for the di(2-ethylhexyl) phthalate (DEHP) molecule. Various concentrations (1-100. ppm) of DEHP in deionized MilliQ water were tested using the functionalized sensing surface to capture the analyte. Frequency response analyzer (FRA) algorithm was used to obtain impedance spectra so as to determine sample conductance and capacitance for evaluation of phthalate concentration in the sample solution. Spectrum analysis algorithm interpreted the experimentally obtained impedance spectra by applying complex nonlinear least square (CNLS) curve fitting in order to obtain electrochemical equivalent circuit and corresponding circuit parameters describing the kinetics of the electrochemical cell. Principal component analysis was applied to deduce the effects of surface immobilized molecular imprinted polymer layer on the evaluated circuit parameters and its electrical response. The results obtained by the testing system were validated using commercially available high performance liquid chromatography diode array detector system.

  2. Macro-mechanics controls quantum mechanics: mechanically controllable quantum conductance switching of an electrochemically fabricated atomic-scale point contact.

    Science.gov (United States)

    Staiger, Torben; Wertz, Florian; Xie, Fangqing; Heinze, Marcel; Schmieder, Philipp; Lutzweiler, Christian; Schimmel, Thomas

    2018-01-12

    Here, we present a silver atomic-scale device fabricated and operated by a combined technique of electrochemical control (EC) and mechanically controllable break junction (MCBJ). With this EC-MCBJ technique, we can perform mechanically controllable bistable quantum conductance switching of a silver quantum point contact (QPC) in an electrochemical environment at room temperature. Furthermore, the silver QPC of the device can be controlled both mechanically and electrochemically, and the operating mode can be changed from 'electrochemical' to 'mechanical', which expands the operating mode for controlling QPCs. These experimental results offer the perspective that a silver QPC may be used as a contact for a nanoelectromechanical relay.

  3. A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO2to CO

    KAUST Repository

    Rasul, Shahid

    2014-12-23

    The challenge in the electrochemical reduction of aqueous carbon dioxide is in designing a highly selective, energy-efficient, and non-precious-metal electrocatalyst that minimizes the competitive reduction of proton to form hydrogen during aqueous CO2 conversion. A non-noble metal electrocatalyst based on a copper-indium (Cu-In) alloy that selectively converts CO2 to CO with a low overpotential is reported. The electrochemical deposition of In on rough Cu surfaces led to Cu-In alloy surfaces. DFT calculations showed that the In preferentially located on the edge sites rather than on the corner or flat sites and that the d-electron nature of Cu remained almost intact, but adsorption properties of neighboring Cu was perturbed by the presence of In. This preparation of non-noble metal alloy electrodes for the reduction of CO2 provides guidelines for further improving electrocatalysis.

  4. Simultaneously Coupled Mechanical-Electrochemical-Thermal Simulation of Lithium-Ion Cells: Preprint

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Chao; Santhanagopalan, Shriram; Sprague, Michael A.; Pesaran, Ahmad A.

    2016-08-01

    Understanding the combined electrochemical-thermal and mechanical response of a system has a variety of applications, for example, structural failure from electrochemical fatigue and the potential induced changes of material properties. For lithium-ion batteries, there is an added concern over the safety of the system in the event of mechanical failure of the cell components. In this work, we present a generic multi-scale simultaneously coupled mechanical-electrochemical-thermal model to examine the interaction between mechanical failure and electrochemical-thermal responses. We treat the battery cell as a homogeneous material while locally we explicitly solve for the mechanical response of individual components using a homogenization model and the electrochemical-thermal responses using an electrochemical model for the battery. A benchmark problem is established to demonstrate the proposed modeling framework. The model shows the capability to capture the gradual evolution of cell electrochemical-thermal responses, and predicts the variation of those responses under different short-circuit conditions.

  5. The Aqueous Electrochemical Response of TiC–Stainless Steel Cermets

    Directory of Open Access Journals (Sweden)

    Chukwuma Onuoha

    2018-05-01

    Full Text Available A family of TiC–stainless steel ceramic–metal composites, or cermets, has been developed in the present study, using steel grades of 304 L, 316 L, or 410 L as the binder phase. Melt infiltration was used to prepare the cermets, with the steel binder contents varying between 10–30 vol. %. The corrosion behaviour was evaluated using a range of electrochemical techniques in an aqueous solution containing 3.5 wt. % NaCl. The test methods included potentiodynamic, cyclic, and potentiostatic polarisation. The corroded samples were subsequently characterised using scanning electron microscopy (SEM and energy dispersive X-ray spectroscopy (EDS, while the post-corrosion solutions were analysed using inductively coupled plasma optical emission spectroscopy (ICP-OES to determine the residual ionic and particulate material removed from the cermets during electrochemical testing. It was demonstrated that the corrosion resistance was enhanced through decreasing the steel binder content, which arises due to the preferential dissolution of the binder phase, while the TiC ceramic remains largely unaffected. Increasing corrosion resistance was observed in the sequence TiC-304 L > TiC-316 L > TiC-410 L.

  6. Toward an Aqueous Solar Battery: Direct Electrochemical Storage of Solar Energy in Carbon Nitrides.

    Science.gov (United States)

    Podjaski, Filip; Kröger, Julia; Lotsch, Bettina V

    2018-03-01

    Graphitic carbon nitrides have emerged as an earth-abundant family of polymeric materials for solar energy conversion. Herein, a 2D cyanamide-functionalized polyheptazine imide (NCN-PHI) is reported, which for the first time enables the synergistic coupling of two key functions of energy conversion within one single material: light harvesting and electrical energy storage. Photo-electrochemical measurements in aqueous electrolytes reveal the underlying mechanism of this "solar battery" material: the charge storage in NCN-PHI is based on the photoreduction of the carbon nitride backbone and charge compensation is realized by adsorption of alkali metal ions within the NCN-PHI layers and at the solution interface. The photoreduced carbon nitride can thus be described as a battery anode operating as a pseudocapacitor, which can store light-induced charge in the form of long-lived, "trapped" electrons for hours. Importantly, the potential window of this process is not limited by the water reduction reaction due to the high intrinsic overpotential of carbon nitrides for hydrogen evolution, potentially enabling new applications for aqueous batteries. Thus, the feasibility of light-induced electrical energy storage and release on demand by a one-component light-charged battery anode is demonstrated, which provides a sustainable solution to overcome the intermittency of solar radiation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Classifying the mechanisms of electrochemical shock in ion-intercalation materials

    OpenAIRE

    Woodford, William; Carter, W. Craig; Chiang, Yet-Ming

    2014-01-01

    Electrochemical shock” – the electrochemical cycling-induced fracture of materials – contributes to impedance growth and performance degradation in ion-intercalation batteries, such as lithium-ion. Using a combination of micromechanical models and acoustic emission experiments, the mechanisms of electrochemical shock are identified, classified, and modeled in targeted model systems with different composition and microstructure. A particular emphasis is placed on mechanical degradation occurr...

  8. Aqueous electrochemical mechanisms in actinide residue processing. 1998 annual progress report

    International Nuclear Information System (INIS)

    Blanchard, D.L. Jr.; Burns, C.J.; Morris, D.E.; Smith, W.H.

    1998-01-01

    'New and/or improved solutions to the stabilization and volume reduction of nuclear materials processing residues are urgently needed. Mediated electrochemical oxidation/reduction (MEO/R) processes are one such approach for incinerator ash, combustibles, and other solid residues. However, questions remain concerning the mechanisms of these processes, and how they might be optimized. In addition, further research is merited to extend their range of applicability. Recent advances in the study of heterogeneous electron transfer in solid substrates have opened the door for the re-examination of electron transfer processes associated with redox mediated actinide dissolution. The authors develop a deeper understanding of the thermodynamic and mechanistic aspects of heterogeneous electron transfer that lie at the heart of these MEO/R processes. They will also develop and test new approaches based on the results of these fundamental studies using actual residue materials. Key aspects of this proposal include: (1) determination of the potential windows for oxidation/reduction of colloidal actinide oxides and actinide-bearing oxide and organic substrates and the e transfer kinetic parameters that govern the current--overpotential characteristics; (2) development of adaptations of mediation schemes and application of co-mediation reagents for oxidative and reductive dissolution based on complexation of the surface-bound or solid-phase actinides and/or the dissolved redox mediator;and (3) execution of bench-scale tests of new MEO/R schemes on actual residue materials.'

  9. Electrochemical transformation of trichloroethylene in aqueous solution by electrode polarity reversal.

    Science.gov (United States)

    Rajic, Ljiljana; Fallahpour, Noushin; Yuan, Songhu; Alshawabkeh, Akram N

    2014-12-15

    Electrode polarity reversal is evaluated for electrochemical transformation of trichloroethylene (TCE) in aqueous solution using flow-through reactors with mixed metal oxide electrodes and Pd catalyst. The study tests the hypothesis that optimizing electrode polarity reversal will generate H2O2 in Pd presence in the system. The effect of polarity reversal frequency, duration of the polarity reversal intervals, current intensity and TCE concentration on TCE removal rate and removal mechanism were evaluated. TCE removal efficiencies under 6 cycles h(-1) were similar in the presence of Pd catalyst (50.3%) and without Pd catalyst (49.8%), indicating that Pd has limited impact on TCE degradation under these conditions. The overall removal efficacies after 60 min treatment under polarity reversal frequencies of 6, 10, 15, 30 and 90 cycles h(-1) were 50.3%, 56.3%, 69.3%, 34.7% and 23.4%, respectively. Increasing the frequency of polarity reversal increases TCE removal as long as sufficient charge is produced during each cycle for the reaction at the electrode. Electrode polarity reversal shifts oxidation/reduction and reduction/oxidation sequences in the system. The optimized polarity reversal frequency (15 cycles h(-1) at 60 mA) enables two reaction zones formation where reduction/oxidation occurs at each electrode surface. Published by Elsevier Ltd.

  10. High voltage AC/AC electrochemical capacitor operating at low temperature in salt aqueous electrolyte

    Science.gov (United States)

    Abbas, Qamar; Béguin, François

    2016-06-01

    We demonstrate that an activated carbon (AC)-based electrochemical capacitor implementing aqueous lithium sulfate electrolyte in 7:3 vol:vol water/methanol mixture can operate down to -40 °C with good electrochemical performance. Three-electrode cell investigations show that the faradaic contributions related with hydrogen chemisorption in the negative AC electrode are thermodynamically unfavored at -40 °C, enabling the system to work as a typical electrical double-layer (EDL) capacitor. After prolonged floating of the AC/AC capacitor at 1.6 V and -40°C, the capacitance, equivalent series resistance and efficiency remain constant, demonstrating the absence of ageing related with side redox reactions at this temperature. Interestingly, when temperature is increased back to 24 °C, the redox behavior due to hydrogen storage reappears and the system behaves as a freshly prepared one.

  11. Macro-mechanics controls quantum mechanics: mechanically controllable quantum conductance switching of an electrochemically fabricated atomic-scale point contact

    Science.gov (United States)

    Staiger, Torben; Wertz, Florian; Xie, Fangqing; Heinze, Marcel; Schmieder, Philipp; Lutzweiler, Christian; Schimmel, Thomas

    2018-01-01

    Here, we present a silver atomic-scale device fabricated and operated by a combined technique of electrochemical control (EC) and mechanically controllable break junction (MCBJ). With this EC-MCBJ technique, we can perform mechanically controllable bistable quantum conductance switching of a silver quantum point contact (QPC) in an electrochemical environment at room temperature. Furthermore, the silver QPC of the device can be controlled both mechanically and electrochemically, and the operating mode can be changed from ‘electrochemical’ to ‘mechanical’, which expands the operating mode for controlling QPCs. These experimental results offer the perspective that a silver QPC may be used as a contact for a nanoelectromechanical relay.

  12. Voltammetry study of quinoxaline in aqueous electrolytes

    International Nuclear Information System (INIS)

    Milshtein, Jarrod D.; Su, Liang; Liou, Catherine; Badel, Andres F.; Brushett, Fikile R.

    2015-01-01

    Organic compounds have recently received considerable attention as active materials in redox flow batteries (RFBs) due to their good electrochemical reversibility, high theoretical energy densities, and promise for low cost production. Until now, organic active material candidates for aqueous RFBs have been limited to the quinone family, a set of aromatic-derived organic molecules, distinguished by an even number of ketone (R−C(=O)−R′) groups. This work aims to elucidate and optimize the electrochemical behavior of quinoxaline, an organic molecule consisting of fused benzene and pyrazine rings, in aqueous electrolytes. More than 30 electrolytes are screened by cyclic voltammetry, and the five most promising electrolytes are investigated further using rotating disk voltammetry. Electrochemical behavior of quinoxaline shows pH dependent thermodynamics and reaction mechanisms, while chloride-containing supporting electrolytes greatly enhance solubility. This study sheds light on the promising characteristics of quinoxaline as a low potential compound for aqueous RFBs; quinoxaline has a redox potential of E° ≈ −0.02 V vs. RHE, is soluble up to ∼4.5 M in water, exhibits a two-electron transfer capability, and possesses a low molecular weight (130.15 g mol"−"1), resulting in a theoretical capacity of 410 mAh g"−"1.

  13. Synthesis and Electrochemical Performance of a Lithium Titanium Phosphate Anode for Aqueous Lithium-Ion Batteries

    KAUST Repository

    Wessells, Colin

    2011-01-01

    Lithium-ion batteries that use aqueous electrolytes offer safety and cost advantages when compared to today\\'s commercial cells that use organic electrolytes. The equilibrium reaction potential of lithium titanium phosphate is -0.5 V with respect to the standard hydrogen electrode, which makes this material attractive for use as a negative electrode in aqueous electrolytes. This material was synthesized using a Pechini type method. Galvanostatic cycling of the resulting lithium titanium phosphate showed an initial discharge capacity of 115 mAh/g and quite good capacity retention during cycling, 84% after 100 cycles, and 70% after 160 cycles at a 1 C cycling rate in an organic electrolyte. An initial discharge capacity of 113 mAh/g and capacity retention of 89% after 100 cycles with a coulombic efficiency above 98% was observed at a C/5 rate in pH -neutral 2 M Li2 S O4. The good cycle life and high efficiency in an aqueous electrolyte demonstrate that lithium titanium phosphate is an excellent candidate negative electrode material for use in aqueous lithium-ion batteries. © 2011 The Electrochemical Society.

  14. Effect of aqueous electrolytes on the electrochemical behaviors of supercapacitors based on hierarchically porous carbons

    Science.gov (United States)

    Zhang, Xiaoyan; Wang, Xianyou; Jiang, Lanlan; Wu, Hao; Wu, Chun; Su, Jingcang

    2012-10-01

    Hierarchically porous carbons (HPCs) have been prepared by sol-gel self-assembly technology with nickel oxide and surfactant as the dual template. The porous carbons are further activated by nitric acid. The electrochemical behaviors of supercapacitors using HPCs as electrode material in different aqueous electrolytes, e.g., (NH4)2SO4, Na2SO4, H2SO4 and KOH are studied by cyclic voltametry, galvanostatic charge/discharge, cyclic life, leakage current, self-discharge and electrochemical impedance spectroscopy. The results demonstrate that the supercapacitors in various electrolytes perform definitely capacitive behaviors; especially in 6 M KOH electrolyte the supercapacitor represents the best electrochemical performance, the shortest relaxation time, and nearly ideal polarisability. The energy density of 8.42 Wh kg-1 and power density of 17.22 kW kg-1 are obtained at the operated voltage window of 1.0 V. Especially, the energy density of 11.54 Wh kg-1 and power density of 10.58 kW kg-1 can be achieved when the voltage is up to 1.2 V.

  15. Investigations of the Electrochemical Stability of Aqueous Electrolytes for Lithium Battery Applications

    KAUST Repository

    Wessells, Colin

    2010-01-01

    The electrolytic stability windows of several aqueous electrolytes were investigated by a constant current method. The electrode potential range depended upon the value of the imposed current. The magnitude of this behavior varied with the salt solution, its concentration, and pH of the electrolyte. At a leakage current density of 50 μA/cm2, a 5 M solution of LiNO3 had an electrolytic window of 2.3 V, spanning from -0.55 to 1.75 V with respect to the standard hydrogen electrode. These results demonstrate the feasibility of operating lithium batteries at voltages appreciably above the theoretical decomposition voltage of water. © 2010 The Electrochemical Society.

  16. Electrochemical study of stress corrosion cracking of copper alloys

    International Nuclear Information System (INIS)

    Malki, Brahim

    1999-01-01

    This work deals with the electrochemical study of stress corrosion of copper alloys in aqueous environment. Selective dissolution and electrochemical oxidation are two key-points of the stress corrosion of these alloys. The first part of this thesis treats of these aspects applied to Cu-Au alloys. Measurements have been performed using classical electrochemical techniques (in potentio-dynamic, potentio-static and galvano-static modes). The conditions of occurrence of an electrochemical noise is analysed using signal processing techniques. The impact on the behavior of Cu 3 Au are discussed. In the second part, the stress corrosion problem is addressed in the case of surface oxide film formation, in particular for Cu-Zn alloys. We have found useful to extend this study to mechanical stress oxidation mechanisms in the presence of an oscillating potential electrochemical system. The aim is to examine the influence of these new electrochemical conditions (galvano-static mode) on the behavior of stressed brass. Finally, the potential distribution at crack tip is calculated in order to compare the different observations [fr

  17. Electrochemical deposition of silver nanostructures from aqueous solutions in the presence of sodium polyacrylate

    OpenAIRE

    Topchak, Roman; Okhremchuk, Yevhen; Kuntyi, Orest

    2013-01-01

    The silver nanostructures obtaining was investigated by electrochemical deposition from aqueous solutions ((1?10) mM AgNO3 + 50 m? NaPA) onto graphite substrate. The influence of the concentration of silver ions and cathodic potential values in the range E = -0,2 ... -1,0 V on surface filling degree and geometry of silver particles was (had been) studied. It is shown, the discrete silver particles ranging in size from 50 to 400 nm with a uniform distribution on the surface of the substrate...

  18. Electrochemical synthesis of polypyrrole on ferrous and non-ferrous metals from sweet aqueous electrolytic medium

    International Nuclear Information System (INIS)

    Bazzaoui, M.; Martins, J.I.; Reis, T.C.; Bazzaoui, E.A.; Nunes, M.C.; Martins, L.

    2005-01-01

    The electrodeposition of polypyrrole (PPy) on oxidizable metals such as aluminum and iron has been achieved in aqueous medium of saccharin and pyrrole. Scanning electron microscopy and X-ray photoelectron spectroscopy analysis reveal a good homogeneity of the obtained PPy film. The electrochemical synthesis of PPy coating has been achieved successfully under potentiodynamic, galvanostatic and potentiostatic techniques. The corrosion experiments performed in HCl show that the PPy coating increases the corrosion potential and decreases the corrosion current density

  19. Electrochemical Study of Modified Glassy Carbon Electrode with Carboxyphenyl Diazonium Salt in Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Mariem BOUROUROU

    2014-05-01

    Full Text Available The covalent grafting of carboxyphenyl functionalities to planar carbon substrates by reaction with 2-carboxybenezenediazonium salt has been studied in aqueous acid solution. The surface was characterized, before and after the functionnalization process, by cyclic voltammetry, electrochemical impedance spectroscopy and linear sweep voltammetry (LSV in order to control and to prove the formation of a coating on the carbon surface. The results indicate the presence of substituted phenyl groups on the investigated surface. Electrochemical impedance measurements show that the slowing down of the electron transfer kinetics was more evident by increasing the number of cycles resulting to higher DEp and RCT parameters. Besides, the effect of the pH on the electron transfer processes of the Fe(CN63-/4- at the modified electrode is studied. By changing the solution pH the terminal group’s charge state would vary, based on which the surface pKa value is estimated.

  20. Non-aqueous electrochemical deposition of lead zirconate titanate films for flexible sensor applications

    Science.gov (United States)

    Joseph, Sherin; Kumar, A. V. Ramesh; John, Reji

    2017-11-01

    Lead zirconate titanate (PZT) is one of the most important piezoelectric materials widely used for underwater sensors. However, PZTs are hard and non-compliant and hence there is an overwhelming attention devoted toward making it flexible by preparing films on flexible substrates by different routes. In this work, the electrochemical deposition of composition controlled PZT films over flexible stainless steel (SS) foil substrates using non-aqueous electrolyte dimethyl sulphoxide (DMSO) was carried out. Effects of various key parameters involved in electrochemical deposition process such as current density and time of deposition were studied. It was found that a current density of 25 mA/cm2 for 5 min gave a good film. The morphology and topography evaluation of the films was carried out by scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively, which showed a uniform morphology with a surface roughness of 2 nm. The PZT phase formation was studied using X-ray diffraction (XRD) and corroborated with Raman spectroscopic studies. The dielectric constant, dielectric loss, hysteresis and I-V characteristics of the film was evaluated.

  1. Electrochemical performance of high specific capacity of lithium-ion cell LiV3O8//LiMn2O4 with LiNO3 aqueous solution electrolyte

    International Nuclear Information System (INIS)

    Zhao Mingshu; Zheng Qingyang; Wang Fei; Dai Weimin; Song Xiaoping

    2011-01-01

    Research highlights: → In this paper, the electrochemical performance of aqueous rechargeable lithium battery with LiV 3 O 8 and LiMn 2 O 4 in saturated LiNO 3 electrolyte is studied. → The electrochemical performance tests show that the specific capacity of LiMn 2 O 4 using as the cathode of ARLB is similar to that of ordinary lithium-ion battery with organic electrolyte, which works much better than the formerly reported. → In addition, the cell systems exhibit good cycling performance. Therefore, it has great potential comparing with other batteries such as lead acid batteries and alkaline manganese batteries. - Abstract: The electrochemical performance of aqueous rechargeable lithium battery (ARLB) with LiV 3 O 8 and LiMn 2 O 4 in saturated LiNO 3 electrolyte is studied. The results indicate that these two electrode materials are stable in the aqueous solution and no hydrogen or oxygen produced, moreover, intercalation/de-intercalation of lithium ions occurred within the range of electrochemical stability of water. The electrochemical performance tests show that the specific capacity of LiMn 2 O 4 using as the cathode of ARLB is similar to that of ordinary lithium-ion battery with organic electrolyte, which works much better than the formerly reported. In addition, the cell systems exhibit good cycling performance. Therefore, it has great potential comparing with other batteries such as lead acid batteries and alkaline manganese batteries.

  2. Electrochemical behavior of LiCoO2 as aqueous lithium-ion battery electrodes

    KAUST Repository

    Ruffo, Riccardo

    2009-02-01

    Despite the large number of studies on the behavior of LiCoO2 in organic electrolytes and its recent application as a positive electrode in rechargeable water battery prototypes, a little information is available about the lithium intercalation reaction in this layered compound in aqueous electrolytes. This work shows that LiCoO2 electrodes can be reversibly cycled in LiNO3 aqueous electrolytes for tens of cycles at remarkably high rates with impressive values specific capacity higher than 100 mAh/g, and with a coulomb efficiency greater than 99.7%. Stable and reproducible cycling measurements have been made using a simple cell design that can be easily applied to the study of other intercalation materials, assuming that they are stable in water and that their intercalation potential range matches the electrochemical stability window of the aqueous electrolyte. The experimental arrangement uses a three-electrode flooded cell in which another insertion compound acts as a reversible source and sink of lithium ions, i.e., as the counter electrode. A commercial reference electrode is also present. Both the working and the counter electrodes have been prepared as thin layers on a metallic substrate using the procedures typical for the study of electrodes for lithium-ion batteries in organic solvent electrolytes. © 2008 Elsevier B.V. All rights reserved.

  3. Neptunium carbonato complexes in aqueous solution: an electrochemical, spectroscopic, and quantum chemical study.

    Science.gov (United States)

    Ikeda-Ohno, Atsushi; Tsushima, Satoru; Takao, Koichiro; Rossberg, André; Funke, Harald; Scheinost, Andreas C; Bernhard, Gert; Yaita, Tsuyoshi; Hennig, Christoph

    2009-12-21

    The electrochemical behavior and complex structure of Np carbonato complexes, which are of major concern for the geological disposal of radioactive wastes, have been investigated in aqueous Na(2)CO(3) and Na(2)CO(3)/NaOH solutions at different oxidation states by using cyclic voltammetry, X-ray absorption spectroscopy, and density functional theory calculations. The end-member complexes of penta- and hexavalent Np in 1.5 M Na(2)CO(3) with pH = 11.7 have been determined as a transdioxo neptunyl tricarbonato complex, [NpO(2)(CO(3))(3)](n-) (n = 5 for Np(V), and 4 for Np(VI)). Hence, the electrochemical reaction of the Np(V/VI) redox couple merely results in the shortening/lengthening of bond distances mainly because of the change of the cationic charge of Np, without any structural rearrangement. This explains the observed reversible-like feature on their cyclic voltammograms. In contrast, the electrochemical oxidation of Np(V) in a highly basic carbonate solution of 2.0 M Na(2)CO(3)/1.0 M NaOH (pH > 13) yielded a stable heptavalent Np complex of [Np(VII)O(4)(OH)(2)](3-), indicating that the oxidation reaction from Np(V) to Np(VII) in the carbonate solution involves a drastic structural rearrangement from the transdioxo configuration to a square-planar-tetraoxo configuration, as well as exchanging the coordinating anions from carbonate ions (CO(3)(2-)) to hydroxide ions (OH(-)).

  4. Influence of Monomer Concentration on the Morphologies and Electrochemical Properties of PEDOT, PANI, and PPy Prepared from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Shalini Kulandaivalu

    2016-01-01

    Full Text Available Poly(3,4-ethylenedioxyhiophene (PEDOT, polyaniline (PANI, and polypyrrole (PPy were prepared on indium tin oxide (ITO substrate via potentiostatic from aqueous solutions containing monomer and lithium perchlorate. The concentration of monomers was varied between 1 and 10 mM. The effects of monomer concentration on the polymers formation were investigated and compared by using Fourier transform infrared spectroscopy (FTIR, Raman spectroscopy, scanning electron microscopy (SEM, cyclic voltammetry (CV, and electrochemical impedance spectroscopy (EIS measurements. FTIR and Raman spectra showed no changes in the peaks upon the increment of the concentration. Based on the SEM images, the increment in monomer concentration gives significant effect on morphologies and eventually affects the electrochemical properties. PEDOT electrodeposited from 10 mM solution showed excellent electrochemical properties with the highest specific capacitance value of 12.8 mF/cm2.

  5. Influence aqueous solutions on the mechanical behavior of argillaceous rocks

    International Nuclear Information System (INIS)

    Wakim, J.

    2005-12-01

    The hydration of the shale with an aqueous solution induces a swelling deformation which plays an important role in the behaviour of the structures excavated in this type of grounds. This deformation is marked by a three-dimensional and anisotropic character and involves several mechanisms like adsorption, osmosis or capillarity. Several researches were dedicated to swelling and were often much debated due to the complexity of the implied phenomena. The goal of this thesis is therefore to contribute to a better understanding of shale swelling when the rock is confined and hydrated with an aqueous solution. The main part of the work accomplished was related to the Lorraine shale and to the Tournemire shale. To characterize swelling and to identify the main governing parameters, it was necessary to start the issue with an experimental approach. Many apparatus were then developed to carry out tests under various conditions of swelling. In order to facilitate the interpretation of the tests and thereafter the modelling of the behaviour, the experimental procedure adopted consisted of studying first the mechanical aspect and then the chemical aspect of swelling. In the mechanical part, swelling was studied by imposing on the sample a mechanical loading while maintaining during the tests the same aqueous solution. The principal parameters which were studied are the effect of the lateral conditions on axial swelling (impeded strain or constant stress) as well as the influence of the axial stress on radial swelling. The anisotropy of swelling was studied by carrying out, for different orientations of the sample, tests of free swelling, impeded swelling and uniaxial swelling. These various mechanical tests allowed to study the three-dimensional anisotropic swelling in all the conditions and to select the most appropriate test to be used in the second phase of the research. The precise analysis performed to explain the mechanisms behind the swelling of an argillaceous rock

  6. Corrosion behaviour of Alloy 800 in high temperature aqueous solutions: Electrochemical studies

    International Nuclear Information System (INIS)

    Olmedo, A.M.; Villegas, M.; Alvarez, M.G.

    1996-01-01

    The anodic behaviour and passivity breakdown of Alloy 800 in aqueous solutions of sodium chloride, sodium sulphate and sodium bicarbonate were studied by electrochemical techniques in the temperature range from 60 C to 280 C. The pitting resistance and pitting morphology of the alloy in chloride plus sulphate and chloride plus bicarbonate mixtures, at 60 C and 280 C, were also examined. Increasing bicarbonate or sulphate additions to chloride solutions shift the characteristic pitting potential of Alloy 800 to higher values, both at low and high temperatures. Changes in pitting morphology were observed in sulphate containing solutions while the morphology of the attack found in bicarbonate containing solutions was similar to that in pure chloride solutions. Finally, no localized or substantial generalized corrosion was detected in pure sulphate or bicarbonate solutions at any temperature. (orig.)

  7. Electrocatalysis aqueous phenol with carbon nanotubes networks as anodes: Electrodes passivation and regeneration and prevention

    International Nuclear Information System (INIS)

    Gao, Guandao; Vecitis, Chad D.

    2013-01-01

    Highlights: ► The electrochemical filtration used carbon nanotube network is effective to remove aqueous pollutants. ► Electrodes passivation is one of the most urgent challenges to overcome to 3-D electrode technology. ► Generally running system at higher potential can avoid generating polymer. ► Washing electrodes with suitable solvents is an effective alternative for removing polymer if it is not the best. -- Abstract: Electrochemical filtration using three-dimensional carbon nanotube (CNT) networks has been reported to increase the electrooxidation rate of aqueous pollutants due to convective mass transfer enhancements resulting from the flow through the electrode. In regards to the long term application of this novel electrochemical technology, electrode passivation is one of the most important challenges to overcome. Here, electrochemical filtration of aqueous phenol in a sodium sulfate electrolyte is utilized to investigate the primary passivation mechanisms and electrode regeneration methodologies, in which chronoamperometry and effluent total organic carbon measurements are utilized to monitor the passivation process in real-time, and electrochemical impedance spectroscopy, linear sweep voltammetry, and scanning electron microscopy are utilized to examine the CNT networks before passivation, after passivation and after regeneration. Finnaly, the carbon nanotube electrode passivation mechanisms and regeneration methods are discussed. Generally it is better choice to run system at higher potential in order to avoid generating polymer firstly other than regenerate complicatedly it after its passivation. Polymer formation can be prevented by application of an anode potential ≥2.1 V, which can completely mineralize phenol to carbon dioxide etc. and prevent polymerization of phenol. If there is still a bit of polymer formed inevitably, washing electrodes with suitable solvents is an effective alternative

  8. Corrosion-electrochemical and mechanical properties of aluminium-berylium alloys alloyed by rare-earth metals

    International Nuclear Information System (INIS)

    Safarov, A.M.; Odinaev, Kh.E.; Shukroev, M.Sh.; Saidov, R.Kh.

    1997-01-01

    In order to study influence of rare earth metals on corrosion-electrochemical and mechanical properties of aluminium-berylium alloys the alloys contain 1 mass % beryllium and different amount of rare earth metals were obtained.-electrochemical and mechanical properties of aluminium-berylium alloys. The electrochemical characteristics of obtained alloys, including stationary potential, potentials of passivation beginning and full passivation, potentials of pitting formation and re passivation were defined.

  9. Electrochemical deposition mechanism of calcium phosphate coating in dilute Ca-P electrolyte system

    Energy Technology Data Exchange (ETDEWEB)

    Hu Ren [State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, CNRS Laboratoire International Associe XiamENS, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (China); Department of Biology, College of Life Science, Xiamen University, Xiamen, Fujian 361005 (China); Lin Changjian, E-mail: cjlin@xmu.edu.cn [State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, CNRS Laboratoire International Associe XiamENS, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (China); Shi Haiyan; Wang Hui [State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, CNRS Laboratoire International Associe XiamENS, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (China)

    2009-06-15

    In this work, the electrochemical deposition behavior of calcium phosphate coating from an aqueous electrolyte containing very dilute calcium and phosphorus species (Ca-P) was studied. The effects of three process parameters, i.e. temperature, current density and duration, were systematically investigated and the underlying mechanism was thoroughly analyzed. It was observed that the coating is mainly composed of hydroxyapatite (HA) in a wide range of temperature and current densities. The temperature had a significant effect on the deposition velocity. An apparent activation energy of 174.9 kJ mol{sup -1} was subsequently derived, indicating the mass-transfer control mechanism for the coating formation. The current density was identified to be an important parameter for structure controllability. The results of DR-FTIR/Raman spectroscopic studies of the initial deposition phase strongly suggested that the HA coating was instantaneously and directly precipitated on the substrate; neither induction period nor precursor was detected in this dilute Ca-P electrolyte system. Finally, a phase diagram of the Ca-P electrolyte system was constructed, which offered a thermodynamic reason for the direct single-phase HA precipitation observed only in this system, but not in conventional concentrated systems.

  10. Electrochemical deposition mechanism of calcium phosphate coating in dilute Ca-P electrolyte system

    International Nuclear Information System (INIS)

    Hu Ren; Lin Changjian; Shi Haiyan; Wang Hui

    2009-01-01

    In this work, the electrochemical deposition behavior of calcium phosphate coating from an aqueous electrolyte containing very dilute calcium and phosphorus species (Ca-P) was studied. The effects of three process parameters, i.e. temperature, current density and duration, were systematically investigated and the underlying mechanism was thoroughly analyzed. It was observed that the coating is mainly composed of hydroxyapatite (HA) in a wide range of temperature and current densities. The temperature had a significant effect on the deposition velocity. An apparent activation energy of 174.9 kJ mol -1 was subsequently derived, indicating the mass-transfer control mechanism for the coating formation. The current density was identified to be an important parameter for structure controllability. The results of DR-FTIR/Raman spectroscopic studies of the initial deposition phase strongly suggested that the HA coating was instantaneously and directly precipitated on the substrate; neither induction period nor precursor was detected in this dilute Ca-P electrolyte system. Finally, a phase diagram of the Ca-P electrolyte system was constructed, which offered a thermodynamic reason for the direct single-phase HA precipitation observed only in this system, but not in conventional concentrated systems.

  11. Thermally responsive polymer electrolytes for inherently safe electrochemical energy storage

    Science.gov (United States)

    Kelly, Jesse C.

    Electrochemical double layer capacitors (EDLCs), supercapacitors and Li-ion batteries have emerged as premier candidates to meet the rising demands in energy storage; however, such systems are limited by thermal hazards, thermal runaway, fires and explosions, all of which become increasingly more dangerous in large-format devices. To prevent such scenarios, thermally-responsive polymer electrolytes (RPEs) that alter properties in electrochemical energy storage devices were designed and tested. These RPEs will be used to limit or halt device operation when temperatures increase beyond a predetermined threshold, therefore limiting further heating. The development of these responsive systems will offer an inherent safety mechanism in electrochemical energy storage devices, while preserving the performance, lifetimes, and versatility that large-format systems require. Initial work focused on the development of a model system that demonstrated the concept of RPEs in an electrochemical device. Aqueous electrolyte solutions of polymers exhibiting properties that change in response to temperature were developed for applications in EDLCs and supercapacitors. These "smart materials" provide a means to control electrochemical systems where polymer phase separation at high temperatures affects electrolyte properties and inhibits device performance. Aqueous RPEs were synthesized using N-isopropylacrylamide, which governs the thermal properties, and fractions of acrylic acid or vinyl sulfonic acids, which provide ions to the solution. The molecular properties of these aqueous RPEs, specifically the ionic composition, were shown to influence the temperature-dependent electrolyte properties and the extent to which these electrolytes control the energy storage characteristics of a supercapacitor device. Materials with high ionic content provided the highest room temperature conductivity and electrochemical activity; however, RPEs with low ionic content provided the highest "on

  12. A facile electrochemical intercalation and microwave assisted exfoliation methodology applied to screen-printed electrochemical-based sensing platforms to impart improved electroanalytical outputs.

    Science.gov (United States)

    Pierini, Gastón D; Foster, Christopher W; Rowley-Neale, Samuel J; Fernández, Héctor; Banks, Craig E

    2018-06-12

    Screen-printed electrodes (SPEs) are ubiquitous with the field of electrochemistry allowing researchers to translate sensors from the laboratory to the field. In this paper, we report an electrochemically driven intercalation process where an electrochemical reaction uses an electrolyte as a conductive medium as well as the intercalation source, which is followed by exfoliation and heating/drying via microwave irradiation, and applied to the working electrode of screen-printed electrodes/sensors (termed EDI-SPEs) for the first time. This novel methodology results in an increase of up to 85% of the sensor area (electrochemically active surface area, as evaluated using an outer-sphere redox probe). Upon further investigation, it is found that an increase in the electroactive area of the EDI-screen-printed based electrochemical sensing platforms is critically dependent upon the analyte and its associated electrochemical mechanism (i.e. adsorption vs. diffusion). Proof-of-concept for the electrochemical sensing of capsaicin, a measure of the hotness of chillies and chilli sauce, within both model aqueous solutions and a real sample (Tabasco sauce) is demonstrated in which the electroanalytical sensitivity (a plot of signal vs. concentration) is doubled when utilising EDI-SPEs over that of SPEs.

  13. Electrochemical studies of the corrosion behavior of a low-carbon steel in aqueous chloride solutions simulating accident conditions of radioactive waste disposal

    International Nuclear Information System (INIS)

    Farvaque-Bera, A.M.; Leistikow, S.

    1991-01-01

    The fine-grained structural steel DIN W.Nr. 1.0566 was exposed to various sulfate and chloride-containing aqueous solutions, the latter ones simulating the potential accidental environment of water intrusion into a salt mine. By electrochemical measurements in salt brines, the following results were achieved: (1) The corrosion rate is highly dependent on salt brine composition, pH and temperature. (2) Active metal dissolution led to formation of shallow pits as surface corrosion phenomenon. Thus, the application of electrochemical techniques - under non-polarized as well as under potentiodynamic conditions - proved to be suitable for fast qualitative testing of the influence of various environmental parameters on steel corrosion. (orig.)

  14. Electrochemical methods to study hydrogen production during interaction of copper with deoxygenated aqueous solution

    International Nuclear Information System (INIS)

    Lilja, Christina; Betova, Iva; Bojinov, Martin

    2016-01-01

    In some countries, spent nuclear fuel is planned to be encapsulated in canisters with a copper shell for corrosion protection, for further disposal in geologic repositories. The possibilities for corrosion after oxygen depletion must be evaluated, even if copper is considered to be immune in oxygen-free water. To follow the interaction of copper with deoxygenated aqueous solution, open-circuit potentiometric and electrochemical impedance measurements have been coupled to in-situ detection of cupric ion, dissolved molecular hydrogen and oxygen concentrations using electrochemical sensors. A kinetic model that considers the production of hydrogen as a catalytic process, the rate of which is proportional to the surface coverage of an intermediate species formed during interaction between copper and the solution is used to interpret the results. Kinetic parameters are estimated by a simultaneous fit of the experimental impedance spectra, the open circuit potential and cupric ion concentration as depending on temperature (22–70 °C) and exposure time (up to 720 h) to the model equations. Using the obtained values and a balance equation of hydrogen production on copper and its diffusion out of the cell through its walls, the kinetic parameters of this process are estimated by fitting dissolved molecular hydrogen concentration vs. time data at the three temperatures.

  15. Electrochemical characteristics of the reduced graphene oxide/carbon nanotube/polypyrrole composites for aqueous asymmetric supercapacitors

    Science.gov (United States)

    Peng, Yu-Jung; Wu, Tzu-Ho; Hsu, Chun-Tsung; Li, Shin-Ming; Chen, Ming-Guan; Hu, Chi-Chang

    2014-12-01

    Polypyrrole (PPy) has been polymerized onto reduced graphene oxide/carbon nanotube (rGO/CNT) to form an rGO/CNT/PPy composite using the chemical oxidation method. The electrochemical characteristics of the above composite in various aqueous electrolytes are systematically compared for the asymmetric supercapacitor application. The electrochemical characteristics of rGO/CNT/PPy in the electrolytes containing K+ show improved reversibility and higher stability. Introducing XC-72 in preparing the electrode has been found to enhance the specific capacitance and the cycle stability of rGO/CNT/PPy. The charge storage stability of rGO/CNT/PPy + XC-72 in various potential windows has been evaluated through the potential bias stress test. An asymmetric supercapacitor (ASC) with a positive electrode of Mn3O4 and a negative electrode of rGO/CNT/PPy + XC-72 is successfully demonstrated, which shows specific energy and power of 14. Wh kg-1 and 6.62 kW kg-1 with a cell voltage of 1.6 V. This ASC with a cell voltage of 1.6 V shows excellent charge-discharge cycle stability and ideal capacitive behavior in NaNO3 even after the application of 3250 charge-discharge cycles.

  16. Microscopic Insights into the Electrochemical Behavior of Non-aqueous Electrolytes in Supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Deen [ORNL; Wu, Jianzhong [ORNL

    2013-01-01

    Electric double-layer capacitors (EDLC) are electrical devices that store energy by adsorption of ionic species at the inner surface of porous electrodes. Compared with aqueous electrolytes, ionic liquid and organic electrolytes have the advantage of larger potential windows, making them attractive for the next generation of EDLC with superior energy and power densities. The performance of both ionic liquid and organic electrolyte EDLC hinges on the judicious selection of the electrode pore size and the electrolyte composition that requires a comprehension of the charging behavior from a microscopic view. In this perspective, we discuss predictions from the classical density functional theory (CDFT) on the dependence of the capacitance on the pore size for ionic-liquid and organic-electrolyte EDLC. CDFT is applicable to electrodes with the pore size ranging from that below the ionic dimensionality to mesoscopic scales, thus unique for investigating the electrochemical behavior of the confined electrolytes for EDLC applications.

  17. Nitrogen-doped reduced graphene oxide electrodes for electrochemical supercapacitors.

    Science.gov (United States)

    Nolan, Hugo; Mendoza-Sanchez, Beatriz; Ashok Kumar, Nanjundan; McEvoy, Niall; O'Brien, Sean; Nicolosi, Valeria; Duesberg, Georg S

    2014-02-14

    Herein we use Nitrogen-doped reduced Graphene Oxide (N-rGO) as the active material in supercapacitor electrodes. Building on a previous work detailing the synthesis of this material, electrodes were fabricated via spray-deposition of aqueous dispersions and the electrochemical charge storage mechanism was investigated. Results indicate that the functionalised graphene displays improved performance compared to non-functionalised graphene. The simplicity of fabrication suggests ease of up-scaling of such electrodes for commercial applications.

  18. Preparation and electrochemical characterization of MnOOH nanowire-graphene oxide

    International Nuclear Information System (INIS)

    Wang Lin; Wang Dianlong

    2011-01-01

    Highlights: → MnOOH nanowire-graphene oxide composites are prepared by hydrothermal reaction in distilled water or 5% ammonia aqueous solution at 130 deg. C, with MnO 2 -graphene oxide composites which are synthesized by a redox reaction between KMnO 4 and graphene oxide. → MnO 2 is deoxidized to MnOOH on graphene oxide through hydrothermal reaction without any extra reductants. → It is found that the electrochemical resistance of MnOOH nanowire-graphene oxide composites decreases and the capacitance increases to 76 F g -1 when hydrothermal reaction is conducted in ammonia aqueous solution. → MnOOH nanowire-graphene oxide composites prepared by hydrothermal reaction in 5% ammonia aqueous solution have excellent capacitance retention ratio at scan rate from 5 mV s -1 to 40 mV s -1 . - Abstract: MnOOH nanowire-graphene oxide composites are prepared by hydrothermal reaction in distilled water or 5% ammonia aqueous solution at 130 deg. C with MnO 2 -graphene oxide composites which are synthesized by a redox reaction between KMnO 4 and graphene oxide. Powder X-ray diffraction (XRD) analyses and energy dispersive X-ray analyses (EDAX) show MnO 2 is deoxidized to MnOOH on graphene oxide through hydrothermal reaction without any extra reductants. The electrochemical capacitance of MnOOH nanowire-graphene oxide composites prepared in 5% ammonia aqueous solution is 76 F g -1 at current density of 0.1 A g -1 . Moreover, electrochemical impedance spectroscopy (EIS) suggests the electrochemical resistance of MnOOH nanowire-graphene oxide composites is reduced when hydrothermal reaction is conducted in ammonia aqueous solution. The relationship between the electrochemical capacitance and the structure of MnOOH nanowire-graphene oxide composites is characterized by cyclic voltammetry (CV) and field emission scanning electron microscopy (FESEM). The results indicate the electrochemical performance of MnOOH nanowire-graphene oxide composites strongly depends on their

  19. Coupled Mechanical-Electrochemical-Thermal Analysis of Failure Propagation in Lithium-ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Chao; Santhanagopalan, Shriram; Pesaran, Ahmad

    2016-07-28

    This is a presentation given at the 12th World Congress for Computational Mechanics on coupled mechanical-electrochemical-thermal analysis of failure propagation in lithium-ion batteries for electric vehicles.

  20. Electrochemical Detection with Preconcentration: Nitroenergetic Contaminants

    Directory of Open Access Journals (Sweden)

    Brandy J. Johnson

    2014-06-01

    Full Text Available This effort evaluated the potential of two prototype devices for enhanced electrochemical detection of 2,4,6-trinitrotoluene (TNT and dinitrotoluene (DNT following preconcentration using an organosilicate sorbent. The bench-scale prototype provides adsorption of the targets from aqueous solution followed by elution in a mixture of methanol and potassium chloride (KCl. Following elution, the eluant is diluted using an aqueous KCl solution to provide sufficient electrolyte for electrochemical analysis. Concentrations of methanol greater than 50% were detrimental to sensor performance and lifetime. Calibration of the electrochemical sensor was completed and results of electrochemical analysis were compared to those of HPLC analysis over a range of concentrations and in varied matrices. TNT detection was found to be consistent and detection limits were improved from 200 ppb to 3 ppb depending on the sample volume utilized. DNT detection showed higher variability and significantly greater false response rates. On the basis of these results, a second, more advanced, prototype was developed and utilized in limited field trials with the intention of moving the technology toward in situ applications.

  1. Can aqueous hydrogen peroxide be used as a stand-alone energy source?

    International Nuclear Information System (INIS)

    Disselkamp, Robert S.

    2010-01-01

    A novel electrochemical scheme to convert a stand-alone supply of aqueous hydrogen peroxide into a fuel cell-ready stream of hydrogen gas plus aqueous hydrogen peroxide is described. The electrochemical cell, consisting of a solid base and solid acid electrocatalyst, together with a proton exchange membrane, comprise the system that converts aqueous hydrogen peroxide into separate gas streams of oxygen and hydrogen. Aqueous hydrogen peroxide is contained in the anode compartment only and exists in the region where oxygen gas is formed, whereas the cathode compartment is where hydrogen gas is generated and therefore exists in a reduced state. A near zero theoretical over-potential can be achieved by the choice of basicity and acidity of the electrode materials. The primary cost of the electrochemical cell is electrode construction and the aqueous hydrogen peroxide energy storage compound. Additional research effort is required to experimentally validate the concept and explore the full economic impact should initial studies, based on the design presented here, prove promising. (author)

  2. Chemical etching of stainless steel 301 for improving performance of electrochemical capacitors in aqueous electrolyte

    Science.gov (United States)

    Jeżowski, P.; Nowicki, M.; Grzeszkowiak, M.; Czajka, R.; Béguin, F.

    2015-04-01

    The main purpose of the study was to increase the surface roughness of stainless steel 301 current collectors by etching, in order to improve the electrochemical performance of electrical double-layer capacitors (EDLC) in 1 mol L-1 lithium sulphate electrolyte. Etching was realized in 1:3:30 (HNO3:HCl:H2O) solution with times varying up to 10 min. For the considered 15 μm thick foil and a mass loss around 0.4 wt.%, pitting was uniform, with diameter of pits ranging from 100 to 300 nm. Atomic force microscopy (AFM) showed an increase of average surface roughness (Ra) from 5 nm for the as-received stainless steel foil to 24 nm for the pitted material. Electrochemical impedance spectroscopy realized on EDLCs with coated electrodes either on as-received or pitted foil in 1 mol L-1 Li2SO4 gave equivalent distributed resistance (EDR) of 8 Ω and 2 Ω, respectively, demonstrating a substantial improvement of collector/electrode interface after pitting. Correlatively, the EDLCs with pitted collector displayed a better charge propagation and low ohmic losses even at relatively high current of 20 A g-1. Hence, chemical pitting of stainless steel current collectors is an appropriate method for optimising the performance of EDLCs in neutral aqueous electrolyte.

  3. In situ electrochemical etching and examination by SPM of titanate ceramics

    International Nuclear Information System (INIS)

    Thorogood, G.J.; Short, K.T; Zhang, Y.

    2002-01-01

    Full text: The aqueous durability of titanate related ceramics is of great importance for the immobilisation of high level radioactive waste-in order to observe the reaction progress at the solid-liquid interface of these durable ceramics, we have attempted to accelerate the dissolution process via electrochemical means by using a SPM cell with electrochemical capability. The experiment involves placing a titanate ceramic disk (with flat polished surfaces) in the electrochemical cell. The cell is then set up with the ceramic acting as one electrode and another electrode being placed in the solution. In a flow through cell it is possible to select the pH and observe the change, not only in surface morphology as dissolution occurs, but also the frictional characteristics of the surface. The SPM tip plays no role in the electrochemical reaction. We will be presenting results from our work and discussing possible mechanisms for dissolution and future directions of the work. Copyright (2002) Australian Society for Electron Microscopy Inc

  4. Electrochemical hydrogen Storage Systems

    International Nuclear Information System (INIS)

    Macdonald, Digby

    2010-01-01

    As the global need for energy increases, scientists and engineers have found a possible solution by using hydrogen to power our world. Although hydrogen can be combusted as a fuel, it is considered an energy carrier for use in fuel cells wherein it is consumed (oxidized) without the production of greenhouse gases and produces electrical energy with high efficiency. Chemical storage of hydrogen involves release of hydrogen in a controlled manner from materials in which the hydrogen is covalently bound. Sodium borohydride and aminoborane are two materials given consideration as chemical hydrogen storage materials by the US Department of Energy. A very significant barrier to adoption of these materials as hydrogen carriers is their regeneration from 'spent fuel,' i.e., the material remaining after discharge of hydrogen. The U.S. Department of Energy (DOE) formed a Center of Excellence for Chemical Hydrogen Storage, and this work stems from that project. The DOE has identified boron hydrides as being the main compounds of interest as hydrogen storage materials. The various boron hydrides are then oxidized to release their hydrogen, thereby forming a 'spent fuel' in the form of a lower boron hydride or even a boron oxide. The ultimate goal of this project is to take the oxidized boron hydrides as the spent fuel and hydrogenate them back to their original form so they can be used again as a fuel. Thus this research is essentially a boron hydride recycling project. In this report, research directed at regeneration of sodium borohydride and aminoborane is described. For sodium borohydride, electrochemical reduction of boric acid and sodium metaborate (representing spent fuel) in alkaline, aqueous solution has been investigated. Similarly to literature reports (primarily patents), a variety of cathode materials were tried in these experiments. Additionally, approaches directed at overcoming electrostatic repulsion of borate anion from the cathode, not described in the

  5. Electrochemical hydrogen Storage Systems

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Digby Macdonald

    2010-08-09

    As the global need for energy increases, scientists and engineers have found a possible solution by using hydrogen to power our world. Although hydrogen can be combusted as a fuel, it is considered an energy carrier for use in fuel cells wherein it is consumed (oxidized) without the production of greenhouse gases and produces electrical energy with high efficiency. Chemical storage of hydrogen involves release of hydrogen in a controlled manner from materials in which the hydrogen is covalently bound. Sodium borohydride and aminoborane are two materials given consideration as chemical hydrogen storage materials by the US Department of Energy. A very significant barrier to adoption of these materials as hydrogen carriers is their regeneration from 'spent fuel,' i.e., the material remaining after discharge of hydrogen. The U.S. Department of Energy (DOE) formed a Center of Excellence for Chemical Hydrogen Storage, and this work stems from that project. The DOE has identified boron hydrides as being the main compounds of interest as hydrogen storage materials. The various boron hydrides are then oxidized to release their hydrogen, thereby forming a 'spent fuel' in the form of a lower boron hydride or even a boron oxide. The ultimate goal of this project is to take the oxidized boron hydrides as the spent fuel and hydrogenate them back to their original form so they can be used again as a fuel. Thus this research is essentially a boron hydride recycling project. In this report, research directed at regeneration of sodium borohydride and aminoborane is described. For sodium borohydride, electrochemical reduction of boric acid and sodium metaborate (representing spent fuel) in alkaline, aqueous solution has been investigated. Similarly to literature reports (primarily patents), a variety of cathode materials were tried in these experiments. Additionally, approaches directed at overcoming electrostatic repulsion of borate anion from the cathode, not

  6. Continuous synthesis of colloidal silver nanoparticles by electrochemical discharge in aqueous solutions

    International Nuclear Information System (INIS)

    Tseng, Kuo-Hsiung; Chen, Yu-Chun; Shyue, Jing-Jong

    2011-01-01

    This article presents an electrochemical discharge (ECD) method that consists of a combination of chemical methods and electric arc discharges. In the method, 140 V is applied to an Ag electrode from a DC power supply. The arc-discharge between the electrodes produces metallic silver nanoparticles and silver ions in the aqueous solution. Compared with the original arc discharge, this ECD method creates smaller nanoparticles, prevents clumping of the nanoparticles, and shortens the production time. The citrate ions also reduce the silver ions to silver nanoparticles. In addition, the citrate ions cap the surface of the produced silver nanoparticles and the zeta potential increases. In this article, the weight loss of the electrodes and the reduction of silver ions to silver nanoparticles as a function of citrate concentration and electric conductivity of the medium are discussed. Furthermore, the properties of the colloidal silver prepared with ECD are analyzed by UV–Vis spectroscopy, dynamic light scattering, electrophoresis light scattering, and scanning electron microscopy. Finally, a continuous production apparatus is presented for the continuous production of colloidal silver.

  7. Aqueous based asymmetrical-bipolar electrochemical capacitor with a 2.4 V operating voltage

    Science.gov (United States)

    Wu, Haoran; Lian, Keryn

    2018-02-01

    A novel asymmetrical-bipolar electrochemical capacitor system leveraging the contributions of a Zn-CNT asymmetrical electrode and a KOH-H2SO4 dual-pH electrolyte was developed. The positive and negative electrodes operated in electrolytes with different pH, exploiting the maximum potential of both electrodes, which led to a cell voltage of 2.4 V. The potential tracking of both electrodes revealed that the Zn negative electrode could maintain a potential at -1.2 V, while the CNT positive electrode can be charged to +1.2 V without significant irreversible reactions. A bipolar ion exchange membrane has effectively separated the acid and alkaline from neutralization, which resulted in stable performance of the device with capacitance retention of 94% and coulombic efficiency of 99% over 10,000 cycles. This asymmetrical-bipolar design overcomes the thermodynamic limit of water decomposition, opening a new avenue towards high energy and high power density aqueous-based ECs.

  8. Electrochemical properties of arc-black and carbon nano-balloon as electrochemical capacitor electrodes

    International Nuclear Information System (INIS)

    Sato, T; Suda, Y; Uruno, H; Takikawa, H; Tanoue, H; Ue, H; Aoyagi, N; Okawa, T; Shimizu, K

    2012-01-01

    In this study, we used two types of carbon nanomaterials, arc-black (AcB) which has an amorphous structure and carbon nano-balloon (CNB) which has a graphitic structure as electrochemical capacitor electrodes. We made a coin electrode from these carbon materials and fabricated an electric double-layer capacitor (EDLC) that sandwiches a separator between the coin electrodes. On the other hand, RuO 2 was loaded on these carbon materials, and we fabricated a pseudo-capacitor that has an ion insertion mechanism into RuO 2 . For comparison with these carbon materials, activated carbon (AC) was also used for a capacitor electrode. The electrochemical properties of all the capacitors were evaluated in 1M H 2 SO 4 aqueous solution. As a result of EDLC performance, AcB electrode had a higher specific capacitance than AC electrode at a high scan rate (≥ 100 mV/s). In the evaluation of pseudo-capacitor performance, RuO 2 -loaded CNB electrode showed a high specific capacitance of 734 F/g per RuO 2 weight.

  9. Octahedral magnesium manganese oxide molecular sieves as the cathode material of aqueous rechargeable magnesium-ion battery

    International Nuclear Information System (INIS)

    Zhang, Hongyu; Ye, Ke; Shao, Shuangxi; Wang, Xin; Cheng, Kui; Xiao, Xue; Wang, Guiling; Cao, Dianxue

    2017-01-01

    Highlights: • The mico-sheet Mg-OMS-1 is synthesized by a simple hydrothermal method. • The mechanism of Mg 2+ insertion/deinsertion from Mg-OMS-1 is explored. • The electrode exhibits a good electrochemical performance in MgCl 2 electrolyte. - Abstract: Aqueous magnesium-ion batteries have shown the desired properties of high safety characteristics, similar electrochemical properties to lithium and low cost for energy storage applications. The micro-sheet morphology of todorokite-type magnesium manganese oxide molecular sieve (Mg-OMS-1) material, which applies as a novel cathode material for magnesium-ion battery, is obtained by the simple hydrothermal method. The structure and morphology of the particles are confirmed by X-ray power diffraction, X-ray photoelectron spectroscopy, inductively coupled plasma, scanning and transmission electron microscopy. The electrochemical performance of Mg-OMS-1 is researched by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and constant current charge-discharge measurement. Mg-OMS-1 shows a good battery behavior for Mg 2+ insertion and deinsertion in the aqueous electrolyte. When discharging at 10 mA g −1 in 0.2 mol dm −3 MgCl 2 aqueous electrolyte, the initial discharge capacity reaches 300 mAh g −1 . The specific capacity retention rate is 83.7% after cycling 300 times at 100 mA g −1 in 0.5 mol dm −3 MgCl 2 electrolyte with a columbic efficiency of nearly 100%.

  10. Highly Stable Aqueous Zinc-ion Storage Using Layered Calcium Vanadium Oxide Bronze Cathode

    KAUST Repository

    Xia, Chuan; Guo, Jing; Li, Peng; Zhang, Xixiang; Alshareef, Husam N.

    2018-01-01

    Cost-effective aqueous rechargeable batteries are attractive alternatives to non-aqueous cells for stationary grid energy storage. Among different aqueous cells, zinc-ion batteries (ZIBs), based on Zn2+ intercalation chemistry, stand out as they can employ high-capacity Zn metal as anode material. Herein, we report a layered calcium vanadium oxide bronze as cathode material for aqueous Zn batteries. For the storage of Zn2+ ions in aqueous electrolyte, we demonstrate that calcium based bronze structure can deliver a high capacity of 340 mAh g-1 at 0.2 C, good rate capability and very long cycling life (96% retention after 3000 cycles at 80 C). Further, we investigate the Zn2+ storage mechanism, and the corresponding electrochemical kinetics in this bronze cathode. Finally, we show that our Zn cell delivers an energy density of 267 Wh kg-1 at a power density of 53.4 W kg-1.

  11. Highly Stable Aqueous Zinc-ion Storage Using Layered Calcium Vanadium Oxide Bronze Cathode

    KAUST Repository

    Xia, Chuan

    2018-02-12

    Cost-effective aqueous rechargeable batteries are attractive alternatives to non-aqueous cells for stationary grid energy storage. Among different aqueous cells, zinc-ion batteries (ZIBs), based on Zn2+ intercalation chemistry, stand out as they can employ high-capacity Zn metal as anode material. Herein, we report a layered calcium vanadium oxide bronze as cathode material for aqueous Zn batteries. For the storage of Zn2+ ions in aqueous electrolyte, we demonstrate that calcium based bronze structure can deliver a high capacity of 340 mAh g-1 at 0.2 C, good rate capability and very long cycling life (96% retention after 3000 cycles at 80 C). Further, we investigate the Zn2+ storage mechanism, and the corresponding electrochemical kinetics in this bronze cathode. Finally, we show that our Zn cell delivers an energy density of 267 Wh kg-1 at a power density of 53.4 W kg-1.

  12. Advances of aqueous rechargeable lithium-ion battery: A review

    Science.gov (United States)

    Alias, Nurhaswani; Mohamad, Ahmad Azmin

    2015-01-01

    The electrochemical characteristic of the aqueous rechargeable lithium-ion battery has been widely investigated in efforts to design a green and safe technology that can provide a highly specific capacity, high efficiency and long life for high power applications such as the smart grid and electric vehicle. It is believed that the advantages of this battery will overcome the limitations of the rechargeable lithium-ion battery with organic electrolytes that comprise safety and create high fabrication cost issues. This review focuses on the opportunities of the aqueous rechargeable lithium-ion battery compared to the conventional rechargeable lithium-ion battery with organic-based electrolytes. Previously reported studies are briefly summarised, together with the presentation of new findings based on the conductivity, morphology, electrochemical performance and cycling stability results. The factors that influence the electrochemical performance, the challenges and potential of the aqueous rechargeable lithium-ion battery are highlighted in order to understand and maintained the excellent battery performance.

  13. Understanding of carbon-based supercapacitors ageing mechanisms by electrochemical and analytical methods

    Science.gov (United States)

    Liu, Yinghui; Soucaze-Guillous, Benoît; Taberna, Pierre-Louis; Simon, Patrice

    2017-10-01

    In order to shed light on ageing mechanisms of Electrochemical Double Layer Capacitor (EDLC), two kinds of activated carbons are studied in tetraethyl ammonium tetrafluoroborate (Et4NBF4) in acetonitrile. In floating mode, it turns out that two different ageing mechanisms are observed, depending on the activated carbon electrode materials used. On one hand, carbon A exhibits a continuous capacitance and series resistance fall-off; on the other hand, for carbon B, only the series resistance degrades after ageing while the capacitance keeps unchanged. Additional electrochemical characterizations (Electrochemical Impedance Spectroscopy - EIS - and diffusion coefficient calculations) were carried out showing that carbon A's ageing behavior is suspected to be primarily related to the carbon degradation while for carbon B a passivation occurs leading to the formation of a Solid Electrolyte Interphase-Like (SEI-L) film. These hypotheses are supported by TG-IR and Raman spectroscopy analysis. The outcome forms the latter is an increase of carbon defects on carbon A on positive electrode.

  14. Electroresponsive Aqueous Silk Protein As “Smart” Mechanical Damping Fluid

    Science.gov (United States)

    2015-01-01

    Here we demonstrate the effectiveness of an electroresponsive aqueous silk protein polymer as a smart mechanical damping fluid. The aqueous polymer solution is liquid under ambient conditions, but is reversibly converted into a gel once subjected to an electric current, thereby increasing or decreasing in viscosity. This nontoxic, biodegradable, reversible, edible fluid also bonds to device surfaces and is demonstrated to reduce friction and provide striking wear protection. The friction and mechanical damping coefficients are shown to modulate with electric field exposure time and/or intensity. Damping coefficient can be modulated electrically, and then preserved without continued power for longer time scales than conventional “smart” fluid dampers. PMID:24750065

  15. Mechanism of glucose electrochemical oxidation on gold surface

    KAUST Repository

    Pasta, Mauro; La Mantia, Fabio; Cui, Yi

    2010-01-01

    The complex oxidation of glucose at the surface of gold electrodes was studied in detail in different conditions of pH, buffer and halide concentration. As observed in previous studies, an oxidative current peak occurs during the cathodic sweep showing a highly linear dependence on glucose concentration, when other electrolyte conditions are unchanged. The effect of the different conditions on the intensity of this peak has stressed the limitations of the previously proposed mechanisms. A mechanism able to explain the presence of this oxidative peak was proposed. The mechanism takes into account ion-sorption and electrochemical adsorption of OH-, buffer species (K2HPO4/KH2PO4) and halides. © 2010 Elsevier Ltd. All rights reserved.

  16. Mechanism of glucose electrochemical oxidation on gold surface

    KAUST Repository

    Pasta, Mauro

    2010-08-01

    The complex oxidation of glucose at the surface of gold electrodes was studied in detail in different conditions of pH, buffer and halide concentration. As observed in previous studies, an oxidative current peak occurs during the cathodic sweep showing a highly linear dependence on glucose concentration, when other electrolyte conditions are unchanged. The effect of the different conditions on the intensity of this peak has stressed the limitations of the previously proposed mechanisms. A mechanism able to explain the presence of this oxidative peak was proposed. The mechanism takes into account ion-sorption and electrochemical adsorption of OH-, buffer species (K2HPO4/KH2PO4) and halides. © 2010 Elsevier Ltd. All rights reserved.

  17. The strategies of DNA immobilization and hybridization detection mechanism in the construction of electrochemical DNA sensor: A review

    Directory of Open Access Journals (Sweden)

    Jahwarhar Izuan Abdul Rashid

    2017-11-01

    Full Text Available In recent years, electrochemical deoxyribonucleic acid (DNA sensor has recently emerged as promising alternative clinical diagnostic devices especially for infectious disease by exploiting DNA recognition events and converting them into an electrochemical signal. This is because the existing DNA diagnostic method possesses certain drawbacks such as time-consuming, expensive, laborious, low selectivity and sensitivity. DNA immobilization strategies and mechanism of electrochemical detection are two the most important aspects that should be considered before developing highly selective and sensitive electrochemical DNA sensor. Here, we focus on some recent strategies for DNA probes immobilization on the surface of electrochemical transducer such as adsorption, covalent bonding and Avidin/Streptavidin-Biotin interaction on the electrode surface for specific interaction with its complementary DNA target. A numerous approach for DNA hybridization detection based electrochemical technique that frequently used including direct DNA electrochemical detection and label based electrochemical (redox-active indicator, enzyme label and nanoparticles were also discussed in aiming to provide general guide for the design of electrochemical DNA sensor. We also discussed the challenges and suggestions to improve the application of electrochemical DNA sensor at point-care setting. Keywords: Electrochemical DNA sensor, DNA immobilization, DNA hybridization, Electrochemical mechanism

  18. Corrosion of conductive polypyrrole: Effects of environmental factors, electrochemical stimulation, and doping anions

    International Nuclear Information System (INIS)

    Qi Kai; Qiu Yubing; Chen Zhenyu; Guo Xingpeng

    2012-01-01

    Highlights: ► Corrosive galvanic cells form on PPy film with the electrochemical reduction of O 2. ► Suitable electrochemical stimulation can inhibit the PPy’s corrosion. ► PPy film doped with larger sized anions has better corrosion resistance performance. - Abstract: The effects of environmental factors, electrochemical stimulation, and doping anions on the corrosion behaviour of conductive polypyrrole (PPy) films in alkaline aqueous media were studied with cyclic voltammetry, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. High concentrations of electrolyte, low dissolved oxygen and low temperatures enhance the stability of PPy. Polarising PPy at a negative potential inhibits its corrosion obviously. PPy doped with large counter anions shows better corrosion resistance than PPy doped with small counter ions. The possible mechanism involved in PPy corrosion process is discussed.

  19. ELECTROCHEMICAL STUDIES OF N'-FERROCENYLMETHYL-N ...

    African Journals Online (AJOL)

    2011-12-31

    Phenylbenzohydrazide. FcX was studied in acetonitrile with tetrabutylammonium hexafluorophosphate as the supporting electrolyte and aqueous ethanol using the electrochemical technique. This study using cyclic (CV) and rotating ...

  20. Electrochemically conductive treatment of TiO2 nanotube arrays in AlCl3 aqueous solution for supercapacitors

    Science.gov (United States)

    Zhong, Wenjie; Sang, Shangbin; Liu, Yingying; Wu, Qiumei; Liu, Kaiyu; Liu, Hongtao

    2015-10-01

    Highly ordered TiO2 nanotube arrays (NTAs) with excellent stability and large specific surface area make them competitive using as supercapacitor materials. Improving the conductivity of TiO2 is of great concern for the construction of high-performance supercapacitors. In this work, we developed a novel approach to improve the performance of TiO2 materials, involving the fabrication of Al-doped TiO2 NTAs by a simple electrochemical cathodic polarization treatment in AlCl3 aqueous solution. The prepared Al-doped TiO2 NTAs exhibited excellent electrochemical performances, attributing to the remarkably improved electrical conductivity (i.e., from approx. 10 kΩ to 20 Ω). Further analysis showed that Al3+ ions rather than H+ protons doped into TiO2 lattice cause this high conductivity. A MnO2/Al-TiO2 composite was evaluated by cyclic voltammetry, and achieved the specific capacitance of 544 F g-1, and the Ragone plot of the sample showed a high power density but less reduction of energy density. These results indicate that the MnO2/Al-TiO2 NTAs sample could be served as a promising electrode material for high -performance supercapacitors.

  1. Electronic structure tautomerism, and mechanism of H-D exchange in imidazole aqueous solutions

    International Nuclear Information System (INIS)

    Borisov, Yu.A.; Vorob'eva, N.P.; Abronin, I.A.; Kolomiets, A.F.

    1988-01-01

    The imidazole electronic structure in a gaseous phase is studied taking into account the influence of solvation effects in aqueous solutions. Possible mechanisms of tautomeric transformations and H-D exchange reactions with water molecules are discussed. Using the quantum chemistry methods, it is shown that the intramolecular mechanism of imidazole isomerization in the gaseous phase and the aqueous solution is unprofitable, and the intermolecular mechanism can proceed through the stage of protonated and carbene form formation

  2. A Review for Aqueous Electrochemical Supercapacitors

    OpenAIRE

    Zhao, Cuimei; Zheng, Weitao

    2015-01-01

    Electrochemical capacitor is the most promising energy-storage device that can meet the demands of high-power supply and long cycle life; however, low-energy density and high-fabrication cost limit its further development. Researchers have paid more attention to the development of electrode material in the past, and very few people attach importance to the research of the electrolyte, especially the redox electrolyte, which is important for improving specific capacitance greatly. This paper p...

  3. Needle-like Co3O4 anchored on the graphene with enhanced electrochemical performance for aqueous supercapacitors.

    Science.gov (United States)

    Guan, Qun; Cheng, Jianli; Wang, Bin; Ni, Wei; Gu, Guifang; Li, Xiaodong; Huang, Ling; Yang, Guangcheng; Nie, Fude

    2014-05-28

    We synthesized the needle-like cobalt oxide/graphene composites with different mass ratios, which are composed of cobalt oxide (Co3O4 or CoO) needle homogeneously anchored on graphene nanosheets as the template, by a facile hydrothermal method. Without the graphene as the template, the cobalt precursor tends to group into urchin-like spheres formed by many fine needles. When used as electrode materials of aqueous supercapacitor, the composites of the needle-like Co3O4/graphene (the mass ratio of graphene oxide(GO) and Co(NO3)2·6H2O is 1:5) exhibit a high specific capacitance of 157.7 F g(-1) at a current density of 0.1 A g(-1) in 2 mol L(-1) KOH aqueous solution as well as good rate capability. Meanwhile, the capacitance retention keeps about 70% of the initial value after 4000 cycles at a current density of 0.2 A g(-1). The enhancement of excellent electrochemical performances may be attributed to the synergistic effect of graphene and cobalt oxide components in the unique multiscale structure of the composites.

  4. Multi-level Quantum Mechanics and Molecular Mechanics Study of Ring Opening Process of Guanine Damage by Hydroxyl Radical in Aqueous Solution.

    Science.gov (United States)

    Liu, Peng; Wang, Qiong; Niu, Meixing; Wang, Dunyou

    2017-08-10

    Combining multi-level quantum mechanics theories and molecular mechanics with an explicit water model, we investigated the ring opening process of guanine damage by hydroxyl radical in aqueous solution. The detailed, atomic-level ring-opening mechanism along the reaction pathway was revealed in aqueous solution at the CCSD(T)/MM levels of theory. The potentials of mean force in aqueous solution were calculated at both the DFT/MM and CCSD(T)/MM levels of the theory. Our study found that the aqueous solution has a significant effect on this reaction in solution. In particular, by comparing the geometries of the stationary points between in gas phase and in aqueous solution, we found that the aqueous solution has a tremendous impact on the torsion angles much more than on the bond lengths and bending angles. Our calculated free-energy barrier height 31.6 kcal/mol at the CCSD(T)/MM level of theory agrees well with the one obtained based on gas-phase reaction profile and free energies of solvation. In addition, the reaction path in gas phase was also mapped using multi-level quantum mechanics theories, which shows a reaction barrier at 19.2 kcal/mol at the CCSD(T) level of theory, agreeing very well with a recent ab initio calculation result at 20.8 kcal/mol.

  5. Evaluation of Iron Nickel Oxide Nanopowder as Corrosion Inhibitor: Effect of Metallic Cations on Carbon Steel in Aqueous NaCl

    Energy Technology Data Exchange (ETDEWEB)

    Chaudhry, A. U.; Mishra, Brajendra [Colorado School of Mines, Denver (United States); Mittal, Vikas [The Petroleum Institute, Abu Dhabi (United Arab Emirates)

    2016-01-15

    The aim of this study was to evaluate the use of iron-nickel oxide (Fe{sub 2}O{sub 3}.NiO) nanopowder (FeNi) as an anti-corrosion pigment for a different application. The corrosion protection ability and the mechanism involved was determined using aqueous solution of FeNi prepared in a corrosive solution containing 3.5 wt.% NaCl. Anti-corrosion abilities of aqueous solution were determined using electrochemical impedance spectroscopy (EIS) on line pipe steel (API 5L X-80). The protection mechanism involved the adsorption of metallic cations on the steel surface forming a protective film. Analysis of EIS spectra revealed that corrosion inhibition occurred at low concentration, whereas higher concentration of aqueous solution produced induction behavior.

  6. Status of the DOE battery and electrochemical technology program. III

    International Nuclear Information System (INIS)

    Roberts, R.

    1982-02-01

    This report reviews the status of the Department of Energy Subelement on Electrochemical Storage Systems. It emphasizes material presented at the Fourth US Department of Energy Battery and Electrochemical Contractors' Conference, held June 2-4, 1981. The conference stressed secondary batteries, however, the aluminum/air mechanically rechargeable battery and selected topics on industrial electrochemical processes were included. The potential contributions of the battery and electrochemical technology efforts to supported technologies: electric vehicles, solar electric systems, and energy conservation in industrial electrochemical processes, are reviewed. The analyses of the potential impact of these systems on energy technologies as the basis for selecting specific battery systems for investigation are noted. The battery systems in the research, development, and demonstration phase discussed include: aqueous mobile batteries (near term) - lead-acid, iron/nickel-oxide, zinc/nickel-oxide; advanced batteries - aluminum/air, iron/air, zinc/bromine, zinc/ferricyanide, chromous/ferric, lithium/metal sulfide, sodium/sulfur; and exploratory batteries - lithium organic electrolyte, lithium/polymer electrolyte, sodium/sulfur (IV) chloroaluminate, calcium/iron disulfide, lithium/solid electrolyte. Supporting research on electrode reactions, cell performance modeling, new battery materials, ionic conducting solid electrolytes, and electrocatalysis is reviewed. Potential energy saving processes for the electrowinning of aluminum and zinc, and for the electrosynthesis of inorganic and organic compounds are included

  7. Corrosion of metallic materials. Dry corrosion, aqueous corrosion and corrosion by liquid metal, methods of protection

    International Nuclear Information System (INIS)

    Helie, Max

    2015-01-01

    This book is based on a course on materials given in an engineering school. The author first gives an overview of metallurgy issues: metallic materials (pure metals, metallic alloys), defects of crystal lattices (point defects, linear defects or dislocations), equilibrium diagrams, steels and cast, thermal processing of steels, stainless steels, aluminium and its alloys, copper and its alloys. The second part addresses the properties and characterization of surfaces and interfaces: singularity of a metal surface, surface energy of a metal, energy of grain boundaries, adsorption at a material surface, metal-electrolyte interface, surface oxide-electrolyte interface, techniques of surface analysis. The third chapter addresses the electrochemical aspects of corrosion: description of the corrosion phenomenon, free enthalpy of a compound and free enthalpy of a reaction, case of dry corrosion (thermodynamic aspect, Ellingham diagram, oxidation mechanisms, experimental study, macroscopic modelling), case of aqueous corrosion (electrochemical thermodynamics and kinetics, experimental determination of corrosion rate). The fourth part addresses the different forms of aqueous corrosion: generalized corrosion (atmospheric corrosion, mechanisms and tests), localized corrosion (galvanic, pitting, cracking, intergranular, erosion and cavitation), particular cases of stress cracking (stress corrosion, fatigue-corrosion, embrittlement by hydrogen), and bi-corrosion (of non alloyed steels, of stainless steels, and of aluminium and copper alloys). The sixth chapter addresses the struggle and the protection against aqueous corrosion: methods of prevention, scope of use of main alloys, geometry-based protection of pieces, use of corrosion inhibitors, use of organic or metallic coatings, electrochemical protection. The last chapter proposes an overview of corrosion types in industrial practices: in the automotive industry, in the oil industry, in the aircraft industry, and in the

  8. Building micro and nanosystems with electrochemical discharges

    International Nuclear Information System (INIS)

    Wuethrich, Rolf; Allagui, Anis

    2010-01-01

    Since the discovery of the electrochemical discharge phenomenon by Fizeau and Foucault, several contributions have expanded the wide range of applications associated with this high current density electrochemical process. The complexity of the phenomenon, from the macroscopic to the microscopic scales, led since then to experimental and theoretical studies from different research fields. This contribution reviews the chemical and electrochemical perspectives where a mechanistic model based on results from radiation chemistry of aqueous solutions is proposed. In addition applications to micro-machining and fabrication of nanoparticles are discussed.

  9. Building micro and nanosystems with electrochemical discharges

    Energy Technology Data Exchange (ETDEWEB)

    Wuethrich, Rolf, E-mail: wuthrich@encs.concordia.c [Department of Mechanical and Industrial Engineering, Concordia University, 1455 de Maisonneuve Blvd. West, Montreal, QC (Canada); Allagui, Anis [Department of Mechanical and Industrial Engineering, Concordia University, 1455 de Maisonneuve Blvd. West, Montreal, QC (Canada)

    2010-11-30

    Since the discovery of the electrochemical discharge phenomenon by Fizeau and Foucault, several contributions have expanded the wide range of applications associated with this high current density electrochemical process. The complexity of the phenomenon, from the macroscopic to the microscopic scales, led since then to experimental and theoretical studies from different research fields. This contribution reviews the chemical and electrochemical perspectives where a mechanistic model based on results from radiation chemistry of aqueous solutions is proposed. In addition applications to micro-machining and fabrication of nanoparticles are discussed.

  10. Probing the characteristics of casein as green binder for non-aqueous electrochemical double layer capacitors' electrodes

    Science.gov (United States)

    Varzi, Alberto; Raccichini, Rinaldo; Marinaro, Mario; Wohlfahrt-Mehrens, Margret; Passerini, Stefano

    2016-09-01

    Casein from bovine milk is evaluated in this work as binding agent for electrochemical double layer capacitors (EDLCs) electrodes. It is demonstrated that casein provides excellent adhesion strength to the current collector (1187 kPa compared to 51 kPa achieved with PVdF), thus leading to mechanically stable electrodes. At the same time, it offers high thermal stability (above 200 °C) and electrochemical stability in organic electrolytes. Apparently though, the casein-based electrodes offer lower electronic conductivity than those based on other state-of-the-art binders, which can limit the rate performance of the resulting EDLC. In the attempt of improving the electrochemical performance, it is found that the application of a pressing step can solve this issue, leading to excellent rate capability (up to 84% capacitance retention at 50 mA cm-2) and cycling stability (96.8% after 10,000 cycles at 10 mA cm-2) in both PC- and ACN-based electrolytes. Although the adhesive power casein is known since ancient times, this report presents the first proof of concept of its employment in electrochemical power sources.

  11. Characterization of a stirred tank electrochemical cell for water disinfection processes

    International Nuclear Information System (INIS)

    Polcaro, A.M.; Vacca, A.; Mascia, M.; Palmas, S.; Pompei, R.; Laconi, S.

    2007-01-01

    Laboratory experiments were performed to characterize the behaviour of an electrochemical cell equipped with boron-doped diamond anodes and to verify its effectiveness in water disinfection. The hydrodynamic regime was determined when the cell worked either in batch or in continuous mode. Galvanostatic electrolyses of aqueous 1 mM Na 2 SO 4 solutions were performed to investigate on the oxidant production in different experimental conditions. The same solutions contaminated by E. coli, enterococci and coliforms were used as test media to verify the effectiveness of the system in the disinfection process. Experimental results indicated that the major inactivation mechanism of bacteria in the electrochemical cell is a disinfection by electrochemically generated oxidants, however a cooperative effect of superficial reaction has to be taken into account. The great capability of BDD anode to produce reactive oxygen species (ROS) and other oxidizing species during the electrolysis allows to establish a chlorine-free disinfection process

  12. Degradation of Acetaminophen and Its Transformation Products in Aqueous Solutions by Using an Electrochemical Oxidation Cell with Stainless Steel Electrodes

    Directory of Open Access Journals (Sweden)

    Miguel Ángel López Zavala

    2016-09-01

    Full Text Available In this study, a novel electrochemical oxidation cell using stainless steel electrodes was found to be effective in oxidizing acetaminophen and its transformation products in short reaction times. Aqueous solutions of 10 mg/L-acetaminophen were prepared at pH 3, 5, 7, and 9. These solutions were electrochemically treated at direct current (DC densities of 5.7 mA/cm2, 7.6 mA/cm2, and 9.5 mA/cm2. The pharmaceutical and its intermediates/oxidation products were determined by using high pressure liquid chromatography (HPLC. The results showed that electrochemical oxidation processes occurred in the cell. Acetaminophen degradation rate constants increased proportionally with the increase of current intensity. High current densities accelerated the degradation of acetaminophen; however, this effect diminished remarkably at pH values greater than 5. At pH 3 and 9.5 mA/cm2, the fastest degradation of acetaminophen and its intermediates/oxidation products was achieved. To minimize the wear down of the electrodes, a current density ramp is recommended, first applying 9.5 mA/cm2 during 2.5 min or 7.6 mA/cm2 during 7.5 min and then continuing the electrochemical oxidation process at 5.7 mA/cm2. This strategy will hasten the acetaminophen oxidation, extend the electrode’s life, and shorten the reaction time needed to degrade the pharmaceutical and its intermediates/oxidation products. DC densities up to 9.5 mA/cm2 can be supplied by photovoltaic cells.

  13. Destructive electronics from electrochemical-mechanically triggered chemical dissolution

    International Nuclear Information System (INIS)

    Sim, Kyoseung; Wang, Xu; Yu, Cunjiang; Li, Yuhang; Linghu, Changhong; Song, Jizhou; Gao, Yang

    2017-01-01

    The considerable need to enhance data and hardware security suggest one possible future for electronics where it is possible to destroy them and even make them disappear physically. This paper reports a type of destructive electronics which features fast transience from chemical dissolution on-demand triggered in an electrochemical-mechanical manner. The detailed materials, mechanics, and device construction of the destructive electronics are presented. Experiment and analysis of the triggered releasing and transience study of electronic materials, resistors and metal-oxide-semiconductor field effect transistors illustrate the key aspects of the destructive electronics. The reported destructive electronics is useful in a wide range of areas from security and defense, to medical applications (paper)

  14. The electrochemical performance of aqueous rechargeable battery of Zn/Na0.44MnO2 based on hybrid electrolyte

    Science.gov (United States)

    Wu, Xianwen; Li, Yehua; Xiang, Yanhong; Liu, Zhixiong; He, Zeqiang; Wu, Xianming; Li, Youji; Xiong, Lizhi; Li, Chuanchang; Chen, Jian

    2016-12-01

    There is a broad application prospect for smart grid about aqueous rechargeable sodium-ion battery. In order to improve its electrochemical performance, a hybrid cationic aqueous-based rechargeable battery system based on the nanostructural Na0.44MnO2 and metallic zinc foil as the positive and negative electrodes respectively is built up. Nano rod-like Na0.44MnO2 is synthesized by sol-gel method followed by calcination at 850 °C for 9 h, and various characterization techniques including the X-ray diffraction (XRD) and scanning electron microscopy (SEM) are used to investigate the structure and morphology of the as-prepared material. The cyclic voltammetry, galvanostatic charge-discharge and self-discharge measurements are performed at the same time. The results show that the battery delivers a very high initial discharge capacity of 186.2 mAh g-1 at 0.2 C-rate in the range of 0.5-2.0 V, and it exhibits a discharge capacity of 113.3 mAh g-1 at high current density of 4 C-rate, indicative of excellent rate capability.

  15. Electrochemical-mechanical coupled modeling and parameterization of swelling and ionic transport in lithium-ion batteries

    Science.gov (United States)

    Sauerteig, Daniel; Hanselmann, Nina; Arzberger, Arno; Reinshagen, Holger; Ivanov, Svetlozar; Bund, Andreas

    2018-02-01

    The intercalation and aging induced volume changes of lithium-ion battery electrodes lead to significant mechanical pressure or volume changes on cell and module level. As the correlation between electrochemical and mechanical performance of lithium ion batteries at nano and macro scale requires a comprehensive and multidisciplinary approach, physical modeling accounting for chemical and mechanical phenomena during operation is very useful for the battery design. Since the introduced fully-coupled physical model requires proper parameterization, this work also focuses on identifying appropriate mathematical representation of compressibility as well as the ionic transport in the porous electrodes and the separator. The ionic transport is characterized by electrochemical impedance spectroscopy (EIS) using symmetric pouch cells comprising LiNi1/3Mn1/3Co1/3O2 (NMC) cathode, graphite anode and polyethylene separator. The EIS measurements are carried out at various mechanical loads. The observed decrease of the ionic conductivity reveals a significant transport limitation at high pressures. The experimentally obtained data are applied as input to the electrochemical-mechanical model of a prismatic 10 Ah cell. Our computational approach accounts intercalation induced electrode expansion, stress generation caused by mechanical boundaries, compression of the electrodes and the separator, outer expansion of the cell and finally the influence of the ionic transport within the electrolyte.

  16. Electrochemical catalytic treatment of phenol wastewater

    International Nuclear Information System (INIS)

    Ma Hongzhu; Zhang Xinhai; Ma Qingliang; Wang Bo

    2009-01-01

    The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

  17. Electrochemical catalytic treatment of phenol wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Ma Hongzhu, E-mail: hzmachem@snnu.edu.cn [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Zhang Xinhai [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Ma Qingliang [Department of Applied Physics, College of Sciences, Taiyuan University of Technology, 030024 Taiyuan (China); Wang Bo [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China)

    2009-06-15

    The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

  18. Study on electrochemical corrosion mechanism of steel foot of insulators for HVDC lines

    Science.gov (United States)

    Zheng, Weihua; Sun, Xiaoyu; Fan, Youping

    2017-09-01

    The main content of this paper is the mechanism of electrochemical corrosion of insulator steel foot in HVDC transmission line, and summarizes five commonly used artificial electrochemical corrosion accelerated test methods in the world. Various methods are analyzed and compared, and the simulation test of electrochemical corrosion of insulator steel feet is carried out by water jet method. The experimental results show that the experimental environment simulated by water jet method is close to the real environment. And the three suspension modes of insulators in the actual operation, the most serious corrosion of the V type suspension hardware, followed by the tension string suspension, and the linear string corrosion rate is the slowest.

  19. Improvement of the electrochemical properties via poly(3,4-ethylenedioxythiophene) oriented micro/nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yu.; Wang, Bichen; Chen, Huimin; Feng, Wei [School of Materials Science and Engineering, Tianjin University, Tianjin 300072 (China); Tianjin Key Laboratory of Composite and Functional Materials, Tianjin 300072 (China)

    2010-05-01

    Arrays of oriented poly(3,4-ethylenedioxythiophene) (PEDOT) micro/nanorods are synthesized by electrochemical galvanostatic method at the current density of 1 mA cm{sup -2} in the cetyltrimethylammonium bromide (CTAB) aqueous solution whose pH value is 1. The CTAB is used both as the surfactant and the supporting salt in the electrolyte solution. The electrochemical properties of PEDOT films are characterized by cyclic voltammetry and galvanostatic charge/discharge techniques, which indicate that the arrays of oriented PEDOT micro/nanorods can be applied as the electrode materials of supercapacitors. In addition, the cycling performance of PEDOT micro/nanorods is much better than that of traditional PEDOT particles. The effects of the concentration of CTAB, the current density, and pH value of electrolyte solutions on the morphologies and electrochemical properties of PEDOT films are investigated. The mechanism of different morphologies formation is discussed in this study as well. (author)

  20. Evaluation of different polymers for fast neutron personnel dosimetry using electrochemical etching

    International Nuclear Information System (INIS)

    Gammage, R.B.; Cotter, S.J.

    1977-01-01

    There is considerable optimism for the enhancement by electrochemical etching of fast neutron-induced recoil tracks in polycarbonate for the purpose of personnel dosimetry. The threshold energy, however, is rather high. A desirable improvement would be to lower this energy below 1 MeV. With this objective in mind, we have commenced an investigation of cellulose acetate, triacetate, and acetobutyrate in addition to polycarbonate. These cellulose derivatives are chemically more reactive and physically weaker than polycarbonate. It might, therefore, be possible to initiate the electrochemical amplification at the sites of shorter recoil atom damage tracks than is possible with polycarbonate. Some characteristics important for electrochemically etching in aqueous electrolytes are listed. Chemical etching is combined with treeing, an electrical breakdown process that starts when the dielectric strength is exceeded. These mechanical and electrical properties pertain to the dry plastics. The absorption of water molecules and electrolyte ions will cause these values to be reduced. Results and conclusions of the study are presented

  1. Highly enhanced electrochemical activity of Ni foam electrodes decorated with nitrogen-doped carbon nanotubes for non-aqueous redox flow batteries

    Science.gov (United States)

    Lee, Jungkuk; Park, Min-Sik; Kim, Ki Jae

    2017-02-01

    Nitrogen-doped carbon nanotubes (NCNTs) are directly grown on the surface of a three-dimensional (3D) Ni foam substrate by floating catalytic chemical vapor deposition (FCCVD). The electrochemical properties of the 3D NCNT-Ni foam are thoroughly examined as a potential electrode for non-aqueous redox flow batteries (RFBs). During synthesis, nitrogen atoms can be successfully doped onto the carbon nanotube (CNT) lattices by forming an abundance of nitrogen-based functional groups. The 3D NCNT-Ni foam electrode exhibits excellent electrochemical activities toward the redox reactions of [Fe (bpy)3]2+/3+ (in anolyte) and [Co(bpy)3]+/2+ (in catholyte), which are mainly attributed to the hierarchical 3D structure of the NCNT-Ni foam electrode and the catalytic effect of nitrogen atoms doped onto the CNTs; this leads to faster mass transfer and charge transfer during operation. As a result, the RFB cell assembled with 3D NCNT-Ni foam electrodes exhibits a high energy efficiency of 80.4% in the first cycle; this performance is maintained up to the 50th cycle without efficiency loss.

  2. Electrochemical behavior of uranyl in anhydrous polar organic media

    Energy Technology Data Exchange (ETDEWEB)

    Burn, Adam G.; Nash, Kenneth L. [Washington State Univ., Pullmann, WA (United States). Dept. of Chemistry

    2017-09-01

    Weak complexes between pentavalent and hexavalent actinyl cations have been reported to exist in acidic, non-complexing high ionic strength aqueous media. Such ''cation-cation complexes'' were first identified in the context of actinide-actinide redox reactions in acidic aqueous media relevant to solvent extraction-based separation systems, hence their characterization is of potential interest for advanced nuclear fuel reprocessing. This chemistry could be relevant to efforts to develop advanced actinide separations based on the upper oxidation states of americium, which are of current interest. In the present study, the chemical behavior of pentavalent uranyl was examined in non-aqueous, aprotic polar organic solvents (propylene carbonate and acetonitrile) to determine whether UO{sub 2}{sup +} cations generated at the reducing working electrode surface would interact with the UO{sub 2}{sup 2+} cations in the bulk phase to form cation-cation complexes in such media. In magnesium perchlorate media, the electrolyte adsorbed onto the working electrode surface and interfered with the uranyl reduction/diffusion process through an ECE (electron transfer/chemical reaction/electron transfer) mechanism. In parallel studies of uranyl redox behavior in tetrabutylammonium hexafluorophosphate solutions, an EC (electron transfer/chemical reaction) mechanism was observed in the cyclic voltammograms. Ultimately, no conclusive electrochemical evidence demonstrated uranyl cation-cation interactions in the non-aqueous, aprotic polar organic solvent solutions, though the results reported do not completely rule out the presence of UO{sub 2}{sup +}.UO{sub 2}{sup 2+} complexes.

  3. Investigation of reaction mechanisms during electroreduction of carbon dioxide on lead electrode for the production of organic compounds

    International Nuclear Information System (INIS)

    Innocent, B.

    2008-09-01

    The aim of this work was to promote the reduction of CO 2 through its electrochemical conversion (electro-synthesis) on a lead electrode into high added value products. Depending on the nature of electrolyte, the electro-reduction of carbon dioxide leads to different products. Various electrolytes (aqueous or organic, protic or aprotic) were used to study two mechanisms: hydrogenation (formation of formate) and electro-dimerization (synthesis of oxalate). Cyclic voltammetry studies have been carried out for electrochemically characterizing CO 2 reduction on Pb. The electrochemical investigation of the electrode electrolyte interface has shown that the process of CO 2 electro-reduction is a mass transfer control both in the organic and aqueous media. Electrochemical experiments (cyclic voltammetry, chrono-amperometry) coupled with in situ infrared reflectance spectroscopic techniques (SPAIRS, SNIFTIRS) have also shown that in aqueous medium (7 ≤pH≤9) hydrogeno-carbonate ions were reduced to formate. The modification of solvent (propylene carbonate) leads selectively to oxalate as the main reaction product. Long-term electrolyses were performed in a filter-press cell to deal large volumes. In aqueous medium, the reduction of HCO 3 - to HCOO - (R F = 89% at -2.5 mA cm -2 and 4 C) is always accompanied by the production of H 2 . (author)

  4. Electrochemical, Chemical and Enzymatic Oxidations of Phenothiazines

    NARCIS (Netherlands)

    Blankert, B.; Hayen, H.; van Leeuwen, S.M.; Karst, U.; Bodoki, E.; Lotrean, S.; Sandulescu, R.; Mora Diaz, N.; Dominguez, O.; Arcos, J.; Kauffmann, J.-M.

    2005-01-01

    The oxidation of several phenothiazine drugs (phenothiazine, promethazine hydrochloride, promazine hydrochloride, trimeprazine hydrochloride and ethopropazine hydrochloride) has been carried out in aqueous acidic media by electrochemical, chemical and enzymatic methods. The chemical oxidation was

  5. Stress corrosion cracking of Inconel 600 in aqueous solutions at elevated temperature. Pt. II. Effects of chloride and sulphate ions on the electrochemical behaviour of Inconel 600

    International Nuclear Information System (INIS)

    Ashour, E.A.; Schneider, F.; Mummert, K.

    1997-01-01

    For pt.I see ibid., p.151-6, 1997. The influencing effects of temperature, potential and electrolyte composition on the electrochemical behaviour of Inconel 600 in aqueous solutions are presented. Considering these effects the connection between the data have been obtained from chemo-mechanical fracture investigation on CT-samples in Part I of this paper and pitting corrosion are discussed. The results have shown that chloride ions depassivate the surfaces of cracks locally and hinder the formation of a new protective oxide layer on the fracture surfaces. Furthermore, chloride promotes the dissolution of metal and initiates the cracking, respectively. The resulting crevice corrosion promotes an increase of hydrogen absorption by the metal. The increase of the hydrogen content of the metal influences the mechanical fracture behaviour. Contrary, sulphate ions inhibit the initiation of corrosion mainly due to a hinderance of chloride ions adsorption on active sites of the fracture surfaces. The initiation of localized corrosion in the crevice region may be stimulated by chromate ions formed by oxidation of chromium from the oxide layer or the base metal in oxygen containing solutions. (orig.)

  6. Influencing Mechanism of Electrochemical Treatment on Preparation of CNTs-grafted on Carbon Fibers

    Directory of Open Access Journals (Sweden)

    SONG Lei

    2017-11-01

    Full Text Available Based on electrochemical anodic oxidation, an innovative technique was developed to efficiently obtain the uniform catalyst coating on continuous carbon fibers. Through systematic investigation on the effect of electrochemical modified strength on the physical and chemical characteristics of carbon fiber surface, catalyst particles and the morphology of CNTs-grafted carbon fibers, tensile strength of multi-scale reinforcement and the interlaminar shear strength of its reinforced composites, the electrochemical modification process on carbon fibre surface was optimized. The results show that the morphology and distribution of catalyst particles not only affect the morphology of CNTs deposited on the surface of carbon fibres,but also affect the mechanical properties of multi-scale reinforcement and its reinforced composites of CNTs-grafted carbon fibers.

  7. Ammonia removal in electrochemical oxidation: Mechanism and pseudo-kinetics

    International Nuclear Information System (INIS)

    Li Liang; Liu Yan

    2009-01-01

    This paper investigated the mechanism and pseudo-kinetics for removal of ammonia by electrochemical oxidation with RuO 2 /Ti anode using batch tests. The results show that the ammonia oxidation rates resulted from direct oxidation at electrode-liquid interfaces of the anode by stepwise dehydrogenation, and from indirect oxidation by hydroxyl radicals were so slow that their contribution to ammonia removal was negligible under the condition with Cl - . The oxidation rates of ammonia ranged from 1.0 to 12.3 mg N L -1 h -1 and efficiency reached nearly 100%, primarily due to the indirect oxidation of HOCl, and followed pseudo zero-order kinetics in electrochemical oxidation with Cl - . About 88% ammonia was removed from the solution. The removed one was subsequently found in the form of N 2 in the produced gas. The rate at which Cl - lost electrons at the anode was a major factor in the overall ammonia oxidation. Current density and Cl - concentration affected the constant of the pseudo zero-order kinetics, expressed by k = 0.0024[Cl - ] x j. The ammonia was reduced to less than 0.5 mg N L -1 after 2 h of electrochemical oxidation for the effluent from aerobic or anaerobic reactors which treated municipal wastewater. This result was in line with the strict discharge requirements

  8. Chemically immobilised carbon nanotubes on silicon: Stable surfaces for aqueous electrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Flavel, Benjamin S., E-mail: ben.flavel@flinders.edu.a [Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch 8140 (New Zealand); School of Chemistry, Physics and Earth Sciences, Flinders University, Sturt Road, Bedford Park, Adelaide, South Australia 5001 (Australia); Garrett, David J.; Lehr, Joshua [Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch 8140 (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology, Private Bag 4800, Christchurch 8140 (New Zealand); Shapter, Joseph G. [School of Chemistry, Physics and Earth Sciences, Flinders University, Sturt Road, Bedford Park, Adelaide, South Australia 5001 (Australia); Downard, Alison J., E-mail: alison.downard@canterbury.ac.n [Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch 8140 (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology, Private Bag 4800, Christchurch 8140 (New Zealand)

    2010-04-30

    Diazonium ion chemistry has been used to electrochemically graft aminophenyl layers onto p-type silicon (1 0 0) substrates. A condensation reaction was used to immobilise single-walled carbon nanotubes with high carboxylic acid functionality directly to this layer. Electrochemical monitoring of the aminophenyl groups confirmed the formation of an amide linkage between the single-walled carbon nanotubes and the aminophenyl layer. The carbon nanotube electrode showed high stability and good electrochemical performance in aqueous solution. At moderate scan rates the Ru(NH{sub 3}){sub 6}{sup +3/+2} couple exhibited quasi-reversible electron transfer kinetics with a standard heterogenous rate constant of 1.2 x 10{sup -3} cm s{sup -1} at the covalently-linked carbon nanotube surface. The electrode thus combines the advantages of a silicon substrate for easy integration into sophisticated electrical and electronic devices, carbon nanotubes for desirable electrochemical properties, and stability in aqueous medium for future applications in environmental sensing.

  9. Chemically immobilised carbon nanotubes on silicon: Stable surfaces for aqueous electrochemistry

    International Nuclear Information System (INIS)

    Flavel, Benjamin S.; Garrett, David J.; Lehr, Joshua; Shapter, Joseph G.; Downard, Alison J.

    2010-01-01

    Diazonium ion chemistry has been used to electrochemically graft aminophenyl layers onto p-type silicon (1 0 0) substrates. A condensation reaction was used to immobilise single-walled carbon nanotubes with high carboxylic acid functionality directly to this layer. Electrochemical monitoring of the aminophenyl groups confirmed the formation of an amide linkage between the single-walled carbon nanotubes and the aminophenyl layer. The carbon nanotube electrode showed high stability and good electrochemical performance in aqueous solution. At moderate scan rates the Ru(NH 3 ) 6 +3/+2 couple exhibited quasi-reversible electron transfer kinetics with a standard heterogenous rate constant of 1.2 x 10 -3 cm s -1 at the covalently-linked carbon nanotube surface. The electrode thus combines the advantages of a silicon substrate for easy integration into sophisticated electrical and electronic devices, carbon nanotubes for desirable electrochemical properties, and stability in aqueous medium for future applications in environmental sensing.

  10. Highly stable aqueous zinc-ion storage using a layered calcium vanadium oxide bronze cathode

    Energy Technology Data Exchange (ETDEWEB)

    Xia, Chuan; Guo, Jing; Li, Peng; Zhang, Xixiang; Alshareef, Husam N. [Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia)

    2018-04-03

    Cost-effective aqueous rechargeable batteries are attractive alternatives to non-aqueous cells for stationary grid energy storage. Among different aqueous cells, zinc-ion batteries (ZIBs), based on Zn{sup 2+} intercalation chemistry, stand out as they can employ high-capacity Zn metal as the anode material. Herein, we report a layered calcium vanadium oxide bronze as the cathode material for aqueous Zn batteries. For the storage of the Zn{sup 2+} ions in the aqueous electrolyte, we demonstrate that the calcium-based bronze structure can deliver a high capacity of 340 mA h g{sup -1} at 0.2 C, good rate capability, and very long cycling life (96 % retention after 3000 cycles at 80 C). Further, we investigate the Zn{sup 2+} storage mechanism, and the corresponding electrochemical kinetics in this bronze cathode. Finally, we show that our Zn cell delivers an energy density of 267 W h kg{sup -1} at a power density of 53.4 W kg{sup -1}. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Electrochemical corrosion testing of metal waste forms

    International Nuclear Information System (INIS)

    Abraham, D. P.; Peterson, J. J.; Katyal, H. K.; Keiser, D. D.; Hilton, B. A.

    1999-01-01

    Electrochemical corrosion tests have been conducted on simulated stainless steel-zirconium (SS-Zr) metal waste form (MWF) samples. The uniform aqueous corrosion behavior of the samples in various test solutions was measured by the polarization resistance technique. The data show that the MWF corrosion rates are very low in groundwaters representative of the proposed Yucca Mountain repository. Galvanic corrosion measurements were also conducted on MWF samples that were coupled to an alloy that has been proposed for the inner lining of the high-level nuclear waste container. The experiments show that the steady-state galvanic corrosion currents are small. Galvanic corrosion will, hence, not be an important mechanism of radionuclide release from the MWF alloys

  12. Electrochemical Single-Molecule Transistors with Optimized Gate Coupling

    DEFF Research Database (Denmark)

    Osorio, Henrry M.; Catarelli, Samantha; Cea, Pilar

    2015-01-01

    Electrochemical gating at the single molecule level of viologen molecular bridges in ionic liquids is examined. Contrary to previous data recorded in aqueous electrolytes, a clear and sharp peak in the single molecule conductance versus electrochemical potential data is obtained in ionic liquids....... These data are rationalized in terms of a two-step electrochemical model for charge transport across the redox bridge. In this model the gate coupling in the ionic liquid is found to be fully effective with a modeled gate coupling parameter, ξ, of unity. This compares to a much lower gate coupling parameter...

  13. Mechanism of the electrochemical hydrogen reaction on smooth tungsten carbide and tungsten electrodes

    International Nuclear Information System (INIS)

    Wiesener, K.; Winkler, E.; Schneider, W.

    1985-01-01

    The course of the electrochemical hydrogen reaction on smooth tungsten-carbide electrodes in hydrogen saturated 2.25 M H 2 SO 4 follows a electrochemical sorption-desorption mechanism in the potential range of -0.4 to +0.1 V. At potentials greater than +0.1 V the hydrogen oxidation is controlled by a preliminary chemical sorption step. Concluding from the similar behaviour of tungsten-carbide and tungsten electrodes after cathodic pretreatment, different tungsten oxides should be involved in the course of the hydrogen reaction on tungsten carbide electrodes. (author)

  14. Use of electrochemically activated aqueous solutions in the manufacture of fur materials.

    Science.gov (United States)

    Danylkovych, Anatoliy G; Lishchuk, Viktor I; Romaniuk, Oksana O

    2016-01-01

    The influence of characteristics of electrochemically activated aqueous processing mediums in the treatment of fur skins with different contents of fatty substances was investigated. The use of electroactive water, namely anolytes and catholytes, forgoing antiseptics or surface-active materials, helped to restore the hydration of fur skins and to remove from them soluble proteins, carbohydrates and fatty substances. The activating effect of anolyte and catholyte in solutions of water on the processes of treating raw furs is explained by their special physical and chemical properties, namely the presence of free radicals, ions and molecules of water which easily penetrate cells' membranes and into the structure of non-collagen components and microfiber structure of dermic collagen. The stage of lengthy acid and salt treatment is excluded from the technical treatment as a result of using electroactivated water with high oxidizing power. A low-cost technology of processing different kinds of fur with the use of electroactivated water provides for substantial economy of water and chemical reagents, a two to threefold acceleration of the soaking and tanning processes and creation of highly elastic fur materials with a specified set of physical and chemical properties. At the same time the technology of preparatory processes of fur treatment excludes the use of such toxic antiseptics as formalin and sodium silicofluoride, which gives grounds to regard it as ecologically safe.

  15. The electrochemical performance and mechanism of cobalt (II) fluoride as anode material for lithium and sodium ion batteries

    International Nuclear Information System (INIS)

    Tan, Jinli; Liu, Li; Guo, Shengping; Hu, Hai; Yan, Zichao; Zhou, Qian; Huang, Zhifeng; Shu, Hongbo; Yang, Xiukang; Wang, Xianyou

    2015-01-01

    Highlights: •The as-prepared CoF 2 shows excellent electrochemical performance as anode material for lithium ion batteries. •The Li insertion/extraction mechanism of CoF 2 below 1.2 V was firstly proposed. •The electrochemical performance of CoF 2 as anode material in sodium ion batteries was firstly studied. -- Abstract: Cobalt (II) fluoride begins to enter into the horizons of people along with the research upsurge of metal fluorides. It is very significative and theoretically influential to make certain its electrochemical reaction mechanism. In this work, we discover a new and unrevealed reversible interfacial intercalation mechanism reacting below 1.2 V for cobalt (II) fluoride electrode material, which contributes a combined discharge capacity of about 400 mA h g −1 with the formation of SEI film at the initial discharge process. A highly reversible storage capacity of 120 mA h g −1 is observed when the cell is cycled over the voltage of 0.01-1.2 V at 0.2 C, and the low-potential voltage reaction process has a significant impact for the whole electrochemical process. Electrochemical analyses suggest that pure cobalt (II) fluoride shows better electrochemical performance when it is cycled at 3.2-0.01 V compared to the high range (1.0-4.5 V). So, we hold that cobalt (II) fluoride is more suitable to serve as anode material for lithium ion batteries. In addition, we also try to reveal the relevant performance and reaction mechanism, and realize the possibility of cobalt (II) fluoride as anode material for sodium ion batteries

  16. Elucidation of the electrochromic mechanism of nanostructured iron oxides films

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Lobato, M.A.; Martinez, Arturo I.; Castro-Roman, M. [Center for Research and Advanced Studies of the National Polytechnic Institute, Cinvestav Campus Saltillo, Carr. Saltillo-Monterrey Km. 13, Ramos Arizpe, Coah. 25900 (Mexico); Perry, Dale L. [Mail Stop 70A1150, Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Zarate, R.A. [Departamento de Fisica, Facultad de Ciencias, Universidad Catolica del Norte, Casilla 1280, Antofagasta (Chile); Escobar-Alarcon, L. (Departamento de Fisica, Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, 11801 Mexico)

    2011-02-15

    Nanostructured hematite thin films were electrochemically cycled in an aqueous solution of LiOH. Through optical, structural, morphological, and magnetic measurements, the coloration mechanism of electrochromic iron oxide thin films was elucidated. The conditions for double or single electrochromic behavior are given in this work. During the electrochemical cycling, it was found that topotactic transformations of hexagonal crystal structures are favored; i.e. {alpha}-Fe{sub 2}O{sub 3} to Fe(OH){sub 2} and subsequently to {delta}-FeOOH. These topotactic redox reactions are responsible for color changes of iron oxide films. (author)

  17. Surface Modification of the LiFePO4 Cathode for the Aqueous Rechargeable Lithium Ion Battery.

    Science.gov (United States)

    Tron, Artur; Jo, Yong Nam; Oh, Si Hyoung; Park, Yeong Don; Mun, Junyoung

    2017-04-12

    The LiFePO 4 surface is coated with AlF 3 via a simple chemical precipitation for aqueous rechargeable lithium ion batteries (ARLBs). During electrochemical cycling, the unfavorable side reactions between LiFePO 4 and the aqueous electrolyte (1 M Li 2 SO 4 in water) leave a highly resistant passivation film, which causes a deterioration in the electrochemical performance. The coated LiFePO 4 by 1 wt % AlF 3 has a high discharge capacity of 132 mAh g -1 and a highly improved cycle life, which shows 93% capacity retention even after 100 cycles, whereas the pristine LiFePO 4 has a specific capacity of 123 mAh g -1 and a poor capacity retention of 82%. The surface analysis results, which include X-ray photoelectron spectroscopy and transmission electron microscopy results, show that the AlF 3 coating material is highly effective for reducing the detrimental surface passivation by relieving the electrochemical side reactions of the fragile aqueous electrolyte. The AlF 3 coating material has good compatibility with the LiFePO 4 cathode material, which mitigates the surface diffusion obstacles, reduces the charge-transfer resistances and improves the electrochemical performance and surface stability of the LiFePO 4 material in aqueous electrolyte solutions.

  18. Measurement of Nitrate Concentration in Aqueous Media Using an Electrochemical Nanosensor Based on Silver Nanoparticles-Nanocellulose/Graphene Oxide

    Directory of Open Access Journals (Sweden)

    Majid Shadfar

    2017-11-01

    Full Text Available Nitrate pollution is at the forefront of groundwater contamination which poses serious environmental and public health hazards.  Nitrate is usually released in solution from agricultural activities and finds its way into groundwater resources. The objective of the present study was to determine, accurately concentrations of nitrate ions in water samples from the environment using sensitive electrochemical methods. For this purpose, a modified glassy carbon electrode modified with a nanocomposite consisting of silver nanoparticles, nanocellulose, and graphene oxide (Ag/NC/GO-GCE was used. The characterization of the nanocomposite was investigated using scanning electron microscope (SEM, X-Ray diffraction (XRD, and electrochemical impedance spectroscopy (EIS. The modified Ag/NC/GO-GCE electrode was used as nanosensor for the electrocatalytic determination of nitrate using the voltammetric method. The effects of the parameters of scan rate, pH, and different nitrate concentrations were studied and the optimum conditions were obtained. A limit of detection of 0.016 µM (S/N=3 was found in the linear range of 0.005 to 10 mM nitrate. The Ag/NC/GO-GCE electrode exhibited a synergistic effect toward voltammetric determination of nitrate in the presence of graphene oxide, nanocellulose, and silver nanocatalyst. The nanosensor developed here showed excellent sensitivity, selectivity, and stability toward nitrate determination in aqueous solutions without any significant interference.

  19. Electrochemical degradation of the chloramphenicol at flow reactor

    International Nuclear Information System (INIS)

    Rezende, Luis Gustavo P.; Prado, Vania M. do; Rocha, Robson S.; Beati, Andre A.G.F.; Sotomayor, Maria del Pilar T.; Lanza, Marcos R.V.

    2010-01-01

    This paper reports a study of electrochemical degradation of the chloramphenicol antibiotic in aqueous medium using a flow-by reactor with DSA anode. The process efficiency was monitored by chloramphenicol concentration analysis with liquid chromatography (HPLC) during the experiments. Analysis of Total Organic Carbon (TOC) was performed to estimate the degradation degree and Ion Chromatography (IC) was performed to determinate inorganic ions formed during the electrochemical degradation process. In electrochemical flow-by reactor, 52% of chloramphenicol was degraded, with 12% TOC reduction. IC analysis showed the production of chloride ions (25 mg L -1 ), nitrate ions (6 mg L -1 ) and nitrite ions (4.5 mg L -1 ). (author)

  20. Cell voltage versus electrode potential range in aqueous supercapacitors

    OpenAIRE

    Dai, Zengxin; Peng, Chuang; Chae, Jung Hoon; Ng, Kok Chiang; Chen, George Z.

    2015-01-01

    Supercapacitors with aqueous electrolytes and nanostructured composite electrodes are attractive because of their high charging-discharging speed, long cycle life, low environmental impact and wide commercial affordability. However, the energy capacity of aqueous supercapacitors is limited by the electrochemical window of water. In this paper, a recently reported engineering strategy is further developed and demonstrated to correlate the maximum charging voltage of a supercapacitor with the c...

  1. Graphene hydrogels deposited in nickel foams for high-rate electrochemical capacitors.

    Science.gov (United States)

    Chen, Ji; Sheng, Kaixuan; Luo, Peihui; Li, Chun; Shi, Gaoquan

    2012-08-28

    Graphene hydrogel/nickel foam composite electrodes for high-rate electrochemical capacitors are produced by reduction of an aqueous dispersion of graphene oxide in a nickel foam (upper half of figure). The micropores of the hydrogel are exposed to the electrolyte so that ions can enter and form electrochemical double-layers. The nickel framework shortens the distances of charge transfer. Therefore, the electrochemical capacitor exhibits highrate performance (see plots). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Self-Assembled Nanorod Structures on Nanofibers for Textile Electrochemical Capacitor Electrodes with Intrinsic Tactile Sensing Capabilities.

    Science.gov (United States)

    Shi, HaoTian H; Khalili, Nazanin; Morrison, Taylor; Naguib, Hani E

    2018-05-21

    A novel polyaniline nanorod (PAniNR) three-dimensional structure was successfully grown on flexible polyacrylonitrile (PAN) nanofiber substrate as the electrode material for electrochemical capacitors (ECs), constructed via self-stabilized dispersion polymerization process. The electrode offered desired mechanical properties such as flexibility and bendability, whereas it maintained optimal electrochemical characteristics. The electrode and the assembled EC cell also achieved intrinsic piezoresistive sensing properties, leading to real-time monitoring of excess mechanical pressure and bending during cell operations. The PAniNR@PAN electrodes show an average diameter of 173.6 nm, with the PAniNR growth of 50.7 nm in length. Compared to the electrodes made from pristine PAni, the gravimetric capacitance increased by 39.8% to 629.6 F/g with aqueous acidic electrolyte. The electrode and the assembled EC cell with gel electrolyte were responsive to tensile, compressive, and bending stresses with a sensitivity of 0.95 MPa -1 .

  3. The use of skewness, kurtosis and neural networks for determining corrosion mechanism from electrochemical noise data

    International Nuclear Information System (INIS)

    Reid, S.; Bell, G.E.C.; Edgemon, G.L.

    1998-01-01

    This paper describes the work undertaken to de-skill the complex procedure of determining corrosion mechanisms derived from electrochemical noise data. The use of neural networks is discussed and applied to the real time generated electrochemical noise data files with the purpose of determining characteristics particular to individual types of corrosion mechanisms. The electrochemical noise signals can have a wide dynamic range and various methods of raw data pre-processing prior to neural network analysis were investigated. Normalized data were ultimately used as input to the final network analysis. Various network schemes were designed, trained and tested. Factors such as the network learning schedule and network design were considered before a final network was implemented to achieve a solution. Neural networks trained using general and localized corrosion data from various material environment systems were used to analyze data from simulated nuclear waste tank environments with favorable results

  4. Electrochemical investigation on the effects of sulfate ion concentration, temperature and medium pH on the corrosion behavior of Mg–Al–Zn–Mn alloy in aqueous ethylene glycol

    Directory of Open Access Journals (Sweden)

    H. Medhashree

    2017-03-01

    Full Text Available The effects of sulfate ion concentration, temperature and medium pH on the corrosion of Mg–Al–Zn–Mn alloy in 30% aqueous ethylene glycol solution have been investigated by electrochemical techniques such as potentiodynamic polarization and electrochemical impedance spectroscopy methods. Surface morphology of the alloy was examined before and after immersing in the corrosive media by scanning electron microscopy (SEM and energy dispersion X-ray (EDX analysis. Activation energy, enthalpy of activation and entropy of activation were calculated from Arrhenius equation and transition state theory equation. The obtained results indicate that, the rate of corrosion increases with the increase in sulfate ion concentration and temperature of the medium and decreases with the increase in the pH of the medium.

  5. Chemical vs. electrochemical extraction of lithium from the Li-excess Li(1.10)Mn(1.90)O4 spinel followed by NMR and DRX techniques.

    Science.gov (United States)

    Martinez, S; Sobrados, I; Tonti, D; Amarilla, J M; Sanz, J

    2014-02-21

    Lithium extraction from the Li-excess Li1.10Mn1.90O4 spinel has been performed by chemical and electrochemical methods in aqueous and in organic media, respectively. De-lithiated samples have been investigated by XRD, SEM, TG, (7)Li and (1)H MAS-NMR techniques. The comparative study has allowed demonstrating that the intermediate de-intercalated samples prepared during the chemical extraction by acid titration are similar to those prepared by the electrochemical way in a non-aqueous electrolyte. LiMn2O4 based spinel with a tailored de-lithiation degree can be prepared as a single phase by controlling the pH used in chemical extraction. (7)Li MAS-NMR spectroscopy has been used to follow the influence of the manganese oxidation state on tetra and octahedral Li-signals detected in Li-extracted samples. The oxidation of Mn(III) ions goes parallel to the partial dissolution of the spinel, following Hunter's mechanism. Based on this mechanism, a generalized chemical reaction has been proposed to explain the formation of intermediate Li(+) de-intercalated samples during acid treatment in aqueous media. By the (1)H MAS NMR study, no evidence of Li-H topotactic exchange in the bulk of the acid treated material was found.

  6. Mechanisms of aqueous wollastonite carbonation as a possible CO2 sequestration process

    International Nuclear Information System (INIS)

    Huijgen, W.J.J.; Comans, R.N.J.; Witkamp, G.J.

    2006-02-01

    The mechanisms of aqueous wollastonite carbonation as a possible carbon dioxide sequestration process were investigated experimentally by systematic variation of the reaction temperature, CO2 pressure, particle size, reaction time, liquid to solid ratio and agitation power. The carbonation reaction was observed to occur via the aqueous phase in two steps: (1) Ca leaching from the CaSiO3 matrix and (2) CaCO3 nucleation and growth. Leaching is hindered by a Ca-depleted silicate rim resulting from incongruent Ca-dissolution. Two temperature regimes were identified in the overall carbonation process. At temperatures below an optimum reaction temperature, the overall reaction rate is probably limited by the leaching rate of Ca. At higher temperatures, nucleation and growth of calcium carbonate is probably limiting the conversion, due to a reduced (bi)carbonate activity. The mechanisms for the aqueous carbonation of wollastonite were shown to be similar to those reported previously for an industrial residue and a Mg-silicate. The carbonation of wollastonite proceeds rapidly relative to Mg-silicates, with a maximum conversion in 15 min of 70% at 200C, 20 bar CO2 partial pressure and a particle size of <38 μm. The obtained insight in the reaction mechanisms enables the energetic and economic assessment of CO2 sequestration by wollastonite carbonation, which forms an essential next step in its further development

  7. Electrochemical capacitor behavior of copper sulfide (CuS) nanoplatelets

    Energy Technology Data Exchange (ETDEWEB)

    Justin Raj, C.; Kim, Byung Chul; Cho, Won-Je; Lee, Won-Gil; Seo, Yongseong; Yu, Kook-Hyun, E-mail: yukook@dongguk.edu

    2014-02-15

    Highlights: • The electrochemical supercapacitor electrode was fabricated using CuS nanoplatelets. • CuS electrodes shows better electrochemical properties in aqueous LiClO{sub 4} electrolyte. • The heat treated CuS electrode shows an excellent pseudocapacitance performance than bare CuS electrode. -- Abstract: Copper sulfide (CuS) nanoplatelets have been fabricated by simple low temperature chemical bath deposition technique for electrochemical supercapacitor electrodes. The morphology and structural properties of the electrodes were analyzed using scanning electron microscopy and X-ray diffraction. The effect of heat treatment on electrochemical properties of CuS electrodes were examined by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge/discharge tests. Results show that bare and heat treated CuS has pseudocapacitive characteristic within the potential range of −0.6 to 0.3 V (vs. Ag/AgCl) in aqueous 1 M LiClO{sub 4} solution. The pseudocapacitance is induced mainly by lithium ions insertion/extraction with the CuS electrodes. The specific capacitance of 72.85 F g{sup −1} was delivered by heat treated CuS film at a scan rate of 5 mV s{sup −1} with an energy and power density of 6.23 W h kg{sup −1} and 1.75 kW kg{sup −1} at 3 Ag{sup −1} constant discharge current which is comparatively higher than that of as deposited CuS electrode.

  8. Catalytic Palladium Film Deposited by Scalable Low-Temperature Aqueous Combustion.

    Science.gov (United States)

    Voskanyan, Albert A; Li, Chi-Ying Vanessa; Chan, Kwong-Yu

    2017-09-27

    This article describes a novel method for depositing a dense, high quality palladium thin film via a one-step aqueous combustion process which can be easily scaled up. Film deposition of Pd from aqueous solutions by conventional chemical or electrochemical methods is inhibited by hydrogen embrittlement, thus resulting in a brittle palladium film. The method outlined in this work allows a direct aqueous solution deposition of a mirror-bright, durable Pd film on substrates including glass and glassy carbon. This simple procedure has many advantages including a very high deposition rate (>10 cm 2 min -1 ) and a relatively low deposition temperature (250 °C), which makes it suitable for large-scale industrial applications. Although preparation of various high-quality oxide films has been successfully accomplished via solution combustion synthesis (SCS) before, this article presents the first report on direct SCS production of a metallic film. The mechanism of Pd film formation is discussed with the identification of a complex formed between palladium nitrate and glycine at low temperature. The catalytic properties and stability of films are successfully tested in alcohol electrooxidation and electrochemical oxygen reduction reaction. It was observed that combustion deposited Pd film on a glassy carbon electrode showed excellent catalytic activity in ethanol oxidation without using any binder or additive. We also report for the first time the concept of a reusable "catalytic flask" as illustrated by the Suzuki-Miyaura cross-coupling reaction. The Pd film uniformly covers the inner walls of the flask and eliminates the catalyst separation step. We believe the innovative concept of a reusable catalytic flask is very promising and has the required features to become a commercial product in the future.

  9. Capacitance-Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation.

    Science.gov (United States)

    Lamb, Katie J; Dowsett, Mark R; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D; Aguiar, Pedro M; North, Michael; Parkin, Alison

    2018-01-10

    An electrochemical cell comprising a novel dual-component graphite and Earth-crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero-carbon energy source. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  10. A Comparative Electrochemical-Ozone Treatment for Removal of Phenolphthalein

    Directory of Open Access Journals (Sweden)

    V. M. García-Orozco

    2016-01-01

    Full Text Available The degradation of aqueous solutions containing phenolphthalein was carried out using ozone and electrochemical processes; the two different treatments were performed for 60 min at pH 3, pH 7, and pH 9. The electrochemical oxidation using boron-doped diamond electrodes processes was carried out using three current density values: 3.11 mA·cm−2, 6.22 mA·cm−2, and 9.33 mA·cm−2, whereas the ozone dose was constantly supplied at 5±0.5 mgL−1. An optimal degradation condition for the ozonation treatment is at alkaline pH, while the electrochemical treatment works better at acidic pH. The electrochemical process is twice better compared with ozonation.

  11. Coupled hygrothermal, electrochemical, and mechanical modelling for deterioration prediction in reinforced cementitious materials

    DEFF Research Database (Denmark)

    Michel, Alexander; Geiker, Mette Rica; Lepech, M.

    2017-01-01

    In this paper a coupled hygrothermal, electrochemical, and mechanical modelling approach for the deterioration prediction in cementitious materials is briefly outlined. Deterioration prediction is thereby based on coupled modelling of (i) chemical processes including among others transport of hea......, i.e. information, such as such as corrosion current density, damage state of concrete cover, etc., are constantly exchanged between the models....... and matter as well as phase assemblage on the nano and micro scale, (ii) corrosion of steel including electrochemical processes at the reinforcement surface, and (iii) material performance including corrosion- and load-induced damages on the meso and macro scale. The individual FEM models are fully coupled...

  12. The analysis of aqueous mixtures using liquid chromatography-electrospray mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Steven [Iowa State Univ., Ames, IA (United States)

    1999-02-12

    The focus of this dissertation is the use of chromatographic methods coupled with electrospray mass spectrometry (ES-MS) for the determination of both organic and inorganic compounds in aqueous solutions. The combination of liquid chromatography (LC) methods and ES-MS offers one of the foremost methods for determining compounds in complex aqueous solutions. In this work, LC-ES-MS methods are devised using ion exclusion chromatography, reversed phase chromatography, and ion exchange chromatography, as well as capillary electrophoresis (CE). For an aqueous sample, these LC-ES-MS and CE-ES-MS techniques require no sample preparation or analyte derivatization, which makes it possible to observe a wide variety of analytes as they exist in solution. The majority of this work focuses on the use of LC-ES-MS for the determination of unknown products and intermediates formed during electrochemical incineration (ECI), an experimental waste remediation process. This report contains a general introduction to the project and the general conclusions. Four chapters have been removed for separate processing. Titles are: Chapter 2: Determination of small carboxylic acids by ion exclusion chromatography with electrospray mass spectrometry; Chapter 3: Electrochemical incineration of benzoquinone in aqueous media using a quaternary metal oxide electrode in the absence of a soluble supporting electrolyte; Chapter 4: The determination of electrochemical incineration products of 4-chlorophenol by liquid chromatography-electrospray mass spectrometry; and Chapter 5: Determination of small carboxylic acids by capillary electrophoresis with electrospray mass spectrometry.

  13. Solvents effects on electrochemical characteristics of graphite fluoride-lithium batteries

    Energy Technology Data Exchange (ETDEWEB)

    Nobuatsu, W.; Hidekazu, T.; Rika, H.; Tsuyoshi, N.

    1982-11-01

    A study was made of the electrochemical characteristics of graphite fluoride-lithium batteries in various non-aqueous solvents. Two types of graphite fluorides (C/sub 2/F) /SUB n/ and (CF) /SUB n/ were used as cathode materials. The discharge characteristics of graphite fluorides were better in dimethylsulfoxide, ..gamma..-butyrolactone, propylene carbonate and sulfolane in that order. The relation between electrod potential of graphite fluoride and solvation energy of lithium ion with each solvent indicates that solvated lithium ion is intercalated into graphite fluoride layers by the electrode reaction. Both the difference in the overpotentials and in the rates of OCV recovery among these solvents further supports the proposed reaction mechanism.

  14. Solvothermal synthesis of Li–Al layered double hydroxides and their electrochemical performance

    International Nuclear Information System (INIS)

    Wei, Jinbo; Gao, Zan; Song, Yanchao; Yang, Wanlu; Wang, Jun; Li, Zhanshuang; Mann, Tom; Zhang, Milin; Liu, Lianhe

    2013-01-01

    In this paper, for the first time, Li/Al layered double hydroxides (LDHs) were synthesized by a facile and environment-friendly solvothermal approach. X-ray diffraction patterns show that the as-prepared products belong to the hexagonal phase. Well-defined LDHs particles with spiral-shape (1–2 μm), hexagonal (2–3 μm) and petal-like structures (10–15 μm) have been successfully fabricated by adjusting the content of water/ethanol in the synthesis process. A possible growth mechanism was proposed for the formation of these structures. Their electrochemical performances were investigated by cyclic voltammetry, galvanostatic charge/discharge test and electrochemical impedance spectroscopy. The hexagonal Li/Al LDHs calcined at 450 °C exhibit the specific capacitance of 848 F g −1 at a current density of 1.25 A g −1 . The high specific capacitance and remarkable rate capacity of Li/Al LDHs are promising for applications in capacitors and low-cost aqueous lithium ion batteries. - Graphical abstract: Hexagonal Li/Al layered double hydroxides (LDHs) with high specific surface area and remarkable rate capacity via a facile and environmentally friendly solvothermal approach. Highlights: ► Li/Al LDHs with different morphologies were fabricated by a solvothermal method. ► Hexagonal Li/Al LDHs display better electrochemical performance. ► A possible growth mechanism to explain the different morphology is proposed

  15. Cobalt and Vanadium Trimetaphosphate Polyanions: Synthesis, Characterization, and Electrochemical Evaluation for Non-aqueous Redox-Flow Battery Applications.

    Science.gov (United States)

    Stauber, Julia M; Zhang, Shiyu; Gvozdik, Nataliya; Jiang, Yanfeng; Avena, Laura; Stevenson, Keith J; Cummins, Christopher C

    2018-01-17

    An electrochemical cell consisting of cobalt ([Co II/III (P 3 O 9 ) 2 ] 4-/3- ) and vanadium ([V III/II (P 3 O 9 ) 2 ] 3-/4- ) bistrimetaphosphate complexes as catholyte and anolyte species, respectively, was constructed with a cell voltage of 2.4 V and Coulombic efficiencies >90% for up to 100 total cycles. The [Co(P 3 O 9 ) 2 ] 4- (1) and [V(P 3 O 9 ) 2 ] 3- (2) complexes have favorable properties for flow-battery applications, including reversible redox chemistry, high stability toward electrochemical cycling, and high solubility in MeCN (1.09 ± 0.02 M, [PPN] 4 [1]·2MeCN; 0.77 ± 0.06 M, [PPN] 3 [2]·DME). The [PPN] 4 [1]·2MeCN and [PPN] 3 [2]·DME salts were isolated as crystalline solids in 82 and 68% yields, respectively, and characterized by 31 P NMR, UV/vis, ESI-MS(-), and IR spectroscopy. The [PPN] 4 [1]·2MeCN salt was also structurally characterized, crystallizing in the monoclinic P2 1 /c space group. Treatment of 1 with [(p-BrC 6 H 4 ) 3 N] + allowed for isolation of the one-electron-oxidized spin-crossover (SCO) complex, [Co(P 3 O 9 ) 2 ] 3- (3), which is the active catholyte species generated during cell charging. The success of the 1-2 cell provides a promising entry point to a potential future class of transition-metal metaphosphate-based all-inorganic non-aqueous redox-flow battery electrolytes.

  16. Synthesis of nano-particles by soft chemistry: structural, morphological and dimensional control. Studies of the electrochemical properties (towards dyes solar cells)

    International Nuclear Information System (INIS)

    Cassaignon, S.; Koelsch, M.; Jolivet, J.P.

    2006-01-01

    In this work are described the electrochemical behaviour of different TiO 2 films (anatase, brookite and rutile) in aqueous solution and the influence of the parameters as the crystal structure and the morphology on the electrochemical answer. To complete this study, the capacity of the double layer has been measured by impedance spectroscopy. Voltage measurements of TiO 2 sensitized by a dye will allow to discuss the reversibility of the system and the rearrangement mechanisms. At last, the influence of the nature of the TiO 2 particles (anatase, rutile and brookite) on the photovoltage has been studied in order to estimate their interest for photovoltaic devices. (O.M.)

  17. Electrochemical degradation of linuron in aqueous solution using Pb/PbO2 and C/PbO2 electrodes

    Directory of Open Access Journals (Sweden)

    Nasser Abu Ghalwa

    2016-09-01

    Full Text Available Two modified electrodes (Pb/PbO2 and C/PbO2 were prepared by electrodeposition and used as anodes for electrochemical degradation of linuron (phenylurea pesticide in aqueous solution. Different operating conditions and factors affecting the treatment process including current density, temperature, initial concentration of linuron, pH, conductive electrolyte and time of electrolysis were studied and optimized. The best degradation occurred in the presence of NaCl (1 gL−1 as conductive electrolyte. After 30 min, nearly complete degradation of linuron was achieved (92% and 84% using C/PbO2 and Pb/PO2 electrodes at pH 7 and 1.5, respectively. Higher degradation efficiency was obtained at low temperature (5–10 °C. The optimum current density for the degradation of linuron on both electrodes was (150 mAcm−2.

  18. Degradation Mechanisms of Electrochemically Cycled Graphite Anodes in Lithium-ion Cells

    Science.gov (United States)

    Bhattacharya, Sandeep

    This research is aimed at developing advanced characterization methods for studying the surface and subsurface damage in Li-ion battery anodes made of polycrystalline graphite and identifying the degradation mechanisms that cause loss of electrochemical capacity. Understanding microstructural aspects of the graphite electrode degradation mechanisms during charging and discharging of Li-ion batteries is of key importance in order to design durable anodes with high capacity. An in-situ system was constructed using an electrochemical cell with an observation window, a large depth-of-field digital microscope and a micro-Raman spectrometer. It was revealed that electrode damage by removal of the surface graphite fragments of 5-10 mum size is the most intense during the first cycle that led to a drastic capacity drop. Once a solid electrolyte interphase (SEI) layer covered the electrode surface, the rate of graphite particle loss decreased. Yet, a gradual loss of capacity continued by the formation of interlayer cracks adjacent to SEI/graphite interfaces. Deposition of co-intercalation compounds, LiC6, Li2CO3 and Li2O, near the crack tips caused partial closure of propagating graphite cracks during cycling and reduced the crack growth rate. Bridging of crack faces by delaminated graphite layers also retarded crack propagation. The microstructure of the SEI layer, formed by electrochemical reduction of the ethylene carbonate based electrolyte, consisted of ˜5-20 nm sized crystalline domains (containing Li2CO3, Li2O 2 and nano-sized graphite fragments) dispersed in an amorphous matrix. During the SEI formation, two regimes of Li-ion diffusion were identified at the electrode/electrolyte interface depending on the applied voltage scan rate (dV/dt). A low Li-ion diffusion coefficient ( DLi+) at dV/dt microscopic information to the electrochemical performance, novel Li2CO3-coated electrodes were fabricated that were durable. The SEI formed on pre-treated electrodes reduced

  19. Electrochemical capacitance of NiO/Ru{sub 0.35}V{sub 0.65}O{sub 2} asymmetric electrochemical capacitor

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Chang-Zhou; Gao, Bo; Zhang, Xiao-Gang [College of Material Science and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016 (China)

    2007-11-08

    A designed asymmetric hybrid electrochemical capacitor was presented where NiO and Ru{sub 0.35}V{sub 0.65}O{sub 2} as the positive and negative electrode, respectively, both stored charge through reversible faradic pseudocapacitive reactions of the anions (OH{sup -}) with electroactive materials. And the two electrodes had been individually tested in 1 M KOH aqueous electrolyte to define the adequate balance of the active materials in the hybrid system as well as the working voltage of the capacitor based on them. The electrochemical tests demonstrated that the maximum specific capacitance and energy density of the asymmetric hybrid electrochemical capacitor were 102.6 F g{sup -1} and 41.2 Wh kg{sup -1}, respectively, delivered at a current density of 7.5 A cm{sup -2}. And the specific energy density decreased to 23.0 Wh kg{sup -1} when the specific power density increased up to 1416.7 W kg{sup -1}. The hybrid electrochemical capacitor also exhibited a good electrochemical stability with 83.5% of the initial capacitance over consecutive 1500 cycle numbers. (author)

  20. Plasmon-driven sequential chemical reactions in an aqueous environment.

    Science.gov (United States)

    Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

    2014-06-24

    Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H(+) in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.

  1. The electrochemical fluorination of polymeric materials for high energy density aqueous and non-aqueous battery and fuel cell separators

    Science.gov (United States)

    Liu, C. C.

    1983-01-01

    A computerized system was established and the electrochemical fluorination of trichloroethylene, polyacrylic acid and polyvinyl alcohol in anhydrous hydrogen fluoride was attempted. Both solid substrates as well as membranes were used. Some difficulties were found in handling and analyzing the solid substrates and membranes. Further studies are needed in this area. A microprocessor aided electrochemical fluorination system capable of obtaining highly reproducible experimental results was established.

  2. Mechanisms of aqueous wollastonite carbonation as a possible CO2 sequestration process

    NARCIS (Netherlands)

    Huijgen, W.J.J.; Witkamp, G.J.; Comans, R.N.J.

    2006-01-01

    The mechanisms of aqueous wollastonite carbonation as a possible carbon dioxide sequestration process were investigated experimentally by systematic variation of the reaction temperature, CO2 pressure, particle size, reaction time, liquid to solid ratio and agitation power. The carbonation reaction

  3. Electrochemical behaviour of a stainless steel coating after thermal fatigue and thermal shocks

    International Nuclear Information System (INIS)

    Boudebane, A.; Darsouni, A.; Chadli, H.; Boudebane, S.

    2012-01-01

    This work aims to study of the influence of thermal fatigue and thermal shock on the corrosion behaviour of coated steel AISI 304L. The coating was welded by TIG welding on specimens in ferritic-pearlitic steel grade AISI 4140. The study concerns three different states of deposit: sensitized, sensitized and strain hardened in surface and no sensitized. We realized electrochemical corrosion in an aqueous solution of NaCl 34 g/l. The corrosion of the specimens were evaluated by comparing the potentiodynamic curves for different states of the coating. Firstly, electrochemical characterization of deposits has shown a localized intergranular corrosion. Furthermore, the increase in the number of cycles of thermal fatigue accelerates the dissolution of deposit. Thermal shocks tend to improve resistance to corrosion. Against, the mechanical treatment of surfaces by burnishing decreases the dissolution rate of deposit cycles in thermal fatigue. (authors)

  4. Characterization and optimization of cathodic conditions for H2O2 synthesis in microbial electrochemical cells

    Science.gov (United States)

    Cathode potential and O2 supply methods were investigated to improve H2O2 synthesis in an electrochemical cell, and optimal cathode conditions were applied for microbial electrochemical cells (MECs). Using aqueous O2 for the cathode significantly improved current density, but H2...

  5. An electrochemical study in aqueous solutions on the binding of dopamine to a sulfonated cyclodextrin host

    International Nuclear Information System (INIS)

    Hendy, Gillian M.; Breslin, Carmel B.

    2012-01-01

    Highlights: ► DA and Sβ-CD form an Inclusion complex. ► Electrochemical techniques demonstrated this inclusion complex. ► The association constant, K, was computed as 331.3. ► 1:1 stoichiometry for the inclusion complex was deduced from a Job's plot analysis. ► NMR studies confirmed the structural information on the inclusion complex. - Abstract: Clear evidence for the formation of a weak inclusion complex between dopamine (DA) and a sulfonated β-CD host in aqueous solution was obtained using a combination of electrochemical approaches. Using cyclic voltammetry, a distinct increase in the oxidation potential of DA and a reduction in the peak oxidation current were observed on adding an excess concentration of the sulfonated β-CD to the electrolyte solution. Equally, a clear increase in the half-wave oxidation potential of DA was observed in the presence of the sulfonated β-CD using rotating disc voltammetry. The association constant, K, was computed as 331.3 ± 5.8, indicating the formation of a weak inclusion complex, while a 1:1 stoichiometry for the inclusion complex was deduced from a Job's plot analysis. The rate constant for the oxidation of DA was found to decrease on formation of the inclusion complex. This was attributed to higher reorganization energy for the oxidation of the included DA. These changes in the electrochemistry of DA were not observed when an excess of the smaller sulfonated α-CD was added to the electrolyte, indicating that these variations are not connected with simple electrostatic interactions between the protonated DA and the anionic sulfonated groups. It is proposed that the aromatic ring of the DA molecule includes within the cyclodextrin cavity, while the protonated amine group remains outside the cavity, bound electrostatically with the anionic sulfonated groups.

  6. Implementation of advanced electrochemical oxidation for radiochemical concentrate treatment

    International Nuclear Information System (INIS)

    Velin, Anna; Bengtsson, Bernt; Lundblad, Magnus

    2012-09-01

    Water treatments in Nuclear Power Plants include ion exchange, evaporation and mechanical filtration techniques. These technologies are used to control the chemical release and to treat coolant in light water reactor types from chemicals and most importantly, from radioactive nuclides. Most of the conventional methods are efficient, but at the same time producing aqueous concentrates with high organic load. Before final storage, the level of organic content of those concentrates must be reduced. Advanced electrochemical oxidation with Boron Doped Diamond (BDD) electrodes are being investigated in laboratory- and pilot scale for treatment of dilute and concentrated aqueous waste streams at Vattenfall-Ringhals NPP. BDD anodes and cathodes are having high over potential against water electrolysis, and therefore well suitable for oxidation of organics. Dilute wastewater, such as laundry water, which has an initial COD level of around 500 mg/l, was reduced to a level of < 20 mg/l in the laboratory. Evaporator concentrates, with a TS content of 3% and pH of 7-8, were treated in pilot scale of 800 liters, working in batch operation mode, at temperatures between 25-50 deg. C. Initial COD levels between 2500 and 8000 mg/l in concentrate was reduced to < 100 mg/l at the first tests and later to < 300 mg/l. The advanced electrochemical oxidation is proven to be a promising technique for radioactive concentrate treatment. Long-term operation is still ongoing to evaluate the performance of the electrodes, cell components and overall process efficiency. (authors)

  7. KDP Aqueous Solution-in-Oil Microemulsion for Ultra-Precision Chemical-Mechanical Polishing of KDP Crystal

    Directory of Open Access Journals (Sweden)

    Hui Dong

    2017-03-01

    Full Text Available A novel functional KH2PO4 (KDP aqueous solution-in-oil (KDP aq/O microemulsion system for KDP crystal ultra-precision chemical-mechanical polishing (CMP was prepared. The system, which consisted of decanol, Triton X-100, and KH2PO4 aqueous solution, was available at room temperature. The functional KDP aq/O microemulsion system was systematically studied and applied as polishing solution to KDP CMP technology. In this study, a controlled deliquescent mechanism was proposed for KDP polishing with the KDP aq/O microemulsion. KDP aqueous solution, the chemical etchant in the polishing process, was caged into the micelles in the microemulsion, leading to a limitation of the reaction between the KDP crystal and KDP aqueous solution only if the microemulsion was deformed under the effect of the external force. Based on the interface reaction dynamics, KDP aqueous solutions with different concentrations (cKDP were applied to replace water in the traditional water-in-oil (W/O microemulsion. The practicability of the controlled deliquescent mechanism was proved by the decreasing material removal rate (MRR with the increasing of the cKDP. As a result, the corrosion pits on the KDP surface were avoided to some degree. Moreover, the roughnesses of KDP with KDP aq/O microemulsion (cKDP was changed from 10 mM to 100 mM as polishing solutions were smaller than that with the W/O microemulsion. The smallest surface root-mean-square roughness of 1.5 nm was obtained at a 30 mmol/L KDP aq solution, because of the most appropriate deliquescent rate and MRR.

  8. In situ AFM investigation of electrochemically induced surface-initiated atom-transfer radical polymerization.

    Science.gov (United States)

    Li, Bin; Yu, Bo; Zhou, Feng

    2013-02-12

    Electrochemically induced surface-initiated atom-transfer radical polymerization is traced by in situ AFM technology for the first time, which allows visualization of the polymer growth process. It affords a fundamental insight into the surface morphology and growth mechanism simultaneously. Using this technique, the polymerization kinetics of two model monomers were studied, namely the anionic 3-sulfopropyl methacrylate potassium salt (SPMA) and the cationic 2-(metharyloyloxy)ethyltrimethylammonium chloride (METAC). The growth of METAC is significantly improved by screening the ammonium cations by the addition of ionic liquid electrolyte in aqueous solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Degradation of zinc oxide thin films in aqueous environment. Pt. II. Coated films

    Energy Technology Data Exchange (ETDEWEB)

    Rosa, L. de; Mitton, D.B.; Monetta, T.; Bellucci, F. [Naples Univ. (Italy). Dept. of Materials and Production Engineering; Springer, J. [Zentrum fuer Sonnenenergie- und Wasserstoff-Forschung Baden-Wuerttemberg (ZSW), Stuttgart (Germany)

    2001-12-01

    cn Part I of this research, the degradation mechanism of two different bare ZnO thin films was assessed. Degradation of the electrical properties of ZnO as well as changes in morphology were observed for both films. In the current paper, the degradation of zinc oxide thin films coated with protective acrylic paint is addressed during exposure to (i) an aqueous 3.5% NaCl solution at 85 C and (ii) a standard damp heat test at 85% R.H. and 85 C. Electrical and electrochemical techniques were employed to monitor zinc oxide degradation during exposure to the test environments. Electrochemical Impedance Spectroscopy was employed to investigate the delamination phenomena at the ZnO/coating interface and a simple equivalent circuit was developed to quantitatively measure the delamination ratio. The effect of different silane based adhesion promoters (glycidil-oxypropyl-trimethoxy-silane and aminopropyl-trimethoxy-silane) was also investigated. (orig.)

  10. Multi-level quantum mechanics theories and molecular mechanics study of the double-inversion mechanism of the F- + CH3I reaction in aqueous solution.

    Science.gov (United States)

    Liu, Peng; Zhang, Jingxue; Wang, Dunyou

    2017-06-07

    A double-inversion mechanism of the F - + CH 3 I reaction was discovered in aqueous solution using combined multi-level quantum mechanics theories and molecular mechanics. The stationary points along the reaction path show very different structures to the ones in the gas phase due to the interactions between the solvent and solute, especially strong hydrogen bonds. An intermediate complex, a minimum on the potential of mean force, was found to serve as a connecting-link between the abstraction-induced inversion transition state and the Walden-inversion transition state. The potentials of mean force were calculated with both the DFT/MM and CCSD(T)/MM levels of theory. Our calculated free energy barrier of the abstraction-induced inversion is 69.5 kcal mol -1 at the CCSD(T)/MM level of theory, which agrees with the one at 72.9 kcal mol -1 calculated using the Born solvation model and gas-phase data; and our calculated free energy barrier of the Walden inversion is 24.2 kcal mol -1 , which agrees very well with the experimental value at 25.2 kcal mol -1 in aqueous solution. The calculations show that the aqueous solution makes significant contributions to the potentials of mean force and exerts a big impact on the molecular-level evolution along the reaction pathway.

  11. A review on the electrochemical applications of room temperature ionic liquids in nuclear fuel cycle

    International Nuclear Information System (INIS)

    Venkatesan, K.A.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    2009-01-01

    A mini review on the electrochemical applications of room temperature ionic liquids (RTIL) in nuclear fuel cycle is presented. It is shown that how the fascinating properties of RTIL can be tuned to deliver desirable application in aqueous and non-aqueous reprocessing and in nuclear waste management. (author)

  12. Corrosion resistance and durability of superhydrophobic surface formed on magnesium alloy coated with nanostructured cerium oxide film and fluoroalkylsilane molecules in corrosive NaCl aqueous solution.

    Science.gov (United States)

    Ishizaki, Takahiro; Masuda, Yoshitake; Sakamoto, Michiru

    2011-04-19

    The corrosion resistant performance and durability of the superhydrophobic surface on magnesium alloy coated with nanostructured cerium oxide film and fluoroalkylsilane molecules in corrosive NaCl aqueous solution were investigated using electrochemical and contact angle measurements. The durability of the superhydrophobic surface in corrosive 5 wt% NaCl aqueous solution was elucidated. The corrosion resistant performance of the superhydrophobic surface formed on magnesium alloy was estimated by electrochemical impedance spectroscopy (EIS) measurements. The EIS measurements and appropriate equivalent circuit models revealed that the superhydrophobic surface considerably improved the corrosion resistant performance of magnesium alloy AZ31. American Society for Testing and Materials (ASTM) standard D 3359-02 cross cut tape test was performed to investigate the adhesion of the superhydrophobic film to the magnesium alloy surface. The corrosion formation mechanism of the superhydrophobic surface formed on the magnesium alloy was also proposed. © 2011 American Chemical Society

  13. Electrochemical and corrosion behavior of a 304 stainless-steel-based metal alloy wasteform in dilute aqueous environments

    International Nuclear Information System (INIS)

    Chen, Jian; Asmussen, R. Matthew; Zagidulin, Dmitrij; Noël, James J.; Shoesmith, David W.

    2013-01-01

    Highlights: ► We investigated the corrosion behavior of a metal alloy in six reference solutions. ► Majority of rhenium used as a technetium surrogate contained within a Fe 2 Mo phase. ► This prototype alloy exhibited generally passive behavior in all environments. ► Passivity breakdown events can occur and lead to localized corrosion. - Abstract: The electrochemical and corrosion behavior of a stainless-steel-based alloy made as a prototype metallic nuclear wasteform to immobilize 99 Tc, has been studied in a number of reference solutions ranging in pH from 4 to 10. The results showed the 47SS(304)-9Zr–23Mo prototype alloy contained at least five distinct phases with the majority of the Re, used as a Tc surrogate, contained within a Fe 2 Mo intermetallic phase. Polarization studies showed this alloy exhibited generally passive behavior in a range of dilute aqueous environments. Impedance measurements indicated passivity breakdown events can occur and lead to localized corrosion, especially in slightly alkaline conditions.

  14. Optimizing the electrochemical performance of aqueous symmetric supercapacitors based on an activated carbon xerogel

    Science.gov (United States)

    Calvo, E. G.; Lufrano, F.; Staiti, P.; Brigandì, A.; Arenillas, A.; Menéndez, J. A.

    2013-11-01

    A highly porous carbon xerogel was synthesized by means of physical activation. The activated carbon xerogel, which displayed a well-developed porous texture (micro- and meso-porosity), was employed as electrode material in different supercapacitors. In assessing the performance of the supercapacitors, special attention was paid to their dimensions and the type of electrolyte used. Both the method of electrode manufacture (rolling and punching of 1 cm2 pellets vs. casting by means of a film applicator to produce 4 cm2 electrodes) and the type of supercapacitor (Swagelok (R) system vs. cell with graphite plate current collectors) were evaluated. The results reveal that the cells with larger electrodes were able to store higher amounts of energy. In addition to the cells, the electrochemical characteristics in aqueous electrolytes with a different pH were studied (H2SO4, Na2SO4 and KOH, 1 M). The highest capacitance values were achieved with sulphuric acid (196 F g-1 as opposed to 140 and 106 F g-1 for Na2SO4 and KOH, respectively), probably due to its higher ionic conductivity and the basic nature of the oxygen functionalities found on the surface of the carbon xerogel. Nevertheless, because of the corrosive character of sulphuric acid, Na2SO4 would be a more suitable electrolyte.

  15. ELECTROCHEMICAL FINGERPRINT STUDIES OF SELECTED MEDICINAL PLANTS RICH IN FLAVONOIDS.

    Science.gov (United States)

    Konieczyński, Paweł

    2015-01-01

    The combination of a size-exclusion column (SEC) with electrochemical (voltammetric) detection at a boron-doped diamond electrode (BDDE) was applied for studying the correlations between electroactive Cu and Fe species with phenolic groups of flavonoids. For comparison with electrochemical results, SEC-HPLC-DAD detection was used. The studied plant material comprised of: Betula verrucosa Ehrh., Equisetun arvense L., Polygonum aviculare L., Viola tricolor L., Crataegus oxyacantha L., Sambucus nigra L. and Helichrysum arenarium (L.) Moench. Based upon the results, high negative correlation was found for the chromatographic peak currents at 45 min with the sum of Cu and Fe for the aqueous extracts of Sambucus, Crataegus and Betula species, and for the peak currents at 65 min of the aqueous extracts of Sambucus, Crataegus, Helichrysum and Betula botanical species. This behavior confirms that it is mainly the flavonoids with easily oxidizable phenolic groups which are strongly influenced by the presence of Cu and Fe. Moreover, the electrochemical profiles obtained thanks to the use of HPLC hyphenated with voltammetric detection can be potentially applied for fingerprint studies of the plant materials used in medicine.

  16. Electrochemical Detection in Stacked Paper Networks.

    Science.gov (United States)

    Liu, Xiyuan; Lillehoj, Peter B

    2015-08-01

    Paper-based electrochemical biosensors are a promising technology that enables rapid, quantitative measurements on an inexpensive platform. However, the control of liquids in paper networks is generally limited to a single sample delivery step. Here, we propose a simple method to automate the loading and delivery of liquid samples to sensing electrodes on paper networks by stacking multiple layers of paper. Using these stacked paper devices (SPDs), we demonstrate a unique strategy to fully immerse planar electrodes by aqueous liquids via capillary flow. Amperometric measurements of xanthine oxidase revealed that electrochemical sensors on four-layer SPDs generated detection signals up to 75% higher compared with those on single-layer paper devices. Furthermore, measurements could be performed with minimal user involvement and completed within 30 min. Due to its simplicity, enhanced automation, and capability for quantitative measurements, stacked paper electrochemical biosensors can be useful tools for point-of-care testing in resource-limited settings. © 2015 Society for Laboratory Automation and Screening.

  17. A highly reversible anthraquinone-based anolyte for alkaline aqueous redox flow batteries

    Science.gov (United States)

    Cao, Jianyu; Tao, Meng; Chen, Hongping; Xu, Juan; Chen, Zhidong

    2018-05-01

    The development of electroactive organic materials for use in aqueous redox flow battery (RFB) electrolytes is highly attractive because of their structural flexibility, low cost and sustainability. Here, we report on a highly reversible anthraquinone-based anolyte (1,8-dihydroxyanthraquinone, 1,8-DHAQ) for alkaline aqueous RFB applications. Electrochemical measurements reveal the substituent position of hydroxyl groups for DHAQ isomers has a significant impact on the redox potential, electrochemical reversibility and water-solubility. 1,8-DHAQ shows the highest redox reversibility and rapidest mass diffusion among five isomeric DHAQs. The alkaline aqueous RFB using 1,8-DHAQ as the anolyte and potassium ferrocyanide as the catholyte yields open-circuit voltage approaching 1.1 V and current efficiency and capacity retention exceeding 99.3% and 99.88% per cycle, respectively. This aqueous RFB produces a maximum power density of 152 mW cm-2 at 100% SOC and 45 °C. Choline hydroxide was used as a hydrotropic agent to enhance the water-solubility of 1,8-DHAQ. 1,8-DHAQ has a maximum solubility of 3 M in 1 M KOH with 4 M choline hydroxide.

  18. Zinc-based electrolyte compositions, and related electrochemical processes and articles

    Science.gov (United States)

    Kniajanski, Sergei; Soloveichik, Grigorii Lev

    2018-02-20

    An aqueous electrolyte composition is described, including a zinc salt based on zinc acetate or zinc glocolate. The saturation concentration of zinc in the electrolyte composition is in the range of about 2.5M to about 3.5M. The composition also contains at least one salt of a monovalent cation. The molar ratio of zinc to the monovalent cation is about 1:2. An aqueous zinc electroplating bath, containing the aqueous electrolyte composition, is also disclosed, along with a method for the electrochemical deposition of zinc onto a substrate surface, using the electroplating bath. Related flow batteries are also described, including a catholyte, as well as an anolyte based on the aqueous electrolyte composition, with a membrane between the catholyte and the anolyte.

  19. Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    Shan, Xiaoqiang [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering; Charles, Daniel S. [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering; Xu, Wenqian [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS). X-ray Science Division; Feygenson, Mikhail [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division and Spallation Neutron Source (SNS) outstation Juelich Centre for Neutron Science (JCNS), Forschungszentrum Juelich GmbH; Su, Dong [Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Teng, Xiaowei [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering

    2017-11-22

    Manganese-based metal oxide electrode materials are of great importance in electrochemical energy storage for their favorable redox behavior, low cost and environmental-friendliness. However, their storage capacity and cycle life in aqueous Na-ion electrolytes is not satisfactory. In this paper, we report the development of a bi-phase cobalt-manganese oxide (Co-Mn-O) nanostructured electrode material, comprised of a layered MnO2.H2O birnessite phase and a (Co0.83Mn0.13Va0.04)tetra(Co0.38Mn1.62)octaO3.72 (Va: vacancy; tetra: tetrahedral sites; octa: octahedral sites) spinel phase, verified by neutron total scattering and pair distribution function analyses. The bi-phase Co-Mn-O material demonstrates an excellent storage capacity towards Na-ions in an aqueous electrolyte (121 mA h g-1 at a scan rate of 1 mV s-1 in the half-cell and 81 mA h g-1 at a current density of 2 A g-1 after 5000 cycles in full-cells), as well as high rate performance (57 mA h g-1 a rate of 360 C). Electro-kinetic analysis and in situ X-ray diffraction measurements further confirm that the synergistic interaction between the spinel and layered phases, as well as the vacancy of the tetrahedral sites of spinel phase, contribute to the improved capacity and rate performance of the Co-Mn-O material by facilitating both diffusion-limited redox and capacitive charge storage processes.

  20. A concentrated electrolyte for zinc hexacyanoferrate electrodes in aqueous rechargeable zinc-ion batteries

    Science.gov (United States)

    Kim, D.; Lee, C.; Jeong, S.

    2018-01-01

    In this study, a concentrated electrolyte was applied in an aqueous rechargeable zinc-ion battery system with a zinc hexacyanoferrate (ZnHCF) electrode to improve the electrochemical performance by changing the hydration number of the zinc ions. To optimize the active material, ZnHCF was synthesized using aqueous solutions of zinc nitrate with three different concentrations. The synthesized materials exhibited some differences in structure, crystallinity, and particle size, as observed by X-ray diffraction and scanning electron microscopy. Subsequently, these well-structured materials were applied in electrochemical tests. A more than two-fold improvement in the charge/discharge capacities was observed when the concentrated electrolyte was used instead of the dilute electrolyte. Additionally, the cycling performance observed in the concentrated electrolyte was superior to that in the dilute electrolyte. This improvement in the electrochemical performance may result from a decrease in the hydration number of the zinc ions in the concentrated electrolyte.

  1. Electrochemical degradation of triazole fungicides in aqueous solution using TiO2-NTs/SnO2-Sb/PbO2 anode: Experimental and DFT studies

    International Nuclear Information System (INIS)

    Han, Weiqing; Zhong, Congqiang; Liang, Linyue; Sun, Yunlong; Guan, Ying; Wang, Lianjun; Sun, Xiuyun; Li, Jiansheng

    2014-01-01

    Triazole fungicides (TFs) are toxic and bio-refractory contaminants widely spread in environment. This study investigated electrochemical degradation of TFs in aqueous solution at TiO 2 -NTs/SnO 2 -Sb/PbO 2 anode with particular attention to the effect of molecular structure. Three TFs with triazole ring in one biologically treated water including tricyclazole (TC), 1H-1,2,4-triazole (Tz) and propiconazole (PPC) were selected as the target compounds. Results of bulk electrolysis showed that degradation of all TFs was fit to a pseudo first-order equation. The three compounds were degraded with the following sequence: PPC > TC> Tz in terms of their rates of oxidation. Quantum chemical calculation using the density function theory (DFT) method was combined with experimental results to describe the degradation sequence of TFs. Atom charge was calculated by DFT method and active sites of TFs were identified respectively. Analysis of intermediates by GC-MS and LC-(ESI)-MS/MS showed agreement with calculation results. In addition, the acute toxicity of TC and PPC treated solution significantly decreased after treatment by electrochemical oxidation

  2. Online Monitoring of Electrochemical Degradation of Paracetamol through a Biomimetic Sensor

    OpenAIRE

    Mariana Calora Quintino de Oliveira; Marcos Roberto de Vasconcelos Lanza; José Luis Paz Jara; Maria Del Pilar Taboada Sotomayor

    2011-01-01

    This paper reports, for the first time, the online monitoring to the electrochemical degradation of the paracetamol using a biomimetic sensor coupled to a Flow Injection Analysis (FIA) system. The electrochemical degradation of the drug was carried out in aqueous medium using a flow-by reactor with a DSA anode. The process efficiency was monitored at real time by the biomimetic sensor constructed by modifying a glassy carbon electrode with a Nafion membrane doped with iron tetrapyridinoporphy...

  3. Manganese oxide/graphene oxide composites for high-energyaqueous asymmetric electrochemical capacitors

    CSIR Research Space (South Africa)

    Jafta, CJ

    2013-11-01

    Full Text Available A high-energy aqueous asymmetric electrochemical capacitor was developed using manganese diox-ide ( -MnO2)/graphene oxide (GO) nanocomposites. The nanostructured -MnO2was prepared frommicron-sized commercial electrolytic manganese dioxide (EMD) via...

  4. Structural, electrical, and electrochemical characterization of Ni--Pr oxide thick films

    Energy Technology Data Exchange (ETDEWEB)

    Mari, C; Scolari, V; Fiori, G; Pizzini, S

    1977-03-01

    Oxides with metallic conductivity could and have been used instead of noble metals as insert electrodes in aqueous solutions as well as electrodes for high temperature fuel cells and electrolyzers and as catalysts for the conversion of exhaust gases from internal combustion engines. The aim of this paper is to report the results of a physico-chemical characterization (structure, morphology, electrochemical behavior) of Ni--Pr oxides which have been proposed as electrode materials for high temperature fuel cells. The electrochemical characterization was carried out in aqueous solutions at room temperature and with solid electrolytes at high temperature. Evidence has been found in the former case for an oxide electrode type of behavior. In the high temperature case, very low overvoltage values have been observed during cathodic oxygen reduction, while the electrode undergoes a reaction with oxygen during anodic oxygen evolution.

  5. Fabrication of LiCoO2 films for lithium rechargeable microbattery in an aqueous solution by electrochemical reflux method

    International Nuclear Information System (INIS)

    Lee, Jin-Ho; Han, Kyoo-Seung; Lee, Bum-Jae; Seo, Seong-Il; Yoshimura, Masahiro

    2004-01-01

    LiCoO 2 films were directly deposited on electron-conducting substrates using electrochemical reflux method in an aqueous solution under ambient atmosphere at a fixed temperature between 100 and 200 o C with a fixed current density between 0.1 and 1.0mAcm -2 . The structural and compositional purities of the deposited LiCoO 2 film were confirmed by elemental analyses, X-ray diffraction pattern analyses, and Raman spectroscopy. According to the Raman spectroscopy and the voltage versus capacity profiles for the deposited LiCoO 2 film, it appears that the deposited film consists of layered LiCoO 2 phase (space group R3-bar m). Although the deposited LiCoO 2 film was fabricated in a very economical and simple way, it exhibits an initial discharge capacity of 54.1μAh/cm 2 μm and the discharge capacity retention of 85.6% over 15 cycles

  6. Technetium removal from aqueous wastes

    International Nuclear Information System (INIS)

    Fletcher, P.A.; Jones, C.P.; Junkison, A.R.; Turner, A.D.; Kavanagh, P.R.

    1992-03-01

    The research discussed in this report has compared several ''state of the art'' techniques for the removal of traces of the radionuclide, technetium, from aqueous wastes. The techniques investigated were: electrochemical reduction to an insoluble oxide, electrochemical ion exchange, seeded ultrafiltration and chemical reduction followed by filtration. Each technique was examined using a simulant based upon the waste generated by the Enhanced Actinide Removal Plant (EARP) at Sellafield. The technique selected for further investigation was direct electrochemical reduction which offers an ideal route for the removal of technetium from the stream (DFs 10-100) and can be operated continuously with a low power consumption 25 kW for the waste generated by EARP. Cell designs for scale up have been suggested to treat the 1000m 3 of waste produced every day. Future work is proposed to investigate the simultaneous removal of other key radionuclides, such as ruthenium, plutonium and cobalt as well as scale up of the resulting process and to investigate the effect of these other radionuclides on the efficiency of the electrochemical reduction technique for the removal of technetium. Total development and full scale plant costs are estimated to be of the order of 5 pounds - 10M, with a time scale of 5 -8 years to realisation. (author)

  7. Lithium1.3Aluminum0.3Titanium1.7Phosphate as a solid state Li-ion conductor: Issues with microcracking and stability in aqueous solutions

    Science.gov (United States)

    Jackman, Spencer D.

    Lithium aluminum titanium phosphate (LATP) with formula Li1.3Al0.3Ti1.7(PO4)3 was analyzed and tested to better understand its applicability as a solid state ion conducting ceramic material for electrochemical applications. Sintered samples were obtained from Ceramatec, Inc. in Salt Lake City and characterized in terms of density, phase-purity, fracture toughness, Young's modulus, thermal expansion behavior, mechanical strength, a.c. and d.c. ionic conductivity, and susceptibility to static and electrochemical corrosion in aqueous Li salt solutions. It was shown that LATP is prone to microcrack generation because of high thermal expansion anisotropy. A.c. impedance spectra of high-purity LATP of varying grain sizes showed that microcracking had a negative impact on the ionic conduction of Li along grain boundaries, with fine-grained (1.7±0.7 µm) LATP having twice the ionic conductivity of the same purity of coarse-grained (4.8±1.9 µm) LATP at 50°C. LATP with detectible secondary phases had lower ionic conductivity for similar grain sizes, as would be expected. The Young's modulus of fine-grained LATP was measured to be 115 GPa, and the highest biaxial strength was 191±11 MPa when tested in mineral oil, 144±13 MPa as measured in air, and 26±7 MPa after exposure to deionized water, suggesting that LATP undergoes stress-corrosion cracking. After exposure to LiOH, the strength was 76±19 MPa. This decrease in strength was observed despite there being no measureable change in a.c. impedance spectra, X-ray diffraction, or sample mass, suggesting phosphate glasses at grain boundaries. The chemical and electrochemical stability of high-purity LATP in aqueous electrochemical cells was evaluated using LiOH, LiCl, LiNO3, and LiCOOCH3 salts as the Li source. LATP was found to be most stable between pH 8-9, with the longest cell operating continuously at 25 mA cm-2 for 625 hours at 40°C in LiCOOCH3. At pH values outside of the 7-10 range, eventual membrane degradation

  8. Mechanical and electrochemical characteristics with welding materials in robotic MIG welding of dissimilar Al alloys

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seong Jong; Han, Min Su; Woo, Yong Bin [Mokpo Maritime Univ., Mokpo (Korea, Republic of)

    2013-05-15

    In this study, mechanical and electrochemical characteristics with welding material in MIG welded with ROBOT for dissimilar Al alloys were investigated using various experiment methods. The MIG welding by ROBOT with ER5183 and ER5556 for the 5456-H116 and 6061-T6 Al alloy were carried out. The hardness of welding zone was lower than that of base metal. In electrochemical experiment, ER5183 welding material presented excellent characteristics. The yield strength and maximum tensile strength in welding with welding material of ER5183 presented lower value than those of ER5556. The elongation and time-to-fracture showed the opposite results.

  9. High voltage rechargeable magnesium batteries having a non-aqueous electrolyte

    Science.gov (United States)

    Doe, Robert Ellis; Lane, George Hamilton; Jilek, Robert E.; Hwang, Jaehee

    2016-03-22

    A rechargable magnesium battery having an non-aqueous electrolyte is provided. The properties of the electrolyte include high conductivity, high Coulombic efficiency, and an electrochemical window that can exceed 3.5 V vs. Mg/Mg.sup.+2. The use of the electrolyte promotes the electrochemical deposition and dissolution of Mg without the use of any Grignard reagents, other organometallic materials, tetraphenyl borate, or tetrachloroaluminate derived anions. Other Mg-containing electrolyte systems that are expected to be suitable for use in secondary batteries are also described.

  10. Electrochemical Multi-Coloration of Molybdenum Oxide Bronzes

    International Nuclear Information System (INIS)

    Lee, Sangmin; Saji, Viswanathan S.; Lee, Chiwoo

    2013-01-01

    We report a simple electrochemical approach in fabricating multiple colored molybdenum (Mo) oxide bronzes on the surface of a Mo-quartz electrode. A three step electrochemical batch process consisting of linear sweep voltammetry and anodic oxidation followed by cathodic reduction in neutral K 2 SO 4 electrolyte at different end potentials, viz. -0.62, -0.80 and -1.60 V (vs. Hg/HgSO 4 ) yielded red, blue and yellow colored bronzes. The samples produced were analyzed by XRD, EDS, and SIMS. The color variation was suggested to be associated with the cations intercalation into the oxide formed and the simultaneous structural changes that occurred during the cathodic reduction in neutral aqueous medium

  11. Electrochemical Multi-Coloration of Molybdenum Oxide Bronzes

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sangmin; Saji, Viswanathan S.; Lee, Chiwoo [Korea Univ., Seoul (Korea, Republic of)

    2013-08-15

    We report a simple electrochemical approach in fabricating multiple colored molybdenum (Mo) oxide bronzes on the surface of a Mo-quartz electrode. A three step electrochemical batch process consisting of linear sweep voltammetry and anodic oxidation followed by cathodic reduction in neutral K{sub 2}SO{sub 4} electrolyte at different end potentials, viz. -0.62, -0.80 and -1.60 V (vs. Hg/HgSO{sub 4}) yielded red, blue and yellow colored bronzes. The samples produced were analyzed by XRD, EDS, and SIMS. The color variation was suggested to be associated with the cations intercalation into the oxide formed and the simultaneous structural changes that occurred during the cathodic reduction in neutral aqueous medium.

  12. Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

    Science.gov (United States)

    Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

    2016-03-10

    Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

  13. Influence aqueous solutions on the mechanical behavior of argillaceous rocks; Influence des solutions aqueuses sur le comportement mecanique des roches argileuses

    Energy Technology Data Exchange (ETDEWEB)

    Wakim, J

    2005-12-15

    The hydration of the shale with an aqueous solution induces a swelling deformation which plays an important role in the behaviour of the structures excavated in this type of grounds. This deformation is marked by a three-dimensional and anisotropic character and involves several mechanisms like adsorption, osmosis or capillarity. Several researches were dedicated to swelling and were often much debated due to the complexity of the implied phenomena. The goal of this thesis is therefore to contribute to a better understanding of shale swelling when the rock is confined and hydrated with an aqueous solution. The main part of the work accomplished was related to the Lorraine shale and to the Tournemire shale. To characterize swelling and to identify the main governing parameters, it was necessary to start the issue with an experimental approach. Many apparatus were then developed to carry out tests under various conditions of swelling. In order to facilitate the interpretation of the tests and thereafter the modelling of the behaviour, the experimental procedure adopted consisted of studying first the mechanical aspect and then the chemical aspect of swelling. In the mechanical part, swelling was studied by imposing on the sample a mechanical loading while maintaining during the tests the same aqueous solution. The principal parameters which were studied are the effect of the lateral conditions on axial swelling (impeded strain or constant stress) as well as the influence of the axial stress on radial swelling. The anisotropy of swelling was studied by carrying out, for different orientations of the sample, tests of free swelling, impeded swelling and uniaxial swelling. These various mechanical tests allowed to study the three-dimensional anisotropic swelling in all the conditions and to select the most appropriate test to be used in the second phase of the research. The precise analysis performed to explain the mechanisms behind the swelling of an argillaceous rock

  14. Development of the electrochemically regenerable carbon dioxide absorber for portable life support system application

    Science.gov (United States)

    Woods, R. R.; Heppner, D. B.; Marshall, R. D.; Quattrone, P. D.

    1979-01-01

    As the length of manned space missions increase, more ambitious extravehicular activities (EVAs) are required. For the projected longer mission the use of expendables in the portable life support system (PLSS) will become prohibited due to high launch weight and volume requirements. Therefore, the development of a regenerable CO2 absorber for the PLSS application is highly desirable. The paper discusses the concept, regeneration mechanism, performance, system design, and absorption/regeneration cycle testing of a most promising concept known as ERCA (Electrochemically Regenerable CO2 Absorber). This concept is based on absorbing CO2 into an alkaline absorbent similar to LiOH. The absorbent is an aqueous solution supported in a porous matrix which can be electrochemically regenerated on board the primary space vehicle. With the metabolic CO2 recovery the ERCA concept results in a totally regenerable CO2 scrubber. The ERCA test hardware has passed 200 absorption/regeneration cycles without performance degradation.

  15. Long-Term Charge/Discharge Cycling Stability of MnO2 Aqueous Supercapacitor under Positive Polarization

    KAUST Repository

    Ataherian, Fatemeh

    2011-01-01

    The long-term charge/discharge cycling stability of MnO 2 electrode under positive polarization in aqueous KCl electrolyte has been studied over different potential windows spanning from the open circuit potential to varied higher-end potential limited by O 2 evolution. Cycling up to 1.2 V (vs Ag/AgCl (aq)) causes partial (35) capacitance fading to a plateau value within the initial cycles, accompanied by morphological reconstruction, reduction of surface Mn ions and oxygen evolution. The surface Mn-ion reduction has been attributed to a two-step oxidation-reduction mechanism involving OH oxidation in electrolyte, based on electrochemical analysis. When cycling potential extends to 1.4 V, extensive oxygen evolution takes place. The combination of surface passivation of current collector and extensive gas bubbling, which deteriorates electrical contact among the constituent particles within the electrode, results in further monotonic capacitance reduction. © 2011 The Electrochemical Society.

  16. Electrochemical advanced oxidation processes: today and tomorrow. A review.

    Science.gov (United States)

    Sirés, Ignasi; Brillas, Enric; Oturan, Mehmet A; Rodrigo, Manuel A; Panizza, Marco

    2014-01-01

    In recent years, new advanced oxidation processes based on the electrochemical technology, the so-called electrochemical advanced oxidation processes (EAOPs), have been developed for the prevention and remediation of environmental pollution, especially focusing on water streams. These methods are based on the electrochemical generation of a very powerful oxidizing agent, such as the hydroxyl radical ((•)OH) in solution, which is then able to destroy organics up to their mineralization. EAOPs include heterogeneous processes like anodic oxidation and photoelectrocatalysis methods, in which (•)OH are generated at the anode surface either electrochemically or photochemically, and homogeneous processes like electro-Fenton, photoelectro-Fenton, and sonoelectrolysis, in which (•)OH are produced in the bulk solution. This paper presents a general overview of the application of EAOPs on the removal of aqueous organic pollutants, first reviewing the most recent works and then looking to the future. A global perspective on the fundamentals and experimental setups is offered, and laboratory-scale and pilot-scale experiments are examined and discussed.

  17. Electroneutrality Breakdown and Specific Ion Effects in Nanoconfined Aqueous Electrolytes Observed by NMR

    OpenAIRE

    Luo, Zhi-Xiang; Xing, Yun-Zhao; Ling, Yan-Chun; Kleinhammes, Alfred; Wu, Yue

    2015-01-01

    Ion distribution in aqueous electrolytes near the interface plays critical roles in electrochemical, biological and colloidal systems and is expected to be particularly significant inside nanoconfined regions. Electroneutrality of the total charge inside nanoconfined regions is commonly assumed a priori in solving ion distribution of aqueous electrolytes nanoconfined by uncharged hydrophobic surfaces with no direct experimental validation. Here, we use a quantitative nuclear magnetic resonanc...

  18. Electrochemical mechanism of eugenol at a Cu doped gold nanoparticles modified glassy carbon electrode and its analytical application in food samples

    International Nuclear Information System (INIS)

    Lin, Xiaoyun; Ni, Yongnian; Kokot, Serge

    2014-01-01

    Graphical abstract: A simple one-step electrodeposition method was used to fabricate a Cu doped gold nanoparticles modified glassy carbon electrode. An electrochemical reaction mechanism for o-methoxy phenols was suggested. In addition, the above Cu@AuNPs/GCE was successfully employed for the analysis of eugenol in food samples. - Highlights: • One-step construction of the Cu@AuNPs/GCE electrode. • The modified electrode showed high sensitivity for the analysis of eugenol. • Electrochemical mechanism of eugenol by use of Cu@AuNPs/GCE was inferred. • The novel method was successfully employed for analysis of eugenol in food samples. - Abstract: A simple one-step electrodeposition method was used to construct a glassy carbon electrode (GCE), which has been modified with Cu doped gold nanoparticles (GNPs), i.e. a Cu@AuNPs/GCE. This electrode was characterized with the use of scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The eugenol was electrocatalytically oxidized at the Cu@AuNPs/GCE. At this electrode, in comparison with the behavior at the GCE alone, the corresponding oxidation peak current was enhanced and the shift of the oxidation potentials to lower values was observed. Electrochemical behavior of eugenol at the Cu@AuNPs/GCE was investigated with the use of the cyclic voltammetry (CV) technique, and additionally, in order to confirm the electrochemical reaction mechanism for o-methoxy phenols, CVs for catechol, guaiacol and vanillin were investigated consecutively. Based on this work, an electrochemical reaction mechanism for o-methoxy phenols was suggested, and in addition, the above Cu@AuNPs/GCE was successfully employed for the analysis of eugenol in food samples

  19. A Graphene-Based Electrochemical Sensor for Rapid Determination of Phenols in Water

    OpenAIRE

    Chen, Kun; Zhang, Zai-Li; Liang, Yong-Mei; Liu, Wei

    2013-01-01

    A glassy carbon electrode (GCE) coated with a graphene/polymer film was fabricated for rapid determination of phenols in aqueous solutions. The electrochemical behavior of different phenols at the graphene/polymer-coated GCE was also investigated. In PBS buffer solution with a pH of 6.5, hydroquinone exhibits a well-defined reduction peak at the modified GCE. Based on this, an electrochemical method for the direct determination of phenols is proposed. Investigating different parameters reveal...

  20. On the possibility of electrochemical unzipping of multiwalled carbon nanotubes to produce graphene nanoribbons

    Energy Technology Data Exchange (ETDEWEB)

    Zehtab Yazdi, Alireza; Roberts, Edward P.L.; Sundararaj, Uttandaraman, E-mail: u.sundararaj@ucalgary.ca

    2016-08-15

    Highlights: • MWCNTs synthesized and electrochemically oxidized to study the formation of GNR • HRTEM, Raman and XPS confirmed no successful unzipping occurred after oxidation • Electrochemical oxidation very unlikely facilitate formation of intercalated MWCNTs - Abstract: Multiwalled carbon nanotubes (MWCNTs) with different geometrical characteristics and chemical doping have been synthesized and electrochemically oxidized to study the possibility of unzipping, and creating graphene nanoribbon (GNR) nanostructures. Modified glassy carbon electrodes of the MWCNTs have been tested in an aqueous electrolyte via anodic scans in a wide range of potentials, followed by keeping at the maximum potential for different times. The microstructural features, structural defects, and functional groups and their elements have been then studied using high resolution transmission electron microscopy (HRTEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), respectively. All results have confirmed that no successful unzipping occurs in the MWCNTs after electrochemical oxidation, even for the nitrogen-doped MWCNTs (CN{sub x}-MWCNTs) with reactive nitrogen groups and defective bamboo structures. In contrast to the report by Shinde et al. (J. Am. Chem. Soc. 2011, 133, 4168–4171), it has been concluded that the electrochemical oxidation in aqueous electrolytes is very unlikely to facilitate sufficient incorporation of the intercalated molecules among the walls of the MWCNTs. These molecules are, however, responsible for unzipping of MWCNTs.

  1. Electrochemical properties and electrochemical impedance spectroscopy of polypyrrole-coated platinum electrodes

    Directory of Open Access Journals (Sweden)

    M. Fall

    2006-12-01

    Full Text Available Polypyrrole (PPy films of different thickness were characterized by electrochemical impedance spectroscopy (EIS measurements in acetonitrile and aqueous solutions, containing 0.1 M NaClO4 or sodium dodecylsulfate as the dopant. The PPy films were electrochemically deposited on Pt, and their electrochemical properties studied by cyclic voltammetry. Impedance spectra were obtained at potentials ranging from 0 to 0.8 V/SCE. The EIS data were fitted using two different equivalent electrical circuits (depending on the nature of the dopant. They involve a diffusive capacitance, which increased with the passing charge during electrosynthesis (i.e. film thickness for ClO4--doped PPy, but was practically unaffected by the film thickness in the case of SDS-doped PPy. Also, a double-layer capacitance was found only in the circuit of ClO4--doped PPy. It increased with the film thickness, and showed a minimum near the open-circuit potential. Finally the charge-transfer resistance (Rct obtained with SDS is nearly 200-fold higher than that obtained with ClO4- in the same solvent (H2O. With the same dopant (ClO4-, Rct is about five times higher in acetonitrile relative to water. All these EIS results of the different types of PPy suggest a relation with the wettability of the polymer.

  2. Electrochemical sensors based on gold nanoparticles modified with rhodamine B hydrazide to sensitively detect Cu(II)

    Energy Technology Data Exchange (ETDEWEB)

    Peng, Donglai; Hu, Bin; Kang, Mengmeng [Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, No. 136, Science Avenue, Zhengzhou 450001 (China); Wang, Minghua [Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, No.136, Science Avenue, Zhengzhou 450001 (China); He, Linghao [Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, No. 136, Science Avenue, Zhengzhou 450001 (China); Zhang, Zhihong, E-mail: mainzhh@163.com [Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, No. 136, Science Avenue, Zhengzhou 450001 (China); Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, No.136, Science Avenue, Zhengzhou 450001 (China); Fang, Shaoming, E-mail: mingfang@zzuli.edu.cn [Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, No. 136, Science Avenue, Zhengzhou 450001 (China); Henan Collaborative Innovation Center of Environmental Pollution Control and Ecological Restoration, Zhengzhou University of Light Industry, No.136, Science Avenue, Zhengzhou 450001 (China)

    2016-12-30

    Highlights: • An electrochemical sensor based on gold nanoparticles modified with rhodamine B hydrazide (AuNPs-RBH) was developed. • The sensor was applied in the highly sensitive and selective detection of Cu{sup 2+} in water. • The electrochemical sensor displays excellent regeneration, stability, and practicability for Cu{sup 2+} detection. • EIS was used to determine Cu{sup 2+} ions in an aqueous solution with the developed AuNPs-RBH-based electrochemical sensor. - Abstract: An electrochemical sensor based on gold nanoparticles (Au NPs) modified with rhodamine B hydrazide (RBH) (AuNPs-RBH) was developed and applied in the highly sensitive and selective detection of Cu{sup 2+} in water. RBH molecules were bounded onto the surface of AuNPs via the strong interaction between the amino groups and Au NPs. The chemical structure variations were characterized by X-ray photoelectron spectroscopy and fluoresence spectroscopy. Additionally, electrochemical impedance spectroscopy was used to determine Cu{sup 2+} ions in an aqueous solution with the developed AuNPs-RBH-based electrochemical sensor. Results show that the fabricated sensor exhibits good electrochemical performance because of the presence of Au NPs and high affinity with the Cu{sup 2+} resulting from the strong coordination chemistry between Cu{sup 2+} and RBH. The as-developed sensor towards detecting Cu{sup 2+} has a detection limitation of 12.5 fM within the concentration range of 0.1 pM–1 nM by using the electrochemical impedance technique. It also displays excellent selectivity, regeneration, stability, and practicability for Cu{sup 2+} detection. Therefore, the new strategy of the RBH-based electrochemical sensor exhibits great potential application in environment treatment and protection.

  3. Organic non-aqueous cation-based redox flow batteries

    Science.gov (United States)

    Zhang, Lu; Huang, Jinhua; Burrell, Anthony

    2018-05-08

    The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte comprises a tetrafluorohydroquinone ether compound or a tetrafluorocatechol ether compound.

  4. Efficient electrochemical degradation of multiwall carbon nanotubes.

    Science.gov (United States)

    Reipa, Vytas; Hanna, Shannon K; Urbas, Aaron; Sander, Lane; Elliott, John; Conny, Joseph; Petersen, Elijah J

    2018-07-15

    As the production mass of multiwall carbon nanotubes (MWCNT) increases, the potential for human and environmental exposure to MWCNTs may also increase. We have shown that exposing an aqueous suspension of pristine MWCNTs to an intense oxidative treatment in an electrochemical reactor, equipped with an efficient hydroxyl radical generating Boron Doped Diamond (BDD) anode, leads to their almost complete mineralization. Thermal optical transmittance analysis showed a total carbon mass loss of over two orders of magnitude due to the electrochemical treatment, a result consistent with measurements of the degraded MWCNT suspensions using UV-vis absorbance. Liquid chromatography data excludes substantial accumulation of the low molecular weight reaction products. Therefore, up to 99% of the initially suspended MWCNT mass is completely mineralized into gaseous products such as CO 2 and volatile organic carbon. Scanning electron microscopy (SEM) images show sporadic opaque carbon clusters suggesting the remaining nanotubes are transformed into structure-less carbon during their electrochemical mineralization. Environmental toxicity of pristine and degraded MWCNTs was assessed using Caenorhabditis elegans nematodes and revealed a major reduction in the MWCNT toxicity after treatment in the electrochemical flow-by reactor. Published by Elsevier B.V.

  5. Electrochemical Synthesis of Mesoporous CoPt Nanowires for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Albert Serrà

    2014-03-01

    Full Text Available A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane’s channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.

  6. Mechanical and Electrochemical Performance of Carbon Fiber Reinforced Polymer in Oxygen Evolution Environment

    Directory of Open Access Journals (Sweden)

    Ji-Hua Zhu

    2016-11-01

    Full Text Available Carbon fiber-reinforced polymer (CFRP is recognized as a promising anode material to prevent steel corrosion in reinforced concrete. However, the electrochemical performance of CFRP itself is unclear. This paper focuses on the understanding of electrochemical and mechanical properties of CFRP in an oxygen evolution environment by conducting accelerated polarization tests. Different amounts of current density were applied in polarization tests with various test durations, and feeding voltage and potential were measured. Afterwards, tensile tests were carried out to investigate the failure modes for the post-polarization CFRP specimens. Results show that CFRP specimens had two typical tensile-failure modes and had a stable anodic performance in an oxygen evolution environment. As such, CFRP can be potentially used as an anode material for impressed current cathodic protection (ICCP of reinforced concrete structures, besides the fact that CFRP can strengthen the structural properties of reinforced concrete.

  7. On the mechanism of electrochemical ammonia synthesis on the Ru catalyst.

    Science.gov (United States)

    Back, Seoin; Jung, Yousung

    2016-04-07

    We theoretically investigate the electrochemical N2 reduction reaction (NRR) mechanism to produce NH3 on the Ru catalyst. All possible N-N dissociation steps during the reduction processes were evaluated along with the conventional associative and dissociative pathways. Based on the calculated free energy diagrams, it is revealed that the kinetically facile intermediate dissociative pathways during the NRR require a thermodynamic limiting potential (-0.71 V) similar to the associative pathway (-0.68 V), although the initial dissociative pathway as in the Haber-Bosch process has a substantial kinetic barrier for the N-N bond dissociation. The competitive hydrogen evolution is found to be a major hurdle for achieving a high efficiency for the electrochemical nitrogen reduction. In the low overpotential region, the hydrogen adsorption is thermodynamically more favorable than the protonation of N2, thereby reducing the number of active sites for the N2 activation. A comparison of free energies in the presence of different H-coverages on the Ru further demonstrates that the H-coverage can significantly increase the energy barrier for the first protonation of N2, resulting in a change of the potential determining step and an increase in the overpotentials.

  8. Rechargeable Aqueous Zinc-Ion Battery Based on Porous Framework Zinc Pyrovanadate Intercalation Cathode

    KAUST Repository

    Xia, Chuan; Guo, Jing; Lei, Yongjiu; Liang, Hanfeng; Zhao, Chao; Alshareef, Husam N.

    2017-01-01

    metal pyrovanadate compounds. The zinc pyrovanadate nanowires show significantly improved electrochemical performance when used as intercalation cathode for aqueous zinc–ion battery. Specifically, the ZVO cathode delivers high capacities of 213 and 76 m

  9. Electrochemical oxidation of synthetic tannery wastewater in chloride-free aqueous media

    International Nuclear Information System (INIS)

    Costa, Carla Regina; Montilla, Francisco; Morallon, Emilia; Olivi, Paulo

    2010-01-01

    The electrochemical treatment of a synthetic tannery wastewater, prepared with several compounds used by finishing tanneries, was studied in chloride-free media. Boron-doped diamond (Si/BDD), antimony-doped tin dioxide (Ti/SnO 2 -Sb), and iridium-antimony-doped tin dioxide (Ti/SnO 2 -Sb-Ir) were evaluated as anode. The influence of pH and current density on the treatment was assessed by means of the parameters used to measure the level of organic contaminants in the wastewater; i.e., total phenols, chemical oxygen demand (COD), total organic carbon (TOC), and absorbance. Results showed that faster decrease in these parameters occurred when the Si/BDD anode was used. Good results were obtained with the Ti/SnO 2 -Sb anode, but its complete deactivation was reached after 4 h of electrolysis at 25 mA cm -2 , indicating that the service life of this electrode is short. The Ti/SnO 2 -Sb-Ir anode is chemically and electrochemically more stable than the Ti/SnO 2 -Sb anode, but it is not suitable for the electrochemical treatment under the studied conditions. No significant changes were observed for electrolyses performed at different pH conditions with Si/BDD, and this electrode led to almost complete mineralization after 4 h of electrolysis at 100 mA cm -2 . The increase in current density resulted in faster wastewater oxidation, with lower current efficiency and higher energy consumption. Si/BBD proved to be the best electrodic material for the direct electrooxidation of tannery wastewaters.

  10. Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation.

    Science.gov (United States)

    Kim, Dong Young; Lim, Younhee; Roy, Basab; Ryu, Young-Gyoon; Lee, Seok-Soo

    2014-12-21

    Since the early nineties there have been a number of reports on the experimental development of Mg electrolytes based on organo/amide-magnesium chlorides and their transmetalations. However, there are no theoretical papers describing the underlying operating mechanisms of Mg electrolytes, and there is no clear understanding of these mechanisms. We have therefore attempted to clarify the operating mechanisms of Mg electrolytes by studying the characteristics of Mg complexes, solvation, chemical equilibrium, Mg-deposition processes, electrolyte-oxidation processes, and oxidative degradation mechanism of RMgCl-based electrolytes, using ab initio calculations. The formation and solvation energies of Mg complexes highly depend on the characteristics of R groups. Thus, changes in R groups of RMgCl lead to changes in the equilibrium position and the electrochemical reduction and oxidation pathways and energies. We first provide a methodological scheme for calculating Mg reduction potential values in non-aqueous electrolytes and electrochemical windows. We also describe a strategy for designing Mg electrolytes to maximize the electrochemical windows and oxidative stabilities. These results will be useful not only for designing improved Mg electrolytes, but also for developing new electrolytes in the future.

  11. Effects of 1000 C oxide surfaces on room temperature aqueous corrosion and environmental embrittlement of iron aluminides

    Energy Technology Data Exchange (ETDEWEB)

    Buchanan, R.A.; Perrin, R.L. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering

    1997-12-01

    Results of electrochemical aqueous-corrosion studies at room temperature indicate that retained in-service-type high-temperature surface oxides (1000 C in air for 24 hours) on FA-129, FAL and FAL-Mo iron aluminides cause major reductions in pitting corrosion resistance in a mild acid-chloride solution designed to simulate aggressive atmospheric corrosion. Removal of the oxides by mechanical grinding restores the corrosion resistance. In a more aggressive sodium tetrathionate solution, designed to simulate an aqueous environment contaminated by sulfur-bearing combustion products, only active corrosion occurs for both the 1000 C oxide and mechanically cleaned surfaces at FAL. Results of slow-strain-rate stress-corrosion-cracking tests on FA-129, FAL and FAL-Mo at free-corrosion and hydrogen-charging potentials in the mild acid chloride solution indicate somewhat higher ductilities (on the order of 50%) for the 1000 C oxides retard the penetration of hydrogen into the metal substrates and, consequently, are beneficial in terms of improving resistance to environmental embrittlement. In the aggressive sodium tetrathionate solution, no differences are observed in the ductilities produced by the 1000 C oxide and mechanically cleaned surfaces for FAL.

  12. Electrochemically assisted photocatalysis using nanocrystalline semiconductor thin films

    Energy Technology Data Exchange (ETDEWEB)

    Vinodgopal, K [Department of Chemistry, Indiana University Northwest, Gary, Indiana (United States); Kamat, Prashant V [Notre Dame Radiation Laboratory, Notre Dame, Indiana (United States)

    1995-08-01

    The principle and usefulness of electrochemically assisted photocatalysis has been illustrated with the examples of 4-chlorophenol and Acid Orange 7 degradation in aqueous solutions. Thin nanocrystalline semiconductor films coated on a conducting glass surface when employed as a photoelectrode in an electrochemical cell are effective for degradation of organic contaminants. The degradation rate can be greatly improved even in the absence of oxygen by applying an anodic bias to the TiO{sub 2} film electrodes. A ten-fold enhancement in the degradation rate was observed when TiO{sub 2} particles were coupled with SnO{sub 2} nanocrystallites at an applied bias potential of 0.83 V versus SCE

  13. Electrochemical characterization of Zr-based thin film metallic glass in hydrochloric aqueous solution

    International Nuclear Information System (INIS)

    Chuang, Ching-Yen; Liao, Yi-Chia; Lee, Jyh-Wei; Li, Chia-Lin; Chu, Jinn P.; Duh, Jenq-Gong

    2013-01-01

    Recently thin film metallic glass represents a class of promising engineering materials for structural applications. In this work, the Zr-based thin film metallic glass (TFMG) was fabricated on the Si and AISI 420 substrates using a Zr–Cu–Ni–Al alloy and pure Zr metal targets by a pulsed DC magnetron sputtering system. The chemical compositions, crystalline structures, microstructures and corrosion behavior in hydrochloric (HCl) aqueous solutions of Zr-based TFMGs were investigated. The results showed that the surface morphologies of Zr-based TFMG were very smooth. A compact and dense structure without columnar structure was observed. The amorphous structure of Zr-based TFMG was characterized by the X-ray diffractometer and transmission electron microscopy analyses. After the potentiodynamic polarization test, the better corrosion resistance was achieved for the Zr-based TFMG coated AISI 420 in 1 mM HCl aqueous solution. Based on the surface morphologies and chemical analysis results of the corroded surfaces, the pitting, crevice corrosion and filiform corrosion were found. The corrosion mechanisms of the Zr-based TFMG were discussed in this work. - Highlights: ► Zr-based thin film metallic glass with amorphous structure. ► Better corrosion resistance of Zr-based thin film metallic glass observed. ► Pitting, crevice and filiform corrosion reactions revealed. ► The Cu-rich corrosion products found in the pit. ► Nanowire and flaky corrosion products formed adjacent to the filiform corrosion path

  14. Application of proton conducting polymeric electrolytes to electrochemical capacitors

    International Nuclear Information System (INIS)

    Morita, Masayuki; Qiao, Jin-Li; Yoshimoto, Nobuko; Ishikawa, Masashi

    2004-01-01

    Non-aqueous polymeric gel complexes composed of poly(ethylene oxide)-modified polymethacrylate (PEO-PMA) dissolving anhydrous H 3 PO 4 have been examined as solid electrolytes of electrochemical capacitors. High ionic conductivity of ∼10 -3 S cm -1 (at 70 deg. C) was obtained for non-aqueous gel systems based on PEO-PMA with proper amounts of organic plasticizers. The ionic conductivity depended on the composition of the gel, especially on the content of the dopant H 3 PO 4 . A test cell of the electric double layer capacitor (EDLC) was assembled using the present gel electrolyte with activated carbon fiber (ACF) cloth electrodes. It gave as high capacity as that obtained for the capacitor using an aqueous liquid electrolyte. High rate capability was obtained for the cell operating at 90 deg. C

  15. Electrical conductivity measurements of aqueous and immobilized potassium hydroxide

    DEFF Research Database (Denmark)

    Allebrod, Frank; Chatzichristodoulou, Christodoulos; Mollerup, Pia Lolk

    2012-01-01

    concentrations was investigated using the van der Pauw method in combination with electrochemical impedance spectroscopy (EIS). Conductivity values as high as 2.7 S cm−1 for 35 wt%, 2.9 S cm−1 for 45 wt%, and 2.8 S cm−1 for 55 wt% concentrated aqueous solutions were measured at 200 °C. Micro- and nano-porous...... solid pellets were produced and used to immobilize aqueous KOH solutions. These are intended to operate as ion-conductive diaphragms (electrolytes) in alkaline electrolysis cells, offering high conductivity and corrosion resistance. The conductivity of immobilized KOH has been determined by the same...

  16. Electrochemical synthesis of novel polymer based on (4-(2,3-dihydrothieno[3,4-6][1,4][dioxin-5-yl) aniline) in aqueous solution: Characterization and application

    Energy Technology Data Exchange (ETDEWEB)

    Shahhosseini, Leyla [Chemistry Department, Kerman Branch, Islamic Azad University, Kerman (Iran, Islamic Republic of); Nateghi, Mohammad Reza, E-mail: mnateghi@iauyazd.ac.ir [Chemistry Department, Yazd Branch, Islamic Azad University, Yazd (Iran, Islamic Republic of); Kazemipour, Maryam [Chemistry Department, Kerman Branch, Islamic Azad University, Kerman (Iran, Islamic Republic of); Borhani Zarandi, Mahmoud [Department of Physics, Yazd University, P.O. Box 97175/615, Yazd (Iran, Islamic Republic of)

    2016-07-01

    4-(2,3-dihydrothieno[3,4-6][1,4][dioxin-5-yl) aniline, an interesting novel monomer was successfully synthesized in which α-carbon on ethylenedioxythiophene was linked to aniline at para position. The structure of the monomer was approved by infrared (IR), gas chromatography-mass spectrometry (GC-MS) and {sup 1}H nuclear magnetic resonance ({sup 1}H NMR) spectroscopies. Poly (4-(2,3-dihydrothieno[3,4-6][1,4][dioxin-5-yl) aniline) and its composite with graphene were electrochemically synthesized in aqueous solution by cyclic potential sweep method. The Polymer was characterized by IR and UV–vis spectroscopies, scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy techniques. Electrochemical synthesis conditions were optimized to prepare high conducting and porous polymer so it can be efficiently used as a counter electrode in fabrication of dye sensitized solar cells. Photovoltaic experiments revealed that energy conversion efficiency of the solar cell fabricated using polymer composite (7.52%) is 21% greater than that prepared by Pt counter electrode (6.19%). - Highlights: • A Novel monomer comprising aniline and EDOT was synthesized by a simple process. • Poly (ANI-EDOT) was synthesized and characterized by cyclic potential sweep method. • The copolymer changes from yellow at −0.9 V to dark green color at +0.9 V reversibly. • Poly (ANI-EDOT)/graphene is porous with electrocatalytic effect on I{sub 3}{sup −} reduction.

  17. Electrochemical synthesis of novel polymer based on (4-(2,3-dihydrothieno[3,4-6][1,4][dioxin-5-yl) aniline) in aqueous solution: Characterization and application

    International Nuclear Information System (INIS)

    Shahhosseini, Leyla; Nateghi, Mohammad Reza; Kazemipour, Maryam; Borhani Zarandi, Mahmoud

    2016-01-01

    4-(2,3-dihydrothieno[3,4-6][1,4][dioxin-5-yl) aniline, an interesting novel monomer was successfully synthesized in which α-carbon on ethylenedioxythiophene was linked to aniline at para position. The structure of the monomer was approved by infrared (IR), gas chromatography-mass spectrometry (GC-MS) and "1H nuclear magnetic resonance ("1H NMR) spectroscopies. Poly (4-(2,3-dihydrothieno[3,4-6][1,4][dioxin-5-yl) aniline) and its composite with graphene were electrochemically synthesized in aqueous solution by cyclic potential sweep method. The Polymer was characterized by IR and UV–vis spectroscopies, scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy techniques. Electrochemical synthesis conditions were optimized to prepare high conducting and porous polymer so it can be efficiently used as a counter electrode in fabrication of dye sensitized solar cells. Photovoltaic experiments revealed that energy conversion efficiency of the solar cell fabricated using polymer composite (7.52%) is 21% greater than that prepared by Pt counter electrode (6.19%). - Highlights: • A Novel monomer comprising aniline and EDOT was synthesized by a simple process. • Poly (ANI-EDOT) was synthesized and characterized by cyclic potential sweep method. • The copolymer changes from yellow at −0.9 V to dark green color at +0.9 V reversibly. • Poly (ANI-EDOT)/graphene is porous with electrocatalytic effect on I_3"− reduction.

  18. Electrochemical reduction of nitrate in the presence of an amide

    Science.gov (United States)

    Dziewinski, Jacek J.; Marczak, Stanislaw

    2002-01-01

    The electrochemical reduction of nitrates in aqueous solutions thereof in the presence of amides to gaseous nitrogen (N.sub.2) is described. Generally, electrochemical reduction of NO.sub.3 proceeds stepwise, from NO.sub.3 to N.sub.2, and subsequently in several consecutive steps to ammonia (NH.sub.3) as a final product. Addition of at least one amide to the solution being electrolyzed suppresses ammonia generation, since suitable amides react with NO.sub.2 to generate N.sub.2. This permits nitrate reduction to gaseous nitrogen to proceed by electrolysis. Suitable amides include urea, sulfamic acid, formamide, and acetamide.

  19. Thermodynamic and electrochemical study on the mechanism of formation of Ag(OH)4− in alkaline media

    International Nuclear Information System (INIS)

    Zamora-Garcia, I.R.; Alatorre-Ordaz, A.; Ibanez, J.G.; Garcia-Jimenez, M.G.; Nosaka, Y.; Kobayashi, T.; Sugita, S.

    2013-01-01

    Highlights: • Sensitive electrochemical techniques were used to evidence the formation of Ag(III). • The required potential for the generation of Ag(III) was found by using UV–vis to monitor species being formed. • A mechanism for the production of Ag(III) in the form of Ag(OH) 4 − is proposed. -- Abstract: A mechanism based on electrochemical, spectrophotometric and scanning electron microscopy (SEM) data in alkaline media is proposed for the generation of Ag(III) in the form of Ag(OH) 4 − . The formation of Ag(III) from Ag 0 is a rather complex multistep process that involves several steps. The presence of soluble Ag(I) species as Ag(OH) 2 − is of paramount importance for the production of soluble Ag(OH) 4 − , whose decomposition time is shown to exceed 8 h

  20. Chemically grown, porous, nickel oxide thin-film for electrochemical supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Inamdar, A.I.; Kim, YoungSam; Im, Hyunsik [Department of Semiconductor Science, Dongguk University, Seoul 100-715 (Korea, Republic of); Pawar, S.M.; Kim, J.H. [Department of Materials Science and Engineering, Chonnam National University, Gwangju 500-757 (Korea, Republic of); Kim, Hyungsang [Department of Physics, Dongguk University, Seoul 100-715 (Korea, Republic of)

    2011-02-15

    A porous nickel oxide film is successfully synthesized by means of a chemical bath deposition technique from an aqueous nickel nitrate solution. The formation of a rock salt NiO structure is confirmed with XRD measurements. The electrochemical supercapacitor properties of the nickel oxide film are examined using cyclic voltammetery (CV), galvanostatic and impedance measurements in two different electrolytes, namely, NaOH and KOH. A specific capacitance of {proportional_to}129.5 F g{sup -1} in the NaOH electrolyte and {proportional_to}69.8 F g{sup -1} in the KOH electrolyte is obtained from a cyclic voltammetery study. The electrochemical stability of the NiO electrode is observed for 1500 charge-discharge cycles. The capacitative behaviour of the NiO electrode is confirmed from electrochemical impedance measurements. (author)

  1. Mechanical and electrochemical characterization of vanadium nitride (VN) thin films

    Energy Technology Data Exchange (ETDEWEB)

    Caicedo, J.C., E-mail: Jcesarca@calima.univalle.edu.co [Grupo de Peliculas Delgadas, Departamento de Fisica, Universidad del Valle, Cali (Colombia); Zambrano, G. [Grupo de Peliculas Delgadas, Departamento de Fisica, Universidad del Valle, Cali (Colombia); Aperador, W. [Ingenieria Mecatronica, Universidad Militar Nueva Granada, Bogota (Colombia); Escobar-Alarcon, L.; Camps, E. [Departamento de Fisica, Instituto Nacional de Investigaciones Nucleares, Apdo. Postal 18-1027, Mexico, DF 11801 (Mexico)

    2011-10-15

    Vanadium nitride (V-N) thin films were grown using a reactive d.c. magnetron sputtering process, from a vanadium target (99.999%) in an Ar/N{sub 2} gas mixture at different deposition bias voltage. Films were deposited onto silicon (1 0 0) and RUS-3 steel substrates at 400 deg. C. Structural, compositional, mechanical and electrochemical characterizations were performed by X-ray diffraction (XRD), elastic forward analysis (EFA), nanoindentation, electrochemical impedance spectroscopy (EIS), and Tafel polarization curves, respectively. X-ray diffraction patterns show the presence of (1 1 1) and (2 0 0) crystallographic orientations associated to the V-N cubic phase. Nanoindentation measurements revealed that when the bias voltage increases from 0 V to -150 V the hardness and elastic modulus are increased from 11 GPa to 20 GPa and from 187 GPa to 221 GPa, respectively. EIS and Tafel curves showed that the corrosion rate of steel, coated with V-N single layer films deposited without bias voltage, diminishes 90% compared to the steel without this coating. On the other hand, when the V-N coating was deposited at the highest d.c. bias voltage (-150 V), the corrosion rate was greater than in the steel coated with zero-voltage (0 V) V-N films. This last result could be attributed to the formation of porosities produced by the ion bombardment during the deposition process.

  2. Mechanical and electrochemical characterization of vanadium nitride (VN) thin films

    International Nuclear Information System (INIS)

    Caicedo, J.C.; Zambrano, G.; Aperador, W.; Escobar-Alarcon, L.; Camps, E.

    2011-01-01

    Vanadium nitride (V-N) thin films were grown using a reactive d.c. magnetron sputtering process, from a vanadium target (99.999%) in an Ar/N 2 gas mixture at different deposition bias voltage. Films were deposited onto silicon (1 0 0) and RUS-3 steel substrates at 400 deg. C. Structural, compositional, mechanical and electrochemical characterizations were performed by X-ray diffraction (XRD), elastic forward analysis (EFA), nanoindentation, electrochemical impedance spectroscopy (EIS), and Tafel polarization curves, respectively. X-ray diffraction patterns show the presence of (1 1 1) and (2 0 0) crystallographic orientations associated to the V-N cubic phase. Nanoindentation measurements revealed that when the bias voltage increases from 0 V to -150 V the hardness and elastic modulus are increased from 11 GPa to 20 GPa and from 187 GPa to 221 GPa, respectively. EIS and Tafel curves showed that the corrosion rate of steel, coated with V-N single layer films deposited without bias voltage, diminishes 90% compared to the steel without this coating. On the other hand, when the V-N coating was deposited at the highest d.c. bias voltage (-150 V), the corrosion rate was greater than in the steel coated with zero-voltage (0 V) V-N films. This last result could be attributed to the formation of porosities produced by the ion bombardment during the deposition process.

  3. Electrochemical characterization of praseodymia doped zircon. Catalytic effect on the electrochemical reduction of molecular oxygen in polar organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Domenech, Antonio, E-mail: antonio.domenech@uv.es [Departament de Quimica Analitica, Universitat de Valencia, Dr. Moliner, 50, 46100 Burjassot, Valencia (Spain); Montoya, Noemi; Alarcon, Javier [Departament de Quimica Inorganica, Universitat de Valencia, Dr. Moliner, 50, 46100 Burjassot, Valencia (Spain)

    2011-08-01

    Highlights: > Electrochemical characterization of Pr centers in praseodymia-doped zircon. > Study of the catalytic effect on the reduction of peroxide radical anion in nonaqueous solvents. > Assessment of non-uniform distribution of Pr centers in the zircon grains. - Abstract: The voltammetry of microparticles and scanning electrochemical microscopy methodologies are applied to characterize praseodymium centers in praseodymia-doped zircon (Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4}; y + z = x; 0.02 < x < 0.10) specimens prepared via sol-gel synthetic routes. In contact with aqueous electrolytes, two overlapping Pr-centered cathodic processes, attributable to the Pr (IV) to Pr (III) reduction of Pr centers in different sites are obtained. In water-containing, air-saturated acetone and DMSO solutions as solvent, Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4} materials produce a significant catalytic effect on the electrochemical reduction of peroxide radical anion electrochemically generated. These electrochemical features denote that most of the Pr centers are originally in its 4+ oxidation state in the parent Pr{sub x}Zr{sub (1-y)}Si{sub (1-z)}O{sub 4} specimens. The variation of the catalytic performance of such specimens with potential scan rate, water concentration and Pr loading suggests that Pr is not uniformly distributed within the zircon grains, being concentrated in the outer region of such grains.

  4. Organic non-aqueous cation-based redox flow batteries

    Science.gov (United States)

    Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai; Zhang, Lu; Brushett, Fikile R.

    2016-03-29

    The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.

  5. Development of oxygen and pH sensors for aqueous systems

    International Nuclear Information System (INIS)

    Stvartak, C.; Alcock, C.B.; Li, B.; Wang, L.; Fergus, J.W.; Bakshi, N.

    1994-04-01

    Corrosion science has long recognized that two of the most important parameters in characterizing the corrosivity of an aqueous environment are oxygen chemical potential and pH. These parameters not only determine the thermodynamic driving forces for various corrosion reactions, but also characterize the rates of these reactions and hence the lifetime of a particular component. The primary goal of this project is to develop an electrochemical oxygen and pH sensor for continuous use in the cycle chemistry control of power plants. In the past year, electrochemical sensors with a metal/metal oxide or metal/metal hydride internal reference electrode and a fluoride-based electrolyte tube have been developed and tested in this laboratory. The corrosion tests showed that the LaF 3 -based solid electrolyte was very stable both chemically and physically in water. Furthermore, its electrical conductivity is 4 to 5 orders of magnitude higher than that of stabilized zirconia below 573 K (300 degree C), which is the main advantage of a fluoride-based electrolyte at low temperatures. With this electrolyte and the selected internal oxygen reference electrode (Ag/Ag 2 O), the electrochemical probe demonstrated Nernstian responses to the oxygen chemical potential and pH of the aqueous solution with good reproducibility. A similar cell with Zr/ZrH 1+x as the internal hydrogen reference electrode showed promising pH sensing characteristics. It is proposed that these two cells be combined to form a double-headed electrochemical probe to determine oxygen chemical potential and pH in the solution simultaneously

  6. Electrochemical behaviour of platinum in hydrogen peroxide solution (1963)

    International Nuclear Information System (INIS)

    Prost, G.H.

    1963-06-01

    The relative stability of hydrogen peroxide in aqueous solution at 25 deg. C, allows its amperometric determination from the theory, using either its cathodic reduction or its anodic oxidation. The cathodic reduction yields a wave on a platinum electrode only when some oxygen is present in the solution. It cannot, therefore, be used for electrochemical determination. On the other hand, the anodic oxidation on platinum produces a wave which might be used. However, a passivation of platinum occurs at the same time. This passivation process is studied by means of potentio-kinetic, potentio-static, intensio-static curves and of pH measurements in the vicinity of the anode. A mechanism for passivation is presented, which takes into account the role of hydrogen peroxide as a reducing agent. This passivation rules out any analytical application of the oxidation reaction of hydrogen peroxide. (author) [fr

  7. Electrochemical machining of burn-resistant Ti40 alloy

    Directory of Open Access Journals (Sweden)

    Xu Zhengyang

    2015-08-01

    Full Text Available This study investigates the feasibility of using electrochemical machining (ECM to produce critical aeroengine components from a new burn-resistant titanium alloy (Ti40, thereby reducing costs and improving efficiency relative to conventional mechanical machining. Through this, it is found that an aqueous mix of sodium chloride and potassium bromide provides the optimal electrolyte and that the surface quality of the Ti40 workpiece is improved by using a pulsed current of 1 kHz rather than a direct current. Furthermore, the quality of cavities produced by ECM and the overall material removal rate are determined to be dependent on a combination of operating voltage, electrolyte inlet pressure, cathode feeding rate and electrolyte concentration. By optimizing these parameters, a surface roughness of 0.371 μm has been achieved in conjunction with a specific removal rate of more than 3.1 mm3/A·min.

  8. EFFECTS OF REACTOR CONDITIONS ON ELECTROCHEMICAL DECHLORINATION OF TRICHLOROETHYLENE USING GRANULAR-GRAPHITE ELECTRODE.

    Science.gov (United States)

    Trichloroethylene (TCE) was electrochemically dechlorinated in aqueous environments using granular graphite cathode in a mixed reactor. Effects of pH, current, electrolyte type, and flow rate on TCE dechlorination rate were evaluated. TCE dechlorination rate constant and gas pr...

  9. Preparation of mesoporous NiO with a bimodal pore size distribution and application in electrochemical capacitors

    Energy Technology Data Exchange (ETDEWEB)

    Wang Dengchao; Ni Wenbin; Pang Huan; Lu Qingyi; Huang Zhongjie [Key Laboratory of Analytical Chemistry for Life Science (MOE), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210008 (China); Zhao Jianwei, E-mail: zhaojw@nju.edu.c [Key Laboratory of Analytical Chemistry for Life Science (MOE), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210008 (China)

    2010-09-01

    Mesoporous nickel oxide with a porous structure exhibiting a bimodal pore size distribution (2.6 and 30.3 nm diameter pores) has been synthesized in this paper. Firstly, a mesoporous precursor of coordination complex Ni{sub 3}(btc){sub 2}.12H{sub 2}O (btc = 1,3,5-benzenrtricarboxylic acid) is synthesized based on the metal-organic coordination mechanism by a hydrothermal method. Then mesoporous NiO with a bimodal size distribution is obtained by calcining the precursor in the air, and characterized by transmission electron microscopy and N{sub 2} adsorption measurements. Such unique multiple porous structure indicates a promising application of the obtained NiO as electrode materials for supercapacitors. The electrochemical behavior has been investigated by cyclic voltammogram, electrochemical impedance spectra and chronopotentiometry in 3 wt.% KOH aqueous electrolyte. The results reveal that the prepared NiO has high-capacitance retention at high scan rate and exhibits excellent cycle-life stability due to its special mesoporous character with bimodal size distribution.

  10. Electrochemical attosyringe.

    Science.gov (United States)

    Laforge, François O; Carpino, James; Rotenberg, Susan A; Mirkin, Michael V

    2007-07-17

    The ability to manipulate ultrasmall volumes of liquids is essential in such diverse fields as cell biology, microfluidics, capillary chromatography, and nanolithography. In cell biology, it is often necessary to inject material of high molecular weight (e.g., DNA, proteins) into living cells because their membranes are impermeable to such molecules. All techniques currently used for microinjection are plagued by two common problems: the relatively large injector size and volume of injected fluid, and poor control of the amount of injected material. Here we demonstrate the possibility of electrochemical control of the fluid motion that allows one to sample and dispense attoliter-to-picoliter (10(-18) to 10(-12) liter) volumes of either aqueous or nonaqueous solutions. By changing the voltage applied across the liquid/liquid interface, one can produce a sufficient force to draw solution inside a nanopipette and then inject it into an immobilized biological cell. A high success rate was achieved in injections of fluorescent dyes into cultured human breast cells. The injection of femtoliter-range volumes can be monitored by video microscopy, and current/resistance-based approaches can be used to control injections from very small pipettes. Other potential applications of the electrochemical syringe include fluid dispensing in nanolithography and pumping in microfluidic systems.

  11. Insights into the potentiometric response behaviour vs. Li+ of LiFePO4 thin films in aqueous medium

    International Nuclear Information System (INIS)

    Sauvage, F.; Tarascon, J.-M.; Baudrin, E.

    2008-01-01

    The potentiometric response of PLD-made LiFePO 4 thin films versus Li + ions in aqueous solutions has been investigated, and a sensitivity of 54 mV dec -1 has been observed in a Li + concentration range of 1-10 -4 M. Physical and electrochemical measurements of electrodes aged in aqueous medium show a slight surface oxidation with formation of heterosite-FePO 4 that we show to be responsible for the stable potential response measured. Cyclic voltamperometry measurements operated in different Li + concentration clearly highlight the key relation between the material lithium ion insertion/de-insertion capability and its potentiometric sensing response implying a faradaic-governed sensing mechanism. Based on such a finding, selection criteria (enlisting among others the potential of the redox couple, the nature of the insertion process) are herein underlined in the search for new sensitive materials

  12. "Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries.

    Science.gov (United States)

    Suo, Liumin; Borodin, Oleg; Gao, Tao; Olguin, Marco; Ho, Janet; Fan, Xiulin; Luo, Chao; Wang, Chunsheng; Xu, Kang

    2015-11-20

    Lithium-ion batteries raise safety, environmental, and cost concerns, which mostly arise from their nonaqueous electrolytes. The use of aqueous alternatives is limited by their narrow electrochemical stability window (1.23 volts), which sets an intrinsic limit on the practical voltage and energy output. We report a highly concentrated aqueous electrolyte whose window was expanded to ~3.0 volts with the formation of an electrode-electrolyte interphase. A full lithium-ion battery of 2.3 volts using such an aqueous electrolyte was demonstrated to cycle up to 1000 times, with nearly 100% coulombic efficiency at both low (0.15 coulomb) and high (4.5 coulombs) discharge and charge rates. Copyright © 2015, American Association for the Advancement of Science.

  13. Pulse electrodeposition of Pt and Pt–Ru methanol-oxidation nanocatalysts onto carbon nanotubes in citric acid aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Chou, Huei-Yu [Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan, ROC (China); Hsieh, Chien-Kuo [Department of Materials Engineering, Ming Chi University of Technology, New Taipei City 24301, Taiwan, ROC (China); Tsai, Ming-Chi; Wei, Yu-Hsuan; Yeh, Tsung-Kuang [Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan, ROC (China); Tsai, Chuen-Horng, E-mail: tsai@aec.gov.tw [Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan, ROC (China)

    2015-06-01

    In this study, platinum nanoparticle/carbon nanotube (Pt NP/CNT) and platinum–ruthenium nanoparticle (Pt–Ru NP/CNT) hybrid nanocatalysts were prepared by the pulse-electrodeposition method in different aqueous solutions containing citric acid (CA) or sulfuric acid (SA). The electrocatalytic properties of the Pt NP/CNT and Pt–Ru NP/CNT electrodes prepared using different aqueous solutions were investigated for methanol oxidation. The results show that the electrochemical mass activities of these hybrid nanocatalysts prepared in the CA aqueous solution were increased by factors of 1.46 and 2.77 for Pt NPs and Pt–Ru NPs, respectively, compared with those prepared in SA aqueous solutions using the same procedure. These increased mass activities are attributed to the CA playing dual roles as both a stabilizing agent and a particle size reducing agent in the aqueous solutions. The approach developed in this work enables further reductions in the particle sizes of noble-metal nanocatalysts. - Highlights: • Pulse-electrodeposition of Pt or Pt–Ru nanoparticles on carbon nanotubes • Carbon nanotubes used as a catalyst-supporting material • Citric acid used as reducing agent in the aqueous electrodeposition solutions • Electrochemical activity for methanol oxidation improved by a factor of 1.46 to 2.77.

  14. Surface modification and electrochemical behaviour of undoped nanodiamonds

    International Nuclear Information System (INIS)

    Zang Jianbing; Wang Yanhui; Bian Linyan; Zhang Jinhui; Meng Fanwei; Zhao Yuling; Ren Shubin; Qu Xuanhui

    2012-01-01

    Surface modifications of undoped nanodiamond (ND) particles were carried out through different annealing treatments. The methods of Fourier transform infrared spectroscopy, Raman spectroscopy, and transmission electron microscopy were used to characterize the ND surface before and after the annealing process. The electrochemical properties of the modified ND powders in aqueous solution were investigated with Fe(CN) 6 3−/4− as a redox probe. When the annealing temperature was below 850 °C, vacuum annealing removed parts of the oxygen-containing surface functionalities from the ND surface and produced more sp 2 carbon atoms in the shell. The charge transfer of the Fe(CN) 6 3−/4− redox couple decreased with increasing annealing temperature. Re-annealing in air restored the original surface conditions: few sp 2 -bonded carbon atoms and similar surface functionalities, and thus the electrochemical activity. When ND was annealed in vacuum at 900–1100 °C, more serious graphitization produced a continuous fullerenic shell wrapped around a diamond core, which had a high conductivity and electrochemical activity. This provides a novel nanoparticle with high conductivity and high stability for electrochemical applications.

  15. Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

    Science.gov (United States)

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for...

  16. In operando observation system for electrochemical reaction by soft X-ray absorption spectroscopy with potential modulation method

    International Nuclear Information System (INIS)

    Nagasaka, Masanari; Kosugi, Nobuhiro; Yuzawa, Hayato; Horigome, Toshio

    2014-01-01

    In order to investigate local structures of electrolytes in electrochemical reactions under the same scan rate as a typical value 100 mV/s in cyclic voltammetry (CV), we have developed an in operando observation system for electrochemical reactions by soft X-ray absorption spectroscopy (XAS) with a potential modulation method. XAS spectra of electrolytes are measured by using a transmission-type liquid flow cell with built-in electrodes. The electrode potential is swept with a scan rate of 100 mV/s at a fixed photon energy, and soft X-ray absorption coefficients at different potentials are measured at the same time. By repeating the potential modulation at each fixed photon energy, it is possible to measure XAS of electrochemical reaction at the same scan rate as in CV. We have demonstrated successful measurement of the Fe L-edge XAS spectra of aqueous iron sulfate solutions and of the change in valence of Fe ions at different potentials in the Fe redox reaction. The mechanism of these Fe redox processes is discussed by correlating the XAS results with those at different scan rates

  17. Charge Transfer into Aqueous Droplets via Kilovolt Potentials

    Science.gov (United States)

    Hamlin, B. S.; Rosenberg, E. R.; Ristenpart, W. D.

    2012-11-01

    When an aqueous droplet immersed in an insulating oil contacts an electrified surface, the droplet acquires net charge. For sufficiently large field strengths, the charged droplet is driven back and forth electrophoretically between the electrodes, in essence ``bouncing'' between them. Although it is clear that the droplet acquires charge, the underlying mechanism controlling the charge transfer process has been unclear. Here we demonstrate that the chemical species present in the droplet strongly affect the charge transfer process into the drop. Using two independent charge measurement techniques, high speed video velocimetry and direct current measurement, we show that the charge acquired during contact is strongly influenced by the droplet pH. We also provide physical evidence that the electrodes undergo electroplating or corrosion for droplets with appropriate chemical species present. Together, the observations strongly suggest that electrochemical reactions govern the charge transfer process into the droplet.

  18. Biosorption of Fe (II) and Cd (II) ions from aqueous solution using a ...

    African Journals Online (AJOL)

    ADOWIE PERE

    Biosorption of Fe (II) and Cd (II) ions from aqueous solution using a low cost ... human activities in the environment poses a lot of risk ... ion exchange or reverse osmosis, electrochemical treatment ..... is the adsorption coefficient, n indicates the.

  19. Fabrication and electrochemical characterization of multi-walled carbon nanotube electrodes for applications to nano-electrochemical sensing

    International Nuclear Information System (INIS)

    Hwang, Sookhyun; Choi, Hyonkwang; Jeon, Minhyon; Vedala, Harindra; Kim, Taehyung; Choi, Wonbong

    2010-01-01

    In this study, we fabricated and electrochemically characterized two types of individual carbon nanotube electrodes: an as-produced multi-walled carbon nanotube (MWNT) electrode and a modified MWNT electrode. As-produced MWNTs were electrically contacted with Au/Ti layers by using nanolithography and RF magnetron sputtering. Open-ended modified MWNT electrodes were fabricated by using a reactive ion etching treatment under an oxygen atmosphere. We also performed cyclic voltammetry measurements to detect aqueous dopamine solutions with different concentrations. We found that an individual MWNT electrode, which had a small effective area, showed good electrochemical performance. The electrocatalytic behavior of the modified electrode, which had 'broken' open ends were better than that of the as-produced electrode with respect to sensitivity. The modified electrode was capable of detecting dopamine at the picomolar level. Therefore, an individual modified MWNT electrode has potential for applications to active components in nanobiosensors.

  20. Electrochemical characterization of tenoxicam using a bare carbon paste electrode under stagnant and forced convection conditions

    International Nuclear Information System (INIS)

    Guzmán-Hernández, D.S.; Ramírez-Silva, M.T.; Palomar-Pardavé, M.; Corona-Avendaño, S.; Galano, Annia; Rojas-Hernández, A.; Romero-Romo, M.

    2012-01-01

    Highlights: ► Tenoxicam electrochemical oxidation was studied from aqueous solution with a CPE. ► Both stagnant and forced convection conditions were considered. ► We found tenoxicam electrochemical oxidation is a mass transfer-controlled process. ► An EC mechanism was found where the electrodic and chemical kinetics are fast. ► It was found that in this case n = 2 and E 1/2 = 0.770 V. ► Calculated D was 4.09 × 10 −6 cm 2 s −1 which compares with theoretically estimated. - Abstract: From potentiostatic current transients and voltammetry studies, carried out under both stagnant and forced convection conditions, the tenoxicam electrochemical behavior on a bare carbon paste rotating disk electrode was assessed in an aqueous solution (pH = 0.403). It was found that tenoxicam's electrochemical oxidation is a mass transfer-controlled process where a current peak is clearly formed at around 0.74 V when the potential scan was varied in the positive direction. However, when the potential was switched to the negative direction, up to the initial potential value, no reduction peak was formed. Tenoxicam's electrochemical oxidation follows an EC mechanism where the electrodic and chemical kinetics are fast. From sample-current voltammetry both the number of electrons, n, that tenoxicam losses during its electro-oxidation and its half-wave potential, E 1/2 , were determined to be 2 and 0.770 V vs. Ag/AgCl, respectively. Moreover, from differential pulse voltammetry plots it was confirmed that effectively in this case n = 2. Considering 2 electrons and both the Randles-Sevcik and Cotrell equations, the tenoxicam's diffusion coefficient, D, was determined to be (3.745 ± 0.077) × 10 −6 and (4.116 ± 0.086) × 10 −6 cm 2 s −1 , respectively. From linear sweep voltammetry plots recorded under forced convection conditions, it was found that Levich's equation describes adequately the limiting current recorded as a function of the electrode rotation rate, from

  1. Adsorption of Pb(II) ions from aqueous solution using lignin from ...

    African Journals Online (AJOL)

    The adsorption of lead(II) ions from aqueous solution onto alkali lignin extracted from Hagenia abyssinica was investigated by electrochemical methods. The effect of solution pH, lignin dosage and contact time were investigated at room temperature in a batch system. Adsorption equilibrium was approached within 80 min.

  2. Studying the electrochemical deposition process of molybdenum from aqueous solution of molybdate ions

    Directory of Open Access Journals (Sweden)

    Samira Fikret Cafarova

    2016-02-01

    Full Text Available In this study, the tracing of the electroreduction process of molybdate ions in aqueous media at different conditions is achieved for obtaining molybdenum metal in a simple and easy way. The kinetics and the mechanism of the electroreduction of molybdate ions are studied using cathodic polarization technique. It is observed that, the speed of the electroreduction process depends on the speed of the change of the cathodic potential sweep as well as on the temperature of the electrodeposition bath. Moreover, it is observed that, at the potential range from the stationary potential (Est = 0.25V to −0.7 V, the electroreduction of molybdate ions occurs into two steps. Moreover it is observed that, after −0.7 V the electroreduction process of molybdate is accompanying with evolution of hydrogen.

  3. Characterisation of material behaviour in high temperature aqueous environments by means of electrochemical techniques

    International Nuclear Information System (INIS)

    Bojinov, M.; Laitinen, T.; Maekelae, K.; Sirkiae, P.; Beverskog, B.

    1998-01-01

    Electrochemical measurements in solutions simulating power plant coolants are complicated by the low conductivity of the water, especially in the case of boiling water reactor (BWR) environments. To be able to obtain useful information also in BWR conditions, electrochemical techniques based on a thin-layer electrode arrangement are introduced. This arrangement makes it possible to perform voltammetric and electrochemical impedance measurements in high-temperature water with a room temperature conductivity (κ) as low as 0.1 μScm -1 . A combination of these results with those obtained by means of measuring the resistance of the surface film using the contact electric resistance (CER) technique facilitates versatile characterisation of oxide film behaviour. Examples are given on impedance and CER measurements of the oxide films formed on AISI 316 stainless steel in high temperature high purity (κ -1 ) water and on OX18H10T stainless steel in VVER water. Correlations between temperature, hydrogen and oxygen content of the solution and the oxide behaviour are discussed. (author)

  4. Electrochemical Exfoliation of Graphite in Aqueous Sodium Halide Electrolytes toward Low Oxygen Content Graphene for Energy and Environmental Applications.

    Science.gov (United States)

    Munuera, J M; Paredes, J I; Enterría, M; Pagán, A; Villar-Rodil, S; Pereira, M F R; Martins, J I; Figueiredo, J L; Cenis, J L; Martínez-Alonso, A; Tascón, J M D

    2017-07-19

    Graphene and graphene-based materials have shown great promise in many technological applications, but their large-scale production and processing by simple and cost-effective means still constitute significant issues in the path of their widespread implementation. Here, we investigate a straightforward method for the preparation of a ready-to-use and low oxygen content graphene material that is based on electrochemical (anodic) delamination of graphite in aqueous medium with sodium halides as the electrolyte. Contrary to previous conflicting reports on the ability of halide anions to act as efficient exfoliating electrolytes in electrochemical graphene exfoliation, we show that proper choice of both graphite electrode (e.g., graphite foil) and sodium halide concentration readily leads to the generation of large quantities of single-/few-layer graphene nanosheets possessing a degree of oxidation (O/C ratio down to ∼0.06) lower than that typical of anodically exfoliated graphenes obtained with commonly used electrolytes. The halide anions are thought to play a role in mitigating the oxidation of the graphene lattice during exfoliation, which is also discussed and rationalized. The as-exfoliated graphene materials exhibited a three-dimensional morphology that was suitable for their practical use without the need to resort to any kind of postproduction processing. When tested as dye adsorbents, they outperformed many previously reported graphene-based materials (e.g., they adsorbed ∼920 mg g -1 for methyl orange) and were useful sorbents for oils and nonpolar organic solvents. Supercapacitor cells assembled directly from the as-exfoliated products delivered energy and power density values (up to 15.3 Wh kg -1 and 3220 W kg -1 , respectively) competitive with those of many other graphene-based devices but with the additional advantage of extreme simplicity of preparation.

  5. Coupled Mechanical and Electrochemical Phenomena in Lithium-Ion Batteries

    Science.gov (United States)

    Cannarella, John

    Lithium-ion batteries are complee electro-chemo-mechanical systems owing to a number of coupled mechanical and electrochemical phenomena that occur during operation. In this thesis we explore these phenomena in the context of battery degradation, monitoring/diagnostics, and their application to novel energy systems. We begin by establishing the importance of bulk stress in lithium-ion batteries through the presentation of a two-year exploratory aging study which shows that bulk mechanical stress can significantly accelerate capacity fade. We then investigate the origins of this coupling between stress and performance by investigating the effects of stress in idealized systems. Mechanical stress is found to increase internal battery resistance through separator deformation, which we model by considering how deformation affects certain transport properties. When this deformation occurs in a spatially heterogeneous manner, local hot spots form, which accelerate aging and in some cases lead to local lithium plating. Because of the importance of separator deformation with respect to mechanically-coupled aging, we characterize the mechanical properties of battery separators in detail. We also demonstrate that the stress state of a lithium-ion battery cell can be used to measure the cell's state of health (SOH) and state of charge (SOC)--important operating parameters that are traditionally difficult to measure outside of a laboratory setting. The SOH is shown to be related to irreversible expansion that occurs with degradation and the SOC to the reversible strains characteristic of the cell's electrode materials. The expansion characteristics and mechanical properties of the constituent cell materials are characterized, and a phenomenological model for the relationship between stress and SOH/SOC is developed. This work forms the basis for the development of on-board monitoring of SOH/SOC based on mechanical measurements. Finally we study the coupling between mechanical

  6. Electrochemical characterization of glassy carbon electrode modified with 1,10-phenanthroline groups by two pathways: reduction of the corresponding diazonium ions and reduction of phenanthroline

    International Nuclear Information System (INIS)

    Shul, Galyna; Weissmann, Martin; Bélanger, Daniel

    2015-01-01

    The electrochemical behaviour of 1,10-phenanthroline molecules immobilized on a glassy carbon electrode surface by electrochemical reduction of the corresponding in-situ generated diazonium ions in an aqueous solution was investigated. Firstly, the derivatization of glassy carbon electrode was confirmed by the presence of the barrier effect in the solution of a redox probe. Secondly, atomic force microscopy measurements revealed the deposition of thin (< 2 nm) uniform 1,10-phenanthroline film on the surface of pyrolyzed photoresist film electrode. Thirdly, the initially electrochemically inactive grafted organic film became electroactive after being subjected to electrochemical reduction and oxidation. Fourthly, the electrochemical behaviour of phenanthroline modified electrode by electrochemical reduction of the corresponding diazonium cations was found to be similar to that of electrode modified by electrochemical reduction of only phenanthroline dissolved in an aqueous acid solution. Finally, cyclic voltammetry experiments using various methyl substituted phenanthroline derivatives provided direct evidence that functional groups responsible for the film electroactivity are formed at 5 or/and 6 positions of grafted phenanthroline molecules. On the other hand, a phenanthroline derivative having these positions blocked by methyl groups can also display electroactivity with position 7 being most likely involved in the observed redox process

  7. Pseudocapacitive Oxides and Sulfides for High-Performance Electrochemical Energy Storage

    KAUST Repository

    Xia, Chuan

    2018-03-22

    The intermittent nature of several sustainable energy sources such as solar and wind energy has ignited the demand of electrochemical energy storage devices in the form of batteries and electrochemical capacitors. The future generation of electrochemical capacitors will in large part depend on the use of pseudocapacitive materials in one or both electrodes. Developing pseudocapacitors to have both high energy and power density is crucial for future energy storage systems. This dissertation evaluates two different material systems to achieve high energy density pseudocapacitive energy storage. This research presents the successful preparation and application of ternary NiCo2S4, which is based on the surface redox mechanism, in the area of pseudocapacitive energy storage. Attention has been paid to understanding its basic physical properties which can impact its electrochemical behavior. Well-defined single- and double-shell NiCo2S4 hollow spheres were fabricated for pseudocapacitor applications, showing much improved electrochemical storage performance with good energy and power densities, as well as excellent cycling stability. To overcome the complexity of the preparation methods of NiCo2S4 nanostructures, a one-step approach was developed for the first time. Asymmetric pseudocapacitors using NiCo2S4 as cathode and graphene as anode were also fabricated to extend the operation voltage in aqueous electrolyte, and thus enhance the overall capacity of the cells. Furthermore, high-performance on-chip pseudocapacitive energy storage was demonstrated using NiCo2S4 as electrochemically active materials. This dissertation also involves another material system, intercalation pseudocapacitive VO2 (B), that displays a different charge storage mechanism from NiCo2S4. By constructing high-quality, atomically-thin two-dimensional (2D) VO2 (B) sheets using a general monomer-assisted approach, we demonstrate that a rational design of atomically thin, 2D nanostructures of

  8. Electrochemistry of potentially bioreductive alkylating quinones : Part 1. Electrochemical properties of relatively simple quinones, as model compounds of mitomycin- and aziridinylquinone-type antitumour agents

    NARCIS (Netherlands)

    Driebergen, R.J.; den Hartigh, J.; Holthuis, J.J.M.; Hulshoff, A.; van Oort, W.J.; Postma kelder, S.J.; Verboom, Willem; Reinhoudt, David; Bos, M.; van der Linden, W.E.

    1990-01-01

    The influence of methyl-, hydroxy and amino substituents on the electrochemical behaviour of simple 1,4-naphtho-and 1,4-benzoquinones, model compounds of many quinoid antitumour agents, in aqueous media was studied. Significant changes in electrochemical behaviour were observed, potentially the

  9. FeSi4P4: A novel negative electrode with atypical electrochemical mechanism for Li and Na-ion batteries

    Science.gov (United States)

    Coquil, Gaël; Fullenwarth, Julien; Grinbom, Gal; Sougrati, Moulay Tahar; Stievano, Lorenzo; Zitoun, David; Monconduit, Laure

    2017-12-01

    The electrochemical mechanism and performance of FeSi4P4, vs. Na and Li were studied using a combination of operando X-ray diffraction, 57Fe Mössbauer spectroscopy, and SQUID magnetometry. This silicon- and phosphorous-rich material exhibits a high capacity of 1750 mAh/g, retaining 1120 mAh/g after 40 cycles, and reacts through an original reversible mechanism surprisingly involving only slight changes in the chemical environment of the iron. Magnetic measurements and 57Fe Mössbauer spectroscopy at low temperature reveal the reversible but incomplete change of the magnetic moment upon charge and discharge. Such a mild reversible process without drastic phase transition (with the exception of the crystalline to amorphous transition during the first lithiation) can explain the satisfying capacity retention. The electrochemical mechanism appears thus to be significantly different from the classical conversion or alloying/dealloying mechanisms usually observed in Lithium ion batteries for p-group element based materials. The same iron silicon phosphide electrode shows also interesting but significantly lower performance vs. Na, with a limited capacity retention 350 mAh/g.

  10. Electrochemical non-enzymatic glucose sensors

    International Nuclear Information System (INIS)

    Park, Sejin; Boo, Hankil; Chung, Taek Dong

    2006-01-01

    The electrochemical determination of glucose concentration without using enzyme is one of the dreams that many researchers have been trying to make come true. As new materials have been reported and more knowledge on detailed mechanism of glucose oxidation has been unveiled, the non-enzymatic glucose sensor keeps coming closer to practical applications. Recent reports strongly imply that this progress will be accelerated in 'nanoera'. This article reviews the history of unraveling the mechanism of direct electrochemical oxidation of glucose and making attempts to develop successful electrochemical glucose sensors. The electrochemical oxidation of glucose molecules involves complex processes of adsorption, electron transfer, and subsequent chemical rearrangement, which are combined with the surface reactions on the metal surfaces. The information about the direct oxidation of glucose on solid-state surfaces as well as new electrode materials will lead us to possible breakthroughs in designing the enzymeless glucose sensing devices that realize innovative and powerful detection. An example of those is to introduce nanoporous platinum as an electrode, on which glucose is oxidized electrochemically with remarkable sensitivity and selectivity. Better model of such glucose sensors is sought by summarizing and revisiting the previous reports on the electrochemistry of glucose itself and new electrode materials

  11. Comparative ion insertion study into a nanostructured vanadium oxide in aqueous salt solutions

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Q.; Ren, S. L.; Zukowski, J.; Pomeroy, M.; Soghomonian, V., E-mail: soghomon@vt.edu [Department of Physics, Virginia Tech, Blacksburg, Virginia 24061 (United States)

    2014-07-07

    We present a comparative study for the electrochemical insertion of different cations into a nanostructured vanadium oxide material. The oxide is hydrothemally synthesized and electrically characterized by variable temperature measurements. The electrochemical reactions are performed in aqueous chloride solutions of lithium, sodium, potassium, and ammonium, and the electrochemical behavior of various cycles are correlated with visual changes in the vanadium oxide nanosheets as observed by scanning electron microscopy. We note an increase in the specific charge per cycle in the cases of sodium and ammonium ions only, correlated with minimal physical changes to the nanosheets. The differing behavior of the various ions has implications for their use in electrical energy storage applications.

  12. Characterization and electrochemical studies of Nafion/nano-TiO2 film modified electrodes

    International Nuclear Information System (INIS)

    Yuan Shuai; Hu Shengshui

    2004-01-01

    A nano-TiO 2 film from stable aqueous dispersion has been modified on a glassy carbon electrode (GCE), and was characterized by scanning electron microscopy (SEM) and surface-enhanced Raman spectroscopy (SERS). This nanostructured film exhibits an ability to improve the electron-transfer rate between electrode and dopamine (DA), and electrocatalyze the redox of DA. The electrocatalytical behavior of DA was examined by cyclic voltammetry (CV). Combined with Nafion, the bilayer-modified electrode (N/T/GCE) gives a sensitive voltammetric response of DA regardless of excess ascorbic acid (AA). Electrochemical impedance spectroscopy (EIS) at a fixed potential was performed at variously treated GCEs. The mechanism of the electrode reaction of DA at N/T/GCE and the equivalent circuits of different GCEs have been proposed

  13. Mechanism of action of electrochemically active carbons on the processes that take place at the negative plates of lead-acid batteries

    Energy Technology Data Exchange (ETDEWEB)

    Pavlov, D.; Rogachev, T.; Nikolov, P.; Petkova, G. [Institute of Electrochemistry and Energy Systems, Bulgarian Academy of Sciences, Acad. G. Bonchev Street, bl. 10, Sofia 1113 (Bulgaria)

    2009-06-01

    It is known that negative plates of lead-acid batteries have low charge acceptance when cycled at high rates and progressively accumulate lead sulphate on high-rate partial-state-of-charge (HRPSoC) operation in hybrid-electric vehicle (HEV) applications. Addition of some carbon or graphite forms to the negative paste mix improves the charge efficiency and slows down sulfation of the negative plates. The present investigation aims to elucidate the contribution of electrochemically active carbon (EAC) additives to the mechanism of the electrochemical reactions of charge of the negative plates. Test cells are assembled with four types of EAC added to the negative paste mix in five different concentrations. Through analysis of the structure of NAM (including specific surface and pore radius measurements) and of the electrochemical parameters of the test cells on HRPSoC cycling, it is established that the electrochemical reaction of charge Pb{sup 2+} + 2e{sup -} {yields} Pb proceeds at 300-400 mV lower over-potentials on negative plates doped with EAC additives as compared to the charge potentials of cells with no carbon additives. Hence, electrochemically active carbons have a highly catalytic effect on the charge reaction and are directly involved in it. Consequently, the reversibility of the charge/discharge processes is improved, which eventually leads to longer battery cycle life. Thus, charging of the negative plates proceeds via a parallel mechanism on the surfaces of both Pb and EAC particles, at a higher rate on the EAC phase. Cells with EAC in NAM have the longest cycle life when their NAM specific surface is up to 4 m{sup 2} g{sup -1} against 0.5 m{sup 2} g{sup -1} for the lead surface. The proposed parallel mechanism of charge is verified experimentally on model Pb/EAC/PbSO{sub 4} and Pb/EAC electrodes. During the charge and discharge cycles of the HRPSoC test, the EAC particles are involved in dynamic adsorption/desorption on the lead sulfate and lead

  14. Electrochemical and in vitro bioactivity of polypyrrole/ceramic nanocomposite coatings on 316L SS bio-implants.

    Science.gov (United States)

    Madhan Kumar, A; Nagarajan, S; Ramakrishna, Suresh; Sudhagar, P; Kang, Yong Soo; Kim, Hyongbum; Gasem, Zuhair M; Rajendran, N

    2014-10-01

    The present investigation describes the versatile fabrication and characterization of a novel composite coating that consists of polypyrrole (PPy) and Nb2O5 nanoparticles. Integration of the two materials is achieved by electrochemical deposition on 316L stainless steel (SS) from an aqueous solution of oxalic acid containing pyrrole and Nb2O5 nanoparticles. Fourier transform infrared spectral (FTIR) and X-ray diffraction (XRD) studies revealed that the existence of Nb2O5 nanoparticles in PPy matrix with hexagonal structure. Surface morphological analysis showed that the presence of Nb2O5 nanoparticles strongly influenced the surface nature of the nanocomposite coated 316L SS. Micro hardness results revealed the enhanced mechanical properties of PPy nanocomposite coated 316L SS due to the addition of Nb2O5 nanoparticles. The electrochemical studies were carried out using cyclic polarization and electrochemical impedance spectroscopy (EIS) measurements. In order to evaluate the biocompatibility, contact angle measurements and in vitro characterization were performed in simulated body fluid (SBF) and on MG63 osteoblast cells. The results showed that the nanocomposite coatings exhibit superior biocompatibility and enhanced corrosion protection performance over 316L SS than pure PPy coatings. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Studies of Redox Equilibria at Elevated Temperatures 2. An Automatic Divided-Function Autoclave and Cell with Flowing Liquid Junction for Electrochemical Measurements on Aqueous Systems.

    Energy Technology Data Exchange (ETDEWEB)

    Johnsson, Kerstin; Lewis, Derek; Pourbaix, Marian de

    1970-10-15

    An apparatus is described that has been developed for electrochemical studies of aqueous systems at temperatures above 100 deg C. It consists essentially of an electrically heated experimental cell enclosed by a separate pressure-vessel the walls of which are kept cool. This construction eliminates or reduces the problems of sealing electrical connections and of the corrosion of the pressure vessel, that commonly arise with conventional, externally-heated autoclaves. Pressure is applied to the cell by means of compressed air, diaphragm valves at the electrolyte outlet automatically maintaining the pressure in the cell about 1 atm lower than that in the pressure vessel. Two independent streams of electrolyte can be pumped into the experimental cell a special form of which has been developed in which may be formed a galvanic cell with a continuously regenerated flowing-liquid junction. In this form the apparatus enables experiments with, for example, one molal chloride solutions with pH 1-10, at temperatures up to about 250 deg C and under pressures up to about 40 atm. The apparatus has been tested in experiments in which classical measurements of the conductance of some aqueous electrolytes have been repeated. Good agreement with the earlier results has been obtained

  16. Continuous electrochemical oxidation of biomass derived 5-(hydroxymethyl)furfural into 2,5-furandicarboxylic acid

    NARCIS (Netherlands)

    Latsuzbaia, R.; Bisselink, R.; Anastasopol, A.; Meer, van der H.; Heck, van R.; Yagüe, M.S.; Zijlstra, M.; Roelands, M.; Crockatt, M.; Goetheer, E.; Giling, E.

    2018-01-01

    Abstract: A continuous electrochemical process with integrated product separation has been developed for production of 2,5-furandicarboxylic acid (FDCA) by oxidation of 5-(hydroxymethyl)furfural (HMF) in aqueous alkaline media on non-noble Ni/NiOOH foam electrodes at ambient conditions. Initially,

  17. Electrochemical analysis in a liposome suspension using lapachol as a hydrophobic electro active species.

    Science.gov (United States)

    Okumura, Noriko; Wakamatsu, Shiori; Uno, Bunji

    2014-01-01

    This study demonstrated that the electro-chemical analysis of hydrophobic quinones can be performed in liposome suspension systems. We prepared and analyzed liposome suspensions containing lapachol, which is a quinone-based anti-tumor activity compound. In this suspension system, a simple one redox couple of lapachol is observed. These results are quite different from those obtained in organic solvents. In addition, the pH dependence of redox behaviors of lapachol could be observed in multilamellar vesicle (MLV) suspension system. This MLV suspension system method may approximate the electrochemical behavior of hydrophobic compounds in aqueous conditions. A benefit of this liposome suspension system for electrochemical analysis is that it enables to observe water-insoluble compounds without using organic solvents.

  18. Instrumentation for in situ flow electrochemical Scanning Transmission X-ray Microscopy (STXM)

    Science.gov (United States)

    Prabu, Vinod; Obst, Martin; Hosseinkhannazer, Hooman; Reynolds, Matthew; Rosendahl, Scott; Wang, Jian; Hitchcock, Adam P.

    2018-06-01

    We report the design and performance of a 3-electrode device for real time in situ scanning transmission X-ray microscopy studies of electrochemical processes under both static (sealed, non-flow) conditions and with a continuous flow of electrolytes. The device was made using a combination of silicon microfabrication and 3D printing technologies. The performance is illustrated by results of a study of copper deposition and stripping at a gold working electrode. X-ray absorption spectromicroscopy at the Cu 2p edge was used to follow the evolution as a function of potential and time of the spatial distributions of Cu(0) and Cu(i) species electro-deposited from an aqueous solution of copper sulphate. The results are interpreted in terms of competing mechanisms for the reduction of Cu(ii).

  19. Chemical splitting of multiwalled carbon nanotubes to enhance electrochemical capacitance for supercapacitors

    Science.gov (United States)

    Li, Xinlu; Li, Tongtao; Zhang, Xinlin; Zhong, Qineng; Li, Hongyi; Huang, Jiamu

    2014-06-01

    Multiwalled carbon nanotubes (MWCNTs) were chemically split and self-assembled to a flexible porous paper made of graphene oxide nanoribbons (GONRs). The morphology and microstructure of the pristine MWCNTs and GONRs were analyzed by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Raman spectroscopy and Fourier transform infrared spectroscopy. And the specific surface area and porosity structure were measured by N2 adsorption-desorption. The longitudinally split MWCNTs show an enhancement in specific capacitance from 21 F g-1 to 156 F g-1 compared with the pristine counterpart at 0.1 A g-1 in a 6 M KOH aqueous electrolytes. The electrochemical experiments prove that the chemical splitting of MWCNTs will make inner carbon layers opened and exposed to electrochemical double layers, which can effectively improve the electrochemical capacitance for supercapacitors.

  20. Electrochemical behavior of Ti and Ti6Al4V in aqueous solutions of citric acid containing halides

    Directory of Open Access Journals (Sweden)

    Anelise Marlene Schmidt

    2006-12-01

    Full Text Available This paper reports on an investigation of the electrochemical behavior of Ti grade 2 and Ti6Al4V alloy in aqueous citric acid solutions with pH 2.0 containing halide ions. Voltammetric studies of Ti and the alloy in citric acid, with and without chloride ions, indicate that the Ti and Ti alloy presented a passive behavior in the test solutions used. Pitting was observed at 3.0 and 2.5 V/SCE for Ti and Ti6Al4V, respectively, when bromide ions were added to the solution. In solutions containing fluoride ions, dissolution of the film occurred at potentials close to - 1.0 V/SCE in both electrodes. The iodide ions oxidized on the passive oxide film at potentials close to 1.0 V/SCE. EIS results of the materials in citric acid solutions containing chloride ions revealed that the film's resistance increased as the applied potential rose from 0 to 1.0 V. In bromide-containing solutions, breakdown of the film was confirmed at potentials above 2.0 V/SCE in both electrodes. These results suggest film reformation for Ti and the alloy in solutions containing fluoride at potentials within the passive region.

  1. Electrochemical Hydrogen Storage in a Highly Ordered Mesoporous Carbon

    Directory of Open Access Journals (Sweden)

    Dan eLiu

    2014-10-01

    Full Text Available A highly order mesoporous carbon has been synthesized through a strongly acidic, aqueous cooperative assembly route. The structure and morphology of the carbon material were investigated using TEM, SEM and nitrogen adsorption-desorption isotherms. The carbon was proven to be meso-structural and consisted of graphitic micro-domain with larger interlayer space. AC impedance and electrochemical measurements reveal that the synthesized highly ordered mesoporous carbon exhibits a promoted electrochemical hydrogen insertion process and improved capacitance and hydrogen storage stability. The meso-structure and enlarged interlayer distance within the highly ordered mesoporous carbon are suggested as possible causes for the enhancement in hydrogen storage. Both hydrogen capacity in the carbon and mass diffusion within the matrix were improved.

  2. Photolysis mechanism of aqueous tyrosine upon excitation of the second absorption band

    International Nuclear Information System (INIS)

    Shimizu, O.

    1984-01-01

    The formation mechanism of tyrosinyl radical was studied for aqueous solutions of tyrosine under irradiation at 235 nm which falls into the second absorption band. The work is based upon the analysis of the rate of bityrosine production for steady-state excitation at low intensity. The results indicate that monophotonic O-H bond cleavage of tyrosine, presumably involving the upper excited triplet state, is the initial photoprocess leading to the tyrosinyl radical when tyrosine is excited into the second absorption band. (author)

  3. Materials for electrochemical capacitors

    Science.gov (United States)

    Simon, Patrice; Gogotsi, Yury

    2008-11-01

    Electrochemical capacitors, also called supercapacitors, store energy using either ion adsorption (electrochemical double layer capacitors) or fast surface redox reactions (pseudo-capacitors). They can complement or replace batteries in electrical energy storage and harvesting applications, when high power delivery or uptake is needed. A notable improvement in performance has been achieved through recent advances in understanding charge storage mechanisms and the development of advanced nanostructured materials. The discovery that ion desolvation occurs in pores smaller than the solvated ions has led to higher capacitance for electrochemical double layer capacitors using carbon electrodes with subnanometre pores, and opened the door to designing high-energy density devices using a variety of electrolytes. Combination of pseudo-capacitive nanomaterials, including oxides, nitrides and polymers, with the latest generation of nanostructured lithium electrodes has brought the energy density of electrochemical capacitors closer to that of batteries. The use of carbon nanotubes has further advanced micro-electrochemical capacitors, enabling flexible and adaptable devices to be made. Mathematical modelling and simulation will be the key to success in designing tomorrow's high-energy and high-power devices.

  4. Coupling of Mechanical Behavior of Lithium Ion Cells to Electrochemical-Thermal (ECT) Models for Battery Crush

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Chao; Santhanagopalan, Shriram; Pesaran, Ahmad; Sahraei, Elham; Wierzbicki, Tom

    2016-06-14

    Vehicle crashes can lead to crushing of the battery, damaging lithium ion battery cells and causing local shorts, heat generation, and thermal runaway. Simulating all the physics and geometries at the same time is challenging and takes a lot of effort; thus, simplifications are needed. We developed a material model for simultaneously modeling the mechanical-electrochemical-thermal behavior, which predicted the electrical short, voltage drop, and thermal runaway behaviors followed by a mechanical abuse-induced short. The effect of short resistance on the battery cell performance was studied.

  5. Flexible Pillared Graphene-Paper Electrodes for High-Performance Electrochemical Supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Gongkai; Sun, Xiang; Lu, Fengyuan; Sun, Hongtao; Yu, Mingpeng; Jiang, Weilin; Liu, Changsheng; Lian, Jie

    2011-12-08

    Flexible graphene paper (GP) pillared by carbon black (CB) nanoparticles using a simple vacuum filtration method is developed as a high-performance electrode material for supercapacitors. Through the introduction of CB nanoparticles as spacers, the self-restacking of graphene sheets during the filtration process is mitigated to a great extent. The pillared GP-based supercapacitors exhibit excellent electrochemical performances and cyclic stabilities compared with GP without the addition of CB nanoparticles. At a scan rate of 10 mV s-1, the specific capacitance of the pillared GP is 138 F g-1 and 83.2 F g-1 with negligible 3.85% and 4.35% capacitance degradation after 2000 cycles in aqueous and organic electrolytes, respectively. At an extremely fast scan rate of 500 mV s-1, the specific capacitance can reach 80 F g-1 in aqueous electrolyte. No binder is needed for assembling the supercapacitor cells and the pillared GP itself may serve as a current collector due to its intrinsic high electrical conductivity. Finally, the pillared GP has great potential in the development of promising flexible and ultralight-weight supercapacitors for electrochemical energy storage.

  6. On the existence of the H3 tautomer of adenine in aqueous solution. Rationalizations based on hybrid quantum mechanics/molecular mechanics predictions

    DEFF Research Database (Denmark)

    Aidas, Kestutis; Mikkelsen, Kurt V; Kongsted, Jacob

    2010-01-01

    The (15)N NMR spectrum of adenine in aqueous solution has been modeled using high-level combined density functional theory/molecular mechanics techniques coupled to a dynamical averaging scheme. The explicit consideration of the three lowest-energy tautomers of adenine-H9, H7 and H3-allows...

  7. Electrochemistry for the Generation of Renewable Chemicals: One-Pot Electrochemical Deoxygenation of Xylose to δ-Valerolactone.

    Science.gov (United States)

    James, Olusola O; Sauter, Waldemer; Schröder, Uwe

    2017-05-09

    In this study, the electrochemical conversion of xylose to δ-valerolactone via carbonyl intermediates is demonstrated. The conversion was achieved in aqueous media and at ambient conditions. This study also demonstrates that the feedstock for production of renewable chemicals and biofuels through electrochemistry can be extended to primary carbohydrate molecules. This is the first report on a one-pot electrochemical deoxygenation of xylose to δ-valerolactone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Potential and pH dependence of photocurrent transients for boron-doped diamond electrodes in aqueous electrolyte

    International Nuclear Information System (INIS)

    Green, S.J.; Mahe, L.S.A.; Rosseinsky, D.R.; Winlove, C.P.

    2013-01-01

    Using illumination at energies below the intrinsic diamond energy gap, photocurrent transients have been recorded for boron-doped diamond (BDD) as an electrode in an aqueous electrolyte of 0.1 M KH 2 PO 4 . The commercially-supplied BDD was in the form of a free-standing, polycrystalline film grown by chemical vapour deposition (CVD), with a boron acceptor concentration of ≥10 20 cm −3 . The effects of mechanical polishing of the BDD, of electrochemical hydrogen evolution and of electrochemical oxygen evolution (in 0.1 M KH 2 PO 4 ), on the potential dependence of the photocurrent transients have been examined. Measurements of the cathodic photocurrent at light switch-on have been used to determine the photocurrent onset potential as a measure of the flatband potential. Comparison with and between related literature observations has shown broad agreement across considerably varying BDD/electrolyte systems. The flatband potential shifted positively following electrochemical oxygen evolution, indicating the formation of oxygen-containing groups on the diamond surface, these increasing the potential drop across the Helmholtz layer. For the electrochemically oxidised electrode, the cathodic photocurrent transient at a fixed potential changed reproducibly with changing solution pH, owing to the participation of the oxygen-containing surface groups in acid–base equilibrium with the solution. This clear demonstration of BDD as a photoelectrochemical pH sensor is in principle extendable to mapping the spatial variation in pH across a BDD surface by use of a focussed light spot

  9. Coupling of Mechanical Behavior of Lithium Ion Cells to Electrochemical-Thermal Models for Battery Crush; NREL (National Renewable Energy Laboratory)

    Energy Technology Data Exchange (ETDEWEB)

    Pesaran, Ahmad; Zhang, Chao; Santhanagopalan, Shriram; Sahraei, Elham; Wierzbiki, Tom

    2015-06-15

    Propagation of failure in lithium-ion batteries during field events or under abuse is a strong function of the mechanical response of the different components in the battery. Whereas thermal and electrochemical models that capture the abuse response of batteries have been developed and matured over the years, the interaction between the mechanical behavior and the thermal response of these batteries is not very well understood. With support from the Department of Energy, NREL has made progress in coupling mechanical, thermal, and electrochemical lithium-ion models to predict the initiation and propagation of short circuits under external crush in a cell. The challenge with a cell crush simulation is to estimate the magnitude and location of the short. To address this, the model includes an explicit representation of each individual component such as the active material, current collector, separator, etc., and predicts their mechanical deformation under different crush scenarios. Initial results show reasonable agreement with experiments. In this presentation, the versatility of the approach for use with different design factors, cell formats and chemistries is explored using examples.

  10. Electronically type-sorted carbon nanotube-based electrochemical biosensors with glucose oxidase and dehydrogenase.

    Science.gov (United States)

    Muguruma, Hitoshi; Hoshino, Tatsuya; Nowaki, Kohei

    2015-01-14

    An electrochemical enzyme biosensor with electronically type-sorted (metallic and semiconducting) single-walled carbon nanotubes (SWNTs) for use in aqueous media is presented. This research investigates how the electronic types of SWNTs influence the amperometric response of enzyme biosensors. To conduct a clear evaluation, a simple layer-by-layer process based on a plasma-polymerized nano thin film (PPF) was adopted because a PPF is an inactive matrix that can form a well-defined nanostructure composed of SWNTs and enzyme. For a biosensor with the glucose oxidase (GOx) enzyme in the presence of oxygen, the response of a metallic SWNT-GOx electrode was 2 times larger than that of a semiconducting SWNT-GOx electrode. In contrast, in the absence of oxygen, the response of the semiconducting SWNT-GOx electrode was retained, whereas that of the metallic SWNT-GOx electrode was significantly reduced. This indicates that direct electron transfer occurred with the semiconducting SWNT-GOx electrode, whereas the metallic SWNT-GOx electrode was dominated by a hydrogen peroxide pathway caused by an enzymatic reaction. For a biosensor with the glucose dehydrogenase (GDH; oxygen-independent catalysis) enzyme, the response of the semiconducting SWNT-GDH electrode was 4 times larger than that of the metallic SWNT-GDH electrode. Electrochemical impedance spectroscopy was used to show that the semiconducting SWNT network has less resistance for electron transfer than the metallic SWNT network. Therefore, it was concluded that semiconducting SWNTs are more suitable than metallic SWNTs for electrochemical enzyme biosensors in terms of direct electron transfer as a detection mechanism. This study makes a valuable contribution toward the development of electrochemical biosensors that employ sorted SWNTs and various enzymes.

  11. Electrochemical behavior of some new pyrimidine derivatives

    Directory of Open Access Journals (Sweden)

    MUSTAFA LUTFU BERKEM

    2004-09-01

    Full Text Available Electrochemical reduction of two recently synthesized pyrimidine compounds, 1-amino-5-benzoyil-4-phenyl-1H-pyrimidine-2-one (I, and 1-amino-5-benzoil-4-phenyl-1H-pyrimidine-2-thione (II were investigated by cyclic volatmmetry at a hanging mercury drop electrode in aqueous methanol (36 % v/v and in non-aqueous methanol. A series of cathodic peaks without the corresponding anodic peaks were observed for I. As the pH of the solution was increased, some of the cathodic peaks overlapped resulting in the loss of the previously observed peaks. For II, three cathodic peaks and one anodic peak were observed in addition to those observed for I. The peak potentials shifted in the negative direction with increasing pH. This shift was measured over a large pH range (1.80 – 12.30 to determine the pKa values of the compounds. The acidity constants related to the amino groups were 4.80 and 9.80 for I and 5.50 and 9.80 for II. A thiol-thione tautomerization was observed for II, which was more pronounced in the non-aqueous methanol medium. The pK values for both protonation and deprotonation of the thiocarbonyl group were also determined. The pK values were 5.80 and 9.80 for protonation and deprotonation in aqueous methanol and 6.80 and 10.80 in non-aqueous methanol.

  12. Electrochemical behavior of current collectors for lithium batteries in non-aqueous alkyl carbonate solution and surface analysis by ToF-SIMS

    International Nuclear Information System (INIS)

    Myung, Seung-Taek; Sasaki, Yusuke; Sakurada, Shuhei; Sun, Yang-Kook; Yashiro, Hitoshi

    2009-01-01

    Several metals (Cu, Fe, Al, Ti, and Cr) as current collector for lithium-ion battery were investigated to understand their electrochemical behavior and passivation process in a non-aqueous alkyl carbonate solution containing LiPF 6 salt. From cyclic voltammetric study, it was found that Cu and Fe metals were dissolved into the electrolyte below 4 V vs. Li/Li + . Alternatively, Al and Ti were stable up to 5 V vs. Li/Li + . Their scratched surfaces at 5 V vs. Li/Li + were polarized in a transient mode and it was found that the surfaces were passivated during the polarization test. Formed passive film was composed of two hybrid layers: outer layer by metal (Al and Ti) fluoride and inner by metal oxide, as confirmed by time-of-flight secondary ion mass spectroscopy. Presence of HF in the electrolyte was indispensible to form the metal fluoride layer on the oxide layer. The outer fluoride layer would protect the inner oxide layer and metal substrate from HF attack, bringing about satisfactory corrosion resistance under lithium-ion battery environment.

  13. Effects of the Formulations of Silicon-Based Composite Anodes on their Mechanical, Storage, and Electrochemical Properties.

    Science.gov (United States)

    Assresahegn, Birhanu Desalegn; Bélanger, Daniel

    2017-10-23

    In this work, the effects of the formulation of silicon-based composite anodes on their mechanical, storage, and electrochemical properties were investigated. The electrode formulation was changed through the use of hydrogenated or modified (through the covalent attachment of a binding additive such as polyacrylic acid) silicon and acetylene black or graphene sheets as conducting additives. A composite anode with a covalently grafted binder had the highest elongation without breakages and strong adhesion to the current collector. These mechanical properties depend significantly on the conductive carbon additive used and the use of graphene sheets instead of acetylene black can improve elongation and adhesion significantly. After 180 days of storage under ambient conditions, the electronic conductivity and discharge capacity of the modified silicon electrode showed much smaller decreases in these properties than those of the hydrogenated silicon composite electrode, indicating that the modification can result in passivation and a constant composition of the active material. Moreover, the composite Si anode has a high packing density. Consequently, thin-film electrodes with very high material loadings can be prepared without decreased electrochemical performance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Electrochemical behavior of meso-substituted iron porphyrins in alkaline aqueous media

    Science.gov (United States)

    Berezina, N. M.; Bazanov, M. I.; Maksimova, A. A.; Semeikin, A. S.

    2017-12-01

    The effect meso-substitution in iron porphyrin complexes has on their redox behavior in alkaline aqueous solutions is studied via cyclic voltammetry. The voltammetric features of the reduction of iron pyridylporphyrins suggest that the sites of electron transfer lie at the ligand, the metal ion, and the pyridyl moieties. The electron transfer reactions between the different forms of these compounds, including the oxygen reduction reaction they mediate, are outlined to show the sequence and potential ranges in which they occur in alkaline aqueous media. Under our experimental conditions, the iron porphyrins exist as μ-oxo dimmers whose activity for the electrocatalytic reduction of oxygen displays a considerable dependence on the nature of the substitutents and nitrogen isomerization (for pyridylporphyrins) and grows in the order (Fe( ms-Ph)4P)2O, (Fe[ ms-(Py-3)Ph3]P)2O, (Fe[ ms-(Py-4)4]P)2O, and (Fe[ ms-(Py-3)4]P)2O.

  15. Mechano-electrochemical study of stress corrosion crack tip area: Case of Zircaloy-4 in halide solution

    International Nuclear Information System (INIS)

    Durif, E.

    2012-01-01

    Stress corrosion cracking (SCC) is a damage phenomenon which results from the synergy between corrosion process (dissolution, adsorption) and mechanical fracture (crack propagation). Although this phenomenon is well known, its modelling is still a challenging issue, especially concerning mechano-electrochemical coupling mechanisms at crack tip, because it depends on model system (metal/aggressive media) and large number of mechanical and electrochemical factors. In this thesis, mutual interactions between dissolution and the stress state around the crack tip (stress intensity factor) are studied in the case of Zircaloy-4 in aqueous halide solution. Samples are first pre-cracked in air by using fatigue load-shedding procedure to control the stress intensity factor. Then, pre-oxidation is used to produce a thin protective passive layer on their surface. The electro-chemical reactions are thus concentrated at the crack tip which also induces a concentration of the mechanical effect. During the test, digital images of the sample surface are acquired. Digital Image Correlation is performed a posteriori in order to obtain the evolution of the crack length and the stress intensity factors. Further, a specific procedure is developed in order to perform the DIC analysis while the test is running. This allows to control the load so that a given value of the stress intensity factor is prescribed. With this innovative experimental technique, we perform experimental tests that allow to discriminate the effects between different stress corrosion cracking mechanisms. It is suggested that once a critical anodic polarization is exceeded, the crack growth rate depends on the stress intensity factor but also on its time derivative. Indeed, a threshold effect is obtained on the stress intensity factor, meaning that plasticity must increase for the dissolution reaction to occur, but also on its rate meaning that time for plasticity to produce new dislocations must not exceed the

  16. Development of techniques for electrochemical studies in power plant environments

    International Nuclear Information System (INIS)

    Maekelae, K.

    2000-01-01

    The properties of the oxide films on the engineering alloys used as construction materials in power plants change as a result of exposure to aqueous environments. The susceptibility of the materials to different forms of corrosion is influenced by the properties of these oxide films. The structure and electrochemical properties of the oxide films are in turn dependent on the applied water chemistry. Therefore, water chemistry control has been used in minimising the impact of different corrosion phenomena in operating power plants. Since there is not only one ideal operational specification for all light water reactors, individually designed water chemistry programs are needed to take into account plant-specific design features and particular problem areas. The applicability of alternative water chemistry practices require fast and reliable in-line electrochemical techniques to monitor possible changes in the oxidation behaviour of nuclear power plant materials. This thesis summarises the work done at the Technical Research Centre of Finland over the past 10 years to increase the knowledge of factors affecting the oxidation behaviour of construction materials in aqueous coolants at high temperatures. The work started with the development of electrodes for measurement of high temperature water chemistry parameters such as pH and the corrosion potential of construction materials. After laboratory testing these electrodes were used both in test reactors and in operating nuclear power plants. These measurements showed that high temperature water chemistry monitoring may be more accurate than corresponding room temperature measurements, particularly during transient situations. However, it was also found that understanding the processes taking place within and on oxide films requires a combination of electrochemical techniques enabling characterisation of the electronic properties of these films. This conclusion resulted in development of a controlled

  17. Cobalt-Doped Nickel Phosphite for High Performance of Electrochemical Energy Storage.

    Science.gov (United States)

    Li, Bing; Shi, Yuxin; Huang, Kesheng; Zhao, Mingming; Qiu, Jiaqing; Xue, Huaiguo; Pang, Huan

    2018-03-01

    Compared to single metallic Ni or Co phosphides, bimetallic Ni-Co phosphides own ameliorative properties, such as high electrical conductivity, remarkable rate capability, upper specific capacity, and excellent cycle performance. Here, a simple one-step solvothermal process is proposed for the synthesis of bouquet-like cobalt-doped nickel phosphite (Ni 11 (HPO 3 ) 8 (OH) 6 ), and the effect of the structure on the pseudocapacitive performance is investigated via a series of electrochemical measurements. It is found that when the cobalt content is low, the glycol/deionized water ratio is 1, and the reaction is under 200 °C for 20 h, the morphology of the sample is uniform and has the highest specific surface area. The cobalt-doped Ni 11 (HPO 3 ) 8 (OH) 6 electrode presents a maximum specific capacitance of 714.8 F g -1 . More significantly, aqueous and solid-state flexible electrochemical energy storage devices are successfully assembled. The aqueous device shows a high energy density of 15.48 mWh cm -2 at the power density of 0.6 KW cm -2 . The solid-state device shows a high energy density of 14.72 mWh cm -2 at the power density of 0.6 KW cm -2 . These excellent performances confirm that the cobalt-doped Ni 11 (HPO 3 ) 8 (OH) 6 are promising materials for applications in electrochemical energy storage devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Electrochemical characterization of anode passivation mechanisms in copper electrorefining

    Science.gov (United States)

    Moats, Michael Scott

    Anode passivation can decrease productivity and quality while increasing costs in modern copper electrorefineries. This investigation utilized electrochemical techniques to characterize the passivation behavior of anode samples from ten different operating companies. It is believed that this collection of anodes is the most diverse set ever to be assembled to study the effect of anode composition on passivation. Chronopotentiometry was the main electrochemical technique, employing a current density of 3820 A m-2. From statistical analysis of the passivation characteristics, increasing selenium, tellurium, silver, lead and nickel were shown to accelerate passivation. Arsenic was the only anode impurity that inhibited passivation. Oxygen was shown to accelerate passivation when increased from 500 to 1500 ppm, but further increases did not adversely affect passivation. Nine electrolyte variables were also examined. Increasing the copper, sulfuric acid or sulfate concentration of the electrolyte accelerated passivation. Arsenic in the electrolyte had no effect on passivation. Chloride and optimal concentrations of thiourea and glue delayed passivation. Linear sweep voltammetry, cyclic voltammetry, and impedance spectroscopy provided complementary information. Analysis of the electrochemical results led to the development of a unified passivation mechanism. Anode passivation results from the formation of inhibiting films. Careful examination of the potential details, especially those found in the oscillations just prior to passivation, demonstrated the importance of slimes, copper sulfate and copper oxide. Slimes confine dissolution to their pores and inhibit diffusion. This can lead to copper sulfate precipitation, which blocks more of the surface area. Copper oxide forms because of the resulting increase in potential at the interface between the copper sulfate and anode. Ultimate passivation occurs when the anode potential is high enough to stabilize the oxide film in

  19. Electrochemical oxidation of organic waste

    International Nuclear Information System (INIS)

    Almon, A.C.; Buchanan, B.R.

    1990-01-01

    Both silver catalyzed and direct electrochemical oxidation of organic species are examined in analytical detail. This paper describes the mechanisms, reaction rates, products, intermediates, capabilities, limitations, and optimal reaction conditions of the electrochemical destruction of organic waste. A small bench-top electrocell being tested for the treatment of small quantities of laboratory waste is described. The 200-mL electrochemical cell used has a processing capacity of 50 mL per day, and can treat both radioactive and nonradioactive waste. In the silver catalyzed process, Ag(I) is electrochemically oxidized to Ag(II), which attacks organic species such as tributylphosphate (TBP), tetraphenylborate (TPB), and benzene. In direct electrochemical oxidation, the organic species are destroyed at the surface of the working electrode without the use of silver as an electron transfer agent. This paper focuses on the destruction of tributylphosphate (TBP), although several organic species have been destroyed using this process. The organic species are converted to carbon dioxide, water, and inorganic acids

  20. ELECTROCHEMICAL STUDIES OF URANIUM METAL CORROSION MECHANISM AND KINETICS IN WATER

    International Nuclear Information System (INIS)

    Boudanova, Natalya; Maslennikov, Alexander; Peretroukhine, Vladimir F.; Delegard, Calvin H.

    2006-01-01

    During long-term underwater storage of low burn-up uranium metal fuel, a corrosion product sludge forms containing uranium metal grains, uranium dioxide, uranates and, in some cases, uranium peroxide. Literature data on the corrosion of non-irradiated uranium metal and its alloys do not allow unequivocal prediction of the paragenesis of irradiated uranium in water. The goal of the present work conducted under the program 'CORROSION OF IRRADIATED URANIUM ALLOYS FUEL IN WATER' is to study the corrosion of uranium and uranium alloys and the paragenesis of the corrosion products during long-term underwater storage of uranium alloy fuel irradiated at the Hanford Site. The elucidation of the physico-chemical nature of the corrosion of irradiated uranium alloys in comparison with non-irradiated uranium metal and its alloys is one of the most important aspects of this work. Electrochemical methods are being used to study uranium metal corrosion mechanism and kinetics. The present part of work aims to examine and revise, where appropriate, the understanding of uranium metal corrosion mechanism and kinetics in water

  1. Manganese oxide electrochemical capacitor with potassium poly(acrylate) hydrogel electrolyte

    Science.gov (United States)

    Lee, Kuang-Tsin; Wu, Nae-Lih

    An aqueous gel electrolyte has for the first time been successfully applied to the MnO 2· nH 2O-based pseudocapacitive electrochemical capacitors (ECs). The gel electrolyte is made of potassium poly(acrylate) (PAAK) polymer and aqueous solution of KCl. With the selected composition, PAAK:KCl:H 2O = 9.0%:6.7%:84.3% by weight, the gel shows no fluidity, possessing an ionic conductivity in the order of 10 -1 S cm -1. The gel electrolyte has been found to give substantially higher specific capacitances than those in the liquid electrolyte with the same salt (KCl) composition (1 M) and high power capability (>10 kW/kg).

  2. Manganese oxide electrochemical capacitor with potassium poly(acrylate) hydrogel electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kuang-Tsin; Wu, Nae-Lih [Department of Chemical Engineering, National Taiwan University, Taipei 106 (China)

    2008-04-15

    An aqueous gel electrolyte has for the first time been successfully applied to the MnO{sub 2}.nH{sub 2}O-based pseudocapacitive electrochemical capacitors (ECs). The gel electrolyte is made of potassium poly(acrylate) (PAAK) polymer and aqueous solution of KCl. With the selected composition, PAAK:KCl:H{sub 2}O = 9.0%:6.7%:84.3% by weight, the gel shows no fluidity, possessing an ionic conductivity in the order of 10{sup -1} S cm{sup -1}. The gel electrolyte has been found to give substantially higher specific capacitances than those in the liquid electrolyte with the same salt (KCl) composition (1 M) and high power capability (>10 kW/kg). (author)

  3. MoOx thin films deposited by magnetron sputtering as an anode for aqueous micro-supercapacitors

    Science.gov (United States)

    Liu, Can; Li, Zhengcao; Zhang, Zhengjun

    2013-12-01

    In order to examine the potential application of non-stoichiometric molybdenum oxide as anode materials for aqueous micro-supercapacitors, conductive MoOx films (2 ⩽ x ⩽ 2.3) deposited via RF magnetron sputtering at different temperatures were systematically studied for composition, structure and electrochemical properties in an aqueous solution of Li2SO4. The MoOx (x ≈ 2.3) film deposited at 150 °C exhibited a higher areal capacitance (31 mF cm-2 measured at 5 mV s-1), best rate capability and excellent stability at potentials below -0.1 V versus saturated calomel electrode, compared to the films deposited at room temperature and at higher temperatures. These superior properties were attributed to the multi-valence composition and mixed-phase microstructure, i.e., the coexistence of MoO2 nanocrystals and amorphous MoOx (2.3 < x ⩽ 3). A mechanism combining Mo(IV) oxidation/reduction on the hydrated MoO2 grain surfaces and cation intercalation/extrusion is proposed to illustrate the pseudo-capacitive process.

  4. MoOx thin films deposited by magnetron sputtering as an anode for aqueous micro-supercapacitors

    Directory of Open Access Journals (Sweden)

    Can Liu

    2013-11-01

    Full Text Available In order to examine the potential application of non-stoichiometric molybdenum oxide as anode materials for aqueous micro-supercapacitors, conductive MoOx films (2 ≤ x ≤ 2.3 deposited via RF magnetron sputtering at different temperatures were systematically studied for composition, structure and electrochemical properties in an aqueous solution of Li2SO4. The MoOx (x ≈ 2.3 film deposited at 150 °C exhibited a higher areal capacitance (31 mF cm−2 measured at 5 mV s−1, best rate capability and excellent stability at potentials below −0.1 V versus saturated calomel electrode, compared to the films deposited at room temperature and at higher temperatures. These superior properties were attributed to the multi-valence composition and mixed-phase microstructure, i.e., the coexistence of MoO2 nanocrystals and amorphous MoOx (2.3 < x ≤ 3. A mechanism combining Mo(IV oxidation/reduction on the hydrated MoO2 grain surfaces and cation intercalation/extrusion is proposed to illustrate the pseudo-capacitive process.

  5. Insights into the potentiometric response behaviour vs. Li{sup +} of LiFePO{sub 4} thin films in aqueous medium

    Energy Technology Data Exchange (ETDEWEB)

    Sauvage, F.; Tarascon, J.-M. [Laboratoire de Reactivite et Chimie des Solides, UMR CNRS 6007, Universite de Picardie Jules Verne, 33 rue St. Leu, 80039 Amiens Cedex (France); Baudrin, E. [Laboratoire de Reactivite et Chimie des Solides, UMR CNRS 6007, Universite de Picardie Jules Verne, 33 rue St. Leu, 80039 Amiens Cedex (France)], E-mail: emmanuel.baudrin@u-picardie.fr

    2008-08-01

    The potentiometric response of PLD-made LiFePO{sub 4} thin films versus Li{sup +} ions in aqueous solutions has been investigated, and a sensitivity of 54 mV dec{sup -1} has been observed in a Li{sup +} concentration range of 1-10{sup -4} M. Physical and electrochemical measurements of electrodes aged in aqueous medium show a slight surface oxidation with formation of heterosite-FePO{sub 4} that we show to be responsible for the stable potential response measured. Cyclic voltamperometry measurements operated in different Li{sup +} concentration clearly highlight the key relation between the material lithium ion insertion/de-insertion capability and its potentiometric sensing response implying a faradaic-governed sensing mechanism. Based on such a finding, selection criteria (enlisting among others the potential of the redox couple, the nature of the insertion process) are herein underlined in the search for new sensitive materials.

  6. Characterization of electrochemically deposited films from aqueous and ionic liquid cobalt precursors toward hydrogen evolution reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dushatinski, Thomas; Huff, Clay; Abdel-Fattah, Tarek M., E-mail: fattah@cnu.edu

    2016-11-01

    Highlights: • Co films deposition via aqueous and ionic liquid Precursors. • Hydrogen evolution produced from reactive surfaces. • Co deposited films characterized by SEM, AFM, EDX and XRD techniques. - Abstract: Electrodepositions of cobalt films were achieved using an aqueous or an ethylene glycol based non-aqueous solution containing choline chloride (vitamin B4) with cobalt chloride hexahydrate precursor toward hydrogen evolution reactions from sodium borohydride (NaBH{sub 4}) as solid hydrogen feedstock (SHF). The resulting cobalt films had reflectivity at 550 nm of 2.2% for aqueously deposited films (ACoF) and 1.3% for non-aqueously deposited films (NCoF). Surface morphology studied by scanning electron microscopy showed a positive correlation between particle size and thickness. The film thicknesses were tunable between >100 μm and <300 μm for each film. The roughness (Ra) value measurements by Dektak surface profiling showed that the NCoF (Ra = 165 nm) was smoother than the ACoF (Ra = 418 nm). The NCoFs and ACoFs contained only α phase (FCC) crystallites. The NCoFs were crystalline while the ACoFs were largely amorphous from X-ray diffraction analysis. The NCoF had an average Vickers hardness value of 84 MPa as compared to 176 MPa for ACoF. The aqueous precursor has a single absorption maximum at 510 nm and the non-aqueous precursor had three absorption maxima at 630, 670, and 695 nm. The hydrogen evolution reactions over a 1 cm{sup 2} catalytic surface with aqueous NaBH{sub 4} solutions generated rate constants (K) = equal to 4.9 × 10{sup −3} min{sup −1}, 4.6 × 10{sup −3} min{sup −1}, and 3.3 × 10{sup −3} min{sup −1} for ACoF, NCoF, and copper substrate respectively.

  7. Low hydrogen containing amorphous carbon films - Growth and electrochemical properties as lithium battery anodes

    Energy Technology Data Exchange (ETDEWEB)

    Subramanian, V.; Masarapu, Charan; Wei, Bingqing [Department of Mechanical Engineering, University of Delaware, 130 Academy Street, Newark, DE 19716 (United States); Karabacak, Tansel [Department of Applied Science, University of Arkansas at Little Rock, 2801 South University Avenue, Little Rock, AR 72204 (United States); Teki, Ranganath [Department of Chemical and Biological Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180 (United States); Lu, Toh-Ming [Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute, Troy, NY 12180 (United States)

    2010-04-02

    Amorphous carbon films were deposited successfully on Cu foils by DC magnetron sputtering technique. Electrochemical performance of the film as lithium battery anode was evaluated across Li metal at 0.2 C rate in a non-aqueous electrolyte. The discharge curves showed unusually low irreversible capacity in the first cycle with a reversible capacity of {proportional_to}810 mAh g{sup -1}, which is at least 2 times higher than that of graphitic carbon. For the first time we report here an amorphous carbon showing such a high reversibility in the first cycle, which is very much limited to the graphitic carbon. The deposited films were extensively characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and step profilometer for the structural and surface properties. The hydrogen content of the synthesized films was studied using residual gas analysis (RGA). The low hydrogen content and the low specific surface area of the synthesized amorphous carbon film are considered responsible for such a high first cycle columbic efficiency. The growth mechanism and the reasons for enhanced electrochemical performance of the carbon films are discussed. (author)

  8. Low hydrogen containing amorphous carbon films-Growth and electrochemical properties as lithium battery anodes

    Science.gov (United States)

    Subramanian, V.; Karabacak, Tansel; Masarapu, Charan; Teki, Ranganath; Lu, Toh-Ming; Wei, Bingqing

    Amorphous carbon films were deposited successfully on Cu foils by DC magnetron sputtering technique. Electrochemical performance of the film as lithium battery anode was evaluated across Li metal at 0.2 C rate in a non-aqueous electrolyte. The discharge curves showed unusually low irreversible capacity in the first cycle with a reversible capacity of ∼810 mAh g -1, which is at least 2 times higher than that of graphitic carbon. For the first time we report here an amorphous carbon showing such a high reversibility in the first cycle, which is very much limited to the graphitic carbon. The deposited films were extensively characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and step profilometer for the structural and surface properties. The hydrogen content of the synthesized films was studied using residual gas analysis (RGA). The low hydrogen content and the low specific surface area of the synthesized amorphous carbon film are considered responsible for such a high first cycle columbic efficiency. The growth mechanism and the reasons for enhanced electrochemical performance of the carbon films are discussed.

  9. Aqueous Binder Enhanced High-Performance GeP5 Anode for Lithium-Ion Batteries

    Directory of Open Access Journals (Sweden)

    Jun He

    2018-02-01

    Full Text Available GeP5 is a recently reported new anode material for lithium ion batteries (LIBs, it holds a large theoretical capacity about 2300 mAh g−1, and a high rate capability due to its bi-active components and superior conductivity. However, it undergoes a large volume change during its electrochemical alloying and de-alloying with Li, a suitable binder is necessary to stable the electrode integrity for improving cycle performance. In this work, we tried to apply aqueous binders LiPAA and NaCMC to GeP5 anode, and compared the difference in electrochemical performance between them and traditional binder PVDF. As can be seen from the test result, GeP5 can keep stable in both common organic solvents and proton solvents such as water and alcohol solvents, it meets the application requirements of aqueous binders. The electrochemistry results show that the use of LiPAA binder can significantly improve the initial Coulombic efficiency, reversible capacity, and cyclability of GeP5 anode as compared to the electrodes based on NaCMC and PVDF binders. The enhanced electrochemical performance of GeP5 electrode with LiPAA binder can be ascribed to the unique high strength long chain polymer structure of LiPAA, which also provide numerous uniform distributed carboxyl groups to form strong ester groups with active materials and copper current collector. Benefit from that, the GeP5 electrode with LiPAA can also exhibit excellent rate capability, and even at low temperature, it still shows attractive electrochemical performance.

  10. Morphological reason for enhancement of electrochemical double layer capacitances of various acetylene blacks by electrochemical polarization

    International Nuclear Information System (INIS)

    Kim, Taegon; Ham, Chulho; Rhee, Choong Kyun; Yoon, Seong-Ho; Tsuji, Masaharu; Mochida, Isao

    2008-01-01

    Enhancement of electrochemical capacitance and morphological variations of various acetylene blacks caused by electrochemical polarization are presented. Acetylene blacks of different mean particle diameters were modified by air-oxidation and heat treatment to diversify the morphologies of the acetylene blacks before electrochemical polarization. The various acetylene blacks were electrochemically oxidized at 1.6 V (vs. Ag/AgCl) for 10 s and the polarization step was repeated until the capacitance values did not change any longer. These polarization steps enhanced the capacitances of the acetylene blacks and the specific enhancement factors range from 2 to 5.5. Such an enhancement is strongly related to morphological modification as revealed by transmission electron microscopic observations. The electrochemical polarization resulted in formation of tiny graphene sheets on the wide graphitic carbon surfaces, which were most responsible for the observed capacitive enhancement. Although the pseudo-capacitance increased after polarization by forming oxygenated species on the surfaces, its contribution to the total capacitance was less than 10%. The mechanism of the formation of the tiny graphene sheets during the electrochemical oxidation is described schematically

  11. Three-dimensional porous hollow fibre copper electrodes for efficient and high-rate electrochemical carbon dioxide reduction

    NARCIS (Netherlands)

    Kas, Recep; Hummadi, Khalid Khazzal; Kortlever, Ruud; de Wit, Patrick; Milbrat, Alexander; Luiten-Olieman, Maria W.J.; Benes, Nieck Edwin; Koper, Marc T.M.; Mul, Guido

    2016-01-01

    Aqueous-phase electrochemical reduction of carbon dioxide requires an active, earth-abundant electrocatalyst, as well as highly efficient mass transport. Here we report the design of a porous hollow fibre copper electrode with a compact three-dimensional geometry, which provides a large area,

  12. Investigations of the Electrochemical Stability of Aqueous Electrolytes for Lithium Battery Applications

    KAUST Repository

    Wessells, Colin; Ruffο, Riccardo; Huggins, Robert A.; Cui, Yi

    2010-01-01

    The electrolytic stability windows of several aqueous electrolytes were investigated by a constant current method. The electrode potential range depended upon the value of the imposed current. The magnitude of this behavior varied with the salt

  13. Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility.

    Science.gov (United States)

    Yang, Chongyin; Suo, Liumin; Borodin, Oleg; Wang, Fei; Sun, Wei; Gao, Tao; Fan, Xiulin; Hou, Singyuk; Ma, Zhaohui; Amine, Khalil; Xu, Kang; Wang, Chunsheng

    2017-06-13

    Leveraging the most recent success in expanding the electrochemical stability window of aqueous electrolytes, in this work we create a unique Li-ion/sulfur chemistry of both high energy density and safety. We show that in the superconcentrated aqueous electrolyte, lithiation of sulfur experiences phase change from a high-order polysulfide to low-order polysulfides through solid-liquid two-phase reaction pathway, where the liquid polysulfide phase in the sulfide electrode is thermodynamically phase-separated from the superconcentrated aqueous electrolyte. The sulfur with solid-liquid two-phase exhibits a reversible capacity of 1,327 mAh/(g of S), along with fast reaction kinetics and negligible polysulfide dissolution. By coupling a sulfur anode with different Li-ion cathode materials, the aqueous Li-ion/sulfur full cell delivers record-high energy densities up to 200 Wh/(kg of total electrode mass) for >1,000 cycles at ∼100% coulombic efficiency. These performances already approach that of commercial lithium-ion batteries (LIBs) using a nonaqueous electrolyte, along with intrinsic safety not possessed by the latter. The excellent performance of this aqueous battery chemistry significantly promotes the practical possibility of aqueous LIBs in large-format applications.

  14. Water-mediated electrochemical nano-writing on thin ceria films

    International Nuclear Information System (INIS)

    Yang, Nan; Doria, Sandra; Tebano, Antonello; Licoccia, Silvia; Balestrino, Giuseppe; Kumar, Amit; Arruda, Thomas M; Jesse, Stephen; Ivanov, Ilia N; Baddorf, Arthur P; Strelcov, Evgheni; Kalinin, Sergei V; Jang, Jae Hyuck; Borisevich, Albina Y

    2014-01-01

    Bias dependent mechanisms of irreversible cathodic and anodic processes on a pure CeO 2 film are studied using modified atomic force microscopy (AFM). For a moderate positive bias applied to the AFM tip an irreversible electrochemical reduction reaction is found, associated with significant local volume expansion. By changing the experimental conditions we are able to deduce the possible role of water in this process. Simultaneous detection of tip height and current allows the onset of conductivity and the electrochemical charge transfer process to be separated, further elucidating the reaction mechanism. The standard anodic/cathodic behavior is recovered in the high bias regime, where a sizable transport current flows between the tip and the film. These studies give insight into the mechanisms of the tip-induced electrochemical reactions as mediated by electronic currents, and into the role of water in these processes, as well as providing a different approach for electrochemical nano-writing. (paper)

  15. Removals of aqueous sulfur dioxide and hydrogen sulfide using CeO2-NiAl-LDHs coating activated carbon and its mix with carbon nano-tubes

    KAUST Repository

    Li, Jing; Chen, Fangping; Jin, Guanping; Feng, Xiaoshuang; Li, Xiaoxuan

    2015-01-01

    Ce-doped NiAl/layered double hydroxide was coated at activated carbon by urea hydrolysis method (CeO2-NiAl-LDHs/AC) in one pot, which was characterized by X-ray diffraction, infrared spectra, field emission scanning electron microscope and electrochemical techniques. CeO2-NiAl-LDHs/AC shows good uptake for aqueous sulfur dioxide (483.09mg/g) and hydrogen sulfide (181.15mg/g), respectively at 25°C. Meanwhile, the electrochemical removals of aqueous sulfur dioxide and hydrogen sulfide were respectively investigated at the mix of CeO2-NiAl-LDHs/AC and carbon nano-tubes modified homed paraffin-impregnated electrode. Both sulfur dioxide and hydrogen sulfide could be effectively oxidized to sulfuric acid at 1.0V in alkaline aqueous solution. © 2015 Elsevier B.V.

  16. Removals of aqueous sulfur dioxide and hydrogen sulfide using CeO2-NiAl-LDHs coating activated carbon and its mix with carbon nano-tubes

    KAUST Repository

    Li, Jing

    2015-07-01

    Ce-doped NiAl/layered double hydroxide was coated at activated carbon by urea hydrolysis method (CeO2-NiAl-LDHs/AC) in one pot, which was characterized by X-ray diffraction, infrared spectra, field emission scanning electron microscope and electrochemical techniques. CeO2-NiAl-LDHs/AC shows good uptake for aqueous sulfur dioxide (483.09mg/g) and hydrogen sulfide (181.15mg/g), respectively at 25°C. Meanwhile, the electrochemical removals of aqueous sulfur dioxide and hydrogen sulfide were respectively investigated at the mix of CeO2-NiAl-LDHs/AC and carbon nano-tubes modified homed paraffin-impregnated electrode. Both sulfur dioxide and hydrogen sulfide could be effectively oxidized to sulfuric acid at 1.0V in alkaline aqueous solution. © 2015 Elsevier B.V.

  17. X-ray Photoelectron Spectroscopy Investigation on Electrochemical Degradation of Proton Exchange Membrane Fuel Cell Electrodes

    DEFF Research Database (Denmark)

    Andersen, Shuang Ma; Dhiman, Rajnish; Skou, Eivind Morten

    2015-01-01

    X-ray photoelectron spectroscopy studies were systematically carried out on the electrodes before and after the electrochemical stress tests in an aqueous electrolyte at 20 °C and 70 °C. The electrodes have different ionomer structures (no ionomer, only ionomer, physically mixed ionomer and hot p...

  18. Catalytic efficiency of natural and synthetic compounds used as laccase-mediators in oxidising veratryl alcohol and a kraft lignin, estimated by electrochemical analysis

    International Nuclear Information System (INIS)

    Gonzalez Arzola, K.; Arevalo, M.C.; Falcon, M.A.

    2009-01-01

    The electrochemical properties of eighteen natural and synthetic compounds commonly used to expand the oxidative capacity of laccases were evaluated in an aqueous buffered medium using cyclic voltammetry. This clarifies which compounds fulfil the requisites to be considered as redox mediators or enhancers. Cyclic voltammetry was also applied as a rapid way to assess the catalytic efficiency (CE) of those compounds which oxidise a non-phenolic lignin model (veratryl alcohol, VA) and a kraft lignin (KL). With the exception of gallic acid and catechol, all assayed compounds were capable of oxidising VA with varying CE. However, only some of them were able to oxidise KL. Although the oxidised forms of HBT and acetovanillone were not electrochemically stable, their reduced forms were quickly regenerated in the presence of VA. They thus act as chemical catalysts. Importantly, HBT and HPI did not attack the KL via the same mechanism as in VA oxidation. Electrochemical evidence suggests that violuric acid oxidises both substrates by an electron transfer mechanism, unlike the other N-OH compounds HBT and HPI. Acetovanillone was found to be efficient in oxidising VA and KL, even better than the synthetic mediators TEMPO, violuric acid or ABTS. Most of the compounds produced a generalised increase in the oxidative charge of KL, probably attributed to chain reactions arising between the phenolic and non-phenolic components of this complex molecule

  19. Catalytic efficiency of natural and synthetic compounds used as laccase-mediators in oxidising veratryl alcohol and a kraft lignin, estimated by electrochemical analysis

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez Arzola, K. [Department of Microbiology and Cell Biology, Faculty of Pharmacy, University of La Laguna, 38206 La Laguna, Tenerife (Spain); Arevalo, M.C. [Department of Physical Chemistry, Faculty of Chemistry, University of La Laguna, 38206 La Laguna, Tenerife (Spain)], E-mail: carevalo@ull.es; Falcon, M.A. [Department of Microbiology and Cell Biology, Faculty of Pharmacy, University of La Laguna, 38206 La Laguna, Tenerife (Spain)], E-mail: mafalcon@ull.es

    2009-03-30

    The electrochemical properties of eighteen natural and synthetic compounds commonly used to expand the oxidative capacity of laccases were evaluated in an aqueous buffered medium using cyclic voltammetry. This clarifies which compounds fulfil the requisites to be considered as redox mediators or enhancers. Cyclic voltammetry was also applied as a rapid way to assess the catalytic efficiency (CE) of those compounds which oxidise a non-phenolic lignin model (veratryl alcohol, VA) and a kraft lignin (KL). With the exception of gallic acid and catechol, all assayed compounds were capable of oxidising VA with varying CE. However, only some of them were able to oxidise KL. Although the oxidised forms of HBT and acetovanillone were not electrochemically stable, their reduced forms were quickly regenerated in the presence of VA. They thus act as chemical catalysts. Importantly, HBT and HPI did not attack the KL via the same mechanism as in VA oxidation. Electrochemical evidence suggests that violuric acid oxidises both substrates by an electron transfer mechanism, unlike the other N-OH compounds HBT and HPI. Acetovanillone was found to be efficient in oxidising VA and KL, even better than the synthetic mediators TEMPO, violuric acid or ABTS. Most of the compounds produced a generalised increase in the oxidative charge of KL, probably attributed to chain reactions arising between the phenolic and non-phenolic components of this complex molecule.

  20. Spray pyrolysed Ru:TiO2 thin film electrodes prepared for electrochemical supercapacitor

    Science.gov (United States)

    Fugare, B. Y.; Thakur, A. V.; Kore, R. M.; Lokhande, B. J.

    2018-04-01

    Ru doped TiO2 thin films are prepared by using 0.06 M aqueous solution of potassium titanium oxalate (pto), and 0.005 M aqueous solution of ruthenium tri chloride (RuCl3) precursors. The deposition was carried on stainless steel (SS) by using well known ultrasonic spray pyrolysis technique (USPT) at 723° K by maintaining the spray rate 12 cc/min and compressed air flow rate 10 Lmin-1. Prepared Ru:TiO2 thin films were characterized by structurally, morphologically and electrochemically. Deposited RuO2 shows amorphous structure and TiO2 shows tetragonal crystal structure with rutile as prominent phase at very low decomposition temperature. SEM micrographs of RuO2 exhibits porous, interconnected, spherical grains type morphology and TiO2 shows porous, nanorods and nanoplates like morphology and also Ru doped TiO2 shows porous, spherical, granular and nanorods type morphology. The electrochemical cyclic voltammetery shows mixed capacitive behavior. The achieved highest value of specific capacitance 2692 F/g was Ru doped TiO2 electrode in 0.5 M H2SO4.

  1. Preparation of the electrochemically formed spinel-lithium manganese oxides

    Energy Technology Data Exchange (ETDEWEB)

    Katakura, Katsumi; Wada, Kohei; Kajiki, Yoshiyuki; Yamamoto, Akiko [Department of Chemical Engineering, Nara National College of Technology, 22 Yata-cho Yamotokoriyama, Nara 639-1080 (Japan); Ogumi, Zempachi [Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)

    2009-04-01

    Electrochemically formed spinel-lithium manganese oxides were synthesized from manganese hydroxides prepared by a cathodic electrochemical precipitation from various concentrations of manganese nitrate solutions. Two types of manganese hydroxides were formed from diluted and concentrated Mn(NO{sub 3}){sub 2} aqueous solutions. Uniform and equi-sized disk shaped Mn(OH){sub 2} crystals of 0.2-5 {mu}m in diameter were obtained on a Pt substrate after the electrochemical precipitation from lower concentration of ranging from 2 mmol dm{sup -3} to 2 mol dm{sup -3} Mn(NO{sub 3}){sub 2} aq., while the grass blade-like precipitate which is ascribed to manganese hydroxide with 20-80 {mu}m long and 1-5 {mu}m wide were formed from concentrated Mn(NO{sub 3}){sub 2} aq. Both manganese hydroxides gave the electrochemically formed spinel-LiMn{sub 2}O{sub 4} onto a Pt sheet, which is ready for electrochemical measurement, after calcination of the Li incorporated precipitate at 750 C without any additives. While the shape and size of the secondary particle frameworks (aggregates) of the electrochemically formed spinel-LiMn{sub 2}O{sub 4} can be controlled by the electrolysis conditions, the nanostructured primary crystals of 200 nm in diameter were obtained in all cases except that the fiber-like nanostructured spinel-LiMn{sub 2}O{sub 4} crystals with 200 nm in diameter were obtained from concentrated Mn(NO{sub 3}){sub 2} aq. Though these two types of electrochemically formed spinel-LiMn{sub 2}O{sub 4} showed well-shaped CVs even in higher scan rates, it would be suitable for high power density battery applications. These behaviors are assumed to be ascribed to the crystal size and shape of the processed spinel-LiMn{sub 2}O{sub 4}. (author)

  2. Electrochemical Selective and Simultaneous Detection of Diclofenac and Ibuprofen in Aqueous Solution Using HKUST-1 Metal-Organic Framework-Carbon Nanofiber Composite Electrode

    Directory of Open Access Journals (Sweden)

    Sorina Motoc

    2016-10-01

    Full Text Available In this study, the detection protocols for the individual, selective, and simultaneous determination of ibuprofen (IBP and diclofenac (DCF in aqueous solutions have been developed using HKUST-1 metal-organic framework-carbon nanofiber composite (HKUST-CNF electrode. The morphological and electrical characterization of modified composite electrode prepared by film casting was studied by scanning electronic microscopy and four-point-probe methods. The electrochemical characterization of the electrode by cyclic voltammetry (CV was considered the reference basis for the optimization of the operating conditions for chronoamperometry (CA and multiple-pulsed amperometry (MPA. This electrode exhibited the possibility to selectively detect IBP and DCF by simple switching the detection potential using CA. However, the MPA operated under optimum working conditions of four potential levels selected based on CV shape in relation to the potential value, pulse time, and potential level number, and order allowed the selective/simultaneous detection of IBP and DCF characterized by the enhanced detection performance. For this application, the HKUST-CNF electrode exhibited a good stability and reproducibility of the results was achieved.

  3. Electrochemical Selective and Simultaneous Detection of Diclofenac and Ibuprofen in Aqueous Solution Using HKUST-1 Metal-Organic Framework-Carbon Nanofiber Composite Electrode.

    Science.gov (United States)

    Motoc, Sorina; Manea, Florica; Iacob, Adriana; Martinez-Joaristi, Alberto; Gascon, Jorge; Pop, Aniela; Schoonman, Joop

    2016-10-17

    In this study, the detection protocols for the individual, selective, and simultaneous determination of ibuprofen (IBP) and diclofenac (DCF) in aqueous solutions have been developed using HKUST-1 metal-organic framework-carbon nanofiber composite (HKUST-CNF) electrode. The morphological and electrical characterization of modified composite electrode prepared by film casting was studied by scanning electronic microscopy and four-point-probe methods. The electrochemical characterization of the electrode by cyclic voltammetry (CV) was considered the reference basis for the optimization of the operating conditions for chronoamperometry (CA) and multiple-pulsed amperometry (MPA). This electrode exhibited the possibility to selectively detect IBP and DCF by simple switching the detection potential using CA. However, the MPA operated under optimum working conditions of four potential levels selected based on CV shape in relation to the potential value, pulse time, and potential level number, and order allowed the selective/simultaneous detection of IBP and DCF characterized by the enhanced detection performance. For this application, the HKUST-CNF electrode exhibited a good stability and reproducibility of the results was achieved.

  4. Pulsed Electrochemical Mass Spectrometry for Operando Tracking of Interfacial Processes in Small-Time-Constant Electrochemical Devices such as Supercapacitors.

    Science.gov (United States)

    Batisse, Nicolas; Raymundo-Piñero, Encarnación

    2017-11-29

    A more detailed understanding of the electrode/electrolyte interface degradation during the charging cycle in supercapacitors is of great interest for exploring the voltage stability range and therefore the extractable energy. The evaluation of the gas evolution during the charging, discharging, and aging processes is a powerful tool toward determining the stability and energy capacity of supercapacitors. Here, we attempt to fit the gas analysis resolution to the time response of a low-gas-generation power device by adopting a modified pulsed electrochemical mass spectrometry (PEMS) method. The pertinence of the method is shown using a symmetric carbon/carbon supercapacitor operating in different aqueous electrolytes. The differences observed in the gas levels and compositions as a function of the cell voltage correlate to the evolution of the physicochemical characteristics of the carbon electrodes and to the electrochemical performance, giving a complete picture of the processes taking place at the electrode/electrolyte interface.

  5. Electrochemical Applications in Metal Bioleaching.

    Science.gov (United States)

    Tanne, Christoph Kurt; Schippers, Axel

    2017-12-10

    Biohydrometallurgy comprises the recovery of metals by biologically catalyzed metal dissolution from solids in an aqueous solution. The application of this kind of bioprocessing is described as "biomining," referring to either bioleaching or biooxidation of sulfide metal ores. Acidophilic iron- and sulfur-oxidizing microorganisms are the key to successful biomining. However, minerals such as primary copper sulfides are recalcitrant to dissolution, which is probably due to their semiconductivity or passivation effects, resulting in low reaction rates. Thus, further improvements of the bioleaching process are recommendable. Mineral sulfide dissolution is based on redox reactions and can be accomplished by electrochemical technologies. The impact of electrochemistry on biohydrometallurgy affects processing as well as analytics. Electroanalysis is still the most widely used electrochemical application in mineralogical research. Electrochemical processing can contribute to bioleaching in two ways. The first approach is the coupling of a mineral sulfide to a galvanic partner or electrocatalyst (spontaneous electron transfer). This approach requires only low energy consumption and takes place without technical installations by the addition of higher redox potential minerals (mostly pyrite), carbonic material, or electrocatalytic ions (mostly silver ions). Consequently, the processed mineral (often chalcopyrite) is preferentially dissolved. The second approach is the application of electrolytic bioreactors (controlled electron transfer). The electrochemical regulation of electrolyte properties by such reactors has found most consideration. It implies the regulation of ferrous and ferric ion ratios, which further results in optimized solution redox potential, less passivation effects, and promotion of microbial activity. However, many questions remain open and it is recommended that reactor and electrode designs are improved, with the aim of finding options for simplified

  6. Nanocomposites of manganese oxides and carbon nanotubes for aqueous supercapacitor stacks

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Shengwen; Peng Chuang; Ng, Kok C. [Department of Chemical and Environmental Engineering, Faculty of Engineering, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom); Chen, George Z., E-mail: george.chen@nottingham.ac.u [Department of Chemical and Environmental Engineering, Faculty of Engineering, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)

    2010-10-30

    Symmetrical supercapacitors and their serially connected two-cell stacks via a bipolar electrode were constructed with nanocomposites of manganese oxides and carbon nanotubes (MnO{sub x}/CNTs) as the electrode materials. Nanocomposites with different contents of MnO{sub x} were synthesised through the redox reaction between KMnO{sub 4} and CNTs in aqueous solutions. The nanocomposites were characterised by scanning and transmission electron microscopy, BET nitrogen adsorption and X-ray diffraction before being examined in a three-electrode cell with a novel trenched graphite disc electrode by electrochemical means, including cyclic voltammetry, galvanostatic charging-discharging, and electrochemical impedance spectroscopy. The nanocomposites demonstrated capacitive behaviour in the potential range of 0-0.85 V (vs Ag/AgCl) in aqueous KCl electrolytes with less than 9% capacitance decrease after 9000 charging-discharging cycles. Symmetrical supercapacitors of identical positive and negative MnO{sub x}/CNTs electrodes showed capacitive performance in good agreement with the individual electrodes (e.g. 0.90 V, 0.53 F, 1.3 cm{sup 2}). The bipolarly connected two-cell stacks of the symmetrical cells exhibited characteristics in accordance with expectation, including a doubled stack voltage and reduced internal resistance per cell.

  7. Non-aqueous electrolytes for lithium ion batteries

    Science.gov (United States)

    Chen, Zonghai; Amine, Khalil

    2015-11-12

    The present invention is generally related to electrolytes containing anion receptor additives to enhance the power capability of lithium-ion batteries. The anion receptor of the present invention is a Lewis acid that can help to dissolve LiF in the passivation films of lithium-ion batteries. Accordingly, one aspect the invention provides electrolytes comprising a lithium salt; a polar aprotic solvent; and an anion receptor additive; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

  8. Flexible pillared graphene-paper electrodes for high-performance electrochemical supercapacitors.

    Science.gov (United States)

    Wang, Gongkai; Sun, Xiang; Lu, Fengyuan; Sun, Hongtao; Yu, Mingpeng; Jiang, Weilin; Liu, Changsheng; Lian, Jie

    2012-02-06

    Flexible graphene paper (GP) pillared by carbon black (CB) nanoparticles using a simple vacuum filtration method is developed as a high-performance electrode material for supercapacitors. Through the introduction of CB nanoparticles as spacers, the self-restacking of graphene sheets during the filtration process is mitigated to a great extent. The pillared GP-based supercapacitors exhibit excellent electrochemical performances and cyclic stabilities compared with GP without the addition of CB nanoparticles. At a scan rate of 10 mV s(-1) , the specific capacitance of the pillared GP is 138 F g(-1) and 83.2 F g(-1) with negligible 3.85% and 4.35% capacitance degradation after 2000 cycles in aqueous and organic electrolytes, respectively. At an extremely fast scan rate of 500 mV s (-1) , the specific capacitance can reach 80 F g(-1) in aqueous electrolyte. No binder is needed for assembling the supercapacitor cells and the pillared GP itself may serve as a current collector due to its intrinsic high electrical conductivity. The pillared GP has great potential in the development of promising flexible and ultralight-weight supercapacitors for electrochemical energy storage. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Electrochemical reduction of disulfide-containing proteins for hydrogen/deuterium exchange monitored by mass spectrometry

    DEFF Research Database (Denmark)

    Mysling, Simon; Salbo, Rune; Ploug, Michael

    2014-01-01

    Characterization of disulfide bond-containing proteins by hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) requires reduction of the disulfide bonds under acidic and cold conditions, where the amide hydrogen exchange reaction is quenched (pH 2.5, 0 °C). The reduction typically...... of TCEP. In the present study, we explore the feasibility of using electrochemical reduction as a substitute for TCEP in HDX-MS analyses. Our results demonstrate that efficient disulfide bond reduction is readily achieved by implementing an electrochemical cell into the HDX-MS workflow. We also identify...... some challenges in using electrochemical reduction in HDX-MS analyses and provide possible conditions to attenuate these limitations. For example, high salt concentrations hamper disulfide bond reduction, necessitating additional dilution of the sample with aqueous acidic solution at quench conditions....

  10. Capacity improvement of the carbon-based electrochemical capacitor by zigzag-edge introduced graphene

    Science.gov (United States)

    Tamura, Naoki; Tomai, Takaaki; Oka, Nobuto; Honma, Itaru

    2018-01-01

    The electrochemical properties of graphene edge has been attracted much attention. Especially, zigzag edge has high electrochemical activity because neutral radical exits on edge. However, due to a lack of efficient production method for zigzag graphene, the electrochemical properties of zigzag edge have not been experimentally demonstrated and the capacitance enhancement of carbonaceous materials in energy storage devices by the control in their edge states is still challenge. In this study, we fabricated zigzag-edge-rich graphene by a one-step method combining graphene exfoliation in supercritical fluid and anisotropic etching by catalytic nanoparticles. This efficient production of zigzag-edge-rich graphene allows us to investigate the electrochemical activity of zigzag edge. By cyclic voltammetry, we revealed the zigzag edge-introduced graphene exhibited unique redox reaction in aqueous acid solution. Moreover, by the calculation on the density function theory (DFT), this unique redox potential for zigzag edge-introduced graphene can be attributed to the proton-insertion/-extraction reactions at the zigzag edge. This finding indicates that the graphene edge modification can contribute to the further increase in the capacitance of the carbon-based electrochemical capacitor.

  11. Electrochemical impedance spectroscopy of polycrystalline boron doped diamond layers with hydrogen and oxygen terminated surface

    Czech Academy of Sciences Publication Activity Database

    Vlčková Živcová, Zuzana; Petrák, Václav; Frank, Otakar; Kavan, Ladislav

    2015-01-01

    Roč. 55, MAY 2015 (2015), s. 70-76 ISSN 0925-9635 R&D Projects: GA ČR GA13-31783S Institutional support: RVO:61388955 ; RVO:68378271 Keywords : Boron doped diamond * Electrochemical impedance spectroscopy * Aqueous electrolyte solution Subject RIV: CG - Electrochemistry Impact factor: 2.125, year: 2015

  12. Comparative investigation of the adhesion of Ce conversion layers and silane layers to a AA 2024-T3 substrate through mechanical and electrochemical tests

    Directory of Open Access Journals (Sweden)

    Luis Enrique Morales Palomino

    2007-12-01

    Full Text Available Cerium conversion layers and silane films are among the potential substitutes for the carcinogenic chromate conversion layers used to protect high-strength Al alloys. In the present work the adhesion of a cerium conversion layer and of a silane film to an aluminium alloy (AA 2024-T3 substrate was investigated using mechanical and electrochemical tests. Scanning electron microscopy (SEM- X ray energy dispersive spectroscopy (EDS, Fourier transform infrared spectroscopy (FT-IR and X ray photoelectron spectroscopy (XPS were used to characterize the layers prior and after the mechanical test consisting of ultrasonic rinse in deionized water during 30 minutes. Mechanically tested and untested layers were also submitted to electrochemical impedance spectroscopy (EIS and anodic polarization measurements in 0.1 M NaCl solution. The results of the characterization tests have pointed to a stronger adhesion of the Ce layer to the substrate in comparison with the silane film, which was confirmed by the electrochemical tests. The adhesion between the silane film and the Ce conversion layer was also tested, to evaluate the possibility of using the system as a protective bi-layer in accordance with the new trends being developed to substitute chromate conversion layers.

  13. Electrochemical catalytic activities of nanoporous palladium rods for methanol electro-oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoguang; Wang, Weimin; Qi, Zhen; Zhao, Changchun; Ji, Hong; Zhang, Zhonghua [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (MOE), School of Materials Science and Engineering, Shandong University, Jingshi Road 73, Jinan 250061 (China)

    2010-10-01

    A novel electrocatalyst, nanoporous palladium (npPd) rods can be facilely fabricated by dealloying a binary Al{sub 80}Pd{sub 20} alloy in a 5 wt.% HCl aqueous solution under free corrosion conditions. The microstructure of these nanoporous palladium rods has been characterized using scanning electron microscopy and transmission electron microscopy. The results show that each Pd rod is several microns in length and several hundred nanometers in diameter. Moreover, all the rods exhibit a typical three-dimensional bicontinuous interpenetrating ligament-channel structure with length scale of 15-20 nm. The electrochemical experiments demonstrate that these peculiar nanoporous palladium rods (mixed with Vulcan XC-72 carbon powders to form a npPd/C catalyst) reveal a superior electrocatalytic performance toward methanol oxidation in the alkaline media. In addition, the electrocatalytic activity obviously depends on the metal loading on the electrode and will reach to the highest level (223.52 mA mg{sup -1}) when applying 0.4 mg cm{sup -2} metal loading on the electrode. Moreover, a competing adsorption mechanism should exist when performing methanol oxidation on the surface of npPd rods, and the electro-oxidation reaction is a diffusion-controlled electrochemical process. Due to the advantages of simplicity and high efficiency in the mass production, the npPd rods can act as a promising candidate for the anode catalyst for direct methanol fuel cells (DMFCs). (author)

  14. N-type organic electrochemical transistors with stability in water

    KAUST Repository

    Giovannitti, Alexander

    2016-10-07

    Organic electrochemical transistors (OECTs) are receiving significant attention due to their ability to efficiently transduce biological signals. A major limitation of this technology is that only p-type materials have been reported, which precludes the development of complementary circuits, and limits sensor technologies. Here, we report the first ever n-type OECT, with relatively balanced ambipolar charge transport characteristics based on a polymer that supports both hole and electron transport along its backbone when doped through an aqueous electrolyte and in the presence of oxygen. This new semiconducting polymer is designed specifically to facilitate ion transport and promote electrochemical doping. Stability measurements in water show no degradation when tested for 2 h under continuous cycling. This demonstration opens the possibility to develop complementary circuits based on OECTs and to improve the sophistication of bioelectronic devices.

  15. N-type organic electrochemical transistors with stability in water

    KAUST Repository

    Giovannitti, Alexander; Nielsen, Christian B.; Sbircea, Dan-Tiberiu; Inal, Sahika; Donahue, Mary; Niazi, Muhammad Rizwan; Hanifi, David A.; Amassian, Aram; Malliaras, George G.; Rivnay, Jonathan; McCulloch, Iain

    2016-01-01

    Organic electrochemical transistors (OECTs) are receiving significant attention due to their ability to efficiently transduce biological signals. A major limitation of this technology is that only p-type materials have been reported, which precludes the development of complementary circuits, and limits sensor technologies. Here, we report the first ever n-type OECT, with relatively balanced ambipolar charge transport characteristics based on a polymer that supports both hole and electron transport along its backbone when doped through an aqueous electrolyte and in the presence of oxygen. This new semiconducting polymer is designed specifically to facilitate ion transport and promote electrochemical doping. Stability measurements in water show no degradation when tested for 2 h under continuous cycling. This demonstration opens the possibility to develop complementary circuits based on OECTs and to improve the sophistication of bioelectronic devices.

  16. Mechanical polishing as an improved surface treatment for platinum screen-printed electrodes

    Directory of Open Access Journals (Sweden)

    Junqiao Lee

    2016-07-01

    Full Text Available The viability of mechanical polishing as a surface pre-treatment method for commercially available platinum screen-printed electrodes (SPEs was investigated and compared to a range of other pre-treatment methods (UV-Ozone treatment, soaking in N,N-dimethylformamide, soaking and anodizing in aqueous NaOH solution, and ultrasonication in tetrahydrofuran. Conventional electrochemical activation of platinum SPEs in 0.5 M H2SO4 solution was ineffective for the removal of contaminants found to be passivating the screen-printed surfaces. However, mechanical polishing showed a significant improvement in hydrogen adsorption and in electrochemically active surface areas (probed by two different redox couples due to the effective removal of surface contaminants. Results are also presented that suggest that SPEs are highly susceptible to degradation by strong acidic or caustic solutions, and could potentially lead to instability in long-term applications due to continual etching of the binding materials. The ability of SPEs to be polished effectively extends the reusability of these traditionally “single-use” devices. Keywords: Screen-printed electrodes, Polishing, Platinum, Activation, Pre-treatment, Cyclic voltammetry

  17. Diversity in electrochemical oxidation of dihydroxybenzenes in the ...

    Indian Academy of Sciences (India)

    Abstract. Electrochemical oxidation of some catechol derivatives (1a–e) have been studied in water/ acetonitrile solution containing 1-methylindole (3) as a nucleophile, using cyclic voltammetry and controlled- potential coulometry. An interesting diversity in the mechanisms has been observed in electrochemical oxidation ...

  18. Metal-free supercapacitor with aqueous electrolyte and low-cost carbon materials

    Science.gov (United States)

    Blomquist, Nicklas; Wells, Thomas; Andres, Britta; Bäckström, Joakim; Forsberg, Sven; Olin, Håkan

    2017-01-01

    Electric double-layer capacitors (EDLCs) or supercapacitors (SCs) are fast energy storage devices with high pulse efficiency and superior cyclability, which makes them useful in various applications including electronics, vehicles and grids. Aqueous SCs are considered to be more environmentally friendly than those based on organic electrolytes. Because of the corrosive nature of the aqueous environment, however, expensive electrochemically stable materials are needed for the current collectors and electrodes in aqueous SCs. This results in high costs for a given energy-storage capacity. To address this, we developed a novel low-cost aqueous SC using graphite foil as the current collector and a mix of graphene, nanographite, simple water-purification carbons and nanocellulose as electrodes. The electrodes were coated directly onto the graphite foil by using casting frames and the SCs were assembled in a pouch cell design. With this approach, we achieved a material cost reduction of greater than 90% while maintaining approximately one-half of the specific capacitance of a commercial unit, thus demonstrating that the proposed SC can be an environmentally friendly, low-cost alternative to conventional SCs.

  19. Design and Application of Electrochemical Processes for Decolorization Treatment of Nylanthrene Red dye Bearing Wastewaters

    Directory of Open Access Journals (Sweden)

    D. Marmanis

    2016-04-01

    Full Text Available The purpose of this paper is the investigation of the capability of electrochemical methods, such as electrocoagulation, electrooxidation and electro-Fenton for decolorization and degradation of synthetic aqueous solutions and actual dye house effluents containing nylanthrene red reactive dye. All electrochemical experiments with the synthetic dye solutions were conducted in electrochemical cell of volume 500 ml containing 200 mL of dye solution at concentration 50 mg/L and interelectrode distance of 1 cm. The three different electrochemical processes were analyzed, and their removal efficiencies were measured and evaluated. In addition, a flow diagram is designed for a continuously operated electrochemical process for remediation of synthetic and actual dye house effluents laden with nylanthrene dye. In the electrocoagulation process with aluminum electrodes, the colored aqueous dye solution was treated at the applied current densities of 5, 10 and 15 mA/cm2 and was quantitatively decolorized in 11, 9 and less than 6 minutes of electroprocessing time respectively. The electrooxidation process conducted with Ti/Pt and boron doped diamond (BDD electrodes, at the applied current density of 10 mA/cm2 led to the quantitative decolorization and destruction of the dye in 25 and 15 min respectively. In the electro-Fenton process with iron electrodes, supply of added hydrogen peroxide and applied current density of 10 mA/cm2, complete decolorization and degradation of the nylanthrene red dye occurred in 6 min. The actual polyamide textile dyeing effluent of same volume 200 mL with initial turbidity of 114 NTU and COD of 1755 mg/L was treated by electrocoagulation at the same applied current density of 10 mA/cm2. The turbidity was quantitatively eliminated in only 10 min, while COD was reduced by 74.5 % in 40 minutes of electrolysis time.

  20. Online Monitoring of Electrochemical Degradation of Paracetamol through a Biomimetic Sensor

    Directory of Open Access Journals (Sweden)

    Mariana Calora Quintino de Oliveira

    2011-01-01

    Full Text Available This paper reports, for the first time, the online monitoring to the electrochemical degradation of the paracetamol using a biomimetic sensor coupled to a Flow Injection Analysis (FIA system. The electrochemical degradation of the drug was carried out in aqueous medium using a flow-by reactor with a DSA anode. The process efficiency was monitored at real time by the biomimetic sensor constructed by modifying a glassy carbon electrode with a Nafion membrane doped with iron tetrapyridinoporphyrazine (FeTPyPz. Simultaneously, we carried out off-line analysis by liquid chromatography (HPLC during the experiments in order to validate the proposed system. In addition, to investigate the degradation products of the paracetamol electrolysis, we used the techniques of UPLC/MS and GC/MS.

  1. Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

    Science.gov (United States)

    Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.

    2018-04-01

    Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.

  2. The impact of electrochemical reduction potentials on the electrocatalytic activity of graphene oxide toward the oxygen reduction reaction in an alkaline medium

    International Nuclear Information System (INIS)

    Toh, Shaw Yong; Loh, Kee Shyuan; Kamarudin, Siti Kartom; Daud, Wan Ramli Wan

    2016-01-01

    We report the synthesis of graphene via the electrochemical reduction of graphene oxide (GO). In this study, GO nanosheets from aqueous dispersion were pre-assembled on a glassy carbon (GC) electrode and then electrochemically reduced in 1 M KOH under various constant reduction potentials in the range of −0.6 V to −1.5 V (vs. Ag/AgCl). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses revealed that the graphitic structure was substantially restored in the resulting electrochemically reduced graphene oxide (ERGO). The ERGO electrodes exhibited significantly enhanced catalytic activity toward the oxygen reduction reaction (ORR) in an alkaline medium compared with the initial GO electrode. Of the ERGO electrodes produced at various cathodic potentials, the ERGO-1.2 V electrode, which was produced at a reduction potential of −1.2 V, demonstrated the best catalytic activity toward the ORR in an alkaline medium. The ORR on GO and ERGO electrodes was shown to proceed via a two-electron mechanism at low overpotentials. The agreement between the spectroscopy results and electrochemical measurements provide strong evidence that the enhanced ORR catalytic activity is mainly attributed to the restoration of GO’s graphitic structure. Furthermore, the ERGO-1.2 V electrode showed excellent tolerance to the methanol poisoning effect compared with a Pt/C catalyst electrode.

  3. Electrochemical redox processes involving soluble cerium species

    International Nuclear Information System (INIS)

    Arenas, L.F.; Ponce de León, C.; Walsh, F.C.

    2016-01-01

    Highlights: • The relevance of cerium in laboratory and industrial electrochemistry is considered. • The history of fundamental electrochemical studies and applications is considered. • The chemistry, redox thermodynamics and electrode kinetics of cerium are summarised. • The uses of cerium ions in synthesis, energy storage, analysis and environmental treatment are illustrated. • Research needs and development perspectives are discussed. - Abstract: Anodic oxidation of cerous ions and cathodic reduction of ceric ions, in aqueous acidic solutions, play an important role in electrochemical processes at laboratory and industrial scale. Ceric ions, which have been used for oxidation of organic wastes and off-gases in environmental treatment, are a well-established oxidant for indirect organic synthesis and specialised cleaning processes, including oxide film removal from tanks and process pipework in nuclear decontamination. They also provide a classical reagent for chemical analysis in the laboratory. The reversible oxidation of cerous ions is an important reaction in the positive compartment of various redox flow batteries during charge and discharge cycling. A knowledge of the thermodynamics and kinetics of the redox reaction is critical to an understanding of the role of cerium redox species in these applications. Suitable choices of electrode material (metal or ceramic; coated or uncoated), geometry/structure (2-or 3-dimensional) and electrolyte flow conditions (hence an acceptable mass transport rate) are critical to achieving effective electrocatalysis, a high performance and a long lifetime. This review considers the electrochemistry of soluble cerium species and their diverse uses in electrochemical technology, especially for redox flow batteries and mediated electrochemical oxidation.

  4. A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery.

    Science.gov (United States)

    Duan, Wentao; Vemuri, Rama S; Hu, Dehong; Yang, Zheng; Wei, Xiaoliang

    2017-02-13

    Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid and deployment of renewable energy technologies. Among the many flow battery chemistries, non-aqueous flow batteries have the potential to achieve high energy density because of the broad voltage windows of non-aqueous electrolytes. However, significant technical hurdles exist currently limiting non-aqueous flow batteries to demonstrate their full potential, such as low redox concentrations, low operating currents, under-explored battery status monitoring, etc. In an attempt to address these limitations, we recently reported a non-aqueous flow battery based on a highly soluble, redox-active organic nitronyl nitroxide radical compound, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). This redox material exhibits an ambipolar electrochemical property, and therefore can serve as both anolyte and catholyte redox materials to form a symmetric flow battery chemistry. Moreover, we demonstrated that Fourier transform infrared (FTIR) spectroscopy could measure the PTIO concentrations during the PTIO flow battery cycling and offer reasonably accurate detection of the battery state of charge (SOC), as cross-validated by electron spin resonance (ESR) measurements. Herein we present a video protocol for the electrochemical evaluation and SOC diagnosis of the PTIO symmetric flow battery. With a detailed description, we experimentally demonstrated the route to achieve such purposes. This protocol aims to spark more interests and insights on the safety and reliability in the field of non-aqueous redox flow batteries.

  5. Mechanism of Electrochemical Delamination of Two-Dimensional Materials from Their Native Substrates by Bubbling.

    Science.gov (United States)

    Sun, Jie; Fan, Xing; Guo, Weiling; Liu, Lihui; Liu, Xin; Deng, Jun; Xu, Chen

    2015-12-16

    A capacitor-based circuit model is proposed to explain the electrochemical delamination of two-dimensional materials from their native substrates where produced gas bubbles squeeze into the interface. The delamination is actually the electric breakdown of the capacitor formed between the solution and substrate. To facilitate the procedure, the backside of the ubstrate has to be shielded so that the capacitor breakdown voltage can be reached. The screening effect can be induced either by nonreactive ions around the electrode or, more effectively, by an undetachable insulator. This mechanism serves as a guideline for the surface science and applications involving the bubbling delamination.

  6. Electrochemical properties of copper-based compounds with polyanion frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Mizuno, Yoshifumi; Hata, Shoma; Suzuki, Kota; Hirayama, Masaaki; Kanno, Ryoji, E-mail: kanno@echem.titech.ac.jp

    2016-03-15

    The copper-based polyanion compounds Li{sub 6}CuB{sub 4}O{sub 10} and Li{sub 2}CuP{sub 2}O{sub 7} were synthesized using a conventional solid-state reaction, and their electrochemical properties were determined. Li{sub 6}CuB{sub 4}O{sub 10} showed reversible capacity of 340 mA g{sup −1} at the first discharge–charge process, while Li{sub 2}CuP{sub 2}O{sub 7} showed large irreversible capacity and thus low charge capacity. Ex situ X-ray diffraction (XRD) and X-ray absorption near edge structure (XANES) measurements revealed that the electrochemical Li{sup +} intercalation/deintercalation reaction in Li{sub 6}CuB{sub 4}O{sub 10} occurred via reversible Cu{sup 2+}/Cu{sup +} reduction/oxidation reaction. These differences in their discharge/charge mechanisms are discussed based on the strength of the Cu–O covalency via their inductive effects. - Graphical abstract: Electrochemical properties for Cu-based polyanion compounds were investigated. The electrochemical reaction mechanisms are strongly affected by their Cu–O covalentcy. - Highlights: • Electrochemical properties of Cu-based polyanion compounds were investigated. • The Li{sup +} intercalation/deintercalation reaction progressed in Li{sub 6}CuB{sub 4}O{sub 10}. • The electrochemical displacement reaction progressed in Li{sub 2}CuP{sub 2}O{sub 7}. • The strength of Cu–O covalency affects the reaction mechanism.

  7. Polypyrrole Composite Film for Highly Sensitive and Selective Electrochemical Determination Sensors

    International Nuclear Information System (INIS)

    Zheng, Xiangli; Tian, Dong; Duan, Shuo; Wei, Maochao; Liu, Shan; Zhou, Changli; Li, Qing; Wu, Gang

    2014-01-01

    In this paper, polypyrrole (PPy) and benz[a]anthracene-7,12-dione (BaD) were electro-polymerized onto a pyrolytic graphite electrode (PGE), constructing a novel BaD/PPy/PGE platform for electrochemical sensoring. The morphology and electrochemical properties of the fabricated BaD/PPy/PGE were characterized by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Furthermore, the electrochemical behavior of benzo[k]fluoranthene (BkF) at the BaD/PPy/PGE was investigated. Due to the specific interactions between BkF and BaD, a wide linear range of BkF detection from 1.0 × 10 −12 to 1.0 × 10 −9 M with good linearity (R 2 = 0.9962) and a low detection limit (1.0 × 10 −13 M, S/N = 3) were demonstrated. Importantly, other similar aromatics which had one ring or more than two rings, such as benzo[a]anthracene, benzo[a]pyrene, pyrene, benzo[ghi]peryle, anthracene, phenanthrene, naphthalene and parachlorophenol, showed insignificant interference on BkF detection. Consequently, this novel BaD/PPy/PGE with excellent stability and selectivity holds promise as an effective BkF electrochemical sensor in aqueous solution. As an example for its practical application, the newly developed sensor was applied to quantitative determination of BkF in waste water samples obtained from a coking plant with satisfactory sensitivity, selectivity, and reversibility

  8. Advanced High-Voltage Aqueous Lithium-Ion Battery Enabled by "Water-in-Bisalt" Electrolyte.

    Science.gov (United States)

    Suo, Liumin; Borodin, Oleg; Sun, Wei; Fan, Xiulin; Yang, Chongyin; Wang, Fei; Gao, Tao; Ma, Zhaohui; Schroeder, Marshall; von Cresce, Arthur; Russell, Selena M; Armand, Michel; Angell, Austen; Xu, Kang; Wang, Chunsheng

    2016-06-13

    A new super-concentrated aqueous electrolyte is proposed by introducing a second lithium salt. The resultant ultra-high concentration of 28 m led to more effective formation of a protective interphase on the anode along with further suppression of water activities at both anode and cathode surfaces. The improved electrochemical stability allows the use of TiO2 as the anode material, and a 2.5 V aqueous Li-ion cell based on LiMn2 O4 and carbon-coated TiO2 delivered the unprecedented energy density of 100 Wh kg(-1) for rechargeable aqueous Li-ion cells, along with excellent cycling stability and high coulombic efficiency. It has been demonstrated that the introduction of a second salts into the "water-in-salt" electrolyte further pushed the energy densities of aqueous Li-ion cells closer to those of the state-of-the-art Li-ion batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance

    Directory of Open Access Journals (Sweden)

    Ying Wu

    2018-02-01

    Full Text Available Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD in the range of ultraviolet and visible (UV-Vis light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ, p-benzoquinone (BQ, co-oligomers of aniline and p-benzoquinone (CAB and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization.

  10. Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance.

    Science.gov (United States)

    Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang

    2018-02-12

    Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization.

  11. Electrochemical organic destruction in support of Hanford tank waste pretreatment

    International Nuclear Information System (INIS)

    Lawrence, W.E.; Surma, J.E.; Gervais, K.L.; Buehler, M.F.; Pillay, G.; Schmidt, A.J.

    1994-10-01

    The US Department of Energy's Hanford Site in Richland, Washington, has 177 underground storage tanks that contain approximately 61 million gallons of radioactive waste. The current cleanup strategy is to retrieve the waste and separate components into high-level and low-level waste. However, many of the tanks contain organic compounds that create concerns associated with tank safety and efficiency of anticipated separation processes. Therefore, a need exists for technologies that can safely and efficiently destroy organic compounds. Laboratory-scale studies conducted during FY 93 have shown proof-of-principle for electrochemical destruction of organics. Electrochemical oxidation is an inherently safe technology and shows promise for treating Hanford complexant concentrate aqueous/ slurry waste. Therefore, in support of Hanford tank waste pretreatment needs, the development of electrochemical organic destruction (ECOD) technology has been undertaken. The primary objective of this work is to develop an electrochemical treatment process for destroying organic compounds, including tank waste complexants. Electroanalytical analyses and bench-scale flow cell testing will be conducted to evaluate the effect of anode material and process operating conditions on the rate of organic destruction. Cyclic voltammetry will be used to identify oxygen overpotentials for the anode materials and provide insight into reaction steps for the electrochemical oxidation of complexants. In addition, a bench-scale flow cell evaluation will be conducted to evaluate the influence of process operating conditions and anode materials on the rate and efficiency of organic destruction using the nonradioactive a Hanford tank waste simulant

  12. Synthesis and characterization of pulsed polymerized poly(3,4-ethylenedioxythiophene) electrodes for high-performance electrochemical capacitors

    International Nuclear Information System (INIS)

    Pandey, G.P.; Rastogi, A.C.

    2013-01-01

    Poly(3,4-ethylenedioxythiophene) (PEDOT) is electrochemically prepared as a film on flexible thin graphite substrate by short galvanic pulse method in organic media. For comparative studies, PEDOT films are also prepared by potentiostatic polymerization method. The nucleation and growth mechanism for PEDOT film polymerized by short current pulses is presented with morphological and structural studies. The growth of PEDOT is continuous during the pulse off period as confirmed by the deposited mass of PEDOT by these two different methods. The SEM studies of pulse polymerized PEDOT films with different pulse on time show the features of highly porous and ridge like structures which help in rapid migration of dopant ClO 4 − ions during the charge and discharge processes. The X-ray photoelectron spectroscopy (XPS) studies confirm that in the pulse polymerized PEDOT films polymer chains are fully conjugated with the dopant ClO 4 − ions. The electrochemical characterization of PEDOT films show that pulse polymerized PEDOT films exhibited high specific capacitance (126.5 F g −1 ) with an improved energy density and rate kinetics as comparison to the potentiostatically deposited PEDOT films (100 F g −1 ) in aqueous electrolyte.

  13. A study of electrochemically-induced corrosion of low carbon steel in a medium modelling acid rain

    International Nuclear Information System (INIS)

    Vertes, C.; Lakatos-Varsanyi, M.; Vertes, A.; Meisel, W.; Guetlich, P.

    1994-01-01

    Complementary electrochemical, spectrophotometric and electron microsopic investigations were made in addition to the conversion electron Moessbauer spectroscopic (CEMS) measurements to learn more about the mechanism of corrosion of low carbon steel samples in aqueous sulfate and sulfite containing sulfate solutions (pH 3.5, 6.5 and 8.5). Passivation of iron in pure sulfate solution was studied in detail in earlier papers. In the present work, we used a solution containing both sulfate and sulfite anions to obtain more information about the effect of acid rain on low carbon steel samples. The compositions and thicknesses of the passive films formed due to the electrochemical treatments were determined from the CEM spectra. γ-FeOOH was found in each case on the surface of the samples; nevertheless, at pH 3.5 the sextet belonging to Fe 3 C appears in the CEM spectra, and also FeSO 4 . H 2 O was detected in low concentration after the shortest polarization time (90 min). The results of the applied methods proved that the sulfite ions induce pitting corrosion at pH 3.5 and 6.5, while the measurements referred to suppressed pitting at pH 8.5. (orig.)

  14. EIS study of the redox reaction of Fe(CN)63-/4- at glassy carbon electrode via diazonium reduction in aqueous and acetonitrile solutions

    Energy Technology Data Exchange (ETDEWEB)

    Khoshroo, M.; Rostami, A. [Mazandaran Univ., Babolsar (Iran, Islamic Republic of). Dept. of Physical Chemistry

    2008-07-01

    This paper reported on a study that characterized soluble electroactive species by cyclic voltammetry to investigate the presence of grafted films and their blocking properties. In particular, the authority of the glassy carbon electrode modification conditions on the cyclic voltammetric response of Fe(CN)63-/4- oxido-reduction was examined for 2 layers grafted by electrochemical reduction of diazonium salts in acetonitrile and aqueous solutions. PAA and Fast Black K modified glassy carbon electrodes exhibited a significant blocking behaviour for oxidation and reduction reactions of the Fe(CN)63-/4- redox system in aqueous and acetonitrile solutions. The study showed that the blocking effect increased which changes in time and concentration of diazonium salts in acetonitrile solution. Electrochemical impedance spectroscopy (EIS) measurements showed that the physical barrier of grafted layers prevent the access of Fe(CN)63-/4- to the underlying glassy carbon electrode. Therefore the RCT resistance increases during the modification treatment. The substituted phenyl layers are much more compact and less permeable in a nonaqueous solvent than with an aqueous solvent. Electrochemical impedance measurements indicate that the kinetics of electron transfer slow down when the time and the concentration used to modify the glassy carbon electrode increase. 4 refs., 1 fig.

  15. A study of tiron in aqueous solutions for redox flow battery application

    International Nuclear Information System (INIS)

    Xu Yan; Wen Yuehua; Cheng Jie; Cao Gaoping; Yang Yusheng

    2010-01-01

    In this study, the electrochemical behavior of tiron in aqueous solutions and the influence of pH were investigated. A change of pH mainly produces the following results. In acidic solutions of pH below 4, the electrode reaction of tiron exhibits a simple process at a relatively high potential with a favorable quasi-reversibility. The tiron redox reaction exhibits fast electrode kinetics and a diffusion-controlled process. In solutions of pH above 4, the electrode reaction of tiron tends to be complicated. Thus, acidic aqueous solutions of pH below 4 are favorable for the tiron as active species of a redox flow battery (RFB). Constant-current electrolysis shows that a part of capacity is irreversible and the structure of tiron is changed for the first electrolysis, which may result from an ECE process for the tiron electro-oxidation. Thus, the tiron needs an activation process for the application of a RFB. Average coulombic and energy efficiencies of the tiron/Pb battery are 93 and 82%, respectively, showing that self-discharge is small during the short-term cycling. The preliminary exploration shows that the tiron is electrochemically promising for redox flow battery application.

  16. The permeation of hydrogen in a steel at elevated temperature by an electrochemical method

    International Nuclear Information System (INIS)

    Tsubakino, H.; Ando, A.; Yamakawa, K.

    1984-01-01

    An electrochemical permeation method has been widely used to study the transport characteristics of hydrogen in metals, i.e., the content, diffusivity and permeability. This electrochemical measurement technique has the following remarkable features: a good detection limit for the measurement of hydrogen content, a simpler measuring apparatus, suitability for successive measurement of the transport characteristics, and flexibility in variation of experimental conditions. However this method has been restricted to temperatures below 373 K because an aqueous solution has been used as an electrode. In this study, an electrochemical permeation method using molten salts at elevated temperatures (673-773 K) in the range of practical interest for hydrogen attack in steel is presented. The introduction of hydrogen by use of molten salts has been reported but it has been performed at 423473 K and at 553 K

  17. Electrochemical and materials aspects of tribocorrosion systems

    International Nuclear Information System (INIS)

    Landolt, D

    2006-01-01

    Tribocorrosion involves mechanical and chemical/electrochemical interactions between surfaces in relative motion in the presence of a corrosive environment. Tribocorrosion phenomena are encountered in many technological areas where they cause damage to installations, machines and devices. Often tribocorrosion damage is a problem for safety or for human health. In other applications tribocorrosion phenomena are put to good use in manufacturing. The chemo-mechanical mechanisms of tribocorrosion are still incompletely understood, they involve the properties of contacting material surfaces, the mechanics of the contact and the corrosion conditions. Electrochemical methods are widely used for the study of tribocorrosion reactions. To yield information about synergistic and antagonistic mechanisms they must be applied in situ under strictly controlled mechanical conditions, using materials with well-characterized surface properties. Recent progress in modelling and understanding of tribocorrosion systems is discussed and some challenges and opportunities for future research are identified

  18. Recent results on aqueous electrolyte cells

    Science.gov (United States)

    Wessells, Colin; Huggins, Robert A.; Cui, Yi

    2011-03-01

    The improved safety of aqueous electrolytes makes aqueous lithium-ion batteries an attractive alternative to commercial cells utilizing flammable and expensive organic electrolytes. Two important issues relating to their use have been addressed in this work. One is the extension of the usable voltage range by the incorporation of lithium salts, and the other is the investigation of a useful negative electrode reactant, LiTi2(PO4)3. The electrochemical stability of aqueous lithium salt solutions containing two lithium salts, LiNO3 and Li2SO4, has been characterized using a constant current technique. In both cases, concentrated solutions had effective electrolyte stability windows substantially greater than that of pure water under standard conditions. At an electrolyte leakage current of 10 μA cm-2 between two platinum electrodes in 5 M LiNO3 the cell voltage can reach 2.0 V, whereas with a leakage current of 50 μA cm-2 it can reach 2.3 V. LiTi2(PO4)3 was synthesized using a Pechini method and cycled in pH-neutral Li2SO4. At a reaction potential near the lower limit of electrolyte stability, an initial discharge capacity of 118 mAh g-1 was measured at a C/5 rate, while about 90% of this discharge capacity was retained after 100 cycles. This work demonstrates that it is possible to have useful aqueous electrolyte lithium-ion batteries using the LiTi2(PO4)3 anode with cell voltages of 2 V and above.

  19. Electrochemical behavior of single-walled carbon nanotube supercapacitors under compressive stress.

    Science.gov (United States)

    Li, Xin; Rong, Jiepeng; Wei, Bingqing

    2010-10-26

    The effect of compressive stress on the electrochemical behavior of flexible supercapacitors assembled with single-walled carbon nanotube (SWNT) film electrodes and 1 M aqueous electrolytes with different anions and cations were thoroughly investigated. The under-pressed capacitive and resistive features of the supercapacitors were studied by means of cyclic voltammetry measurements and electrochemical impedance analysis. The results demonstrated that the specific capacitance increased first and saturated in corresponding decreases of the series resistance, the charge-transfer resistance, and the Warburg diffusion resistance under an increased pressure from 0 to 1723.96 kPa. Wettability as well as ion-size effect of different aqueous electrolytes played important roles to determine the pressure dependence behavior of the suerpcapacitors under an applied pressure. An improved high-frequency capacitive response with 1172 Hz knee frequency, which is significantly higher compared to reported values, was observed under the compressive pressure of 1723.96 kPa, indicating an improving and excellent high-power capability of the supercapacitors under the pressure. The experimental results and the thorough analysis described in this work not only provide fundamental insight of pressure effects on supercapacitors but also give an important guideline for future design of next generation flexible/stretchable supercapacitors for industrial and consumer applications.

  20. Liquid / liquid biphasic electrochemistry in ultra-turrax dispersed acetonitrile / aqueous electrolyte systems

    International Nuclear Information System (INIS)

    Watkins, John D.; Amemiya, Fumihiro; Atobe, Mahito; Bulman-Page, Philip C.; Marken, Frank

    2010-01-01

    Unstable acetonitrile | aqueous emulsions generated in situ with ultra-turrax agitation are investigated for applications in dual-phase electrochemistry. Three modes of operation for liquid / liquid aqueous-organic electrochemical processes are demonstrated with no intentionally added electrolyte in the organic phase based on (i) the formation of a water-soluble product in the aqueous phase in the presence of the organic phase, (ii) the formation of a product and ion transfer at the liquid / liquid-electrode triple phase boundary, and (iii) the formation of a water-insoluble product in the aqueous phase which then transfers into the organic phase. A three-electrode electrolysis cell with ultra-turrax agitator is employed and characterised for acetonitrile / aqueous 2 M NaCl two phase electrolyte. Three redox systems are employed in order to quantify the electrolysis cell performance. The one-electron reduction of Ru(NH 3 ) 6 3+ in the aqueous phase is employed to determine the rate of mass transport towards the electrode surface and the effect of the presence of the acetonitrile phase. The one-electron oxidation of n-butylferrocene in acetonitrile is employed to study triple phase boundary processes. Finally, the one-electron reduction of cobalticenium cations in the aqueous phase is employed to demonstrate the product transfer from the electrode surface into the organic phase. Potential applications in biphasic electrosynthesis are discussed.

  1. Electrochemical Sensors Based on Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Md. Aminur Rahman

    2009-03-01

    Full Text Available This review focuses on recent contributions in the development of the electrochemical sensors based on carbon nanotubes (CNTs. CNTs have unique mechanical and electronic properties, combined with chemical stability, and behave electrically as a metal or semiconductor, depending on their structure. For sensing applications, CNTs have many advantages such as small size with larger surface area, excellent electron transfer promoting ability when used as electrodes modifier in electrochemical reactions, and easy protein immobilization with retention of its activity for potential biosensors. CNTs play an important role in the performance of electrochemical biosensors, immunosensors, and DNA biosensors. Various methods have been developed for the design of sensors using CNTs in recent years. Herein we summarize the applications of CNTs in the construction of electrochemical sensors and biosensors along with other nanomaterials and conducting polymers.

  2. Electrochemical Investigation of the Interaction between Catecholamines and ATP.

    Science.gov (United States)

    Taleat, Zahra; Estévez-Herrera, Judith; Machado, José D; Dunevall, Johan; Ewing, Andrew G; Borges, Ricardo

    2018-02-06

    The study of the colligative properties of adenosine 5'-triphosphate (ATP) and catecholamines has received the attention of scientists for decades, as they could explain the capabilities of secretory vesicles (SVs) to accumulate neurotransmitters. In this Article, we have applied electrochemical methods to detect such interactions in vitro, at the acidic pH of SVs (pH 5.5) and examined the effect of compounds having structural similarities that correlate with functional groups of ATP (adenosine, phosphoric acid and sodium phosphate salts) and catecholamines (catechol). Chronoamperometry and fast scan cyclic voltammetry (FSCV) provide evidence compatible with an interaction of the catechol and adenine rings. This interaction is also reinforced by an electrostatic interaction between the phosphate group of ATP and the protonated ammonium group of catecholamines. Furthermore, chronoamperometry data suggest that the presence of ATP subtlety reduces the apparent diffusion coefficient of epinephrine in aqueous media that adds an additional factor leading to a slower rate of catecholamine exocytosis. This adds another plausible mechanism to regulate individual exocytosis events to alter communication.

  3. Nano-structured textiles as high-performance aqueous cathodes for microbial fuel cells

    KAUST Repository

    Xie, Xing; Pasta, Mauro; Hu, Liangbing; Yang, Yuan; McDonough, James; Cha, Judy; Criddle, Craig S.; Cui, Yi

    2011-01-01

    A carbon nanotube (CNT)-textile-Pt cathode for aqueous-cathode microbial fuel cells (MFCs) was prepared by electrochemically depositing Pt nanoparticles on a CNT-textile. An MFC equipped with a CNT-textile-Pt cathode revealed a 2.14-fold maximum power density with only 19.3% Pt loading, compared to that with a commercial Pt coated carbon cloth cathode. © 2011 The Royal Society of Chemistry.

  4. MWCNTs/Cellulose Hydrogels Prepared from NaOH/Urea Aqueous Solution with Improved Mechanical Properties

    Directory of Open Access Journals (Sweden)

    Yingpu Zhang

    2015-01-01

    Full Text Available Novel high strength composite hydrogels were designed and synthesized by introducing multiwalled carbon nanotubes (MWCNTs into cellulose/NaOH/urea aqueous solution and then cross-linked by epichlorohydrin. MWCNTs were used to modify the matrix of cellulose. The structure and morphology of the hydrogels were characterized by Fourier transform infrared (FT-IR spectroscopy, high resolution transmission electron microscopy (HR-TEM, and scanning electron microscopy (SEM. The results from swelling testing revealed that the equilibrium swelling ratio of hydrogels decreased with the increment of MWCNTs content. Thermogravimetric analysis (TGA and dynamic mechanical analysis (DMA results demonstrated that the introduction of MWCNT into cellulose hydrogel networks remarkably improved both thermal and mechanical properties of the composite hydrogels. The preparation of MWCNTs modifiedcellulose-based composites with improved mechanical properties was the first important step towards the development of advanced functional materials.

  5. On the electrochemical migration mechanism of tin in electronics

    DEFF Research Database (Denmark)

    Minzari, Daniel; Jellesen, Morten Stendahl; Møller, Per

    2011-01-01

    Electrochemical migration (ECM) of tin can result in the growth of a metal deposit with a dendritic structure from cathode to anode. In electronics, such growth can lead to short circuit of biased electrodes, potentially leading to intermittent or complete failure of an electronic device...

  6. Rocking-Chair Ammonium-Ion Battery: A Highly Reversible Aqueous Energy Storage System.

    Science.gov (United States)

    Wu, Xianyong; Qi, Yitong; Hong, Jessica J; Li, Zhifei; Hernandez, Alexandre S; Ji, Xiulei

    2017-10-09

    Aqueous rechargeable batteries are promising solutions for large-scale energy storage. Such batteries have the merit of low cost, innate safety, and environmental friendliness. To date, most known aqueous ion batteries employ metal cation charge carriers. Here, we report the first "rocking-chair" NH 4 -ion battery of the full-cell configuration by employing an ammonium Prussian white analogue, (NH 4 ) 1.47 Ni[Fe(CN) 6 ] 0.88 , as the cathode, an organic solid, 3,4,9,10-perylenetetracarboxylic diimide (PTCDI), as the anode, and 1.0 m aqueous (NH 4 ) 2 SO 4 as the electrolyte. This novel aqueous ammonium-ion battery demonstrates encouraging electrochemical performance: an average operation voltage of ca. 1.0 V, an attractive energy density of ca. 43 Wh kg -1 based on both electrodes' active mass, and excellent cycle life over 1000 cycles with 67 % capacity retention. Importantly, the topochemistry results of NH 4 + in these electrodes point to a new paradigm of NH 4 + -based energy storage. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. An Aqueous Metal-ion Capacitor with Oxidised Carbon Nanotubes and Metallic Zinc Electrodes

    Directory of Open Access Journals (Sweden)

    Yuheng Tian

    2016-10-01

    Full Text Available An aqueous metal ion capacitor comprising of a zinc anode, an oxidized carbon nanotubes (oCNTs cathode and a zinc sulfate electrolyte is reported. Since the shuttling cation is Zn2+, this typical metal ion capacitor is named as zinc-ion capacitor (ZIC. The ZIC integrates the divalent zinc stripping/plating chemistry with the surface-enabled pseudocapacitive cation adsorption/desorption on oCNTs. The surface chemistry and crystallographic structure of oCNTs were extensively characterized by combining X-ray photoelectron spectroscopy, Fourier-transformed infrared spectroscopy, Raman spectroscopy and X-ray powder diffraction. The function of the surface oxygen groups in surface cation storage was elucidated by a series of electrochemical measurement and the surface-enabled ZIC showed better performance than the ZIC with an un-oxidized CNT cathode. The reaction mechanism at the oCNT cathode involves the additional reversible Faradaic process, while the CNTs merely show electric double layer capacitive behavior involving a non-Faradaic process. The aqueous hybrid ZIC comprising the oCNT cathode exhibited a specific capacitance of 20 mF cm-2 (corresponding to 53 F g-1 in the range of 0-1.8 V at 10 mV s-1 and a stable cycling performance up to 5000 cycles.

  8. An Aqueous Metal-Ion Capacitor with Oxidized Carbon Nanotubes and Metallic Zinc Electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Yuheng; Amal, Rose; Wang, Da-Wei, E-mail: da-wei.wang@unsw.edu.au [School of Chemical Engineering, The University of New South Wales (UNSW), Sydney, NSW (Australia)

    2016-10-03

    An aqueous metal ion capacitor comprising of a zinc anode, oxidized carbon nanotubes (oCNTs) cathode, and a zinc sulfate electrolyte is reported. Since the shuttling cation is Zn{sup 2+}, this typical metal ion capacitor is named as zinc-ion capacitor (ZIC). The ZIC integrates the divalent zinc stripping/plating chemistry with the surface-enabled pseudocapacitive cation adsorption/desorption on oCNTs. The surface chemistry and crystallographic structure of oCNTs were extensively characterized by combining X-ray photoelectron spectroscopy, Fourier-transformed infrared spectroscopy, Raman spectroscopy, and X-ray powder diffraction. The function of the surface oxygen groups in surface cation storage was elucidated by a series of electrochemical measurement and the surface-enabled ZIC showed better performance than the ZIC with an un-oxidized CNT cathode. The reaction mechanism at the oCNT cathode involves the additional reversible Faradaic process, while the CNTs merely show electric double layer capacitive behavior involving a non-Faradaic process. The aqueous hybrid ZIC comprising the oCNT cathode exhibited a specific capacitance of 20 mF cm{sup −2} (corresponding to 53 F g{sup −1}) in the range of 0–1.8 V at 10 mV s{sup −1} and a stable cycling performance up to 5000 cycles.

  9. Service water electrochemical monitoring development at Ontario Hydro

    International Nuclear Information System (INIS)

    Brennenstuhl, A.M.

    1994-01-01

    Ontario Hydro (OH) is currently investigating the feasibility of using electrochemical techniques for the corrosion monitoring of service water systems. To date all evaluations have been carried out in a field simulator. The studies include examining the effects of; system startup after periods of stagnation, sodium hypochlorite injection, and zebra mussel settlement on metallic surfaces. Carbon steel and Type 304L stainless steel have been evaluated. Electrochemical potential noise (EPN), electrochemical current noise (ECN) potential and coupling current were semi-continuously monitored over a period of up to one year. Data obtained from the electrochemical noise monitoring has given OH valuable insights into the mechanisms of degradation in service water systems. The high sensitivity of the electrochemical noise technique, particularly to localized corrosion has proved to be the major attraction of the system

  10. Pitting morphologies of zirconium base alloys in aqueous and non aqueous chloride media

    International Nuclear Information System (INIS)

    Palit, G.C.; Gadiyar, H.S.

    1988-01-01

    Pitting morphology of zirconium and Zr-Cr alloys in aqueous chloride and nonaqueous methanol + 0.4 per cent HCl solution was investigated and observed to follow different modes in these two environments. While in aqueous chloride solution pitting was transgranular and randomly oriented, in methanol-chloride solution pits were observed to initiate and propagate along the grain boundaries. In aqueous chloride solution very irregular and sponge like zirconium metal was formed inside the pit while in methanol-chloride solution the pits were crystallographic in nature. Optical microscopy has revealed that pits preferentially initiate and propagate along scratch line in aqueous chloride solution, but such was not the case in nonaqueous methanol-chloride solution. The nature and the mechanism operating in the catastropic failure of these materials are investigated. (author). 10 refs., 11 figs

  11. Undoped CVD diamond films for electrochemical applications

    International Nuclear Information System (INIS)

    Mosinska, Lidia; Fabisiak, Kazimierz; Paprocki, Kazimierz; Kowalska, Magdalena; Popielarski, Pawel; Szybowicz, Miroslaw

    2013-01-01

    By using different deposition conditions, the CVD diamond films with different qualities and orientation were grown by the hot-filament CVD technique. The object of this article is to summarize and discuss relation between structural, physical and electrochemical properties of different diamond electrodes. The physical properties of the Hot Filament CVD microcrystalline diamond films are analyzed by scanning electron microscopy and Raman spectroscopy. In presented studies two different electrodes were used of the diamond grain sizes around 200 nm and 10 μm, as it was estimated from SEM picture. The diamond layers quality was checked on basis of FWHM (Full width at Half Maximum) of 1332 cm −1 diamond Raman peak. The ratio of sp 3 /sp 2 carbon bonds was determined by 1550 cm −1 G band and 1350 cm −1 D band in the Raman spectrum. The electrochemical properties were analyzed using (CV) cyclic voltammetry measurements in aqueous solutions. The sensitivity of undoped diamond electrodes depends strongly on diamond film quality and concentration of amorphous carbon phase in the diamond layer

  12. "Water-in-salt" electrolytes enable the use of cost-effective aluminum current collectors for aqueous high-voltage batteries.

    Science.gov (United States)

    Kühnel, R-S; Reber, D; Remhof, A; Figi, R; Bleiner, D; Battaglia, C

    2016-08-16

    The extended electrochemical stability window offered by highly concentrated electrolytes allows the operation of aqueous batteries at voltages significantly above the thermodynamic stability limit of water, at which the stability of the current collector potentially limits the cell voltage. Here we report the observation of suppressed anodic dissolution of aluminum in "water-in-salt" electrolytes enabling roll-to-roll electrode fabrication for high-voltage aqueous lithium-ion batteries on cost-effective light-weight aluminum current collectors using established lithium-ion battery technology.

  13. In situ fabrication of electrochemically grown mesoporous metallic thin films by anodic dissolution in deep eutectic solvents.

    Science.gov (United States)

    Renjith, Anu; Roy, Arun; Lakshminarayanan, V

    2014-07-15

    We describe here a simple electrodeposition process of forming thin films of noble metallic nanoparticles such as Au, Ag and Pd in deep eutectic solvents (DES). The method consists of anodic dissolution of the corresponding metal in DES followed by the deposition on the cathodic surface. The anodic dissolution process in DES overcomes the problems associated with copious hydrogen and oxygen evolution on the electrode surface when carried out in aqueous medium. The proposed method utilizes the inherent abilities of DES to act as a reducing medium while simultaneously stabilizing the nanoparticles that are formed. The mesoporous metal films were characterized by SEM, XRD and electrochemical techniques. Potential applications of these substrates in surface enhanced Raman spectroscopy and electrocatalysis have been investigated. A large enhancement of Raman signal of analyte was achieved on the mesoporous silver substrate after removing all the stabilizer molecules from the surface by calcination. The highly porous texture of the electrodeposited film provides superior electro catalytic performance for hydrogen evolution reaction (HER). The mechanisms of HER on the fabricated substrates were studied by Tafel analysis and electrochemical impedance spectroscopy (EIS). Copyright © 2014 Elsevier Inc. All rights reserved.

  14. Corrosion Behavior of Surface-Treated Implant Ti-6Al-4V by Electrochemical Polarization and Impedance Studies

    Science.gov (United States)

    Paul, Subir; Yadav, Kasturi

    2011-04-01

    Implant materials for orthopedic and heart surgical services demand a better corrosion resistance material than the presently used titanium alloys, where protective oxide layer breaks down on a prolonged stay in aqueous physiological human body, giving rise to localized corrosion of pitting, crevice, and fretting corrosion. A few surface treatments on Ti alloy, in the form of anodization, passivation, and thermal oxidation, followed by soaking in Hank solution have been found to be very effective in bringing down the corrosion rate as well as producing high corrosion resistance surface film as reflected from electrochemical polarization, cyclic polarization, and Electrochemical Impedance Spectroscopy (EIS) studies. The XRD study revealed the presence of various types of oxides along with anatase and rutile on the surface, giving rise to high corrosion resistance film. While surface treatment of passivation and thermal oxidation could reduce the corrosion rate by 1/5th, anodization in 0.3 M phosphoric acid at 16 V versus stainless steel cathode drastically brought down the corrosion rate by less than ten times. The mechanism of corrosion behavior and formation of different surface films is better understood from the determination of EIS parameters derived from the best-fit equivalent circuit.

  15. Mechanism of Electrochemical Delamination of Two-Dimensional Materials from Their Native Substrates by Bubbling

    Directory of Open Access Journals (Sweden)

    Jie Sun

    2015-12-01

    Full Text Available A capacitor-based circuit model is proposed to explain the electrochemical delamination of two-dimensional materials from their native substrates where produced gas bubbles squeeze into the interface. The delamination is actually the electric breakdown of the capacitor formed between the solution and substrate. To facilitate the procedure, the backside of the ubstrate has to be shielded so that the capacitor breakdown voltage can be reached. The screening effect can be induced either by nonreactive ions around the electrode or, more effectively, by an undetachable insulator. This mechanism serves as a guideline for the surface science and applications involving the bubbling delamination.

  16. Mechanisms of saccharide protection against epigallocatechin-3-gallate deterioration in aqueous solutions.

    Science.gov (United States)

    Shpigelman, Avi; Zisapel, Adi; Cohen, Yifat; Livney, Yoav D

    2013-08-15

    We investigated the mechanisms of the protection conferred by sugars to epigallocatechin-3-gallate (EGCG) against deterioration. Additionally, we present a rapid method for evaluating the deterioration rate of EGCG using absorbance spectroscopy. We found that various sugars provided different levels of protection at identical weight percentage, and the combination of sugars and β-lactoglobulin nanocomplexes provided greater protection for EGCG than each protective component alone. We suggest that the concentration-dependent protection by sugars resulted from a combination of mechanisms, including: (1) reduced aqueous O2 solubility, (2) scavenging of reactive oxygen species, and (3) chelation of traces of transition metal ions, which is suggested to be the main reason for the differences among the sugars. The observed protective effect of sugars can be easily applied by the industry in proper selection of sugars for enrichment of syrups or concentrates with EGCG and for the preparation of enriched beverages and foods for health promotion. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. A potentiodynamic study of aluminum-lithium alloys in an aqueous sodium chloride environment

    Science.gov (United States)

    Tsao, C.-H. T.; Pizzo, P. P.

    1985-01-01

    The characteristics of the potentiodynamic curves for Al-Li alloys in 3.5 percent NaCl aqueous solution are explained and the electrochemical parameters of the potentiodynamic technique are correlated to observed pitting and intergranular cracking behavior. It is shown that the oxygen content of the sodium chloride electrolyte plays an important role in the electrochemical behavior of Al-Li alloys. The potentiodynamic behavior of the alloys is found to be insensitive to variation in compositional content and heat treatment, both of which affect the stress-corrosion behavior. Stringer oxide particle attack and random pitting are observed. It is shown that alternate-immersion exposure prior to potentiodynamic polarization may offer a means of assessing susceptibility to stress-corrosion cracking.

  18. Aqueous phase oxidation techniques as an alternative to incineration

    International Nuclear Information System (INIS)

    Gray, L.W.; Adamson, M.G.; Hickman, R.G.; Farmer, J.C.; Chiba, Z.; Gregg, D.W.; Wang, F.T.

    1992-03-01

    The Lawrence Livermore National Laboratory (LLNL) has three aqueous phase techniques under development for oxidation of high value or high risk waste steams. One is direct electrochemical oxidation and one is mediated electrochemical oxidation utilizing regenerable, strongly oxidizing cations such as Ag(II), Co (III), Ce(IV), etc. These cations can either attack oxidizable materials directly and/or indirectly via first reacting with water to generate OH radicals which then attack the oxidizable materials. The third system utilizes H 2 O 2 and UV light to generate OH radicals directly which in turn attack the oxidizable materials. All systems have the advantage of a chemical off-switch in that when the power is turned off, the reaction quickly subsides. All systems operate with low concentrations (typically <5 wt %) of oxidizable materials, therefore, the stored energy for possible run-away reactions is very low. 15 figures, 22 references

  19. Synthesis of nano-particles by soft chemistry: structural, morphological and dimensional control. Studies of the electrochemical properties (towards dyes solar cells); Synthese de nanoparticules par chimie douce: controle structural, morphologique et dimensionnel. Etudes des proprietes electrochimiques (vers les cellules solaires a colorants)

    Energy Technology Data Exchange (ETDEWEB)

    Cassaignon, S.; Koelsch, M.; Jolivet, J.P. [Paris-6 Univ. Pierre et Marie Curie, Chimie de la Matiere Condensee de Paris, CNRS UMR 7574, 75 - Paris (France)

    2006-07-01

    In this work are described the electrochemical behaviour of different TiO{sub 2} films (anatase, brookite and rutile) in aqueous solution and the influence of the parameters as the crystal structure and the morphology on the electrochemical answer. To complete this study, the capacity of the double layer has been measured by impedance spectroscopy. Voltage measurements of TiO{sub 2} sensitized by a dye will allow to discuss the reversibility of the system and the rearrangement mechanisms. At last, the influence of the nature of the TiO{sub 2} particles (anatase, rutile and brookite) on the photovoltage has been studied in order to estimate their interest for photovoltaic devices. (O.M.)

  20. Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

    Directory of Open Access Journals (Sweden)

    Y. Tan

    2012-01-01

    Full Text Available Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA. Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM–10 mM was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

  1. The effect of aqueous media on the mechanical properties of fluorapatite-mullite glass-ceramics.

    Science.gov (United States)

    Mollazadeh, S; Ajalli, Siamak; Kashi, Tahereh S Jafarzadeh; Yekta, Bijan Eftekhai; Javadpour, Jafar; Jafari, S; Youssefi, Abbas; Fazel, Akbar

    2015-11-01

    To verify the effects of alternating thermal changes in aqueous media and chemical composition on mechanical properties of apatite-mullite glass-ceramics and to investigate concentration of ions eluted from glass-ceramics in aqueous media. The glass compositions were from SiO2Al2O3P2O5CaOTiO2BaOZrO2CaF2 system. Glass-ceramics were prepared by heat-treating at 1100°C for 3h samples alternately immersed in water at 5 and 60°C. The 3-point bending strength (n=10) were determined using 3×4×25mm/bar and a universal testing machine, at a cross-head speed of 0.1mm/min. Vickers micro hardness were evaluated by applying a total of 15-20 indentations under a 100g load for 30s. Concentrations of ions eluted from glass-ceramics immersed in 60±5°C double distilled water were determined by ion chromatography. The toxicity of glass-ceramics was assessed by seeding the osteosarcoma cells (MG63) on powder for different days and their cell proliferation assessment was investigated by MTT assay. The data were analyzed using one way analysis of variance and the means were compared by Tukey's test (5% significance level). The highest flexural strength and hardness values after thermal changes belonged to TiO2 and ZrO2 containing glass-ceramics which contained lower amount of released ions. BaO containing glass-ceramic and sample with extra amount of silica showed the highest amount of reduction in their mechanical strength values. These additives enhanced the concentration of eluted ions in aqueous media. MTT results showed that glass-ceramics were almost equivalent concerning their in-vitro biological behavior. Thermal changes and chemical compositions had significant effects on flexural strength and Vickers micro-hardness values. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  2. Optimizing the surfactant for the aqueous processing of LiFePO{sub 4} composite electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Porcher, W.; Jouanneau, S. [Commissariat a l' Energie Atomique, 38054 Grenoble Cedex 9 (France); Lestriez, B.; Guyomard, D. [Institut des Materiaux Jean Rouxel (IMN), Universite de Nantes, CNRS, 44322 Nantes Cedex 3 (France)

    2010-05-01

    Aqueous processing would reduce the costs associated with the making of the composite electrode. To achieve the incorporation and the dispersion of the carbon black (CB) conductive agent in aqueous slurries, a surfactant is needed. In this paper, three surfactants are compared, an anionic one, the sodium dodecyle sulphate (SDS), a non-ionic one, the isooctylphenylether of polyoxyethylene called commercially Triton X-100 and a cationic one, the hexadecyltrimethylammonium bromide (CTAB), by using rheology and laser granulometry measurements on electrode slurries on one hand, and SEM observations, porosity and adhesion measurements and electrochemical testing on composite electrodes on the other hand. Ionic surfactants were found to be not suitable because a corrosion of the aluminium current collector occurred. The utilization of Triton X-100 favoured a more homogeneous CB distribution, resulted in a better electronic wiring of the active material particles and higher rate behavior of the electrode. Optimal electrochemical performances are obtained for an optimal surfactant concentration which depends on the BET surface area of the CB powder. (author)

  3. Material Characterization in the Electro-Analytic Approach for Applications in Chemical Mechanical Planarization and Electrochemical Energy Systems

    Science.gov (United States)

    Rock, Simon E.

    The work presented in this thesis covers electro-analytical characterization for multiple applications in material science. Electrochemical techniques were used to investigate soluble film formation on metals used in chemical mechanical planarization in order to better understand the removal rate process by studying new chemicals proposed by groups in industry. Second, an ionic liquid was used as an electrolyte in a lithium ion cathode half cell to show the essential functionality of the IL and the temperature advantage over traditional electrolytes. Lastly, a comprehensive measurement for charge recombination in dye-sensitized solar cells was performed using both open-circuit voltage decay and impedance spectroscopy, which may be used to better understand the limiting factors that affect the cell's efficiently. Electrochemical techniques were applied to new methods and materials to extend the development of material manufacturing and advance the measurement process. The fabrication of interconnect structures for semiconductor devices requires low down-pressure chemical mechanical planarization (CMP) of Ta barrier layers. Guanidine carbonate (GC) serves as an effective surface-complexing agent for such CMP applications, where the rate of Ta removal can be chemically controlled through pH-tuned selectivity with respect to the removal of Cu lines. Electrochemical techniques are employed in this work to study the surface-modifying roles of GC that make this chemical an attractive complexing agent for Ta CMP. In addition, the effects of including H2O2 (an oxidizer) and dodecyl benzene sulfonic acid (DBSA, a dissolution inhibitor for Cu) in GC-based CMP solutions are investigated to examine the selective CMP mechanisms of Ta and Cu in these solutions. The results suggest that the removal of Ta is supported in part by structurally weak guanidinium-tantalic-acid surface complexes formed on Ta/Ta2O5. The bicarbonate/carbonate anions of GC also facilitate Ta removal through

  4. Mechanisms of chemical vapor generation by aqueous tetrahydridoborate. Recent developments toward the definition of a more general reaction model

    Science.gov (United States)

    D'Ulivo, Alessandro

    2016-05-01

    A reaction model describing the reactivity of metal and semimetal species with aqueous tetrahydridoborate (THB) has been drawn taking into account the mechanism of chemical vapor generation (CVG) of hydrides, recent evidences on the mechanism of interference and formation of byproducts in arsane generation, and other evidences in the field of the synthesis of nanoparticles and catalytic hydrolysis of THB by metal nanoparticles. The new "non-analytical" reaction model is of more general validity than the previously described "analytical" reaction model for CVG. The non-analytical model is valid for reaction of a single analyte with THB and for conditions approaching those typically encountered in the synthesis of nanoparticles and macroprecipitates. It reduces to the previously proposed analytical model under conditions typically employed in CVG for trace analysis (analyte below the μM level, borane/analyte ≫ 103 mol/mol, no interference). The non-analytical reaction model is not able to explain all the interference effects observed in CVG, which can be achieved only by assuming the interaction among the species of reaction pathways of different analytical substrates. The reunification of CVG, the synthesis of nanoparticles by aqueous THB and the catalytic hydrolysis of THB inside a common frame contribute to rationalization of the complex reactivity of aqueous THB with metal and semimetal species.

  5. Electrochemical procedures in the treatment of the spent nuclear fuel

    International Nuclear Information System (INIS)

    Oliveira Forbicini, Christina Aparecida L.G. de.

    1994-01-01

    Taking into account the advantages of the electrochemical technique and operational features of contactors, type mixer-settler, a new electrolytic extraction equipment is presented. Preliminary studies on electrochemical reduction behavior were carried out with a single stage prototype to set the reliable parameters for the final multistage mixer-settler design (MIRELE). Titanium was the housing material (cathode) and platinum the anode. MIRELE was designed and manufactured at IPEN workshop. After operational tests, the equipment was installed in a glove-box and U/Pu electrochemical partitioning studies were accomplished. The influences of parameters, as hydrazine as scavenger agent in nitric acid medium, current density control in each transference unit and organic and aqueous flow rate on the process efficiency were verified. An uranium separation higher than 99,5% has been achieved. Based on these studies, a flowsheet for spent nuclear fuel treatment was performed, including: an U-Pu co-extraction and scrubbing step, a partial partitioning, followed by final partitioning both using electrochemical Pu reduction, and an uranium reextraction as last step. The product with Pu/U ratio 2,2 times higher than the initial one, with suitable composition for the MOX fuel re-fabrication, has been achieved, showing an important application of the equipment in the new concept of fuel recycling. Also, waste volume reduction, one of the important aspects of the process, has been obtained. Concluding the works, an electrochemical procedure for residual hydrazine decomposition, present in the plutonium product solution, was used to provide a safety operation during the concentration step. (author). 94 refs., 44 figs., 15 tabs

  6. Low level radioactive liquid waste decontamination by electrochemical way

    International Nuclear Information System (INIS)

    Tronche, E.

    1994-10-01

    As part of the work on decontamination treatments for low level radioactive aqueous liquid wastes, the study of an electro-chemical process has been chosen by the C.E.A. at the Cadarache research centre. The first part of this report describes the main methods used for the decontamination of aqueous solutions. Then an electro-deposition process and an electro-dissolution process are compared on the basis of the decontamination results using genuine radioactive aqueous liquid waste. For ruthenium decontamination, the former process led to very high yields (99.9 percent eliminated). But the elimination of all the other radionuclides (antimony, strontium, cesium, alpha emitters) was only favoured by the latter process (90 percent eliminated). In order to decrease the total radioactivity level of the waste to be treated, we have optimized the electro-dissolution process. That is why the chemical composition of the dissolved anode has been investigated by a mixture experimental design. The radionuclides have been adsorbed on the precipitating products. The separation of the precipitates from the aqueous liquid enabled us to remove the major part of the initial activity. On the overall process some operations have been investigated to minimize waste embedding. Finally, a pilot device (laboratory scale) has been built and tested with genuine radioactive liquid waste. (author). 77 refs., 41 tabs., 55 figs., 4 appendixes

  7. Study on the Electrochemical Property of Microporous Cobalt Phosphite[Co_11(HPO_3)_8(OH)_6

    International Nuclear Information System (INIS)

    Lee, Dong Heon; Kang, Myunggoo; Jung, Hyun; Paek, Seung-Min

    2016-01-01

    Crystalline microporous cobalt phosphite, Co_11(HPO_3)_8(OH)_6, was prepared via facile hydrothermal route without the use of any templates or surfactants. The cobalt chloride hexahydrate (CoCl_2·6H_2O) and sodium hypophosphite monohydrate (NaH_2PO_2·H_2O) were employed as reactants, and sodium bicarbonate(NaHCO_3) was added to adjust the pH. The resultant Co_11(HPO_3)_8(OH)_6 shows dumbbell-like shape witha size of several micrometers. The obtained materials were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermal gravimetric analysis (TGA), field-emission scanning electron microscopy (FE-SEM), and energy dispersive spectrometry (EDS). The Co_11(HPO_3)_8(OH)_6 is applied as electrochemical energy storage electrode material because of its unique microporous nature. Different aqueous electrolytes (LiOH, NaOH, and KOH) have been tested in order to study the effect of electrolyte cations on electrochemical behavior. To investigate the capacity and stability of Co_11(HPO_3)_8(OH)_6 electrode, cyclic voltammetry (CV), galvanostatic charge-discharge (GC), and cycle stability were performed in aqueous electrolytes with different cations at room temperature. We found that the electrochemical behavior of these materials is strongly dependent on the species of electrolyte cations (Li"+,Na"+, and K"+).

  8. Electrochemical Capacitors Based on Aligned Carbon Nanotubes Directly Synthesized on Tantalum Substrates

    International Nuclear Information System (INIS)

    Kim, Byung Woo; Chung, Hae Geun; Kim, Woong; Min, Byoung Koun; Kim, Hong Gon

    2010-01-01

    We demonstrate that vertically aligned carbon nanotubes can be synthesized directly on tantalum substrate via waterassisted chemical vapor deposition and evaluate their properties as electrochemical capacitors. The mean diameter of the carbon nanotubes was 7.1 ± 1.5 nm, and 70% of them had double walls. The intensity ratio of G-band to D-band in Raman spectra was as high as 5, indicating good quality of the carbon nanotubes. Owing to the alignment and low equivalent series resistance, the carbon nanotube based supercapacitors showed good rate performance. Rectangular shape of cyclic voltammogram was maintained even at the scan rate of > 1 V/s in 1 M sulfuric acid aqueous solution. Specific capacitance was well-retained (∼94%) even when the discharging current density dramatically increased up to 145 A/g. Consequently, specific power as high as 60 kW/kg was obtained from as-grown carbon nanotubes in aqueous solution. Maximum specific energy of ∼20 Wh/kg was obtained when carbon nanotubes were electrochemically oxidized and operated in organic solution. Demonstration of direct synthesis of carbon nanotubes on tantalum current collectors and their applications as supercapacitors could be an invaluable basis for fabrication of high performance carbon nanotube supercapacitors

  9. Mediated electrochemical oxidation treatment for Rocky Flats combustible low-level mixed waste. Final report, FY 1993 and 1994

    International Nuclear Information System (INIS)

    Chiba, Z.; Lewis, P.R.; Murguia, L.C.

    1994-09-01

    Mediated Electrochemical Oxidation (MEO) is an aqueous process which destroys hazardous organics by oxidizing a mediator at the anode of an electrochemical cell; the mediator in turn oxidizes the organics within the bulk of the electrolyte. With this process organics can be nearly completely destroyed, that is, the carbon and hydrogen present in the hydrocarbon are almost entirely mineralized to carbon dioxide and water. The MEO process is also capable of dissolving radioactive materials, including difficult-to-dissolve compounds such as plutonium oxide. Hence, this process can treat mixed wastes, by destroying the hazardous organic components of the waste, and dissolving the radioactive components. The radioactive material can be recovered if desired, or disposed of as non-mixed radioactive waste. The process is inherently safe, since the hazardous and radioactive materials are completely contained in the aqueous phase, and the system operates at low temperatures (below 80 degree C) and at ambient pressures

  10. Electrochemical behaviour of silver in borate buffer solutions

    International Nuclear Information System (INIS)

    Zaky, Ayman M.; Assaf, Fawzi H.; Abd El Rehim, Sayed S.; Mohamed, Basheer

    2004-01-01

    The electrochemical behaviour of Ag in aqueous 0.15 M borax and 0.15 M boric acid buffer solution was studied under various conditions using cyclic voltammetry and potentiostatic techniques. It was found that the anodic polarization curve of Ag in borate buffer solution was characterized by the appearance of two potential regions, active and passive, prior to the oxygen evolution reaction. The active potential region was characterized by the appearance of three anodic peaks, the first two peaks A 1 and A 2 correspond to the oxidation of Ag and formation of [Ag(OH) 2 ] - soluble compound and a passive film of Ag 2 O on the electrode surface. The third anodic peak corresponds to the conversion of both [Ag(OH) 2 ] - and Ag 2 O to Ag 2 O 2 . X-ray diffraction patterns confirmed the existence of Ag 2 O and Ag 2 O 2 passive layers on the electrode surface potentiodynamically polarized up to 800 mV. Potentiostatic current transient measurements showed that the formation of Ag 2 O and Ag 2 O 2 involves a nucleation and growth mechanism under diffusion control

  11. Microstructural, mechanical and electrochemical behaviour of a 7017 Al–Zn–Mg alloy of different tempers

    Energy Technology Data Exchange (ETDEWEB)

    Rout, Prasanta Kumar, E-mail: prasantonnet55@yahoo.com; Ghosh, M.M.; Ghosh, K.S., E-mail: ksghosh2001@yahoo.co.uk

    2015-06-15

    The aim of the investigation is to assess the microstructural features and associated physical, mechanical and electrochemical properties of a 7017 Al–Zn–Mg alloy of various tempers. A 7017 Al–Zn–Mg alloy was subjected to different ageing schedules to produce under-(T4), peak-(T6), over-(T7) and highly over-aged tempers. Optical microscopy, hardness measurement, electrical conductivity measurement, tensile testing and SEM fractographs, differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and electrochemical polarization studies have been used to characterize the alloy tempers. Hardness measurement and tensile testing showed the characteristic age hardening phenomenon of aluminium alloys. Optical and TEM micrographs have revealed the variation in size of matrix strengthening η′ (MgZn{sub 2}) and also the size and distribution of grain boundary η (MgZn{sub 2}) precipitate with ageing time. DSC thermograms exhibiting exothermic and endothermic peaks indicated the characteristic solid state reaction sequence of the 7017 alloy. Potentiodynamic polarization study of the 7017 alloy of various tempers in 3.5 wt.% NaCl solution at near neutral pH showed typical active metal dissolution behaviour, but at pH 12 an active–passive–transpassive transition behaviour has been observed. - Graphical abstract: TEM micrograph of the 7017 aluminium alloy of various tempers (a, b) under aged (T4), (c, d) peak aged (T6), (e, f) over aged (T7) and (g, h) highly over-aged. Display Omitted - Highlights: • 7017 Al-Zn-Mg alloy was subjected to different artificial ageing treatments. • Characterization of 7017 alloy tempers by hardness, tensile, DSC, TEM and electrochemical behaviour. • Structure-properties relationship of the 7017 Al-Zn-Mg alloy of various tempers.

  12. Electrochemical fabrication of nanoporous polypyrrole thin films

    Energy Technology Data Exchange (ETDEWEB)

    Li Mei [Key Laboratory of Organic Optoelectronics and Molecular Engineering (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing, 100084 (China); Yuan Jinying [Key Laboratory of Organic Optoelectronics and Molecular Engineering (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing, 100084 (China)], E-mail: yuanjy@mail.tsinghua.edu.cn; Shi Gaoquan [Key Laboratory of Organic Optoelectronics and Molecular Engineering (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing, 100084 (China)], E-mail: gshi@mail.tsinghua.edu.cn

    2008-04-30

    Polypyrrole thin films with pores in nanometer scale were synthesized by direct electrochemical oxidation of pyrrole in a mixed electrolyte of isopropyl alcohol, boron trifluoride diethyl etherate, sodium dodecylsulfonate and poly(ethylene glycol) using well-aligned ZnO nanowires arrays as templates. The thin films exhibit high conductivity of ca. {sigma}{sub rt} {approx} 20.5 s/cm and can be driven to bend during redox processes in 1.0 M lithium perchlorate aqueous solution. The movement rate of an actuator based on this nanoporous film was measured to be over 90{sup o}/s at a driving potential of 0.8 V (vs. Ag/AgCl)

  13. Electrochemical fabrication of nanoporous polypyrrole thin films

    International Nuclear Information System (INIS)

    Li Mei; Yuan Jinying; Shi Gaoquan

    2008-01-01

    Polypyrrole thin films with pores in nanometer scale were synthesized by direct electrochemical oxidation of pyrrole in a mixed electrolyte of isopropyl alcohol, boron trifluoride diethyl etherate, sodium dodecylsulfonate and poly(ethylene glycol) using well-aligned ZnO nanowires arrays as templates. The thin films exhibit high conductivity of ca. σ rt ∼ 20.5 s/cm and can be driven to bend during redox processes in 1.0 M lithium perchlorate aqueous solution. The movement rate of an actuator based on this nanoporous film was measured to be over 90 o /s at a driving potential of 0.8 V (vs. Ag/AgCl)

  14. Gamma radiation grafting process for preparing separator membranes for electrochemical cells

    International Nuclear Information System (INIS)

    Agostino, V.F. D'; Lee, J.Y.

    1982-01-01

    An irradiation grafting process for preparing separator membranes for use in electrochemical cells, comprises contacting a polymeric base film with an aqueous solution of a hydrophilic monomer and a polymerization retardant; and irradiating said contacted film to form a graft membrane having low electrical resistivity and having monomer molecules uniformly grafted thereon. In the examples (meth) acrylic acid is grafted on to polyethylene, polypropylene and polytetrafluoroethylene in the presence of ferrous sulphate or cupric sulphate as polymerization retardants. (author)

  15. Preparation and electrochemical capacitance performances of super-hydrophilic conducting polyaniline

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xingwei; Li, Xiaohan; Dai, Na; Wang, Gengchao; Wang, Zhun [Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai 200237 (China)

    2010-08-15

    Super-hydrophilic conducting polyaniline was prepared by surface modification of polyaniline using tetraethyl orthosilicate in water/ethanol solution, whereas its conductivity was 4.16 S cm{sup -1} at 25 C. And its electrochemical capacitance performances as an electrode material were evaluated by the cyclic voltammetry and galvanostatic charge/discharge test in 0.1 M H{sub 2}SO{sub 4} aqueous solution. Its initial specific capacitance was 500 F g{sup -1} at a constant current density of 1.5 A g{sup -1}, and the capacitance still reached about 400 F g{sup -1} after 5000 consecutive cycles. Moreover, its capacitance retention ratio was circa 70% with the growth of current densities from 1.5 to 20 A g{sup -1}, indicating excellent rate capability. It would be a promising electrode material for aqueous redox supercapacitors. (author)

  16. (Spectro) Electrochemical investigation of reduction mechanism of a new energetic molecule 2,2-dinitroethene-1,1-diamine (FOX-7) in aprotic solvents

    Czech Academy of Sciences Publication Activity Database

    Šimková, Ludmila; Dmitrieva, E.; Klíma, Jiří; Dunsch, L.; Ludvík, Jiří

    2015-01-01

    Roč. 19, č. 1 (2015), s. 103-112 ISSN 1432-8488 R&D Projects: GA ČR GA13-21704S Institutional support: RVO:61388955 Keywords : FOX -7 * electrochemical reduction * Autoprotonation mechanism Subject RIV: CG - Electrochemistry Impact factor: 2.327, year: 2015

  17. Recent results on aqueous electrolyte cells

    KAUST Repository

    Wessells, Colin

    2011-03-01

    The improved safety of aqueous electrolytes makes aqueous lithium-ion batteries an attractive alternative to commercial cells utilizing flammable and expensive organic electrolytes. Two important issues relating to their use have been addressed in this work. One is the extension of the usable voltage range by the incorporation of lithium salts, and the other is the investigation of a useful negative electrode reactant, LiTi 2(PO 4) 3. The electrochemical stability of aqueous lithium salt solutions containing two lithium salts, LiNO 3 and Li 2SO 4, has been characterized using a constant current technique. In both cases, concentrated solutions had effective electrolyte stability windows substantially greater than that of pure water under standard conditions. At an electrolyte leakage current of 10 μA cm -2 between two platinum electrodes in 5 M LiNO 3 the cell voltage can reach 2.0 V, whereas with a leakage current of 50 μA cm -2 it can reach 2.3 V. LiTi 2(PO 4) 3 was synthesized using a Pechini method and cycled in pH-neutral Li 2SO 4. At a reaction potential near the lower limit of electrolyte stability, an initial discharge capacity of 118 mAh g -1 was measured at a C/5 rate, while about 90% of this discharge capacity was retained after 100 cycles. This work demonstrates that it is possible to have useful aqueous electrolyte lithium-ion batteries using the LiTi 2(PO 4) 3 anode with cell voltages of 2 V and above. © 2010 Elsevier B.V. All rights reserved.

  18. Molecular Design of Semiconducting Polymers for High-Performance Organic Electrochemical Transistors

    KAUST Repository

    Nielsen, Christian B.

    2016-07-22

    The organic electrochemical transistor (OECT), capable of transducing small ionic fluxes into electronic signals in an aqueous envi-ronment, is an ideal device to utilize in bioelectronic applications. Currently, most OECTs are fabricated with commercially availa-ble conducting poly(3,4-ethylenedioxythiophene) (PEDOT)-based suspensions and are therefore operated in depletion mode. Here, we present a series of semiconducting polymers designed to elucidate important structure-property guidelines required for accumulation mode OECT operation. We discuss key aspects relating to OECT performance such as ion and hole transport, elec-trochromic properties, operational voltage and stability. The demonstration of our molecular design strategy is the fabrication of accumulation mode OECTs that clearly outperform state-of-the-art PEDOT based devices, and show stability under aqueous oper-ation without the need for formulation additives and cross-linkers.

  19. Machinability of a Stainless Steel by Electrochemical Discharge Microdrilling

    International Nuclear Information System (INIS)

    Coteata, Margareta; Pop, Nicolae; Slatineanu, Laurentiu; Schulze, Hans-Peter; Besliu, Irina

    2011-01-01

    Due to the chemical elements included in their structure for ensuring an increased resistance to the environment action, the stainless steels are characterized by a low machinability when classical machining methods are applied. For this reason, sometimes non-traditional machining methods are applied, one of these being the electrochemical discharge machining. To obtain microholes and to evaluate the machinability by electrochemical discharge microdrilling, test pieces of stainless steel were used for experimental research. The electrolyte was an aqueous solution of sodium silicate with different densities. A complete factorial plan was designed to highlight the influence of some input variables on the sizes of the considered machinability indexes (electrode tool wear, material removal rate, depth of the machined hole). By mathematically processing of experimental data, empirical functions were established both for stainless steel and carbon steel. Graphical representations were used to obtain more suggestive vision concerning the influence exerted by the considered input variables on the size of the machinability indexes.

  20. Kelvin probe force microscopy in liquid using electrochemical force microscopy

    Directory of Open Access Journals (Sweden)

    Liam Collins

    2015-01-01

    Full Text Available Conventional closed loop-Kelvin probe force microscopy (KPFM has emerged as a powerful technique for probing electric and transport phenomena at the solid–gas interface. The extension of KPFM capabilities to probe electrostatic and electrochemical phenomena at the solid–liquid interface is of interest for a broad range of applications from energy storage to biological systems. However, the operation of KPFM implicitly relies on the presence of a linear lossless dielectric in the probe–sample gap, a condition which is violated for ionically-active liquids (e.g., when diffuse charge dynamics are present. Here, electrostatic and electrochemical measurements are demonstrated in ionically-active (polar isopropanol, milli-Q water and aqueous NaCl and ionically-inactive (non-polar decane liquids by electrochemical force microscopy (EcFM, a multidimensional (i.e., bias- and time-resolved spectroscopy method. In the absence of mobile charges (ambient and non-polar liquids, KPFM and EcFM are both feasible, yielding comparable contact potential difference (CPD values. In ionically-active liquids, KPFM is not possible and EcFM can be used to measure the dynamic CPD and a rich spectrum of information pertaining to charge screening, ion diffusion, and electrochemical processes (e.g., Faradaic reactions. EcFM measurements conducted in isopropanol and milli-Q water over Au and highly ordered pyrolytic graphite electrodes demonstrate both sample- and solvent-dependent features. Finally, the feasibility of using EcFM as a local force-based mapping technique of material-dependent electrostatic and electrochemical response is investigated. The resultant high dimensional dataset is visualized using a purely statistical approach that does not require a priori physical models, allowing for qualitative mapping of electrostatic and electrochemical material properties at the solid–liquid interface.

  1. Electrochemical corrosion potential and noise measurement in high temperature water

    International Nuclear Information System (INIS)

    Fong, Clinton; Chen, Yaw-Ming; Chu, Fang; Huang, Chia-Shen

    2000-01-01

    Hydrogen water chemistry (HWC) is one of the most important methods in boiling water reactor(BWR) system to mitigate and prevent stress corrosion cracking (SCC) problems of stainless steel components. Currently, the effectiveness of HWC in each BWR is mainly evaluated by the measurement of electrochemical corrosion potentials (ECP) and on-line monitoring of SCC behaviors of stainless steels. The objective of this work was to evaluate the characteristics and performance of commercially available high temperature reference electrodes. In addition, SCC monitoring technique based on electrochemical noise analysis (ECN) was also tested to examine its crack detection capability. The experimental work on electrochemical corrosion potential (ECP) measurements reveals that high temperature external Ag/AgCl reference electrode of highly dilute KCl electrolyte can adequately function in both NWC and HWC environments. The high dilution external Ag/AgCl electrode can work in conjunction with internal Ag/AgCl reference electrode, and Pt electrode to ensure the ECP measurement reliability. In simulated BWR environment, the electrochemical noise tests of SCC were carried out with both actively and passively loaded specimens of type 304 stainless steel with various electrode arrangements. From the coupling current and corrosion potential behaviors of the passive loading tests during immersion test, it is difficult to interpret the general state of stress corrosion cracking based on the analytical results of overall current and potential variations, local pulse patterns, statistical characteristics, or power spectral density of electrochemical noise signals. However, more positive SCC indication was observed in the power spectral density analysis. For aqueous environments of high solution impedance, successful application of electrochemical noise technique for SCC monitoring may require further improvement in specimen designs and analytical methods to enhance detection sensitivity

  2. Correlation among physical and electrochemical behaviour of nanostructured electrolytic manganese dioxide from leach liquor and synthetic for aqueous asymmetric capacitor.

    Science.gov (United States)

    Minakshi Sundaram, Manickam; Biswal, Avijit; Mitchell, David; Jones, Rob; Fernandez, Carlos

    2016-02-14

    An attempt has been made to correlate the differences in structural parameters, surface areas, morphology etc. with the electrochemical capacitive behaviour of the EMDs. The nanostructured electrolytic manganese dioxides (EMD) have been synthesized through electrodepositing MnO2 from two different leach liquors and a synthetic analogue thereof. The structural and chemical state was determined using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) respectively. Multiplet structure determination led to estimates of the manganese valence states present in the EMD. The EMDs have been tested in an asymmetric capacitor which we have developed. This used activated carbon as the negative electrode and the various EMDs as the positive electrode. Aqueous 2 M NaOH solution was used as the electrolyte. The capacitor achieved 1.6 V corresponding to a capacitance of ∼50 F g(-1) of the EMDs from leach liquors. The EMD derived from the synthetic solution showed an inferior capacitance of 25 F g(-1). Extended cycling (2000 cycles), showed 100% capacity retention was achieved for one EMD produced from the leach liquor derived from low-grade manganese ore/residue. This outstanding capacitor performance was correlated with the presence of a nanofibrous morphology. These findings open up the possibility of extracting a high performance EMD product from a low cost, low-grade source of manganese.

  3. A new approach of the understanding of sulfur dioxide reduction in non-aqueous solvent; Une nouvelle approche de la comprehension de la reduction du dioxyde de soufre en solvant non aqueux

    Energy Technology Data Exchange (ETDEWEB)

    Potteau, E.; Levillain, E.; Lelieur, J.P. [Laboratoire de Spectrochimie Infrarouge et Raman (LASIR, UPR 2631 CNRS) Haute Etudes Industrielles (HEI), 59 - Lille (France)

    1996-12-31

    The study of SO{sub 2} reduction in non-aqueous solvent can help to understand the functioning of Li/SO{sub 2} batteries and to find a simpler way for the synthesis of Li{sub 2}S{sub 2}O{sub 4} dithionite. This paper presents the results of electrochemical studies (cycle volt-amperometry in semi-infinite and thin film diffusion conditions, visible spectro-electrochemistry) and spectroscopic studies (UV, visible and RPE) performed on SO{sub 2} solutions. A mechanism of SO{sub 2} reduction is proposed and discussed. (J.S.) 18 refs.

  4. A new approach of the understanding of sulfur dioxide reduction in non-aqueous solvent; Une nouvelle approche de la comprehension de la reduction du dioxyde de soufre en solvant non aqueux

    Energy Technology Data Exchange (ETDEWEB)

    Potteau, E; Levillain, E; Lelieur, J P [Laboratoire de Spectrochimie Infrarouge et Raman (LASIR, UPR 2631 CNRS) Haute Etudes Industrielles (HEI), 59 - Lille (France)

    1997-12-31

    The study of SO{sub 2} reduction in non-aqueous solvent can help to understand the functioning of Li/SO{sub 2} batteries and to find a simpler way for the synthesis of Li{sub 2}S{sub 2}O{sub 4} dithionite. This paper presents the results of electrochemical studies (cycle volt-amperometry in semi-infinite and thin film diffusion conditions, visible spectro-electrochemistry) and spectroscopic studies (UV, visible and RPE) performed on SO{sub 2} solutions. A mechanism of SO{sub 2} reduction is proposed and discussed. (J.S.) 18 refs.

  5. Recent Advances in Electrochemical Glycobiosensing

    Directory of Open Access Journals (Sweden)

    Germarie Sánchez-Pomales

    2011-01-01

    Full Text Available Biosensors based on electrochemical transduction mechanisms have recently made advances into the field of glycan analysis. These glyco-biosensors offer simple, rapid, sensitive, and economical approaches to the measurement need for rapid glycan analysis for biomarker detection, cancer and disease diagnostics, and bioprocess monitoring of therapeutic glycoproteins. Although the prevalent methods of glycan analysis (high-performance liquid chromatography, mass spectrometry, and nuclear magnetic resonance spectroscopy provide detailed identification and structural analysis of glycan species, there are significantly few low-cost, rapid glycan assays available for diagnostic and screening applications. Here we review instances in which glyco-biosensors have been used for glycan analysis using a variety of electrochemical transduction mechanisms (e.g., amperometric, potentiometric, impedimetric, and voltammetric, selective binding agents (e.g., lectins and antibodies, and redox species (e.g., enzyme substrates, inorganic, and nanomaterial.

  6. Electrochemistry of actinide on electrochemically reduced graphene oxide: Electrocatalysis of Np(VI)O22+/Np(V)O2+ in nitric acid solution

    International Nuclear Information System (INIS)

    Ambolikar, Arvind S.; Guin, Saurav K.; Kasar, U.M.; Kamat, J.V.

    2015-01-01

    Highlights: • First report of aqueous electrochemistry of neptunium on electrochemically reduced graphene oxide (ERGNO). • First report on the electrochemical impedance spectroscopy of Np (VI) O 2 2+ /Np (V) O 2 + . • The electrochemical reversibility of Np (VI) O 2 2+ /Np (V) O 2 + redox couple improves on ERGNO compared to GC. • ERGNO shows higher sensitivity for the determination of Np compared to bare GC electrode. • The efficiency of detection of Np by ERGNO is improved by virtue of the electrocatalysis. - Abstract: Driven by the academic interest, we have studied the aqueous electrochemistry of neptunium (Np) in 1 M nitric acid solution on the electrochemically reduced graphene oxide (ERGNO) modified glassy carbon (GC) electrode. Similar to our previous experiences on the electrocatalytic action of ERGNO on the electrochemistry of uranium(VI)/uranium(IV) and plutonium(IV)/plutonium(III) redox couples, the present study confirms the robust electrocatalytic ability of ERGNO for the redox reaction of Np (VI) O 2 2+ /Np (V) O 2 + in acidic solution even at high anodic working potentials. The extent of the electrochemical reversibility of Np (VI) O 2 2+ /Np (V) O 2 + redox couple increases on ERGNO compared to the bare GC electrode. For the first time, the electron transfer reaction of Np (VI) O 2 2+ /Np (V) O 2 + redox couple is investigated by electrochemical impedance spectroscopy. The improved sensitivity as well as the lower limit of detection of Np by anodic square wave voltammetry on ERGNO compared to bare GC opens up the application of ERGNO in the nuclear science and technology.

  7. 3D printed stretchable capacitive sensors for highly sensitive tactile and electrochemical sensing

    Science.gov (United States)

    Li, Kai; Wei, Hong; Liu, Wenguang; Meng, Hong; Zhang, Peixin; Yan, Chaoyi

    2018-05-01

    Developments of innovative strategies for the fabrication of stretchable sensors are of crucial importance for their applications in wearable electronic systems. In this work, we report the successful fabrication of stretchable capacitive sensors using a novel 3D printing method for highly sensitive tactile and electrochemical sensing applications. Unlike conventional lithographic or templated methods, the programmable 3D printing technique can fabricate complex device structures in a cost-effective and facile manner. We designed and fabricated stretchable capacitive sensors with interdigital and double-vortex designs and demonstrated their successful applications as tactile and electrochemical sensors. Especially, our stretchable sensors exhibited a detection limit as low as 1 × 10-6 M for NaCl aqueous solution, which could have significant potential applications when integrated in electronics skins.

  8. Parabens abatement from surface waters by electrochemical advanced oxidation with boron doped diamond anodes.

    Science.gov (United States)

    Domínguez, Joaquín R; Muñoz-Peña, Maria J; González, Teresa; Palo, Patricia; Cuerda-Correa, Eduardo M

    2016-10-01

    The removal efficiency of four commonly-used parabens by electrochemical advanced oxidation with boron-doped diamond anodes in two different aqueous matrices, namely ultrapure water and surface water from the Guadiana River, has been analyzed. Response surface methodology and a factorial, composite, central, orthogonal, and rotatable (FCCOR) statistical design of experiments have been used to optimize the process. The experimental results clearly show that the initial concentration of pollutants is the factor that influences the removal efficiency in a more remarkable manner in both aqueous matrices. As a rule, as the initial concentration of parabens increases, the removal efficiency decreases. The current density also affects the removal efficiency in a statistically significant manner in both aqueous matrices. In the water river aqueous matrix, a noticeable synergistic effect on the removal efficiency has been observed, probably due to the presence of chloride ions that increase the conductivity of the solution and contribute to the generation of strong secondary oxidant species such as chlorine or HClO/ClO - . The use of a statistical design of experiments made it possible to determine the optimal conditions necessary to achieve total removal of the four parabens in ultrapure and river water aqueous matrices.

  9. Studies on electrochemical hydrodebromination mechanism of 2,5-dibromobenzoic acid on Ag electrode by in situ FTIR spectroscopy

    International Nuclear Information System (INIS)

    Li Meichao; Bao Dandan; Ma Chunan

    2011-01-01

    Research highlights: → Silver is a good catalyst for the hydrodebromination of 2,5-dibromobenzoic acid. → 3-Bromobenzoic acid as main intermediate product. → The finally product is benzoic acid. → In situ FTIR is useful to study the electrochemical hydrodebromination mechanism. - Abstract: Cyclic voltammetry and in situ FTIR were employed to study the electrochemical hydrodebromination (EHB) mechanism of 2,5-dibromobenzoic acid (2,5-DBBA) in NaOH solution. Compared with titanium and graphite electrodes, silver electrode exhibited a high electrocatalytic activity for the hydrodebromination reaction of 2,5-DBBA. On the basis of in situ FTIR data, EHB reaction of 2,5-DBBA on Ag cathode might be represented as a sequence of electron additions and bromine expulsions. Firstly, from potential at approximately -1100 mV, 2,5-DBBA received an electron to form 2,5-DBBA radical anion, which lost a bromine ion in the 2-position to form 3-bromobenzoic acid (3-BBA) free radical. Then the free radical received a proton to give 3-BBA. Finally, 3-BBA further took off another bromine ion to produce benzoic acid free radical and the end product benzoic acid was obtained by receiving another electron and a proton with the potential shifting to more negative values.

  10. Electrochemical impedance spectroscopy of fully hydrated Nafion membranes at high and low hydrogen partial pressures

    International Nuclear Information System (INIS)

    Tsampas, M.N.; Brosda, S.; Vayenas, C.G.

    2011-01-01

    The proton transport mechanism in fully hydrated Nafion 117 membranes was examined via electrochemical impedance spectroscopy (EIS) and steady-state current–potential measurements both in a symmetric H 2 , Pt|Nafion|Pt, H 2 cell and in a H 2 , Pt|Nafion|Pt, air PEM fuel cell with hydrogen partial pressure values, P H 2 , varied between 0.5 kPa and 100 kPa. In agreement with recent studies it is found that for low P H 2 values the steady-state current–potential curves exhibit bistability and regions of positive slope. In these regions the Nyquist plots are found to exhibit negative real part impedance with a large imaginary component, while the Bode plots show a pronounced negative phase shift. These observations are consistent with the mechanism involving two parallel routes of proton conduction in fully hydrated Nafion membranes, one due to proton migration in the aqueous phase, the other due to proton transfer, probably involving tunneling, between adjacent sulfonate groups in narrow pores. The former mechanism dominates at high P H 2 values and the latter dominates in the low P H 2 region where the real part of the impedance is negative.

  11. Piezo-Electrochemical Energy Harvesting with Lithium-Intercalating Carbon Fibers.

    Science.gov (United States)

    Jacques, Eric; Lindbergh, Göran; Zenkert, Dan; Leijonmarck, Simon; Kjell, Maria Hellqvist

    2015-07-01

    The mechanical and electrochemical properties are coupled through a piezo-electrochemical effect in Li-intercalated carbon fibers. It is demonstrated that this piezo-electrochemical effect makes it possible to harvest electrical energy from mechanical work. Continuous polyacrylonitrile-based carbon fibers that can work both as electrodes for Li-ion batteries and structural reinforcement for composites materials are used in this study. Applying a tensile force to carbon fiber bundles used as Li-intercalating electrodes results in a response of the electrode potential of a few millivolts which allows, at low current densities, lithiation at higher electrode potential than delithiation. More electrical energy is thereby released from the cell at discharge than provided at charge, harvesting energy from the mechanical work of the applied force. The measured harvested specific electrical power is in the order of 1 μW/g for current densities in the order of 1 mA/g, but this has a potential of being increased significantly.

  12. One step paired electrochemical synthesis of iron and iron oxide nanoparticles

    Directory of Open Access Journals (Sweden)

    Ordoukhanian Juliet

    2016-09-01

    Full Text Available In this study, a new one step paired electrochemical method is developed for simultaneous synthesis of iron and iron oxide nanoparticles. iron and iron oxide are prepared as cathodic and anodic products from iron (ii sulfate aqueous solution in a membrane divided electrolytic cell by the pulsed current electrosynthesis. Because of organic solvent-free and electrochemical nature of the synthesis, the process could be considered as green and environmentally friendly. The reduction of energy consumption and low cost are the other significant advantages of this new method that would have a great application potential in the chemical industry. The nanostructure of prepared samples was characterized by Fourier transform infrared spectroscopy (FT-IR, X-ray diffraction (XRD, scanning electron microscopy (SEM and transmission electron microscopy (TEM. The magnetic properties were studied by vibrating sample magnetometer (VsM.

  13. Disease-Related Detection with Electrochemical Biosensors: A Review.

    Science.gov (United States)

    Huang, Ying; Xu, Jin; Liu, Junjie; Wang, Xiangyang; Chen, Bin

    2017-10-17

    Rapid diagnosis of diseases at their initial stage is critical for effective clinical outcomes and promotes general public health. Classical in vitro diagnostics require centralized laboratories, tedious work and large, expensive devices. In recent years, numerous electrochemical biosensors have been developed and proposed for detection of various diseases based on specific biomarkers taking advantage of their features, including sensitivity, selectivity, low cost and rapid response. This article reviews research trends in disease-related detection with electrochemical biosensors. Focus has been placed on the immobilization mechanism of electrochemical biosensors, and the techniques and materials used for the fabrication of biosensors are introduced in details. Various biomolecules used for different diseases have been listed. Besides, the advances and challenges of using electrochemical biosensors for disease-related applications are discussed.

  14. Cyclic voltammetric study of tin hexacyanoferrate for aqueous battery applications

    Directory of Open Access Journals (Sweden)

    Denys Gromadskyi

    2016-09-01

    Full Text Available A hybrid composite containing 65 mass % of tin hexacyanoferrate mixed with 35 mass % of carbon nanotubes has been synthesized and its electrochemical behavior as a negative electrode in alkali metal-ion batteries has been studied in 1 mol L-1 aqueous solution of sodium sulfate. The specific capacity of pure tin hexacyanoferrate is 58 mAh g-1, whereas the specific capacity normalized per total electrode mass of the composite studied reaches 34 mAh g-1. The estimated maximal specific power of an aqueous alkali-metal ion battery with a tin hexacyanoferrate electrode is ca. 3.6 kW kg-1 being comparable to characteristics of industrial electric double-layer capacitors. The maximal specific energy accumulated by this battery may reach 25.6 Wh kg-1 at least three times exceeding the specific energy for supercapacitors.

  15. Electrochemical Oxidation of EDTA in Nuclear Wastewater Using Platinum Supported on Activated Carbon Fibers

    Science.gov (United States)

    Zhao, Bo; Zhu, Wenkun; Mu, Tao; Hu, Zuowen; Duan, Tao

    2017-01-01

    A novel Pt/ACF (Pt supported on activated carbon fibers) electrode was successfully prepared with impregnation and electrodeposition method. Characterization of the electrodes indicated that the Pt/ACF electrode had a larger effective area and more active sites. Electrochemical degradation of ethylenediaminetetra-acetic acid (EDTA) in aqueous solution with Pt/ACF electrodes was investigated. The results showed that the 3% Pt/ACF electrode had a better effect on EDTA removal. The operational parameters influencing the electrochemical degradation of EDTA with 3% Pt/ACF electrode were optimized and the optimal removal of EDTA and chemical oxygen demand (COD) were 94% and 60% after 100 min on condition of the electrolyte concentration, initial concentration of EDTA, current density and initial value of pH were 0.1 mol/L, 300 mg/L, 40 mA/cm2 and 5.0, respectively. The degradation intermediates of EDTA in electrochemical oxidation with 3% Pt/ACF electrode were identified by gas chromatography-mass spectrum (GC-MS). PMID:28754016

  16. Synthesis and electrochemical properties of MnO2 nanorods/graphene composites for supercapacitor applications

    International Nuclear Information System (INIS)

    Deng, SiXu; Sun, Dan; Wu, ChunHui; Wang, Hao; Liu, JingBing; Sun, YuXiu; Yan, Hui

    2013-01-01

    MnO 2 nanorods/graphene composite materials have been fabricated using a facile hydrothermal method for supercapacitor applications. The prepared composite materials are characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and transmission electron microscope (TEM). Electrochemical performances are evaluated using cyclic voltammetry (CV), galvanostatic charge–discharge and electrochemical impedance spectrometry (EIS). It indicates that ratio of MnO 2 nanorods to graphene in composite materials has significant influence on the electrochemical performance of composite electrodes. We have achieved the maximum specific capacitance of 218 F g −1 at the scan rate of 5 mV s −1 in 1 M Na 2 SO 4 aqueous solution. Additionally, MnO 2 nanorods/graphene composite materials exhibit highest energy density of 16 Wh kg −1 at power density of 95 W kg −1 and excellent capacitance retention with no more than 6% capacitance loss after 1000 cycles at the most favorable composites ratio

  17. Electrochemical Oxidation of EDTA in Nuclear Wastewater Using Platinum Supported on Activated Carbon Fibers.

    Science.gov (United States)

    Zhao, Bo; Zhu, Wenkun; Mu, Tao; Hu, Zuowen; Duan, Tao

    2017-07-21

    A novel Pt/ACF (Pt supported on activated carbon fibers) electrode was successfully prepared with impregnation and electrodeposition method. Characterization of the electrodes indicated that the Pt/ACF electrode had a larger effective area and more active sites. Electrochemical degradation of ethylenediaminetetra-acetic acid (EDTA) in aqueous solution with Pt/ACF electrodes was investigated. The results showed that the 3% Pt/ACF electrode had a better effect on EDTA removal. The operational parameters influencing the electrochemical degradation of EDTA with 3% Pt/ACF electrode were optimized and the optimal removal of EDTA and chemical oxygen demand (COD) were 94% and 60% after 100 min on condition of the electrolyte concentration, initial concentration of EDTA, current density and initial value of pH were 0.1 mol/L, 300 mg/L, 40 mA/cm² and 5.0, respectively. The degradation intermediates of EDTA in electrochemical oxidation with 3% Pt/ACF electrode were identified by gas chromatography-mass spectrum (GC-MS).

  18. Highly Durable Na2V6O16·1.63H2O Nanowire Cathode for Aqueous Zinc-Ion Battery.

    Science.gov (United States)

    Hu, Ping; Zhu, Ting; Wang, Xuanpeng; Wei, Xiujuan; Yan, Mengyu; Li, Jiantao; Luo, Wen; Yang, Wei; Zhang, Wencui; Zhou, Liang; Zhou, Zhiqiang; Mai, Liqiang

    2018-03-14

    Rechargeable aqueous zinc-ion batteries are highly desirable for grid-scale applications due to their low cost and high safety; however, the poor cycling stability hinders their widespread application. Herein, a highly durable zinc-ion battery system with a Na 2 V 6 O 16 ·1.63H 2 O nanowire cathode and an aqueous Zn(CF 3 SO 3 ) 2 electrolyte has been developed. The Na 2 V 6 O 16 ·1.63H 2 O nanowires deliver a high specific capacity of 352 mAh g -1 at 50 mA g -1 and exhibit a capacity retention of 90% over 6000 cycles at 5000 mA g -1 , which represents the best cycling performance compared with all previous reports. In contrast, the NaV 3 O 8 nanowires maintain only 17% of the initial capacity after 4000 cycles at 5000 mA g -1 . A single-nanowire-based zinc-ion battery is assembled, which reveals the intrinsic Zn 2+ storage mechanism at nanoscale. The remarkable electrochemical performance especially the long-term cycling stability makes Na 2 V 6 O 16 ·1.63H 2 O a promising cathode for a low-cost and safe aqueous zinc-ion battery.

  19. Enhancement of the electrochemical behaviour and biological performance of Ti–25Ta–5Zr alloy by thermo-mechanical processing

    Energy Technology Data Exchange (ETDEWEB)

    Cimpean, Anisoara [Department of Biochemistry and Molecular Biology, University of Bucharest, Spl. Independentei, 91-95, 050095 Bucharest (Romania); Vasilescu, Ecaterina; Drob, Paula [Department of Electrochemistry and Corrosion, Institute of Physical Chemistry “Ilie Murgulescu” of Romanian Academy, Spl. Independentei 202, 060021 Bucharest (Romania); Cinca, Ion, E-mail: ion_cinca@hotmail.com [Faculty of Material Science and Engineering, Politehnica University, Spl. Independentei 313, 060042 Bucharest (Romania); Vasilescu, Cora; Anastasescu, Mihai [Department of Electrochemistry and Corrosion, Institute of Physical Chemistry “Ilie Murgulescu” of Romanian Academy, Spl. Independentei 202, 060021 Bucharest (Romania); Mitran, Valentina [Department of Biochemistry and Molecular Biology, University of Bucharest, Spl. Independentei, 91-95, 050095 Bucharest (Romania); Drob, Silviu Iulian [Department of Electrochemistry and Corrosion, Institute of Physical Chemistry “Ilie Murgulescu” of Romanian Academy, Spl. Independentei 202, 060021 Bucharest (Romania)

    2014-05-01

    A new Ti–25Ta–5Zr alloy based only on non-toxic and non-allergic elements was elaborated in as-cast and thermo-mechanical processed, recrystallized states (XRD and SEM) in order to be used as candidate material for implant applications. Its long-term interactions with Ringer–Brown and Ringer solutions of different pH values and its cytocompatibility were determined. The thermo-mechanically processed alloy has nobler electrochemical behaviour than as-cast alloy due to finer microstructure obtained after the applied treatment. Corrosion and ion release rates presented the lowest values for the treated alloy. Nyquist and Bode plots displayed higher impedance values and phase angles for the processed alloy, denoting a more protective passive film. SEM micrographs revealed depositions from solutions that contain calcium, phosphorous and oxygen ions (EDX analysis), namely calcium phosphate. An electric equivalent circuit with two time constants was modelled. Cell culture experiments with MC3T3-E1 pre-osteoblasts demonstrated that thermo-mechanically processed Ti–25Ta–5Zr alloy supports a better cell adhesion and spreading, and enhanced cell proliferation. Altogether, these data indicate that thermo-mechanical treatment endows the alloy with improved anticorrosion and biological performances. - Highlights: • Ti–25Ta–5Zr alloy exhibited noble electrochemical, passive behaviour in simulated biofluids. • An electric equivalent circuit with two time constants was modelled. • Corrosion rates show the lowest values for the recrystallized Ti–25Ta–5Zr alloy. • In vitro tests revealed good cytocompatibility of as-cast and processed alloy. • Recrystallized treatment endows the alloy with superior biological performances.

  20. Enhancement of the electrochemical behaviour and biological performance of Ti–25Ta–5Zr alloy by thermo-mechanical processing

    International Nuclear Information System (INIS)

    Cimpean, Anisoara; Vasilescu, Ecaterina; Drob, Paula; Cinca, Ion; Vasilescu, Cora; Anastasescu, Mihai; Mitran, Valentina; Drob, Silviu Iulian

    2014-01-01

    A new Ti–25Ta–5Zr alloy based only on non-toxic and non-allergic elements was elaborated in as-cast and thermo-mechanical processed, recrystallized states (XRD and SEM) in order to be used as candidate material for implant applications. Its long-term interactions with Ringer–Brown and Ringer solutions of different pH values and its cytocompatibility were determined. The thermo-mechanically processed alloy has nobler electrochemical behaviour than as-cast alloy due to finer microstructure obtained after the applied treatment. Corrosion and ion release rates presented the lowest values for the treated alloy. Nyquist and Bode plots displayed higher impedance values and phase angles for the processed alloy, denoting a more protective passive film. SEM micrographs revealed depositions from solutions that contain calcium, phosphorous and oxygen ions (EDX analysis), namely calcium phosphate. An electric equivalent circuit with two time constants was modelled. Cell culture experiments with MC3T3-E1 pre-osteoblasts demonstrated that thermo-mechanically processed Ti–25Ta–5Zr alloy supports a better cell adhesion and spreading, and enhanced cell proliferation. Altogether, these data indicate that thermo-mechanical treatment endows the alloy with improved anticorrosion and biological performances. - Highlights: • Ti–25Ta–5Zr alloy exhibited noble electrochemical, passive behaviour in simulated biofluids. • An electric equivalent circuit with two time constants was modelled. • Corrosion rates show the lowest values for the recrystallized Ti–25Ta–5Zr alloy. • In vitro tests revealed good cytocompatibility of as-cast and processed alloy. • Recrystallized treatment endows the alloy with superior biological performances

  1. Biosorption of Sr(II) from aqueous solutions using aerobic granules. Equilibrium and mechanisms

    International Nuclear Information System (INIS)

    Li Wang; Xiang Liu; Xiao-feng Chen; Duu-Jong Lee; Joo-Hwa Tay; Yi Zhang; Chun-li Wan

    2015-01-01

    Aqueous strontium biosorption using aerobic granules was investigated. Parameters affecting the biosorption were optimized, including initial pH, biomass dosage, temperature, and rotation speed. The equilibrium data were fitted using Langmuir and Freundlich models, and both could well describe the process (R 2 = 0.987 and 0.989, respectively). Ion exchange and water-desorption experiments were conducted, and ion exchange together with physical adsorption were found to be the main mechanisms. The aerobic granules were characterized with methods including scanning electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The results showed that surface complexation could also be involved in the Sr(II) biosorption. (author)

  2. Morphology and electrical properties of electrochemically synthesized pyrrole–formyl pyrrole copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Gholami, Mehrdad, E-mail: mehrdad897@um.edu.my [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Department of Chemistry, Marvdasht Branch, Islamic Azad University, P.O. Box 465, Marvdasht (Iran, Islamic Republic of); Nia, Pooria Moozarm, E-mail: pooriamn@yahoo.com [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Alias, Yatimah, E-mail: yatimah70@um.edu.my [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia)

    2015-12-01

    Graphical abstract: - Highlights: • The (Py–co-FPy) copolymer was synthesized electrochemically. • This copolymer has 1.6 times higher surface coverage compared to polypyrrole. • This copolymer showed 2.5 times lower resistance compared to polypyrrole. • The conjugated structure between Py and FPy causes enhancement of conductivity. • This conducting copolymer has a strong potential to be used in various applications. - Abstract: A direct electrochemical copolymerization of pyrrole–formyl pyrrole (Py–co-FPy) was carried out by oxidative copolymerization of formyl pyrrole and pyrrole in LiClO{sub 4} aqueous solution through galvanostatic method. The (Py–co-FPy) copolymer was characterized using Fourier-transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FESEM), energy-filtering transmission electron microscope (EFTEM), thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The FESEM images showed that the synthesized copolymer had a hollow whelk-like helixes structure, which justifies the enhancement of charge transportation through the copolymer film. Cyclic voltammetry studies revealed that the electrocatalytic activity of synthesized copolymer has improved and the surface coverage in copolymer enhanced 1.6 times compared to polypyrrole alone. Besides, (Py–co-FPy) copolymer showed 2.5 times lower electrochemical charge transfer resistance (R{sub ct}) value in impedance spectroscopy. Therefore, this copolymer has a strong potential to be used in several applications such as sensor applications.

  3. Enhanced electrochemical performances of PANI using redox additive of K{sub 4}[Fe(CN){sub 6}] in aqueous electrolyte for symmetric supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Shanmugavani, A.; Kaviselvi, S.; Sankar, K.Vijaya; Selvan, R.Kalai, E-mail: selvankram@buc.edu.in

    2015-02-15

    Highlights: • Effect of K{sub 4}[Fe(CN){sub 6}] in H{sub 2}SO{sub 4} studied on the electrochemical properties of PANI. • The polaron band – π* transition reveals the emeraldine salt (conductive) form. • CV curves exhibit quasi-reversible redox behavior. • Symmetric PANI SC shows 228 F g{sup −1} at 1 mA cm{sup −2} in K{sub 4}[Fe (CN){sub 6}] added 1 M H{sub 2}SO{sub 4}. • PANI-1 symmetric supercapacitor shows almost 100% of capacity retention. - Abstract: Polyaniline (PANI) particles were prepared by reflux assisted chemical oxidative polymerization method with the aid of ammonium per sulfate/ferric chloride as oxidants and HCl/H{sub 2}SO{sub 4} as the medium. Amorphous nature and the emeraldine state of PANI were revealed from X-ray diffraction and Fourier transform infrared analysis. Moreover, ultra violet–visible spectra attributes to the polaron band – π* transition of polyaniline. The scanning electron microscopic image shows that the particle size is in the range of 0.2–2 μm. The electrochemical performances of the material were investigated in 1 M H{sub 2}SO{sub 4} and 0.08 M K{sub 4}[Fe(CN){sub 6}] added 1 M H{sub 2}SO{sub 4} aqueous electrolytes. Cyclic voltammetry and galvanostatic charge–discharge studies were carried out to find its suitability as a supercapacitor electrode material. The charge discharge analysis of the fabricated symmetric supercapacitors revealed the fact that the electrolyte containing redox additive (0.08 M K{sub 4}[Fe(CN){sub 6}]) delivered an enhanced specific capacitance of 228 F g{sup −1} (∼912 F g{sup −1} for single electrode) than that of 1 M H{sub 2}SO{sub 4} (100 F g{sup −1}) at 1 mA cm{sup −2}. Further cycling stability is performed at 5 mA cm{sup −2} ensures the durability of the supercapacitor.

  4. Electrochemical and spectroscopic evidences of corrosion inhibition of bronze by a triazole derivative

    International Nuclear Information System (INIS)

    Dermaj, A.; Hajjaji, N.; Joiret, S.; Rahmouni, K.; Srhiri, A.; Takenouti, H.; Vivier, V.

    2007-01-01

    The electrochemical behavior of the bronze (Cu-8Sn in wt%) was investigated in 3% NaCl aqueous solution, in presence and in absence of a corrosion inhibitor, the 3-phenyl-1,2,4-triazole-5-thione (PTS). The inhibiting effect of the PTS was evidenced for concentrations higher than 1 mM for the cathodic process whereas its effect was clearly seen with a concentration as low as 0.1 mM for the anodic process. A significant positive shift of the corrosion potential was also observed, and its inhibiting effect increased with both its concentration and the immersion time of the sample. From voltammetry and electrochemical impedance spectroscopy experiments, the inhibiting efficiency of the PTS was found to be in the 94-99% range for 1 mM concentration. Scanning electron microscopy and X-ray energy dispersion analysis of the specimen surface show the presence of sulphur on the surface. Raman micro-spectrometry study confirms the protective effect of the PTS in aqueous solution through three types of interactions with the electrode, namely the adsorption of the inhibitor in a flat configuration, the formation of copper-thiol molecules, and when copper is released, the formation of a polymeric complex

  5. Treated Carbon Nanofibers for Storing Energy in Aqueous KOH

    Science.gov (United States)

    Firsich, David W.

    2004-01-01

    A surface treatment has been found to enhance the performances of carbon nanofibers as electrode materials for electrochemical capacitors in which aqueous solutions of potassium hydroxide are used as the electrolytes. In the treatment, sulfonic acid groups are attached to edge plane sites on carbon atoms. The treatment is applicable to a variety of carbon nanofibers, including fibrils and both single- and multiple-wall nanotubes. The reason for choosing nanofibers over powders and other forms of carbon is that nanofibers offer greater power features. In previous research, it was found that the surface treatment of carbon nanofibers increased energy-storage densities in the presence of acid electrolytes. Now, it has been found that the same treatment increases energy-storage densities of carbon nanofibers in the presence of alkaline electrolytes when the carbon is paired with a NiOOH electrode. This beneficial effect varies depending on the variety of carbon substrate to which it is applied. It has been conjectured that the sulfonic acid groups, which exist in a deprotonated state in aqueous KOH solutions, undergo reversible electro-chemical reactions that are responsible for the observed increases in energystorage capacities. The increases can be considerable: For example, in one case, nanofibers exhibited a specific capacitance of 34 Farads per gram before treatment and 172 Farads per gram (an increase of about 400 percent) after treatment. The most promising application of this development appears to lie in hybrid capacitors, which are devices designed primarily for storing energy. These devices are designed to be capable of (1) discharge at rates greater than those of batteries and (2) storing energy at densities approaching those of batteries. A hybrid capacitor includes one electrode like that of a battery and one electrode like that of an electrochemical capacitor. For example, a hybrid capacitor could contain a potassium hydroxide solution as the electrolyte

  6. Effect of porosity variation on the electrochemical behavior of vertically aligned multi-walled carbon nanotubes.

    Science.gov (United States)

    Raut, Akshay S; Parker, Charles B; Stoner, Brian R; Glass, Jeffrey T

    2012-06-01

    Electrochemical charge storage characteristics of vertically aligned multi-walled carbon nanotubes (MWCNTs) as a function of varying diameter and spacing are reported. It was observed that the specific capacitance of the MWCNTs increased as both diameter and inter-tube spacing decreased. The MWCNT films with 229 nm inter-MWCNT spacing exhibited specific capacitance of 228 F/g versus 70 F/g for 506 nm spacing, when tested in a non-aqueous electrolyte. Further, a trend in specific capacitance versus pore size is proposed. Coupled with previously reported trends observed in the sub-10 nm pore size regime, this is expected to offer better understanding of electrochemical behavior of porous carbon materials over a wide range of pore sizes.

  7. Fabrication of hematite (α-Fe{sub 2}O{sub 3}) nanoparticles using electrochemical deposition

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Qingling; Wang, Zuobin, E-mail: wangz@cust.edu.cn; Chai, Xiangyu; Weng, Zhankun; Ding, Ran; Dong, Litong

    2016-04-15

    Graphical abstract: - Highlights: • Cathodic electrochemical deposition proposed to fabricate hematite nanoparticles. • Hematite nanoparticles were fabricated on indium-tin-oxide coated glass substrates. • The size and shape of nanoparticles were determined by deposition conditions. • The nanoparticles were well decentralized for different potential applications. • Electrochemical deposition is a useful approach in fabricating nanoparticles. - Abstract: In this work, cathodic electrochemical deposition was proposed to fabricate reproducible and homogeneous hematite (α-Fe{sub 2}O{sub 3}) nanoparticles on indium-tin-oxide (ITO) films. The α-Fe{sub 2}O{sub 3} nanoparticles, which were quasi-hexagonally shaped, were deposited in an aqueous mixture of FeCl{sub 2} and FeCl{sub 3} at the temperatures 16.5 °C, 40 °C and 60 °C. The electrochemically deposited α-Fe{sub 2}O{sub 3} nanoparticles showed excellent stability and good crystallinity. The α-Fe{sub 2}O{sub 3} nanoparticles were characterized by Raman spectroscope and X-ray diffractometer (XRD). A scanning electron microscope (SEM) was used to measure the size and shape of the nanoparticles. The experiment results have shown that the size and shape of nanoparticles were determined by electrochemical deposition conditions including the deposition time, current density, reaction temperature and solution concentration. The proposed electrochemical deposition method has been proven to be a cost-effective, environment friendly and highly efficient approach in fabricating well decentralized α-Fe{sub 2}O{sub 3} nanoparticles for different potential applications.

  8. Water/ionic liquid/organic three-phase interfacial synthesis of coral-like polypyrrole toward enhanced electrochemical capacitance

    International Nuclear Information System (INIS)

    Hou Linrui; Yuan Changzhou; Li Diankai; Yang Long; Shen Laifa; Zhang Fang; Zhang Xiaogang

    2011-01-01

    Highlights: → Interfacial synthesis strategies are proposed to synthesize PPy samples. → Water/ionic liquid /organic three-phase interface for preparing coral-like PPy. → Coral-like PPy with more ordered structure and better electronic conductivity. → Coral-like PPy owns higher rate performance and better electrochemical stability. - Abstract: Two interfacial synthesis strategies are proposed to synthesize polypyrrole samples for electrochemical capacitors (ECs). In contrast to water/organic two-phase route, unique water/ionic liquid (IL)/organic three-phase interface strategy is first performed to prepare coral-like polypyrrole with even better electrochemical capacitance, where 1-Ethyl-3-methylimidazolium tetrafluoroborate IL, as a 'buffering zone', is set between the water and organic phases to control the morphology and micro-structure of the polypyrrole phase during polymerization. The polypyrrole synthesized by three-phase interfacial route owns more ordered structure, less charge transfer resistance and better electronic conductivity, compared with two-phase method, and delivers larger specific capacitance, higher rate performance and better electrochemical stability at large current densities in 3 M KCl aqueous electrolyte.

  9. Facile electrochemical synthesis of tellurium nanorods and their photoconductive properties

    Energy Technology Data Exchange (ETDEWEB)

    Li, H.H. [Center for Photon Manufacturing Science and Technology, School of Materials Science and Engineering, Jiangsu University, Zhenjiang - 212013 (China); Zhang, P. [Dongguan University of Technology, Dongguan-523808 (China); School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou - 510275 (China); Liang, C.L. [Instrumental Analysis and Research Center, SunYat-sen University, Guangzhou - 510275 (China); Yang, J. [School of Materials Science and Engineering, Jiangsu University, Zhenjiang - 212013 (China); Zhou, M. [Center for Photon Manufacturing Science and Technology, School of Materials Science and Engineering, Jiangsu University, Zhenjiang - 212013 (China); The State Key Laboratory of Tribology, Tsinghua University, Beijing - 10084 (China); Lu, X.H. [School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou - 510275 (China); Hope, G.A. [School of Biomolecular and Physical Sciences, Griffith University, Nathan - Qld 4111 (Australia)

    2012-10-15

    Tellurium nanorods have been successfully fabricated by template and surfactant-free electrochemical technique from an aqueous solution at room temperature. The as-prepared tellurium nanorods were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectrometry, UV-vis spectroscopy and photoluminescence spectroscopy. Films based on tellurium nanorods were constructed to study the photoresponse and I-V curves. These photoresponse measurements demonstrate that tellurium nanorods exhibited enhanced conductivity under illumination compared to in the dark measurement. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Corrosion detection of carbon steel in water/oil two phases environment by electrochemical noise analysis

    International Nuclear Information System (INIS)

    Gusmano, G.; Montesperelli, G.; De Grandis, A.

    1998-01-01

    The aim of this paper is to demonstrate the effectiveness of the electrochemical noise analysis to detect the onset of corrosion phenomena in a very high resistivity medium. Tests were carried out on carbon steel electrodes immersed in a water/mineral oil two phases environment with high concentration of CO 2 , different aqueous/organic phase ratio, sulphide content between 0 and 0.5 g/l and pH between 1 and 5. The evolution of corrosion phenomena were followed by collecting current and potential noise between three nominally identical electrodes. The noise data were analysed in the time and in the frequency domain. In spite of a great loss of sensitivity of the method with respect to tests performed in aqueous solution, the data indicate a good agreement between the standard deviations and the power level of power spectra density (PSD) of current and potential noise signals and corrosion rates by means of weight loss. The values of the PSD slope, indicate the form of corrosion. The effect of water/oil ratio, sulphide concentration and pH on the corrosion rate was determined. Finally two methods to increase the sensitivity of the electrochemical noise are proposed. (orig.)

  11. Microstructure and mechanical properties of friction welded AISI 1040/AISI 304L steels before and after electrochemical corrosion

    Energy Technology Data Exchange (ETDEWEB)

    Sarsilmaz, Furkan [Firat Univ., Elazig (Turkey). Dept. of Mechatronics Engineering; Kirik, Ihsan [Batman Univ. (Turkey); Ozdemir, Niyazi [Firat Univ., Elazig (Turkey)

    2018-03-01

    The aim of the present study is to investigate the effect of welding parameters both on the electrochemical corrosion behavior and tensile strength of pre- and post-electrochemical corrosion of friction welded dissimilar steels. The microstructural changes of AISI 1040/AISI 304L friction welded couples and also parent materials were analyzed by using scanning electron microscopy. The electrochemical behaviors of AISI1040/AISI304L joints were comparatively investigated by potentiodynamic polarization curve test and by electrochemical impedance spectra. Moreover, tensile strength experiments were carried out determining the behavior of friction welded joints of pre- and post-electrochemical corrosion and results indicated that the maximum tensile test value of the dissimilar welded pre-electrochemical corrosion was higher than those of post-electrochemical corrosion and was also very close to AISI 1040 parent material value.

  12. Disease-Related Detection with Electrochemical Biosensors: A Review

    Directory of Open Access Journals (Sweden)

    Ying Huang

    2017-10-01

    Full Text Available Rapid diagnosis of diseases at their initial stage is critical for effective clinical outcomes and promotes general public health. Classical in vitro diagnostics require centralized laboratories, tedious work and large, expensive devices. In recent years, numerous electrochemical biosensors have been developed and proposed for detection of various diseases based on specific biomarkers taking advantage of their features, including sensitivity, selectivity, low cost and rapid response. This article reviews research trends in disease-related detection with electrochemical biosensors. Focus has been placed on the immobilization mechanism of electrochemical biosensors, and the techniques and materials used for the fabrication of biosensors are introduced in details. Various biomolecules used for different diseases have been listed. Besides, the advances and challenges of using electrochemical biosensors for disease-related applications are discussed.

  13. Surface-treated commercially pure titanium for biomedical applications: Electrochemical, structural, mechanical and chemical characterizations

    International Nuclear Information System (INIS)

    Ogawa, Erika S.; Matos, Adaias O.; Beline, Thamara; Marques, Isabella S.V.; Sukotjo, Cortino; Mathew, Mathew T.; Rangel, Elidiane C.; Cruz, Nilson C.; Mesquita, Marcelo F.; Consani, Rafael X.

    2016-01-01

    Modified surfaces have improved the biological performance and biomechanical fixation of dental implants compared to machined (polished) surfaces. However, there is a lack of knowledge about the surface properties of titanium (Ti) as a function of different surface treatment. This study investigated the role of surface treatments on the electrochemical, structural, mechanical and chemical properties of commercial pure titanium (cp-Ti) under different electrolytes. Cp-Ti discs were divided into 6 groups (n = 5): machined (M—control); etched with HCl + H_2O_2 (Cl), H_2SO_4 + H_2O_2 (S); sandblasted with Al_2O_3 (Sb), Al_2O_3 followed by HCl + H_2O_2 (SbCl), and Al_2O_3 followed by H_2SO_4 + H_2O_2 (SbS). Electrochemical tests were conducted in artificial saliva (pHs 3; 6.5 and 9) and simulated body fluid (SBF—pH 7.4). All surfaces were characterized before and after corrosion tests using atomic force microscopy, scanning electron microscopy, energy dispersive microscopy, X-ray diffraction, surface roughness, Vickers microhardness and surface free energy. The results indicated that Cl group exhibited the highest polarization resistance (R_p) and the lowest capacitance (Q) and corrosion current density (I_c_o_r_r) values. Reduced corrosion stability was noted for the sandblasted groups. Acidic artificial saliva decreased the R_p values of cp-Ti surfaces and produced the highest I_c_o_r_r values. Also, the surface treatment and corrosion process influenced the surface roughness, Vickers microhardness and surface free energy. Based on these results, it can be concluded that acid-etching treatment improved the electrochemical stability of cp-Ti and all treated surfaces behaved negatively in acidic artificial saliva. - Highlights: • Characterization of surface treatment for biomedical implants was investigated. • Sandblasting reduced the corrosion stability of cp-Ti. • Acid etching is a promising dental implants surface treatment.

  14. Surface-treated commercially pure titanium for biomedical applications: Electrochemical, structural, mechanical and chemical characterizations

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, Erika S.; Matos, Adaias O.; Beline, Thamara [Department of Prosthodontics and Periodontology, Piracicaba Dental School, University of Campinas (UNICAMP), Av Limeira, 901, Piracicaba, São Paulo 13414-903 (Brazil); IBTN/Br—Institute of Biomaterials, Tribocorrosion and Nanomedicine—Brazilian Branch (Brazil); Marques, Isabella S.V. [Department of Prosthodontics and Periodontology, Piracicaba Dental School, University of Campinas (UNICAMP), Av Limeira, 901, Piracicaba, São Paulo 13414-903 (Brazil); Sukotjo, Cortino [Department of Restorative Dentistry, University of Illinois at Chicago, College of Dentistry, 801 S Paulina, Chicago, IL, USA, 60612 (United States); IBTN—Institute of Biomaterials, Tribocorrosion and Nanomedicine (United States); Mathew, Mathew T. [IBTN—Institute of Biomaterials, Tribocorrosion and Nanomedicine (United States); Department of Biomedical Sciences, University of Illinois, College of Medicine at Rockford, 1601 Parkview Avenue, Rockford, IL, USA, 61107 (United States); Rangel, Elidiane C.; Cruz, Nilson C. [IBTN/Br—Institute of Biomaterials, Tribocorrosion and Nanomedicine—Brazilian Branch (Brazil); Laboratory of Technological Plasmas, Engineering College, Univ Estadual Paulista (UNESP), Av Três de Março, 511, Sorocaba, São Paulo 18087-180 (Brazil); Mesquita, Marcelo F.; Consani, Rafael X. [Department of Prosthodontics and Periodontology, Piracicaba Dental School, University of Campinas (UNICAMP), Av Limeira, 901, Piracicaba, São Paulo 13414-903 (Brazil); and others

    2016-08-01

    Modified surfaces have improved the biological performance and biomechanical fixation of dental implants compared to machined (polished) surfaces. However, there is a lack of knowledge about the surface properties of titanium (Ti) as a function of different surface treatment. This study investigated the role of surface treatments on the electrochemical, structural, mechanical and chemical properties of commercial pure titanium (cp-Ti) under different electrolytes. Cp-Ti discs were divided into 6 groups (n = 5): machined (M—control); etched with HCl + H{sub 2}O{sub 2} (Cl), H{sub 2}SO{sub 4} + H{sub 2}O{sub 2} (S); sandblasted with Al{sub 2}O{sub 3} (Sb), Al{sub 2}O{sub 3} followed by HCl + H{sub 2}O{sub 2} (SbCl), and Al{sub 2}O{sub 3} followed by H{sub 2}SO{sub 4} + H{sub 2}O{sub 2} (SbS). Electrochemical tests were conducted in artificial saliva (pHs 3; 6.5 and 9) and simulated body fluid (SBF—pH 7.4). All surfaces were characterized before and after corrosion tests using atomic force microscopy, scanning electron microscopy, energy dispersive microscopy, X-ray diffraction, surface roughness, Vickers microhardness and surface free energy. The results indicated that Cl group exhibited the highest polarization resistance (R{sub p}) and the lowest capacitance (Q) and corrosion current density (I{sub corr}) values. Reduced corrosion stability was noted for the sandblasted groups. Acidic artificial saliva decreased the R{sub p} values of cp-Ti surfaces and produced the highest I{sub corr} values. Also, the surface treatment and corrosion process influenced the surface roughness, Vickers microhardness and surface free energy. Based on these results, it can be concluded that acid-etching treatment improved the electrochemical stability of cp-Ti and all treated surfaces behaved negatively in acidic artificial saliva. - Highlights: • Characterization of surface treatment for biomedical implants was investigated. • Sandblasting reduced the corrosion stability of cp

  15. A Comparison Between Mechanical And Electrochemical Tests on Ti6Al4V Welded By LBW

    Science.gov (United States)

    Serroni, G.; Bitondo, C.; Astarita, A.; Scala, A.; Gloria, A.; Prisco, U.; Squillace, A.; Bellucci, F.

    2011-05-01

    Titanium and its alloys are nowadays widely used in many sectors: in the medical field (orthopedic and dental ones), in the architectural field, in the chemical plants field and in aeronautic. In this last field it is more and more used both for its contribution to make lightweight and time durable structures and for its compatibility with new materials, first of all Carbon Fiber Reinforced Plastics (CFRP). To this aim, lots of researches are now focusing on new and emerging technologies capable to make titanium objects and, at the same time, reducing the scrap, since titanium alloys for aeronautic application are very expensive. This paper examines Grade 5 Titanium Alloy (Ti6Al4V) welded by Laser Beam (LBW) in butt-joint configuration. The source was Nd:YAG laser, moreover two inert gases were used, in order to provide a shield both on the top and on the bottom of the weld bead. The joints were studied by varying two process parameters: welding speed and power of the laser beam. It was not possible to realize a full experimental plan, due to technological limits in making titanium laser beam welds. The joints were tested to measure their mechanical properties and the corrosion resistance. The process parameters do not significantly affect the maximum static strength of the joints. Microscopic analysis showed that welds made with high power and low welding speed have a uniform weld bead, and no macroscopic defect occurs. Fatigue test results, instead, show a marked influence of the morphology of the weld bead: the occurrence of some defects, such as the undercut, both on the top and on the bottom of the weld bead, dramatically reduced fatigue resistance of the joints. Corrosion resistance was studied using the electrochemical micro cell technique, which allows to distinguish electrochemical properties of each zone of the weld bead, even when, as in this case, they are very narrow. By a general point of view, it has been demonstrated that the joints showing the best

  16. Mediated electrochemical hazardous waste destruction

    International Nuclear Information System (INIS)

    Hickman, R.G.; Farmer, J.C.; Wang, F.T.

    1992-03-01

    There are few permitted processes for mixed waste (radioactive plus chemically hazardous) treatment. We are developing an electrochemical process, based upon mediated electrochemical oxidation (MEO), that converts toxic organic components of mixed waste to water, carbon dioxide, and chloride or chloride precipitates. Aggressive oxidizer ions such as Ag 2+ , Co 3+ , or Fe 3+ are produced at an anode. These can attack organic molecules directly, and may also produce hydroxyl free radicals that promote destruction. Solid and liquid radioactive waste streams containing only inorganic radionuclide forms may be treated with existing technology and prepared for final disposal. The coulombic efficiency of the process has been determined, as well as the destruction efficiency for ethylene glycol, a surrogate waste. In addition, hazardous organic materials are becoming very expensive to dispose of and when they are combined with transuranic radioactive elements no processes are presently permitted. Mediated electrochemical oxidation is an ambient- temperature aqueous-phase process that can be used to oxidize organic components of mixed wastes. Problems associated with incineration, such as high-temperature volatilization of radionuclides, are avoided. Historically, Ag(II) has been used as a mediator in this process. Fe(III) and Co(III) are attractive alternatives to Ag(II) since they form soluble chlorides during the destruction of chlorinated solvents. Furthermore, silver itself is toxic heavy metal. Quantitative data have been obtained for the complete oxidation of ethylene glycol by Fe(III) and Co(III). Though ethylene glycol is a nonhalogenated organic, these data have enabled us to make direct comparisons of activities of Fe(III) and Co(III) with Ag(II). Very good quantitative data for the oxidation of ethylene glycol by Ag(II) had already been collected

  17. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

    KAUST Repository

    Giovannitti, Alexander

    2018-04-24

    We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

  18. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

    KAUST Repository

    Giovannitti, Alexander; Maria, Iuliana P.; Hanifi, David; Donahue, Mary J.; Bryant, Daniel; Barth, Katrina J.; Makdah, Beatrice E.; Savva, Achilleas; Moia, Davide; Zetek, Matyá š; Barnes, Piers R.F.; Reid, Obadiah G.; Inal, Sahika; Rumbles, Garry; Malliaras, George G.; Nelson, Jenny; Rivnay, Jonathan; McCulloch, Iain

    2018-01-01

    We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

  19. Scanning electrochemical microscopy determination of hydrogen flux at liquid|liquid interface with potentiometric probe

    OpenAIRE

    Jedraszko, Justyna; Nogala, Wojciech; Adamiak, Wojciech; Girault, Hubert H.; Opallo, Marcin

    2014-01-01

    Scanning electrochemical microscopy potentiometric determination of local hydrogen concentration and its flux next to the liquid|liquid interface was demonstrated. This method is based on the shift of open circuit potential of Pt-based reversible hydrogen electrode. The detection system was verified with a system generating hydrogen under galvanostatic conditions. Then, it was applied to aqueous|1,2-dichloroethane interface where hydrogen is produced with decamethylferrocene as electron donor.

  20. Feasibility of Cr (VI Removal from Aqueous Solution Using Electrochemical Bipolar Aluminum Electrodes

    Directory of Open Access Journals (Sweden)

    Abbas Rezaei

    2013-08-01

    Full Text Available Electrocoagulation is one of the technologies which have been considered by many researchers in recent years. This process has many advantages including high efficiency, no need to chemical addition, low sludge production, capability of process control, easy to operation and maintenance. Bipolar electrodes system is one of the electrocoagulation techniques which can be used for increasing the process efficiency and better distribution of the electric current. The aim of this study was to remove hexavalent chromium from aqueous solution by electrocoagulation technique. Response surface methodology (RSM was used to optimize the parameters involving in the process, and the effect of current density, initial chromium concentration and pH on the process were investigated. At optimal conditions, for the highest chromium removal (>90%, the optimum initial chromium, reaction time, current density and pH were found to be 117 mg/L, 50 min, 11.75 mA cm-2 and 4.5, respectively. It can be stated that electrocoagulation is an efficient technique for separation and removing high chromium concentration from aqueous solutions.

  1. On-line electrochemical monitoring of microbially influenced corrosion

    International Nuclear Information System (INIS)

    Dowling, N.J.E.; Stansbury, E.E.; White, D.C.; Borenstein, S.W.; Danko, J.C.

    1989-01-01

    Newly emerging electrochemical measurement techniques can provide on-line, non-destructive monitoring of the average corrosion rate and indications of localized pitting corrosion together with insight into fundamental electrochemical mechanisms responsible for the corrosion process. This information is relevant to evaluating, monitoring, understanding and controlling microbially influenced corrosion (MIC). MIC of coupons exposed in sidestream devices on site or in laboratory-based experiments, where the corrosion response is accelerated by exposure to active consortia of microbes recovered from specific sites, can be utilized to evaluate mitigation strategies. The average corrosion rates can be determined by small amplitude cyclic voltametry (SACV), and AC impedance spectroscopy (EIS). EIS can also give insight into the mechanisms of the MIC and indications of localized corrosion. Pitting corrosion can be detected non-destructively with open circuit potential monitoring (OCP). OCP also responds to bacterial biofilm activities such as oxygen depletion and other electrochemical activities. Utilizing these methods, accelerated tests can be designed to direct the selection of materials, surface treatments of materials, and welding filler materials, as well as the optimization of chemical and mechanical countermeasures with the microbial consortia recovered and characterized from the specific sites of interest

  2. Electrochemical processes for the environmental remediation of toxic Cr(VI): A review

    International Nuclear Information System (INIS)

    Jin, Wei; Du, Hao; Zheng, Shili; Zhang, Yi

    2016-01-01

    Highlights: • Recent advances in electrochemical technologies for practical Cr(VI) treatment applications was reviewed. • The mechanism and performance of electrocoagulation, electrochemical reduction, electrodialysis, electro-electrodialysis and electrodeionization were discussed and compared. • The remained challenges and future perspectives were commented. - Abstract: Hexavalent chromium Cr(VI) is extremely toxic and classified as one of the 17 chemicals posing the greatest threat to humans. Large amounts of Cr(VI) compounds are directly or indirectly discharged into the environment, therefore considerable efforts have been made to control the Cr(VI) concentration below the recommended level. It has been demonstrated that electrochemical technique is one of the most efficient and environmental benign approach for the Cr(VI) removal. This review aims at recent advances in electrochemical technology for practical Cr(VI) treatment applications. By using the “clean reagent” of electron, Cr(VI) can be completely eliminated or separated via different electrochemical techniques such as electrocoagulation, electrochemical reduction, electrodialysis, electro-electrodialysis and electrodeionization. Besides, the mechanism and performance of different strategies are commented and compared. The treatment process is largely dependent on variables such as pH, electrode materials, cell configuration and techniques integration. Furthermore, the remained limitation and challenges for the electrochemical Cr(VI) remediation are also discussed.

  3. Reversible pH Stimulus-Response Material Based on Amphiphilic Block Polymer Self-Assembly and Its Electrochemical Application

    Directory of Open Access Journals (Sweden)

    Tianyi Wang

    2016-06-01

    Full Text Available Stimulus-responsive microporous solid thin films were successfully fabricated by simple molecular self-assembly via an amphiphilic block polymer, polystryene–b–polyacrylic acid (PS–b–PAA. The solid thin films exhibit different surface morphologies in response to external stimuli, such as environments with different pH values in aqueous solutions. The experiments have successfully applied atomic force microscope (AFM technology to observe in-situ surface morphological changes. There is a reversible evolution of the microstructures in buffer solutions over a pH range of 2.4–9.2. These observations have been explained by positing that there is no conventional PAA swelling but that the PAA chains in the micropores stretch and contract with changes in the pH of the solution environment. The hydrophobicity of the solid thin film surface was transformed into super-hydrophilicity, as captured by optical contact angle measurements. The stimulus-responsive dynamics of pore sizes was described by a two-stage mechanism. A promising electrochemical application of this film is suggested via combination with an electrochemical impedance technique. This study is aimed at strategies for the functionalization of stimulus-responsive microporous solid thin films with reversible tunable surface morphologies, and exploring new smart materials with switch-on/switch-off behavior.

  4. Microelectrode array fabrication for electrochemical detection with carbon nanotubes

    Science.gov (United States)

    Clark, James

    Understanding how the brain works remains one of the key challenges for scientists. To further this understanding a wide variety of technologies and research methods have been developed. One such technology is conductive electrodes, used to measure the electrical signals elicited from neuronal cells and tissues. These electrodes can be fabricated as a singular electrode or as a multi-electrode array (MEA). This permits bio-electrical measurements from one particular area or simultaneous measurements from multiple areas, respectively. Studying electrical and chemical signals of individual cells in situ requires the use of electrodes with ≤20 µm diameter. However, electrodes of this size generally produce high impedance, perturbing recording of the small signals generated from individual cells. Nanomaterials, such as carbon nanotubes (CNTs), can be deposited to increase the real surface area of these electrodes, producing higher sensitivity measurements. This thesis investigates the potential for using photo-thermal chemical vapour deposition grown CNTs as the electrode material for a de novo fabricated MEA. This device aimed to measure electrochemical signals in the form of dopamine, an important mammalian neurotransmitter, as well as conventional bio-electrical signals that the device is designed for. Realising this aim began with improving CNT aqueous wetting behaviour via oxygen plasma functionalisation. This procedure demonstrated grafting of oxygen functional groups to the CNT structure, and dramatic improvements in aqueous wetting behaviour, with CNTs attached to the device. Subsequently, oxygen plasma functionalised CNT-based MEAs were fabricated and tested, allowing comparisons with a non-functionalised CNT MEA and a state-of-the-art commercial MEA. The functionalised CNT MEA demonstrated an order of magnitude improvement compared to commercial MEAs (2.75 kΩ vs. 25.6 kΩ), at the biologically relevant frequency of 1 kHz. This was followed by measurement

  5. Adsorption mechanism of alkyl polyglucoside (APG) on calcite nanoparticles in aqueous medium at varying pH

    Science.gov (United States)

    Suh, Seokjin; Choi, Kyeong-Ok; Yang, Seung-Chul; Kim, Yeong Eun; Ko, Sanghoon

    2017-07-01

    In this study, adsorption mechanism of alkyl polyglucoside (APG) on calcium carbonate (CaCO3) nanoparticles (CCNPs) in aqueous medium at varying pH was identified. An initial adsorption of APG on CCNP surface seemed to be occurred due to the van der Waals force. An initial surface charge influenced determination of a major driving force, which resulted in hydrogen bonds (pH 7) and the hydrophobic interaction (pH 10) as a main sources of adsorption of APG on the CCNP surface. Even if the initial surface charge of CCNPs had little effect on a quantitative adsorption of APG on CCNPs, eventually, it influence on the definitive adsorption structure between APG and CCNPs and improvement of dispersion stability of CCNPs in water. In conclusion, it was revealed that 0.39% APG aqueous solution was most appropriate to improve the dispersion stability of CCNPs, which is postulated to be used effectively in food and pharmaceutical fields.

  6. High-energy MnO2 nanowire/graphene and graphene asymmetric electrochemical capacitors.

    Science.gov (United States)

    Wu, Zhong-Shuai; Ren, Wencai; Wang, Da-Wei; Li, Feng; Liu, Bilu; Cheng, Hui-Ming

    2010-10-26

    In order to achieve high energy and power densities, we developed a high-voltage asymmetric electrochemical capacitor (EC) based on graphene as negative electrode and a MnO(2) nanowire/graphene composite (MGC) as positive electrode in a neutral aqueous Na(2)SO(4) solution as electrolyte. MGC was prepared by solution-phase assembly of graphene sheets and α-MnO(2) nanowires. Such aqueous electrolyte-based asymmetric ECs can be cycled reversibly in the high-voltage region of 0-2.0 V and exhibit a superior energy density of 30.4 Wh kg(-1), which is much higher than those of symmetric ECs based on graphene//graphene (2.8 Wh kg(-1)) and MGC//MGC (5.2 Wh kg(-1)). Moreover, they present a high power density (5000 W kg(-1) at 7.0 Wh kg(-1)) and acceptable cycling performance of ∼79% retention after 1000 cycles. These findings open up the possibility of graphene-based composites for applications in safe aqueous electrolyte-based high-voltage asymmetric ECs with high energy and power densities.

  7. Overview on recent developments in energy storage: Mechanical, electrochemical and hydrogen technologies

    International Nuclear Information System (INIS)

    Amirante, Riccardo; Cassone, Egidio; Distaso, Elia; Tamburrano, Paolo

    2017-01-01

    Highlights: • World energy demand is analyzed. • Promising energy storage systems are shown to explore their potentials. • Different storage are considered and compared. • The efficiency and costs of each are shown. • Easy guidelines for selection of energy storage are provided. - Abstract: Energy production is changing in the world because of the need to reduce greenhouse gas emissions, to reduce the dependence on carbon/fossil sources and to introduce renewable energy sources. Despite the great amount of scientific efforts, great care to energy storage systems is necessary to overcome the discontinuity in the renewable production. A wide variety of options and complex characteristic matrices make it difficult and so in this paper the authors show a clear picture of the available state-of-the-art technologies. The paper provides an overview of mechanical, electrochemical and hydrogen technologies, explaining operation principles, performing technical and economic features. Finally a schematic comparison among the potential utilizations of energy storage systems is presented.

  8. Concentric-Electrode Organic Electrochemical Transistors: Case Study for Selective Hydrazine Sensing

    Directory of Open Access Journals (Sweden)

    Sébastien Pecqueur

    2017-03-01

    Full Text Available We report on hydrazine-sensing organic electrochemical transistors (OECTs with a design consisting of concentric annular electrodes. The design engineering of these OECTs was motivated by the great potential of using OECT sensing arrays in fields such as bioelectronics. In this work, poly(3,4-ethylenedioxythiophene:poly(styrenesulfonate (PEDOT:PSS-based OECTs have been studied as aqueous sensors that are specifically sensitive to the lethal hydrazine molecule. These amperometric sensors have many relevant features for the development of hydrazine sensors, such as a sensitivity down to 10−5 M of hydrazine in water, an order of magnitude higher selectivity for hydrazine than for nine other water-soluble common analytes, the capability to entirely recover its base signal after water flushing, and a very low operation voltage. The specificity for hydrazine to be sensed by our OECTs is caused by its catalytic oxidation at the gate electrode, and enables an increase in the output current modulation of the devices. This has permitted the device-geometry study of the whole series of 80 micrometric OECT devices with sub-20-nm PEDOT:PSS layers, channel lengths down to 1 µm, and a specific device geometry of coplanar and concentric electrodes. The numerous geometries unravel new aspects of the OECT mechanisms governing the electrochemical sensing behaviours of the device—more particularly the effect of the contacts which are inherent at the micro-scale. By lowering the device cross-talk, micrometric gate-integrated radial OECTs shall contribute to the diminishing of the readout invasiveness and therefore further promote the development of OECT biosensors.

  9. Self-Assembled α-Fe2O3 mesocrystals/graphene nanohybrid for enhanced electrochemical capacitors.

    Science.gov (United States)

    Yang, Shuhua; Song, Xuefeng; Zhang, Peng; Sun, Jing; Gao, Lian

    2014-06-12

    Self-assembled α-Fe2O3 mesocrystals/graphene nanohybrids have been successfully synthesized and have a unique mesocrystal porous structure, a large specific surface area, and high conductivity. Mesocrystal structures have recently attracted unparalleled attention owing to their promising application in energy storage as electrochemical capacitors. However, mesocrystal/graphene nanohybrids and their growth mechanism have not been clearly investigated. Here we show a facile fabrication of short rod-like α-Fe2O3 mesocrystals/graphene nanohybrids by self-assembly of FeOOH nanorods as the primary building blocks on graphene under hydrothermal conditions, accompanied and promoted by concomitant phase transition from FeOOH to α-Fe2O3. A systematic study of the formation mechanism is also presented. The galvanostatic charge/discharge curve shows a superior specific capacitance of the as-prepared α-Fe2O3 mesocrystals/graphene nanohybrid (based on total mass of active materials), which is 306.9 F g(-1) at 3 A g(-1) in the aqueous electrolyte under voltage ranges of up to 1 V. The nanohybrid with unique sufficient porous structure and high electrical conductivity allows for effective ion and charge transport in the whole electrode. Even at a high discharge current density of 10 A g(-1), the enhanced ion and charge transport still yields a higher capacitance (98.2 F g(-1)), exhibiting enhanced rate capability. The α-Fe2O3 mesocrystal/graphene nanohybrid electrode also demonstrates excellent cyclic performance, which is superior to previously reported graphene-based hematite electrode, suggesting it is highly stable as an electrochemical capacitor. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Writing nanopatterns with electrochemical oxidation on redox responsive organometallic multilayers by AFM

    NARCIS (Netherlands)

    Song, Jing; Hempenius, Mark A.; Chung, H.J.; Vancso, Gyula J.

    2015-01-01

    Nanoelectrochemical patterning of redox responsive organometallic poly(ferrocenylsilane) (PFS) multilayers is demonstrated by electrochemical dip pen lithography (EDPN). Local electrochemical oxidation and Joule heating of PFS multilayers from the tip are considered as relevant mechanisms related to

  11. Synthesis and Biochemical effects of magnetite nanoparticle by surfactant-free electrochemical method in an aqueous system:the current density effect

    Directory of Open Access Journals (Sweden)

    Mousa Aliahmad

    2016-07-01

    Full Text Available Obejective(s: In this research, magnetite nanoparticles with an average size of 23-36 nm were successfully synthesized via surfactant-free electrochemical method using iron as the anode and water as the electrolyte in a closed aqueous system in the presence of NaOH at room temperature. Methods: The effect of the current density on product formation and particle size was investigated. Particle size was controlled by adjusting the current density. It was found that particle size decreases by decreasing the current density. In addition, the effect of current density  on the structural and optical properties of nanostructures were studied by X-ray diffraction, Field emission scanning electron microscopy, Fourier transformed infrared, and vibrating sample magnetometer techniques.  Results: The results obtained from the magnetization property study of samples at room temperature showed coactivity and saturation manetization of 0-100 Oe and 27.2- 40.5 emu. g-1, respectively. Finally, the results of biological activity study of nanoparticles on liver and kidney function in male wistar rats demonstrated that oral administration of NPs caused significant alterations to the levels of aspartate transaminase, alanine transaminase, and alkaline phosphatase in serum. Conclusions: No significant changes were detected in the groups treated with 10 and 100 ppm/ day nanostructure (P>0.05. There was a significant increase in the serum level of creatinine and blood urea nitrogen level (p

  12. Electrochemical techniques to detect corrosion in concrete structures in nuclear installations - Technical note

    International Nuclear Information System (INIS)

    2002-01-01

    The mechanism of corrosion in aqueous media is of electrochemical nature. This means that the oxidation of the metal is counterbalanced by the reduction of another substance in another region of the metallic surface. Therefore, zones (anodes and cathodes) with different electrochemical potential, develop. In the case of concrete the electrolyte is constituted by the pore solution, which is very alkaline. This pore solution is formed by mainly a mixture of KOH and NaOH presenting pH values ranging between 12.6-14. The solution is saturated in Ca(OH) 2 . Steel embedded in concrete is naturally protected by this high alkalinity and by the barrier effect of the cover itself. The two main causes of electrochemical corrosion are carbonation and the presence of chlorides. Carbonation usually induces a generalized corrosion while chloride will lead into pitting or localized attack. The corrosion can be easily recognized by the rust presence on the rebar and by the appearance of cracks running parallel to the rebars. The objective of this report is to describe the electrochemical non-destructive techniques that can be used in real size reinforced concrete structures to assess the corrosion condition of their reinforcement. These techniques can be used indistinctly in conventional civil engineering structures or in those of nuclear installations. Electrochemical techniques are used to detect electrochemical corrosion activity of metallic reinforcements. They cannot quantify stress corrosion cracking or hydrogen embrittlement although may give some qualitative information about them. The aims of their applications may be one of the following circumstances: 1. Quality control of new constructions; 2. Condition evaluation of existing structures for: - Identification of steel de-passivation, - Detecting corroding areas for rehabilitation purposes, - Calculation of residual load-bearing capacity of the structure, - Prediction of the damage evolution, - Determination of the

  13. Porous MnO2 prepared by sol-gel method for electrochemical supercapacitor

    Science.gov (United States)

    Bazzi, K.; Kumar, A.; Jayakumar, O. D.; Nazri, G. A.; Naik, V. M.; Naik, R.

    2015-03-01

    MnO2 has attracted great attention as material for electrochemical pseudocapacitor due to its high theoretical specific faradic capacitance (~ 1370 F .g-1) , environmental friendliness and wide potential window in both aqueous and nonaqueous electrolytes. However, the MnO2 has a low surface area which depresses its electrochemical performance. The amorphous α-MnO2 composite was synthesized by sol gel method in the presence of the tri-block copolymer P123. Our aim is to investigate the role of P123 on the electrochemical performance of MnO2. The samples with and without P123 were prepared and characterized by x-ray diffraction (XRD), SEM, TEM and Brunauer-Emmett-Teller (BET) method. The electrochemical performances of the amorphous MnO2 composites as the electrode materials for supercapacitors were evaluated by cyclic voltammetry and AC impedance measurements in a 1M Na2SO4 solution. The results show that the sample prepared without P123 exhibited a relatively low specific capacitance of 28F .g-1, whereas the porous MnO2 prepared with P123 exhibited 117 F .g-1at 5 mV/s. The results of crystalline MnO2 composites will also be presented. The authors acknowledge the support from the Richard J. Barber Foundation for Interdisciplinary Research.

  14. Electrochemical impedance spectroscopic study of passive zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Ai Jiahe; Chen Yingzi [Center for Electrochemical Science and Technology, Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802 (United States); Urquidi-Macdonald, Mirna [Department of Engineering Science and Mechanics, Pennsylvania State University, University Park, PA 16802 (United States); Macdonald, Digby D. [Center for Electrochemical Science and Technology, Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802 (United States)], E-mail: ddm2@psu.edu

    2008-09-30

    Spent, unreproccessed nuclear fuel is generally contained within the operational fuel sheathing fabricated from a zirconium alloy (Zircaloy 2, Zircaloy 4, or Zirlo) and is then stored in a swimming pool and/or dry storage facilities until permanent disposal in a licensed repository. During this period, which begins with irradiation of the fuel in the reactor during operation, the fuel sheathing is exposed to various, aggressive environments. The objective of the present study was to characterize the nature of the passive film that forms on pure zirconium in contact with an aqueous phase [0.1 M B(OH){sub 3} + 0.001 M LiOH, pH 6.94] at elevated temperatures (in this case, 250 deg. C), prior to storage, using electrochemical impedance spectroscopy (EIS) with the data being interpreted in terms of the point defect model (PDM). The results show that the corrosion resistance of zirconium in high temperature, de-aerated aqueous solutions is dominated by the outer layer. The extracted model parameter values can be used in deterministic models for predicting the accumulation of general corrosion damage to zirconium under a wide range of conditions that might exist in some repositories.

  15. Electrochemically cathodic exfoliation of graphene sheets in room temperature ionic liquids N-butyl, methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and their electrochemical properties

    International Nuclear Information System (INIS)

    Yang, Yingchang; Lu, Fang; Zhou, Zhou; Song, Weixin; Chen, Qiyuan; Ji, Xiaobo

    2013-01-01

    Graphical abstract: Electrochemically cathodic exfoliation of graphite into few-layer graphene sheets in room temperature ionic liquids (RTILs) N-butyl, methylpyrrolidinium bis(trifluoromethylsulfonyl)-imide (BMPTF 2 N). -- Highlights: • Few-layer graphene sheets were prepared through electrochemically cathodic exfoliation in room temperature ionic liquids. • The mechanism of cathodic exfoliation in ionic liquids was proposed. • The derived activated graphene sheets show enhanced electrochemical properties. -- Abstract: Electrochemically cathodic exfoliation in room temperature ionic liquids N-butyl, methylpyrrolidinium bis(trifluoromethylsulfonyl)-imide (BMPTF 2 N) has been developed for few-layer graphene sheets, demonstrating low levels of oxygen (2.7 at% of O) with a nearly perfect structure (I D /I G 2 N involves the intercalation of ionic liquids cation [BMP] + under highly negatively charge followed by graphite expansion. Porous activated graphene sheets were also obtained by activation of graphene sheets in KOH. Transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy were used to characterize these graphene materials. The electrochemical performances of the graphene sheets and porous activated graphene sheets for lithium-ion battery anode materials were evaluated using cyclic voltammetry, galvanostatic charge–discharge cycling, and electrochemical impedance spectroscopy

  16. Stabilizers of edaravone aqueous solution and their action mechanisms. 2. Glutathione

    OpenAIRE

    Tanaka, Masahiko; Motomiya, Satsuki; Fujisawa, Akio; Yamamoto, Yorihiro

    2017-01-01

    Edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one) has garnered attention since its approval for amyotrophic lateral sclerosis in Japan (2015) and the United States (2017). Edaravone is administered intravenously, and as such, is distributed in the form of an aqueous solution. However, aqueous solutions of edaravone are very unstable because they present as edaravone anions, which become edaravone radicals when the anion donates an electron to free radicals including oxygen. In this study, gluta...

  17. Electrocatalytic oxygen reduction and hydrogen evolution reactions on phthalocyanine modified electrodes: Electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring

    Energy Technology Data Exchange (ETDEWEB)

    Koca, Atif, E-mail: akoca@eng.marmara.edu.tr [Department of Chemical Engineering, Faculty of Engineering, Marmara University, Goeztepe, 34722 Istanbul (Turkey); Kalkan, Ayfer; Bayir, Zehra Altuntas [Department of Chemistry, Technical University of Istanbul, Maslak, 34469 Istanbul (Turkey)

    2011-06-30

    Highlights: > Electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines were performed. > The presence of O{sub 2} influences both oxygen reduction reaction and the electrochemical behaviors of the complexes. > Homogeneous catalytic ORR process occurs via an 'inner sphere' chemical catalysis process. > CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. - Abstract: This study describes electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring of the electrocatalytic reduction of molecular oxygen and hydronium ion on the phthalocyanine-modified electrodes. For this purpose, electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines (MPc) bearing tetrakis-[4-((4'-trifluoromethyl)phenoxy)phenoxy] groups were performed. While CoPc gives both metal-based and ring-based redox processes, H{sub 2}Pc, ZnPc and CuPc show only ring-based electron transfer processes. In situ electrocolorimetric method was applied to investigate the color of the electrogenerated anionic and cationic forms of the complexes. The presence of O{sub 2} in the electrolyte system influences both oxygen reduction reaction and the electrochemical and spectral behaviors of the complexes, which indicate electrocatalytic activity of the complexes for the oxygen reduction reaction. Perchloric acid titrations monitored by voltammetry represent possible electrocatalytic activities of the complexes for hydrogen evolution reaction. CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. The nature of the metal center changes the electrocatalytic activities for hydrogen evolution reaction in aqueous solution. Although CuPc has an inactive metal center, its electrocatalytic activity is recorded more than CoPc for H{sup +} reduction in aqueous

  18. Electrochemical oxidation of selective estrogen receptor modulator raloxifene

    International Nuclear Information System (INIS)

    Li, Xi-Qian; He, Jian-Bo; Liu, Lu; Cui, Ting

    2013-01-01

    Highlights: ► Application and analysis of in situ thin-layer spectroelectrochemistry. ► Cyclic voltabsorptometry used for a drug study. ► Highly pH-dependent oxidative metabolism of raloxifene. ► A complex parallel-consecutive mechanism proposed for oxidation of raloxifene. -- Abstract: Raloxifene is a selective estrogen receptor modulator that may produce toxic oxidative species in metabolism. The oxidation mechanism of raloxifene with different pH values was studied by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), in situ UV–vis spectral analysis and cyclic voltabsorptometry based on a long optical-path thin-layer electrochemical cell. Time-derivative cyclic voltabsorptograms were obtained for comparative discussion with the corresponding cyclic voltammograms. Raloxifene was initially oxidized to reactive phenoxyl radicals, followed by a series of transformation steps leading to different final products in different pH media. A parallel-consecutive reaction mechanism was proposed for the pH-dependent formation of 7-hydroxyraloxifene, raloxifene 6,7-o-quinone and two raloxifene dimers, each pathway following a complex electrochemical-chemical mechanism. Both raloxifene diquinone methide and its N-oxides were not detected by in situ UV–vis spectroscopy and XPS analysis. This work provides an electrochemical viewpoint and comparable information for better understanding of the oxidative metabolism and chemical toxicology of raloxifene under physiological conditions in vivo or in vitro

  19. Electrochemical treatment of wastewaters containing 4-chlororesorcinol using boron doped diamond anodes

    International Nuclear Information System (INIS)

    Nasr, B.; Abdelatif, G.

    2009-01-01

    The electrochemical oxidation of aqueous wastes polluted with 4-chlororesorcinol has been studied on boron-doped diamond electrodes on acidic medium. The voltammetric results showed that in the potential region where the supporting electrolyte is stable, reactions occur, resulting in the loss of activity due to electrode fouling. Galvanostatic electrolysis study showed that the oxidation of these wastes in single-compartment electrochemical flow cell with boron doped diamond anodes deal to the complete mineralization of the organics but is no indication of electrode fouling. Resorcinol, 1,2,4-trihydroxybenzene, benzoquinone, maleic, fumaric, and oxalic acids have been detected as soluble organics and chlorides (Cl - ) and hypochlorites (ClO - ) as mineral products during the electrolysis of 4-chlororesorcinol. The electrochemical oxidation of 4-chlororesorcinol consists of a sequence of steps: Release of Cl and/or hydroxylation of the aromatic ring; formation of quinonic compounds; oxidative opening of aromatic ring to form carboxylic acids; and oxidation of carboxylic acids to carbon dioxide. Both, direct oxidation at boron doped diamond surface and mediated oxidation by powerful oxidants electrogenerated from electrolyte oxidation at anode surface are involved in these stages. (author)

  20. Nanostructured core-shell electrode materials for electrochemical capacitors

    Science.gov (United States)

    Jiang, Long-bo; Yuan, Xing-zhong; Liang, Jie; Zhang, Jin; Wang, Hou; Zeng, Guang-ming

    2016-11-01

    Core-shell nanostructure represents a unique system for applications in electrochemical energy storage devices. Owing to the unique characteristics featuring high power delivery and long-term cycling stability, electrochemical capacitors (ECs) have emerged as one of the most attractive electrochemical storage systems since they can complement or even replace batteries in the energy storage field, especially when high power delivery or uptake is needed. This review aims to summarize recent progress on core-shell nanostructures for advanced supercapacitor applications in view of their hierarchical architecture which not only create the desired hierarchical porous channels, but also possess higher electrical conductivity and better structural mechanical stability. The core-shell nanostructures include carbon/carbon, carbon/metal oxide, carbon/conducting polymer, metal oxide/metal oxide, metal oxide/conducting polymer, conducting polymer/conducting polymer, and even more complex ternary core-shell nanoparticles. The preparation strategies, electrochemical performances, and structural stabilities of core-shell materials for ECs are summarized. The relationship between core-shell nanostructure and electrochemical performance is discussed in detail. In addition, the challenges and new trends in core-shell nanomaterials development have also been proposed.

  1. Local Fine Structural Insight into Mechanism of Electrochemical Passivation of Titanium.

    Science.gov (United States)

    Wang, Lu; Yu, Hongying; Wang, Ke; Xu, Haisong; Wang, Shaoyang; Sun, Dongbai

    2016-07-20

    Electrochemically formed passive film on titanium in 1.0 M H2SO4 solution and its thickness, composition, chemical state, and local fine structure are examined by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure. AES analysis reveals that the thickness and composition of oxide film are proportional to the reciprocal of current density in potentiodynamic polarization. XPS depth profiles of the chemical states of titanium exhibit the coexistence of various valences cations in the surface. Quantitative X-ray absorption near edge structure analysis of the local electronic structure of the topmost surface (∼5.0 nm) shows that the ratio of [TiO2]/[Ti2O3] is consistent with that of passivation/dissolution of electrochemical activity. Theoretical calculation and analysis of extended X-ray absorption fine structure spectra at Ti K-edge indicate that both the structures of passivation and dissolution are distorted caused by the appearance of two different sites of Ti-O and Ti-Ti. And the bound water in the topmost surface plays a vital role in structural disorder confirmed by XPS. Overall, the increase of average Ti-O coordination causes the electrochemical passivation, and the dissolution is due to the decrease of average Ti-Ti coordination. The structural variations of passivation in coordination number and interatomic distance are in good agreement with the prediction of point defect model.

  2. Electrochemical treatment of evaporated residue of soak liquor generated from leather industry

    International Nuclear Information System (INIS)

    Boopathy, R.; Sekaran, G.

    2013-01-01

    Highlights: • Electrochemical treatment of evaporated residue of soak liquor (ERSL) generated in Tannery. • Copper coating on electrode surface and horizontal mounting of electrodes for ERSL treatment. • Electrochemical oxidation of organic pollutants under high saline condition. • The treated solution may be evaporated to dryness to get NaCl salt for hide/skin preservation. -- Abstract: The organic and suspended solids present in soak liquor, generated from leather industry, demands treatment. The soak liquor is being segregated and evaporated in solar evaporation pans/multiple effect evaporator due to non availability of viable technology for its treatment. The residue left behind in the pans/evaporator does not carry any reuse value and also faces disposal threat due to the presence of high concentration of sodium chloride, organic and bacterial impurities. In the present investigation, the aqueous evaporated residue of soak liquor (ERSL) was treated by electrochemical oxidation. Graphite/graphite and SS304/graphite systems were used in electrochemical oxidation of organics in ERSL. Among these, graphite/graphite system was found to be effective over SS304/graphite system. Hence, the optimised conditions for the electrochemical oxidation of organics in ERSL using graphite/graphite system was evaluated by response surface methodology (RSM). The mass transport coefficient (k m ) was calculated based on pseudo-first order rate kinetics for both the electrode systems (graphite/graphite and SS304/graphite). The thermodynamic properties illustrated the electrochemical oxidation was exothermic and non-spontaneous in nature. The calculated specific energy consumption at the optimum current density of 50 mA cm −2 was 0.41 kWh m −3 for the removal of COD and 2.57 kWh m −3 for the removal of TKN

  3. Controllable synthesis of hierarchical nickel cobalt sulfide with enhanced electrochemical activity

    Science.gov (United States)

    Tie, Jinjin; Han, Jiaxi; Diao, Guiqiang; Liu, Jiwen; Xie, Zhuopeng; Cheng, Gao; Sun, Ming; Yu, Lin

    2018-03-01

    The composition of nickel cobalt sulfide has great influence on its electrochemical performance. Herein, the nickel cobalt sulfide with different composition and mixed phase were synthesized by one-step solvothermal method through changing the molar ratio of Ni to Co in the reaction system. The electrochemical measurements showed that the nickel cobalt sulfide with a theoretical molar ratio of Ni/Co to be 1.5:1.5 (NCS-2) demonstrates the superior pseudocapacitive performance with a high specific capacitance (6.47 F cm-2 at 10 mA cm-2) and a favorable Coulombic efficiency (∼99%). Whereas, when applied as the catalyst for hydrogen evolution reaction in 1 M KOH aqueous electrolyte, the nickel cobalt sulfide with a theoretical molar ratio of Ni/Co is 1:2 (NCS-1) displays better catalytic activity, and it requires a relatively lower overpotential of 282 mV to deliver the current density of 10 mA cm-2.

  4. Photoassisted electrochemical recirculation system with boron-doped diamond anode and carbon nanotubes containing cathode for degradation of a model azo dye

    International Nuclear Information System (INIS)

    Vahid, Behrouz; Khataee, Alireza

    2013-01-01

    In this research work, a photoassisted electrochemical system under recirculation mode and with UV irradiation was designed for treatment of C.I. Acid Blue 92 (AB92) as a model anionic azo dye in aqueous solution. Degradation experiments were carried out with boron-doped diamond (BDD) anode and carbon nanotubes-polytetrafluoroethylene (CNTs-PTFE) cathode in the presence of sulfate as an electrolyte. A comparative study of AB92 degradation by photolysis, electrochemical oxidation and photoassisted electrochemical processes after 45 min of treatment demonstrated that degradation efficiency was 27.89, 37.65 and 95.86%, respectively. Experimental data revealed that the degradation rate of AB92 in all of the processes obeyed pseudo-first-order kinetics and application of photoassisted electrochemical system reduced electrical energy per order (E EO ), considerably. Degradation efficiency of photoassisted electrochemical process enhanced by increasing applied current and flow rate values, but vice versa trend was observed for initial dye concentration and an optimum amount of 6 was obtained for initial pH. The TOC measurement results demonstrated that 93.24% of organic substrates were mineralized after 120 min of photoassisted electrochemical process and GC–Mass analysis was performed for identification of degradation intermediates

  5. Bioactivation of diclofenac in vitro and in vivo: correlation to electrochemical studies

    DEFF Research Database (Denmark)

    Madsen, Kim G; Skonberg, Christian; Jurva, Ulrik

    2008-01-01

    Diclofenac is widely used in the treatment of, for example, arthritis and muscle pain. The use of diclofenac has been associated with hepatotoxicity, which has been linked to the formation of reactive metabolites. Diclofenac can be metabolized to 4'-OH- and 5-OH-diclofenac, both of which are able...... oxidation of diclofenac to a +16 Da metabolite was shown to be identical to a synthetic standard of 5-OH-diclofenac. Furthermore, two different experimental designs were investigated with respect to the electrochemical oxidation of 4'-OH- and 5-OH-diclofenac. In the first approach, the oxidized sample...... was collected in an aqueous solution of GSH, whereas in the other approach, GSH was added to the sample before the oxidation was performed. From these electrochemical oxidations, a range of GSH conjugates of 4'-OH- and 5-OH-diclofenac were observed and characterized by MS/MS. This allowed the development...

  6. Performance of Liquid Phase Exfoliated Graphene As Electrochemical Double Layer Capacitors Electrodes

    Science.gov (United States)

    Huffstutler, Jacob; Wasala, Milinda; Richie, Julianna; Winchester, Andrew; Ghosh, Sujoy; Kar, Swastik; Talapatra, Saikat

    2014-03-01

    We will present the results of our investigations of electrochemical double layer capacitors (EDLCs) or supercapacitors (SC) fabricated using liquid-phase exfoliated graphene. Several electrolytes, such as aqueous potassium hydroxide KOH (6M), ionic 1-Butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], and ionic 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate[BMP][FAP] were used. These EDLC's show good performance compared to other carbon nanomaterials based EDLC's devices. We found that the liquid phase exfoliated graphene based devices possess specific capacitance values as high as 262 F/g, when used with ionic liquid electrolyte[BMP][FAP], with power densities (~ 454 W/kg) and energy densities (~ 0.38Wh/kg). Further, these devices indicated rapid charge transfer response even without the use of any binders or specially prepared current collectors. A detailed electrochemical impedance spectroscopy analysis in order to understand the phenomenon of charge storage in these materials will be presented.

  7. Development of an Electrochemical Metal-Ion Biosensor Using Self-Assembled Peptide Nanofibrils

    DEFF Research Database (Denmark)

    Viguier, Bruno; Zor, Kinga; Kasotakis, Emmanouil

    2011-01-01

    . These nanofibrils were obtained under aqueous conditions, at room temperature and outside the clean room. The functionalized gold electrode was evaluated by cyclic voltammetry, impedance spectroscopy, energy dispersive X-ray and atomic force microscopy. The obtained results displayed a layer of nanofibrils able......This article describes the combination of self-assembled peptide nanofibrils with metal electrodes for the development of an electrochemical metal-ion biosensor. The biological nanofibrils were immobilized on gold electrodes and used as biorecognition elements for the complexation with copper ions...

  8. Towards a stable ion-solvating polymer electrolyte for advanced alkaline water electrolysis

    DEFF Research Database (Denmark)

    Aili, David; Wright, Andrew G.; Kraglund, Mikkel Rykær

    2017-01-01

    Advanced alkaline water electrolysis using ion-solvating polymer membranes as electrolytes represents a new direction in the field of electrochemical hydrogen production. Polybenzimidazole membranes equilibrated in aqueous KOH combine the mechanical robustness and gas-tightness of a polymer...... stability in alkaline environments. The novel electrolytes are extensively characterized with respect to physicochemical and electrochemical properties and the chemical stability is assessed in 0-50 wt% aqueous KOH for more than 6 months at 88 degrees C. In water electrolysis tests using porous 3...

  9. Non-aqueous hybrid supercapacitors fabricated with mesoporous TiO2 microspheres and activated carbon electrodes with superior performance

    Science.gov (United States)

    Cai, Yong; Zhao, Bote; Wang, Jie; Shao, Zongping

    2014-05-01

    Mesoporous TiO2 microspheres, synthesized by a facile template-free solvothermal method and subsequent heat treatment, are exploited as the electrode for hybrid supercapacitors. The effects of the calcination temperature on the phase composition, particulate microstructure and morphology are characterized by XRD, Raman, FE-SEM and N2 adsorption/desorption measurements. Hybrid supercapacitors utilizing the as-prepared TiO2 mesoporous microspheres as the negative electrode and activated carbon (AC) as the positive electrode in a non-aqueous electrolyte are fabricated. The electrochemical performance of these hybrid supercapacitors is studied by galvanostatic charge-discharge and cyclic voltammetry (CV). The hybrid supercapacitor built from TiO2 microspheres calcined at 400 °C shows the best performance, delivering an energy density of 79.3 Wh kg-1 at a power density of 178.1 W kg-1. Even at a power density of 9.45 kW kg-1, an energy density of 31.5 Wh kg-1 is reached. These values are much higher than the AC-AC symmetric supercapacitor. In addition, the hybrid supercapacitor exhibits excellent cycling performance, retaining 98% of the initial energy density after 1000 cycles. Such outstanding electrochemical performance of the hybrid supercapacitor is attributed to the matched reaction kinetics between the two electrodes with different energy storage mechanisms.

  10. Dispersion of silver particles in aqueous solutions visualized by polarography/voltammetry

    Energy Technology Data Exchange (ETDEWEB)

    Korshunov, Andrey [Department of General and Inorganic Chemistry, Tomsk Polytechnic University, 634050 Tomsk (Russian Federation); Heyrovsky, Michael [J.Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejskova 3, 182 23 Prague (Czech Republic)], E-mail: heyrovsk@jh-inst.cas.cz

    2009-11-01

    The State of silver particles in aqueous dispersions and the course of their coagulation can be followed on voltammetric curves recorded with hanging mercury drop electrode. Sharp irregular cathodic current peaks produced by partial electroreduction of the species adsorbed on the surface of silver particles during their fortuitous impingements upon the electrode surface appear in time sequence on the curves. A change in the electrochemical behavior of silver sols in the time course of particles aggregation and growth was interpreted in agreement with the data of UV-vis spectroscopy and electron microscopy observations.

  11. Electrochemical lithiation performance and characterization of silicon-graphite composites with lithium, sodium, potassium, and ammonium polyacrylate binders.

    Science.gov (United States)

    Han, Zhen-Ji; Yamagiwa, Kiyofumi; Yabuuchi, Naoaki; Son, Jin-Young; Cui, Yi-Tao; Oji, Hiroshi; Kogure, Akinori; Harada, Takahiro; Ishikawa, Sumihisa; Aoki, Yasuhito; Komaba, Shinichi

    2015-02-07

    Poly(acrylic acid) (PAH), which is a water soluble polycarboxylic acid, is neutralized by adding different amounts of LiOH, NaOH, KOH, and ammonia (NH4OH) aqueous solutions to fix neutralization degrees. The differently neutralized polyacid, alkali and ammonium polyacrylates are examined as polymeric binders for the preparation of Si-graphite composite electrodes as negative electrodes for Li-ion batteries. The electrode performance of the Si-graphite composite depends on the alkali chemicals and neutralization degree. It is found that 80% NaOH-neutralized polyacrylate binder (a pH value of the resultant aqueous solution is ca. 6.7) is the most efficient binder to enhance the electrochemical lithiation and de-lithiation performance of the Si-graphite composite electrode compared to that of conventional PVdF and the other binders used in this study. The optimum polyacrylate binder highly improves the dispersion of active material in the composite electrode. The binder also provides the strong adhesion, suitable porosity, and hardness for the composite electrode with 10% (m/m) binder content, resulting in better electrochemical reversibility. From these results, the factors of alkali-neutralized polyacrylate binders affecting the electrode performance of Si-graphite composite electrodes are discussed.

  12. Nanosized {alpha}-LiFeO{sub 2} as electrochemical supercapacitor electrode in neutral sulfate electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Santos-Pena, J., E-mail: iq2sanpe@uco.e [Departamento de Quimica Inorganica e Ingenieria Quimica, Edificio Marie Curie, Campus de Rabanales, Universidad de Cordoba, 14071 Cordoba (Spain); Crosnier, O.; Brousse, T. [Laboratoire de Genie des Materiaux et Procedes Associes, Ecole Polytechnique de l' Universite de Nantes, Site de la Chantrerie, rue Christian Pauc s/n, 44376 Nantes Cedex 3 (France)

    2010-10-30

    In this work we have explored the electrochemical properties of two lithiated iron oxide powders for supercapacitor purposes. These samples mainly consisted of {alpha}-LiFeO{sub 2} in nanosized or micrometric form. Electrolyte was an aqueous 0.5 M Li{sub 2}SO{sub 4} solution and voltage range studied was between 0 and -0.7 V vs. a Ag/AgCl reference electrode. As expected, electrochemical performance was dependent on the particle size. When electrolyte was deaerated a stable capacitance of {approx}50 F g{sup -1} is provided by the nanosized sample for several hundred cycles. Other sulfate based salts (Na{sub 2}SO{sub 4}, K{sub 2}SO{sub 4}, Cs{sub 2}SO{sub 4}) were investigated as electrolytes but only Li{sub 2}SO{sub 4} leads to a stable capacitance upon cycling, probably due to lithium intercalation. An hybrid cell consisting of this sample and MnO{sub 2} as negative and positive electrodes, respectively, delivered 0.3 F cm{sup -2} (10 F g{sup -1}). Although these values are lower than reported for other aqueous hybrid cell, {alpha}-LiFeO{sub 2}/MnO{sub 2} asymmetric capacitor is interesting from both, an economic and an environmental point of view.

  13. Carbon nanoparticle stabilised liquid|liquid micro-interfaces for electrochemically driven ion-transfer processes

    International Nuclear Information System (INIS)

    MacDonald, Stuart M.; Fletcher, Paul D.I.; Cui Zhenggang; Opallo, Marcin; Chen Jingyuan; Marken, Frank

    2007-01-01

    Stabilised liquid|liquid interfaces between an organic 4-(3-phenylpropyl)-pyridine (PPP) phase and an aqueous electrolyte phase are obtained in the presence of suitable nanoparticles. The use of nanoparticulate stabilisers (ca. 30 nm diameter laponite or 9-18 nm diameter carbon) in 'Pickering' emulsion systems allows stable organic microdroplets to be formed and these are readily deposited onto conventional tin-doped indium oxide (ITO) electrodes. In contrast to the electrically insulating laponite nanoparticles, conducting carbon nanoparticles are shown to effectively catalyse the simultaneous electron transfer and ion transfer process at triple phase boundary junctions. Anion transfer processes between the aqueous and organic phase are driven electrochemically at the extensive triple phase junction carbon nanoparticle|4-(3-phenylpropyl)-pyridine|aqueous electrolyte. The organic phase consists of a redox active reagent 5,10,15,20-tetraphenyl-21H,23H-porphinato manganese(III) (MnTPP + ), 5,10,15,20-tetraphenyl-21H,23H-porphinato iron(III) (FeTPP + ), or proto-porphyrinato-IX iron(III) (hemin) dissolved in 4-(3-phenylpropyl)-pyridine (PPP). The composition of the aqueous electrolyte phase determines the reversible potential for the Nernstian anion transfer process. The methodology is shown to be versatile and, in future, could be applied more generally in liquid|liquid electroanalysis

  14. Electrochemical capacity fading of polyaniline electrode in supercapacitor: An XPS analysis

    Directory of Open Access Journals (Sweden)

    Jinxing Deng

    2017-04-01

    Full Text Available To understand the electrochemical capacity fading of the polyaniline (PANI electrodes in supercapacitors, for the first time, their chemical structure change during electrochemical cycles was traced with XPS analysis after the HCl doped PANI electrodes were subjected to the cyclic voltammetry test in 1.0 M H2SO4 electrolyte for different cycle numbers. The results showed that the chlorine disappeared in the electrode surface, while the surface element contents of sulfur and oxygen increased with the electrochemical cycles increased. It demonstrated that the hydrolytic degradation of the PANI chains and exchange of dopant occurred during the electrochemical cycling, causing the fading in the mechanical and electrochemical performance of the PANI electrodes. This understanding should lead to better design of the conductive polymer-based energy storage devices.

  15. Electrochemical Study of Bromide in the Presence of 1,3-Indandione. Application to the Electrochemical Synthesis of Bromo Derivatives of 1,3-Indandione

    OpenAIRE

    Nematollahi, D.; Akaberi, N.

    2001-01-01

    The electrochemical oxidation of bromide in the presence of 1,3-indandione (1) in water/acetic acid and methanol/acetic acid mixtures has been studied by cyclic voltammetry and controlled-potential coulometry. The results indicate the participation of 1,3-indandione in the bromination reaction. On the basis of the electroanalytical and preparative results a reaction mechanism including electron transfer, chemical reaction and regeneration of bromide was discussed. The electrochemical synthesi...

  16. Synthesis and Electrochemical Performance of a Lithium Titanium Phosphate Anode for Aqueous Lithium-Ion Batteries

    KAUST Repository

    Wessells, Colin; La Mantia, Fabio; Deshazer, Heather; Huggins, Robert A.; Cui, Yi

    2011-01-01

    Lithium-ion batteries that use aqueous electrolytes offer safety and cost advantages when compared to today's commercial cells that use organic electrolytes. The equilibrium reaction potential of lithium titanium phosphate is -0.5 V with respect

  17. Polyvinylpyrrolidone/polyvinyl butyral composite as a stable binder for castable supercapacitor electrodes in aqueous electrolytes

    Science.gov (United States)

    Aslan, M.; Weingarth, D.; Herbeck-Engel, P.; Grobelsek, I.; Presser, V.

    2015-04-01

    Mixtures of polyvinylpyrrolidone/polyvinyl butyral (PVP/PVB) are attractive binders for the preparation of carbon electrodes for aqueous electrolyte supercapacitors. The use of PVP/PVB offers several key advantages: They are soluble in ethanol and can be used to spray coat or drain cast activated carbon (AC) electrodes directly on a current collector. Infrared spectroscopy and contact angle measurements show that the PVP-to-PVB ratio determines the degree of binder hydrophilicity. Within our study, the most favorable performance was obtained for AC electrodes with a composition of AC + 1.5 mass% PVP + 6.0 mass% PVB; such electrodes were mechanically stabile and water resistant with a PVP release of less than 5% of total PVP while PVB itself is water insoluble. Compared to when using PVDF, the specific surface area (SSA) of the assembled electrodes was 10% higher, indicating a reduced pore blocking tendency. A good electrochemical performance was observed in different aqueous electrolytes for composite electrodes with the optimized binder composition: 160 F g-1 at 1 A g-1 for 1 M H2SO4 and 6 M KOH and 120 F g-1 for 1 M NaCl. The capacitance was slightly reduced by 2.5% after cycling to 1.2 V with 1.28 A g-1 in 1 M NaCl for 10,000 times.

  18. An electrochemical-cantilever platform for hybrid sensing applications

    DEFF Research Database (Denmark)

    Fischer, Lee MacKenzie; Dohn, Søren; Boisen, Anja

    2011-01-01

    This work presents a fully-functional, microfabricated electrochemical-cantilever hybrid platform with flow control. A new cantilever chip format is designed, fabricated, and mounted in a custom polymer flow cell. Issues such as leakage and optical/electrical access are addressed, and combined...... mechanical and electrochemical performance is investigated. Lastly, a cantilever is “defunctionalized” in situ to create a reference cantilever for differential measurements in detection of Cu2+ ions at concentrations of 10 μM and 100 nM....

  19. Sensitive detection of pyoverdine with an electrochemical sensor based on electrochemically generated graphene functionalized with gold nanoparticles.

    Science.gov (United States)

    Gandouzi, Islem; Tertis, Mihaela; Cernat, Andreea; Bakhrouf, Amina; Coros, Maria; Pruneanu, Stela; Cristea, Cecilia

    2018-04-01

    The design and development of an electrochemical sensor for the sensitive and selective determination of pyoverdine, a virulence factor secreted by Pseudomonas aeruginosa, bacteria involved in nosocomial infections is presented in this work. The presence of pyoverdine in water and body fluids samples can be directly linked to the presence of the Pseudomonas bacteria, thus being a nontoxic and low cost marker for the detection of water pollution as well as for the biological contamination of other media. The sensor was elaborated using layer-by-layer technique for the deposition of a graphene‑gold nanoparticles composite film on the graphite-based screen printed electrode, from aqueous suspension. Under optimal conditions, the electrochemical signal corresponding to the pyoverdine oxidation process was proportional to its concentration, showing a wide linear range from 1 to 100μmolL -1 and a detection limit of 0.33μmolL -1 . This sensor discriminate with satisfactory recoveries the target analyte in different real matrices and also exhibited low response to other interfering species, proving that this technique is promising for medical and environmental applications. In addition, the proposed nanocomposite platform presented good reproducibility, high and long term stability, the sensitivity for pyoverdine remain unchanged after being stored at 4°C for four weeks. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Electrochemically induced chemical sensor properties in graphite screen-printed electrodes: The case of a chemical sensor for uranium

    International Nuclear Information System (INIS)

    Kostaki, Vasiliki T.; Florou, Ageliki B.; Prodromidis, Mamas I.

    2011-01-01

    Highlights: → Electrochemical treatment endows analytical characteristics to SPEs. → A sensitive chemical sensor for uranium is described. → Performance is due to a synergy between electrochemical treatment and ink's solvents. → The amount of the solvent controls the achievable sensitivity. - Abstract: We report for the first time on the possibility to develop chemical sensors based on electrochemically treated, non-modified, graphite screen-printed electrodes (SPEs). The applied galvanostatic treatment (5 μA for 6 min in 0.1 M H 2 SO 4 ) is demonstrated to be effective for the development of chemical sensors for the determination of uranium in aqueous solutions. A detailed study of the effect of various parameters related to the fabrication of SPEs on the performance of the resulting sensors along with some diagnostic experiments on conventional graphite electrodes showed that the inducible analytical characteristics are due to a synergy between electrochemical treatment and ink's solvents. Indeed, the amount of the latter onto the printed working layer controls the achievable sensitivity. The preconcentration of the analyte was performed in an electroless mode in an aqueous solutions of U(VI), pH 4.6, and then, the accumulated species was reduced by means of a differential pulse voltammetry scan in 0.1 M H 3 BO 3 , pH 3. Under selected experimental conditions, a linear calibration curve over the range 5 x 10 -9 to 10 -7 M U(VI) was constructed. The 3σ limit of detection at a preconcentration time of 30 min, and the relative standard deviation of the method were 4.5 x 10 -9 M U(VI) and >12% (n = 5, 5 x 10 -8 M U(VI)), respectively. The effect of potential interferences was also examined.

  1. Electrochemical treatment of evaporated residue of soak liquor generated from leather industry.

    Science.gov (United States)

    Boopathy, R; Sekaran, G

    2013-09-15

    The organic and suspended solids present in soak liquor, generated from leather industry, demands treatment. The soak liquor is being segregated and evaporated in solar evaporation pans/multiple effect evaporator due to non availability of viable technology for its treatment. The residue left behind in the pans/evaporator does not carry any reuse value and also faces disposal threat due to the presence of high concentration of sodium chloride, organic and bacterial impurities. In the present investigation, the aqueous evaporated residue of soak liquor (ERSL) was treated by electrochemical oxidation. Graphite/graphite and SS304/graphite systems were used in electrochemical oxidation of organics in ERSL. Among these, graphite/graphite system was found to be effective over SS304/graphite system. Hence, the optimised conditions for the electrochemical oxidation of organics in ERSL using graphite/graphite system was evaluated by response surface methodology (RSM). The mass transport coefficient (km) was calculated based on pseudo-first order rate kinetics for both the electrode systems (graphite/graphite and SS304/graphite). The thermodynamic properties illustrated the electrochemical oxidation was exothermic and non-spontaneous in nature. The calculated specific energy consumption at the optimum current density of 50 mA cm(-2) was 0.41 kWh m(-3) for the removal of COD and 2.57 kWh m(-3) for the removal of TKN. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Mechanisms of catalytic cleavage of benzyl phenyl ether in aqueous and apolar phases

    Energy Technology Data Exchange (ETDEWEB)

    He, Jiayue; Lu, Lu; Zhao, Chen; Mei, Donghai; Lercher, Johannes A.

    2014-03-01

    Catalytic pathways for the cleavage of ether bonds in benzyl phenyl ether (BPE) in liquid phase using Ni- and zeolite-based catalysts are explored. In the absence of catalysts, the C-O bond is selectively cleaved in water by hydrolysis, forming phenol and benzyl alcohol as intermediates, followed by alkylation. The hydronium ions catalyzing the reactions are provided by the dissociation of water at 523 K. Upon addition of HZSM-5, rates of hydrolysis and alkylation are markedly increased in relation to proton concentrations. In the presence of Ni/SiO2, the selective hydrogenolysis dominates for cleaving the Caliphatic-O bond. Catalyzed by the dual-functional Ni/HZSM-5, hydrogenolysis occurs as the major route rather than hydrolysis (minor route). In apolar undecane, the non-catalytic thermal pyrolysis route dominates. Hydrogenolysis of BPE appears to be the major reaction pathway in undecane in the presence of Ni/SiO2 or Ni/HZSM-5, almost completely suppressing radical reactions. Density functional theory (DFT) calculations strongly support the proposed C-O bond cleavage mechanisms on BPE in aqueous and apolar phases. These calculations show that BPE is initially protonated and subsequently hydrolyzed in the aqueous phase. Finally, DFT calculations suggest that the radical reactions in non-polar solvents lead to primary benzyl and phenoxy radicals in undecane, which leads to heavier condensation products as long as metals are absent for providing dissociated hydrogen.

  3. Effect of different solutions on electrochemical deposition of ZnO

    International Nuclear Information System (INIS)

    Asil, H.; Chinar, K.; Gur, E.; Tuzemen, S.

    2010-01-01

    ZnO thin films were grown by electrochemical deposition (ECD) onto indium tin oxide using different compounds such as Zn(NO 3 ) 2 , Zn(C 2 H 3 O 2 ) 2 , ZnCl 2 , Zn(ClO 4 ) 2 and different solvents such as dimethylsulfoxide (DMSO) and 18 M deionized water. Furthermore, solutions were prepared using different electrolytes and concentrations in order to determine the optimum deposition parameters of ZnO. All the grown films were characterized by X-ray diffraction, optical absorption and photoluminescence measurement techniques. It is indicated that films grown by using Zn(ClO 4 ) 2 show high crystallinity and optical quality. The X-ray diffraction analysis showed that ZnO thin films which were grown electrochemically in a non-aqueous solution (DMSO) prepared by Zn(ClO 4 ) 2 have highly c-axis preferential orientation. PL measurements showed that ZnO thin films grown in Zn(ClO 4 ) 2 indicates high quality emission characteristics compared to the thin films grown by other solutions

  4. Electrochemical corrosion behavior of carbon steel with bulk coating holidays

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    With epoxy coal tar as the coating material, the electrochemical corrosion behavior of Q235 with different kinds of bulk coating holidays has been investigated with EIS (Electrochemical Impedance Spectroscopy) in a 3.5vol% NaCl aqueous solution.The area ratio of bulk coating holiday to total coating area of steel is 4.91%. The experimental results showed that at free corrosionpotential, the corrosion of carbon steel with disbonded coating holiday is heavier than that with broken holiday and disbonded & broken holiday with time; Moreover, the effectiveness of Cathodic Protection (CP) of carbon steel with broken holiday is better than that with disbonded holiday and disbonded & broken holiday on CP potential -850 mV (vs CSE). Further analysis indicated that the two main reasons for corrosion are electrolyte solution slowly penetrating the coating, and crevice corrosion at steel/coating interface near holidays. The ratio of impedance amplitude (Z) of different frequency to minimum frequency is defined as K value. The change rate of K with frequency is related to the type of coating holiday.

  5. Hydrothermal-reduction synthesis of manganese oxide nanomaterials for electrochemical supercapacitors.

    Science.gov (United States)

    Zhang, Xiong; Chen, Yao; Yu, Peng; Ma, Yanwei

    2010-11-01

    In the present work, amorphous manganese oxide nanomaterials have been synthesized by a common hydrothermal method based on the redox reaction between MnO4(-) and Fe(2+) under an acidic condition. The synthesized MnO2 samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and electrochemical studies. XRD results showed that amorphous manganese oxide phase was obtained. XPS quantitative analysis revealed that the atomic ratio of Mn to Fe was 3.5 in the MnO2 samples. TEM images showed the porous structure of the samples. Electrochemical properties of the MnO2 electrodes were studied using cyclic voltammetry and galvanostatic charge-discharge cycling in 1 M Na2SO4 aqueous electrolyte, which showed excellent pseudocapacitance properties. A specific capacitance of 192 Fg(-1) at a current density of 0.5 Ag(-1) was obtained at the potential window from -0.1 to 0.9 V (vs. SCE).

  6. Cell voltage versus electrode potential range in aqueous supercapacitors

    Science.gov (United States)

    Dai, Zengxin; Peng, Chuang; Chae, Jung Hoon; Ng, Kok Chiang; Chen, George Z.

    2015-01-01

    Supercapacitors with aqueous electrolytes and nanostructured composite electrodes are attractive because of their high charging-discharging speed, long cycle life, low environmental impact and wide commercial affordability. However, the energy capacity of aqueous supercapacitors is limited by the electrochemical window of water. In this paper, a recently reported engineering strategy is further developed and demonstrated to correlate the maximum charging voltage of a supercapacitor with the capacitive potential ranges and the capacitance ratio of the two electrodes. Beyond the maximum charging voltage, a supercapacitor may still operate, but at the expense of a reduced cycle life. In addition, it is shown that the supercapacitor performance is strongly affected by the initial and zero charge potentials of the electrodes. Further, the differences are highlighted and elaborated between freshly prepared, aged under open circuit conditions, and cycled electrodes of composites of conducting polymers and carbon nanotubes. The first voltammetric charging-discharging cycle has an electrode conditioning effect to change the electrodes from their initial potentials to the potential of zero voltage, and reduce the irreversibility. PMID:25897670

  7. A comprehensive investigation on electrophoretic self-assembled nano-Co_3O_4 films in aqueous solution as electrode materials for supercapacitors

    International Nuclear Information System (INIS)

    Guo, Xiaogang; Li, Xueming; Xiong, Zhongshu; Lai, Chuan; Li, Yu; Huang, Xinyue; Bao, Hebin; Yin, Yanjun; Zhu, Yuhua; Zhang, Daixiong

    2016-01-01

    In this study, the nano-Co_3O_4 films (NCOFs) have been prepared by a one-step cathodic electrophoretic deposition (C-EPD) in aqueous solutions with micro-additive polyethylenimine at ambient temperature and pressure for oxide film-based supercapacitors. The phase composition and morphology of the NCOFs were studied by X-ray diffraction (XRD) and focused ion beam scanning electron microscope (FIB-SEM), respectively. In addition, the deposition kinetics of nano-Co_3O_4 particles using C-EPD process were investigated in detail. The electrochemical capacitance behaviors of the NCOFs electrode were analyzed by cyclic voltammetry, galvanostatic charge–discharge studies, and electrochemical impedance spectroscopy in 2 M KOH solution. The electrochemical experiments revealed that the highest capacitance of 233.6 F g"−"1 at 0.5 A g"−"1, 93.5 % of which still be maintained after 2000 charge–discharge cycles. These findings suggested the potential application of the NCOFs prepared by C-EPD in the electrochemical supercapacitors.

  8. NaTi2(PO4)3 as an Aqueous Anode: Degradation Mechanisms and Mitigation Techniques

    Science.gov (United States)

    Mohamed, Alexander I.

    With the proliferation of renewable energy sources, there has been a growing interest in battery chemistries for grid scale energy storage. Aqueous sodium ion batteries are particularly interesting for large scale energy storage because of their low cost and high safety, however, they tend to show poor long term stability. NaTi2(PO4)3 (NTP) shows promise as an anode for these systems with excellent long term stability when cycled quickly. When cycled slowly, NaTi2(PO4) 3 shows rapid capacity fade. The reasons for this rate depend capacity fade is poorly understood and is the topic of this document. It has been found that the products of the hydrogen evolution reaction, H2(g) and OH-, are the two largest contributors to capacity fade. High electrolyte pH caused by generation of OH- promotes dissolution of NTP during extend cycling, this is exacerbated when the pH increase above 11. The single greatest cause of apparent capacity fade for this material is loss of electrochemical surface area due to hydrogen gas entrapment within the porous structure of the electrode. Capacity lost in this manner can be recovered through reinfiltration of the electrode. The detrimental effects of gas entrapment within the electrode can be partially mitigated through compositing of the electrode with activated carbon and enhancing the wettability of the pores through addition of a surfactant to the electrolyte.

  9. Corrosion-electrochemical behaviour and mechanical properties ofaluminium alloy-321, alloyed by barium

    International Nuclear Information System (INIS)

    Ganiev, I.; Mukhiddinov, G.N.; Kargapolova, T.V.; Mirsaidov, U.

    1995-01-01

    The purpose of present work is studying of influence of barium additionson electrochemical corrosion of casting aluminium-copper alloy Al-321,containing as base alloying components copper, chromium, manganese, titanium,zirconium, cadmium

  10. Corrosion control of vanadium in aqueous solutions by amino acids

    International Nuclear Information System (INIS)

    El-Rabiee, M.M.; Helal, N.H.; El-Hafez, Gh.M. Abd; Badawy, W.A.

    2008-01-01

    The electrochemical behavior of vanadium in amino acid free and amino acid containing aqueous solutions of different pH was studied using open-circuit potential measurements, polarization techniques and electrochemical impedance spectroscopy (EIS). The corrosion current density, i corr , the corrosion potential, E corr and the corrosion resistance, R corr , were calculated. A group of amino acids, namely, glycine, alanine, valine, histidine, glutamic and cysteine has been investigated as environmentally safe inhibitors. The effect of Cl - on the corrosion inhibition efficiency especially in acid solutions was investigated. In neutral and basic solutions, the presence of amino acids increases the corrosion resistance of the metal. The electrochemical behavior of V before and after the corrosion inhibition process has shown that some amino acids like glutamic acid and histidine have promising corrosion inhibition efficiency at low concentration (≅25 mM). The inhibition efficiency (η) was found to depend on the structure of the amino acid and the constituents of the corrosive medium. The corrosion inhibition process is based on the adsorption of the amino acid molecules on the metal surface and the adsorption process follows the Freundlich isotherm. The adsorption free energy for valine on V in acidic solutions was found to be -9.4 kJ/mol which reveals strong physical adsorption of the amino acid molecules on the vanadium surface

  11. Electrochemical cleaning of Sv-08G2S wire surface

    International Nuclear Information System (INIS)

    Kozlov, E.I.; Degtyarev, V.G.; Novikov, M.P.

    1981-01-01

    Results of industrial tests of the Sv-08G2S wire with different state of surface fwith technological lubrication, after mechanical cleaning, with electrochemically cleaned surface) are presented. Advantages of welding-technological properties of the wire with electroe chemically cleaned surface are shown. An operation principle of the electrochemical cleaning facility is described. A brief specf ification f of the facility is given [ru

  12. Gas-Phase Functionalization of Macroscopic Carbon Nanotube Fiber Assemblies: Reaction Control, Electrochemical Properties, and Use for Flexible Supercapacitors.

    Science.gov (United States)

    Iglesias, Daniel; Senokos, Evgeny; Alemán, Belén; Cabana, Laura; Navío, Cristina; Marcilla, Rebeca; Prato, Maurizio; Vilatela, Juan J; Marchesan, Silvia

    2018-02-14

    The assembly of aligned carbon nanotubes (CNTs) into fibers (CNTFs) is a convenient approach to exploit and apply the unique physico-chemical properties of CNTs in many fields. CNT functionalization has been extensively used for its implementation into composites and devices. However, CNTF functionalization is still in its infancy because of the challenges associated with preservation of CNTF morphology. Here, we report a thorough study of the gas-phase functionalization of CNTF assemblies using ozone which was generated in situ from a UV source. In contrast with liquid-based oxidation methods, this gas-phase approach preserves CNTF morphology, while notably increasing its hydrophilicity. The functionalized material is thoroughly characterized by Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy. Its newly acquired hydrophilicity enables CNTF electrochemical characterization in aqueous media, which was not possible for the pristine material. Through comparison of electrochemical measurements in aqueous electrolytes and ionic liquids, we decouple the effects of functionalization on pseudocapacitive reactions and quantum capacitance. The functionalized CNTF assembly is successfully used as an active material and a current collector in all-solid supercapacitor flexible devices with an ionic liquid-based polymer electrolyte.

  13. Electrochemical and conversion electron Moessbauer study of corrosion induced by acid rain

    International Nuclear Information System (INIS)

    Vertes, C.; Lakatos-Varsanyi, M.; Vertes, A.; Meisel, W.; Guetlich, P.

    1993-01-01

    The passivation of low carbon steel was studied in aqueous solution of 0.5M Na 2 SO 4 +0.001M NaHSO 3 (pH 3.5, 6.5 and 8.5) which can be considered as a model of acid rain. The used conversion electron Moessbauer spectroscopy (CEMS) with the complementary electrochemical investigations proved that the sulfite ions induce pitting corrosion at pH 3.5 and 6.5, while the measurements showed much weaker pitting at pH 8.5. The compositions and thicknesses of the passive films formed during the electrochemical treatments are determined from the CEM spectra. Only γ-FeOOH was found on the surface of the samples at pH 6.5 and 8.5. Nevertheless, at pH 3.5 the sextet belonging to Fe 3 C appears in the spectra, and also FeSO 4 .H 2 O could be detected in low concentration. (orig.)

  14. Facile synthesis of polypyrrole nanofiber and its enhanced electrochemical performances in different electrolytes

    Directory of Open Access Journals (Sweden)

    C. K. Das

    2012-12-01

    Full Text Available A porous nanocomposite based on polypyrrole (PPy and sodium alginate (SA has been synthesized by easy, inexpensive, eco-friendly method. As prepared nanocomposite showed fibrillar morphology in transmission electron microscopic (TEM analysis. The average diameter of ~100 nm for the nanofibers was observed from scanning electron microscopic (SEM analysis. As prepared nanofiber, was investigated as an electrode material for supercapacitor application in different aqueous electrolyte solutions. PPy nanofiber showed enhanced electrochemical performances in 1M KCl solution as compared to 1M Na2SO4 solution. Maximum specific capacitance of 284 F/g was found for this composite in 1 M KCl electrolyte. It showed 76% specific capacitance retention after 600 cycles in 1 M KCl solution. Electrochemical Impedance Spectra showed moderate capacitive behavior of the composite in both the electrolytes. Further PPy nanofiber demonstrated higher thermal stability as compared to pure PPy.

  15. Well-ordered structure of methylene blue monolayers on Au(111) surface: electrochemical scanning tunneling microscopy studies.

    Science.gov (United States)

    Song, Yonghai; Wang, Li

    2009-02-01

    Well-ordered structure of methylene blue (MB) monolayers on Au(111) surface has been successfully obtained by controlling the substrate potential. Electrochemical scanning tunneling microscopy (ECSTM) examined the monolayers of MB on Au(111) in 0.1 M HClO(4) and showed long-range ordered, interweaved arrays of MB with quadratic symmetry on the substrate in the potential range of double-layer charging. High-resolution ECSTM image further revealed the details of the MB monolayers structure of c(5 x 5 radical 3)rect and the flat-lying orientation of ad-molecules. The dependence of molecular organization on the substrate potential and the formation mechanism of well-ordered structure on Au(111) surface were investigated in detail. The obtained well-ordered structure at the interface between a metal and an aqueous electrolyte might possibly be used as high-density device for signal memory and templates for the advanced nanopatterning of surfaces. (c) 2008 Wiley-Liss, Inc.

  16. Two-step controllable electrochemical etching of tungsten scanning probe microscopy tips

    KAUST Repository

    Khan, Yasser; Al-Falih, Hisham; Ng, Tien Khee; Ooi, Boon S.; Zhang, Yaping

    2012-01-01

    Dynamic electrochemical etching technique is optimized to produce tungsten tips with controllable shape and radius of curvature of less than 10 nm. Nascent features such as dynamic electrochemical etching and reverse biasing after drop-off are utilized, and two-step dynamic electrochemical etching is introduced to produce extremely sharp tips with controllable aspect ratio. Electronic current shut-off time for conventional dc drop-off technique is reduced to ?36 ns using high speed analog electronics. Undesirable variability in tip shape, which is innate to static dc electrochemical etching, is mitigated with novel dynamic electrochemical etching. Overall, we present a facile and robust approach, whereby using a novel etchant level adjustment mechanism, 30° variability in cone angle and 1.5 mm controllability in cone length were achieved, while routinely producing ultra-sharp probes. © 2012 American Institute of Physics.

  17. Electrochemical and Capacitive Properties of Carbon Dots/Reduced Graphene Oxide Supercapacitors.

    Science.gov (United States)

    Dang, Yong-Qiang; Ren, Shao-Zhao; Liu, Guoyang; Cai, Jiangtao; Zhang, Yating; Qiu, Jieshan

    2016-11-14

    There is much recent interest in graphene-based composite electrode materials because of their excellent mechanical strengths, high electron mobilities, and large specific surface areas. These materials are good candidates for applications in supercapacitors. In this work, a new graphene-based electrode material for supercapacitors was fabricated by anchoring carbon dots (CDs) on reduced graphene oxide (rGO). The capacitive properties of electrodes in aqueous electrolytes were systematically studied by galvanostatic charge-discharge measurements, cyclic voltammetry, and electrochemical impedance spectroscopy. The capacitance of rGO was improved when an appropriate amount of CDs were added to the material. The CD/rGO electrode exhibited a good reversibility, excellent rate capability, fast charge transfer, and high specific capacitance in 1 M H₂SO₄. Its capacitance was as high as 211.9 F/g at a current density of 0.5 A/g. This capacitance was 74.3% higher than that of a pristine rGO electrode (121.6 F/g), and the capacitance of the CD/rGO electrode retained 92.8% of its original value after 1000 cycles at a CDs-to-rGO ratio of 5:1.

  18. Electrochemical and Capacitive Properties of Carbon Dots/Reduced Graphene Oxide Supercapacitors

    Directory of Open Access Journals (Sweden)

    Yong-Qiang Dang

    2016-11-01

    Full Text Available There is much recent interest in graphene-based composite electrode materials because of their excellent mechanical strengths, high electron mobilities, and large specific surface areas. These materials are good candidates for applications in supercapacitors. In this work, a new graphene-based electrode material for supercapacitors was fabricated by anchoring carbon dots (CDs on reduced graphene oxide (rGO. The capacitive properties of electrodes in aqueous electrolytes were systematically studied by galvanostatic charge-discharge measurements, cyclic voltammetry, and electrochemical impedance spectroscopy. The capacitance of rGO was improved when an appropriate amount of CDs were added to the material. The CD/rGO electrode exhibited a good reversibility, excellent rate capability, fast charge transfer, and high specific capacitance in 1 M H2SO4. Its capacitance was as high as 211.9 F/g at a current density of 0.5 A/g. This capacitance was 74.3% higher than that of a pristine rGO electrode (121.6 F/g, and the capacitance of the CD/rGO electrode retained 92.8% of its original value after 1000 cycles at a CDs-to-rGO ratio of 5:1.

  19. The study of redox mechanism of dobutamine at different pH media by electrochemical and in situ spectroelectrochemical methods

    International Nuclear Information System (INIS)

    Yang Gongjun; Xu Jingjuan; Chen Hongyuan

    2004-01-01

    Based on the comprehensive analyses of the experimental results of the electrochemical methods, in situ UV-Vis absorption spectra, in situ electron spin resonance (ESR), and attenuated total-internal reflection (ATR) as well as the calculation of UV-Vis absorption data by PM3 Semi-Empirical method, a reaction mechanism for the redox processes of dobutamine was presented. When the anodic sweep is carried out, dobutamine firstly undergoes a free radical reaction with one-electron and one-proton to form semi-quinone free radicals, which will continuously convert to its corresponding quinone form by further electrochemical oxidation reaction. The formed quinone cannot only undergo a cyclization process by chemical reaction to produce a new compound, which can be reduced at more negative potential, but also be reduced to form dobutamine again when subsequent cathodic sweep is followed. The cyclization rate is depended upon pH values, and it increases with the increase of pH. In neutral medium, the corresponding oxidation form of the cyclization reaction product is easy to convert to melanin

  20. Fabrication of Microcomponents by Electrochemical Manufacturing: Advanced Feed-Through Metallisation on Silicon and Nickel Micromechanical Resonators

    DEFF Research Database (Denmark)

    Tang, Peter Torben; Heschel, Matthias; Ravnkilde, Jan Tue

    2000-01-01

    Electrochemical processes such as electroplating, wet selective etching (or controlled corrosion) and electroless plating are powerful tools for fabrication of MEMS (Micro ElectroMechanical Systems) products. Especially when the electrochemical processes are used in combination with UV-lithograph......Electrochemical processes such as electroplating, wet selective etching (or controlled corrosion) and electroless plating are powerful tools for fabrication of MEMS (Micro ElectroMechanical Systems) products. Especially when the electrochemical processes are used in combination with UV......, as well as nickel/gold pads for conductive adhesive bonding, are also deposited by electroplating. The second example is a simple, inexpensive, low-temperature electroplating process for fabrication of released, stress-free nickel comb resonators. Since the manufacturing sequence only involves low...

  1. Correlation between electrochemical impedance measurements and corrosion rate of magnesium investigated by real-time hydrogen measurement and optical imaging

    OpenAIRE

    Curioni, M.; Scenini, F.; Monetta, T.; Bellucci, F.

    2015-01-01

    The corrosion behaviour of magnesium in chloride-containing aqueous environment was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) performed simultaneously with real-time hydrogen evolution measurements and optical imaging of the corroding surface. The potentiodynamic investigation revealed substantial deviations from linearity in close proximity of the corrosion potential. In particular, differences in the slope of the current/potential curves w...

  2. Removal of Diazinon from aqueous solution by electrocoagulation process using aluminum electrodes

    International Nuclear Information System (INIS)

    Amooey, Ali Akbar; Ghasemi, Shahram; Mirsoleimani-azizi, Seyed Mohammad; Gholaminezhad, Zohreh; Chaichi, Mohammad Javad

    2014-01-01

    Electrocoagulation (EC) is an electrochemical method to treat polluted wastewaters and aqueous solutions. In this paper, the removal of Diazinon was studied by EC on aluminum electrode. The effect of several parameters such as initial concentration of Diazinon, current density, solution conductivity, effect of pH, and electrolysis time were investigated on EC performance. The obtained results showed that the removal efficiency of EC depends on the current density, initial concentration of Diazinon and electrolysis time. The optimum pH is 3 and also the solution conductivity has no significant effect on removal efficiency

  3. Removal of Diazinon from aqueous solution by electrocoagulation process using aluminum electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Amooey, Ali Akbar; Ghasemi, Shahram; Mirsoleimani-azizi, Seyed Mohammad; Gholaminezhad, Zohreh; Chaichi, Mohammad Javad [University of Mazandaran, Babolsar (Iran, Islamic Republic of)

    2014-06-15

    Electrocoagulation (EC) is an electrochemical method to treat polluted wastewaters and aqueous solutions. In this paper, the removal of Diazinon was studied by EC on aluminum electrode. The effect of several parameters such as initial concentration of Diazinon, current density, solution conductivity, effect of pH, and electrolysis time were investigated on EC performance. The obtained results showed that the removal efficiency of EC depends on the current density, initial concentration of Diazinon and electrolysis time. The optimum pH is 3 and also the solution conductivity has no significant effect on removal efficiency.

  4. Role of polymeric binders on mechanical behavior and cracking resistance of silicon composite electrodes during electrochemical cycling

    Science.gov (United States)

    Li, Dawei; Wang, Yikai; Hu, Jiazhi; Lu, Bo; Dang, Dingying; Zhang, Junqian; Cheng, Yang-Tse

    2018-05-01

    This work focuses on understanding the role of various binders, including sodium alginate (SA), Nafion, and polyvinylidene fluoride (PVDF), on the mechanical behavior and cracking resistance of silicon composite electrodes during electrochemical cycling. In situ curvature measurement of bilayer electrodes, consisting of a silicon-binder-carbon black composite layer on a copper foil, is used to determine the effects of binders on bending deformation, elastic modulus, and stress on the composite electrodes. It is found that the lithiation induced curvature and the modulus of the silicon/SA electrodes are larger than those of electrodes with Nafion and PVDF as binders. Although the modulus of Nafion is smaller than that of PVDF, the curvature and the modulus of silicon/Nafion composite are larger than those of silicon/PVDF electrodes. The moduli of all three composites decrease not only during lithiation but also during delithiation. Based on the measured stress and scanning electron microscopy observations of cracking in the composite electrodes, we conclude that the stress required to crack the composite electrodes with SA and Nafion binders is considerably higher than that of the silicon/PVDF electrode during electrochemical cycling. Thus, the cracking resistance of silicon/SA and silicon/Nafion composite electrodes is higher than that of silicon/PVDF electrodes.

  5. Rechargeable Aqueous Zinc-Ion Battery Based on Porous Framework Zinc Pyrovanadate Intercalation Cathode

    KAUST Repository

    Xia, Chuan

    2017-12-11

    In this work, a microwave approach is developed to rapidly synthesize ultralong zinc pyrovanadate (Zn3V2O7(OH)2·2H2O, ZVO) nanowires with a porous crystal framework. It is shown that our synthesis strategy can easily be extended to fabricate other metal pyrovanadate compounds. The zinc pyrovanadate nanowires show significantly improved electrochemical performance when used as intercalation cathode for aqueous zinc–ion battery. Specifically, the ZVO cathode delivers high capacities of 213 and 76 mA h g−1 at current densities of 50 and 3000 mA g−1, respectively. Furthermore, the Zn//ZVO cells show good cycling stability up to 300 cycles. The estimated energy density of this Zn cell is ≈214Wh kg−1, which is much higher than commercial lead–acid batteries. Significant insight into the Zn-storage mechanism in the pyrovanadate cathodes is presented using multiple analytical methods. In addition, it is shown that our prototype device can power a 1.5 V temperature sensor for at least 24 h.

  6. A multi-level quantum mechanics and molecular mechanics study of SN2 reaction at nitrogen: NH2Cl + OH(-) in aqueous solution.

    Science.gov (United States)

    Lv, Jing; Zhang, Jingxue; Wang, Dunyou

    2016-02-17

    We employed a multi-level quantum mechanics and molecular mechanics approach to study the reaction NH2Cl + OH(-) in aqueous solution. The multi-level quantum method (including the DFT method with both the B3LYP and M06-2X exchange-correlation functionals and the CCSD(T) method, and both methods with the aug-cc-pVDZ basis set) was used to treat the quantum reaction region in different stages of the calculation in order to obtain an accurate potential of mean force. The obtained free energy activation barriers at the DFT/MM level of theory yielded a big difference of 21.8 kcal mol(-1) with the B3LYP functional and 27.4 kcal mol(-1) with the M06-2X functional respectively. Nonetheless, the barrier heights become very close when shifted from DFT to CCSD(T): 22.4 kcal mol(-1) and 22.9 kcal mol(-1) at CCSD(T)(B3LYP)/MM and CCSD(T)(M06-2X)/MM levels of theory, respectively. The free reaction energy obtained using CCSD(T)(M06-2X)/MM shows an excellent agreement with the one calculated using the available gas-phase data. Aqueous solution plays a significant role in shaping the reaction profile. In total, the water solution contributes 13.3 kcal mol(-1) and 14.6 kcal mol(-1) to the free energy barrier heights at CCSD(T)(B3LYP)/MM and CCSD(T)(M06-2X)/MM respectively. The title reaction at nitrogen is a faster reaction than the corresponding reaction at carbon, CH3Cl + OH(-).

  7. Electrical and Electrochemical Properties of Conducting Polymers

    Directory of Open Access Journals (Sweden)

    Thanh-Hai Le

    2017-04-01

    Full Text Available Conducting polymers (CPs have received much attention in both fundamental and practical studies because they have electrical and electrochemical properties similar to those of both traditional semiconductors and metals. CPs possess excellent characteristics such as mild synthesis and processing conditions, chemical and structural diversity, tunable conductivity, and structural flexibility. Advances in nanotechnology have allowed the fabrication of versatile CP nanomaterials with improved performance for various applications including electronics, optoelectronics, sensors, and energy devices. The aim of this review is to explore the conductivity mechanisms and electrical and electrochemical properties of CPs and to discuss the factors that significantly affect these properties. The size and morphology of the materials are also discussed as key parameters that affect their major properties. Finally, the latest trends in research on electrochemical capacitors and sensors are introduced through an in-depth discussion of the most remarkable studies reported since 2003.

  8. In Situ Real-Time Mechanical and Morphological Characterization of Electrodes for Electrochemical Energy Storage and Conversion by Electrochemical Quartz Crystal Microbalance with Dissipation Monitoring.

    Science.gov (United States)

    Shpigel, Netanel; Levi, Mikhael D; Sigalov, Sergey; Daikhin, Leonid; Aurbach, Doron

    2018-01-16

    Quartz crystal microbalance with dissipation monitoring (QCM-D) generates surface-acoustic waves in quartz crystal plates that can effectively probe the structure of films, particulate composite electrodes of complex geometry rigidly attached to quartz crystal surface on one side and contacting a gas or liquid phase on the other side. The output QCM-D characteristics consist of the resonance frequency (MHz frequency range) and resonance bandwidth measured with extra-ordinary precision of a few tenths of Hz. Depending on the electrodes stiffness/softness, QCM-D operates either as a gravimetric or complex mechanical probe of their intrinsic structure. For at least 20 years, QCM-D has been successfully used in biochemical and environmental science and technology for its ability to probe the structure of soft solvated interfaces. Practical battery and supercapacitor electrodes appear frequently as porous solids with their stiffness changing due to interactions with electrolyte solutions or as a result of ion intercalation/adsorption and long-term electrode cycling. Unfortunately, most QCM measurements with electrochemical systems are carried out based on a single (fundamental) frequency and, as such, provided that the resonance bandwidth remains constant, are suitable for only gravimetric sensing. The multiharmonic measurements have been carried out mainly on conducting/redox polymer films rather than on typical composite battery/supercapacitor electrodes. Here, we summarize the most recent publications devoted to the development of electrochemical QCM-D (EQCM-D)-based methodology for systematic characterization of mechanical properties of operating battery/supercapacitor electrodes. By varying the electrodes' composition and structure (thin/thick layers, small/large particles, binders with different mechanical properties, etc.), nature of the electrolyte solutions and charging/cycling conditions, the method is shown to be operated in different application modes. A

  9. Electrochemical degradation of sulfonamides at BDD electrode: Kinetics, reaction pathway and eco-toxicity evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Fabiańska, Aleksandra; Białk-Bielińska, Anna; Stepnowski, Piotr [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland); Stolte, Stefan [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland); UFT-Centre of Environmental Research and Sustainable Technology, University of Bremen, Leobener Straße UFT, D-28359 Bremen (Germany); Siedlecka, Ewa Maria, E-mail: ewa.siedlecka@ug.edu.pl [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland)

    2014-09-15

    Highlights: • SNs were electrochemically oxidized at BDD in one compartment reactor. • The efficiency of SN degradation was the highest in effluents from municipal WWTP. • The electro-degradation SNs based on oxidation but reduction was also possible. • Electrochemical oxidation of SNs led in some cases to mixtures toxic to L. minor. - Abstract: The investigation dealt with electrochemical oxidation of five sulfonamides (SNs): sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMN) and sulfadimethoxine (SDM) in aqueous solution at boron-doped diamond (BDD) electrode. All studied sulfonamides were degraded according to a pseudo first order kinetics. The structure of SNs had no significant effect on the values of pseudo first order rate constants. Increased degradation efficiency was observed in higher temperature and in acidic pH. Due to the presence of chlorine and nitrate SNs were more effectively oxidized from municipal wastewater treatment plant (WWTP) effluents than from pure supporting electrolyte Na{sub 2}SO{sub 4}. The intermediates identified by LC–MS and GC–MS analysis suggested that the hydroxyl radicals attack mainly the S-N bond, but also the aromatic ring systems (aniline, pyrimidine or triazole) of SNs. Finally, the toxicity of the SNs solutions and effluents after electrochemical treatment was assessed through the measurement of growth inhibition of green algae (Scenedesmus vacualatus) and duckweed (Lemna minor). Toxicity of SMR, STZ, SMN solutions before and after electrochemical oxidation and SDM solution after the process in L. minor test was observed. No significant toxicity of studied SNs was observed in algae test.

  10. Electrochemical degradation of sulfonamides at BDD electrode: Kinetics, reaction pathway and eco-toxicity evaluation

    International Nuclear Information System (INIS)

    Fabiańska, Aleksandra; Białk-Bielińska, Anna; Stepnowski, Piotr; Stolte, Stefan; Siedlecka, Ewa Maria

    2014-01-01

    Highlights: • SNs were electrochemically oxidized at BDD in one compartment reactor. • The efficiency of SN degradation was the highest in effluents from municipal WWTP. • The electro-degradation SNs based on oxidation but reduction was also possible. • Electrochemical oxidation of SNs led in some cases to mixtures toxic to L. minor. - Abstract: The investigation dealt with electrochemical oxidation of five sulfonamides (SNs): sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMN) and sulfadimethoxine (SDM) in aqueous solution at boron-doped diamond (BDD) electrode. All studied sulfonamides were degraded according to a pseudo first order kinetics. The structure of SNs had no significant effect on the values of pseudo first order rate constants. Increased degradation efficiency was observed in higher temperature and in acidic pH. Due to the presence of chlorine and nitrate SNs were more effectively oxidized from municipal wastewater treatment plant (WWTP) effluents than from pure supporting electrolyte Na 2 SO 4 . The intermediates identified by LC–MS and GC–MS analysis suggested that the hydroxyl radicals attack mainly the S-N bond, but also the aromatic ring systems (aniline, pyrimidine or triazole) of SNs. Finally, the toxicity of the SNs solutions and effluents after electrochemical treatment was assessed through the measurement of growth inhibition of green algae (Scenedesmus vacualatus) and duckweed (Lemna minor). Toxicity of SMR, STZ, SMN solutions before and after electrochemical oxidation and SDM solution after the process in L. minor test was observed. No significant toxicity of studied SNs was observed in algae test

  11. UNIQUAC interaction parameters for molecules with -OH groups on adjacent carbon atoms in aqueous solution determined by molecular mechanics - glycols, glycerol and glucose

    DEFF Research Database (Denmark)

    Jonsdottir, Svava Osk; Klein, R. A.

    1997-01-01

    UNIQUAC interaction parameters have been determined, using molecular mechanics calculations, for 1,2-ethanediol, 1,2-propanediol, glycerol and glucose with water in aqueous solution. Conformational space for individual pairs of molecules was explored using a stochastic method, the Boltzmann Jump...

  12. The atomic force microscope as a mechano–electrochemical pen

    Directory of Open Access Journals (Sweden)

    Christian Obermair

    2011-10-01

    Full Text Available We demonstrate a method that allows the controlled writing of metallic patterns on the nanometer scale using the tip of an atomic force microscope (AFM as a “mechano–electrochemical pen”. In contrast to previous experiments, no voltage is applied between the AFM tip and the sample surface. Instead, a passivated sample surface is activated locally due to lateral forces between the AFM tip and the sample surface. In this way, the area of tip–sample interaction is narrowly limited by the mechanical contact between tip and sample, and well-defined metallic patterns can be written reproducibly. Nanoscale structures and lines of copper were deposited, and the line widths ranged between 5 nm and 80 nm, depending on the deposition parameters. A procedure for the sequential writing of metallic nanostructures is introduced, based on the understanding of the passivation process. The mechanism of this mechano–electrochemical writing technique is investigated, and the processes of site-selective surface depassivation, deposition, dissolution and repassivation of electrochemically deposited nanoscale metallic islands are studied in detail.

  13. Stabilizers of edaravone aqueous solution and their action mechanisms. 1. Sodium bisulfite

    OpenAIRE

    Tanaka, Masahiko; Sugimura, Natsuhiko; Fujisawa, Akio; Yamamoto, Yorihiro

    2017-01-01

    Edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one) has been used as a free radical scavenging drug for the treatment of acute ischemic stroke in Japan since 2001. Edaravone is given to patients intravenously; therefore, it is distributed in the form of an aqueous solution. However, aqueous solutions of edaravone are very unstable because it is present as edaravone anion, which is capable of transferring an electron to free radicals including oxygen, and becomes edaravone radical. We observed the...

  14. Electrochemical and hydrothermal deposition of ZnO on silicon: from continuous films to nanocrystals

    International Nuclear Information System (INIS)

    Balucani, M.; Nenzi, P.; Chubenko, E.; Klyshko, A.; Bondarenko, V.

    2011-01-01

    This article presents the study of the electrochemical deposition of zinc oxide from the non-aqueous solution based on dimethyl sulfoxide and zinc chloride into the porous silicon matrix. The features of the deposition process depending on the thickness of the porous silicon layer are presented. It is shown that after deposition process the porous silicon matrix is filled with zinc oxide nanocrystals with a diameter of 10–50 nm. The electrochemically deposited zinc oxide layers on top of porous silicon are shown to have a crystalline structure. It is also shown that zinc oxide crystals formed by hydrothermal method on the surface of electrochemically deposited zinc oxide film demonstrate ultra-violet luminescence. The effect of the porous silicon layer thickness on the morphology of the zinc oxide is shown. The structures obtained demonstrated two luminescence bands peaking at the 375 and 600 nm wavelengths. Possible applications of ZnO nanostructures, porous and continuous polycrystalline ZnO films such as gas sensors, light-emitting diodes, photovoltaic devices, and nanopiezo energy generators are considered. Aspects of integration with conventional silicon technology are also discussed.

  15. Electrochemical characterisation speeds up prediction of corrosion behaviour

    Energy Technology Data Exchange (ETDEWEB)

    Schuring, E.W.; Hooijmans, J.W. [ECN Environment and Energy Engineering, Petten (Netherlands)

    2013-04-15

    The contents of this presentation show the following elements: Introduction; Corrosion in real life; Why Electrochemical characterisation of corrosion; Applications (corrosion resistance coatings, corrosion behaviour (brazed) joints); Available electrochemical corrosion techniques; Standards; Conclusions. In the Conclusions the corrosion screening method is summarized: ECN method fast; within 1h -1 week results depending on test method; Fast pre-selection of promising materials/combinations (cost savings); Determining of corrosion initiation; Determination of corrosion mechanisms and propagation; Life time predictions possible; Strong combination with metallographic post-investigation; Ranking materials / constructions for corrosion performance.

  16. Acidic aqueous uranium electrodeposition for target fabrication

    International Nuclear Information System (INIS)

    Saliba-Silva, A.M.; Oliveira, E.T.; Garcia, R.H.L.; Durazzo, M.

    2013-01-01

    Direct irradiation of targets inside nuclear research or multiple purpose reactors is a common route to produce 99 Mo- 99m Tc radioisotopes. The electroplating of low enriched uranium over nickel substrate might be a potential alternative to produce targets of 235 U. The electrochemistry of uranium at low temperature might be beneficial for an alternative route to produce 99 Mo irradiation LEU targets. Electrodeposition of uranium can be made using ionic and aqueous solutions producing uranium oxide deposits. The performance of uranium electrodeposition is relatively low because a big competition with H 2 evolution happens inside the window of electrochemical reduction potential. This work explores possibilities of electroplating uranium as UO 2 2+ (Uranium-VI) in order to achieve electroplating uranium in a sufficient amount to be commercially irradiated in the future Brazilian RMB reactor. Electroplated nickel substrate was followed by cathodic current electrodeposition from aqueous UO 2 (NO 3 ) 2 solution. EIS tests and modeling showed that a film formed differently in the three tested cathodic potentials. At the lower level, (-1.8V) there was an indication of a double film formation, one overlaying the other with ionic mass diffusion impaired at the interface with nickel substrate as showed by the relatively lower admittance of Warburg component. (author)

  17. Removal mechanism of phosphate from aqueous solution by fly ash.

    Science.gov (United States)

    Lu, S G; Bai, S Q; Zhu, L; Shan, H D

    2009-01-15

    This work studied the effectiveness of fly ash in removing phosphate from aqueous solution and its related removal mechanism. The adsorption and precipitation of phosphate by fly ash were investigated separately in order to evaluate their role in the removal of phosphate. Results showed that the removal of phosphate by fly ash was rapid. The removal percentage of phosphate in the first 5min reached 68-96% of the maximum removal of phosphate by fly ash. The removal processes of phosphate by fly ash included a fast and large removal representing precipitation, then a slower and longer removal due to adsorption. The adsorption of phosphate on fly ash could be described well by Freundlich isotherm equation. The pH and Ca2+ concentration of fly ash suspension were decreased with the addition of phosphate, which suggests that calcium phosphate precipitation is a major mechanism of the phosphate removal. Comparison of the relative contribution of the adsorption and precipitation to the total removal of phosphate by fly ash showed that the adsorption accounted for 30-34% of the total removal of phosphate, depending on the content of CaO in fly ash. XRD patterns of the fly ash before and after phosphate adsorption revealed that phosphate salt (CaHPO4 x 2H2O) was formed in the adsorption process. Therefore, the removal of phosphate by fly ash can be attributed to the formation of phosphate precipitation as a brushite and the adsorption on hydroxylated oxides. The results suggested that the use of fly ash could be a promising solution to the removal of phosphate in the wastewater treatment and pollution control.

  18. Electro-gravimetric recovery of silver from aqueous solutions and its precursors

    Directory of Open Access Journals (Sweden)

    A. Shah,

    2016-08-01

    Full Text Available A simple electrolytic cell was used for electrochemical recovery of silver from aqueous solutions containing 100 mg/L Ag(I. Two different sets of electrodes were applied to find the enhanced recovery of silver. Rocks and ores samples were processed through fire assay method and acid digestion. A set of electrodes comprised of stainless steel anode and aluminum cathode gave maximum recovery (96.5% of silver. This simple, robust, environment friendly and highly sensitive method was effectively applied to various ores and rock samples. The developed method with slight modifications can also be applied for the recovery of other metals.

  19. Advanced Proton Conducting Polymer Electrolytes for Electrochemical Capacitors

    Science.gov (United States)

    Gao, Han

    Research on solid electrochemical energy storage devices aims to provide high performance, low cost, and safe operation solutions for emerging applications from flexible consumer electronics to microelectronics. Polymer electrolytes, minimizing device sealing and liquid electrolyte leakage, are key enablers for these next-generation technologies. In this thesis, a novel proton-conducing polymer electrolyte system has been developed using heteropolyacids (HPAs) and polyvinyl alcohol for electrochemical capacitors. A thorough understanding of proton conduction mechanisms of HPAs together with the interactions among HPAs, additives, and polymer framework has been developed. Structure and chemical bonding of the electrolytes have been studied extensively to identify and elucidate key attributes affecting the electrolyte properties. Numerical models describing the proton conduction mechanism have been applied to differentiate those attributes. The performance optimization of the polymer electrolytes through additives, polymer structural modifications, and synthesis of alternative HPAs has achieved several important milestones, including: (a) high proton mobility and proton density; (b) good ion accessibility at electrode/electrolyte interface; (c) wide electrochemical stability window; and (d) good environmental stability. Specifically, high proton mobility has been addressed by cross-linking the polymer framework to improve the water storage capability at normal-to-high humidity conditions (e.g. 50-80% RH) as well as by incorporating nano-fillers to enhance the water retention at normal humidity levels (e.g. 30-60% RH). High proton density has been reached by utilizing additional proton donors (i.e. acidic plasticizers) and by developing different HPAs. Good ion accessibility has been achieved through addition of plasticizers. Electrochemical stability window of the electrolyte system has also been investigated and expanded by utilizing HPAs with different heteroatoms

  20. Electrochemical biosensors

    CERN Document Server

    Cosnier, Serge

    2015-01-01

    "This is an excellent book on modern electrochemical biosensors, edited by Professor Cosnier and written by leading international experts. It covers state-of-the-art topics of this important field in a clear and timely manner."-Prof. Joseph Wang, UC San Diego, USA  "This book covers, in 13 well-illustrated chapters, the potential of electrochemical methods intimately combined with a biological component for the assay of various analytes of biological and environmental interest. Particular attention is devoted to the description of electrochemical microtools in close contact with a biological cell for exocytosis monitoring and to the use of nanomaterials in the electrochemical biosensor architecture for signal improvement. Interestingly, one chapter describes the concept and design of self-powered biosensors derived from biofuel cells. Each topic is reviewed by experts very active in the field. This timely book is well suited for providing a good overview of current research trends devoted to electrochemical...