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Sample records for electrochemical oxidation process

  1. Removal of estrogens by electrochemical oxidation process.

    PubMed

    Cong, Vo Huu; Iwaya, Sota; Sakakibara, Yutaka

    2014-06-01

    Treatments of estrogens such as Estrone (E1), Estradiol (E2) and Ethinylestradiol (EE2) were conducted using an electrolytic reactor equipped with multi-packed granular glassy carbon electrodes. Experimental results showed that E1, E2 and EE2 were oxidized in the range of 0.45-0.85 V and were removed through electro-polymerization. Observed data from continuous experiments were in good agreement with calculated results by a mathematical model constructed based on mass transfer limitation. In continuous treatment of trace estrogens (1 μg/L), 98% of E1, E2 and EE2 were stably removed. At high loading rate (100 μg/L), removal efficiency of E1 was kept around 74%-88% for 21 days, but removal efficiency reduced due to passivation of electrodes. However, removal efficiency was recovered after electrochemical regeneration of electrodes in presence of ozone. Electric energy consumption was observed in the range of 1-2 Wh/m(3). From these results, we concluded that the present electrochemical process would be an alternative removal of estrogens. PMID:25079848

  2. Solid oxide electrochemical cell fabrication process

    DOEpatents

    Dollard, Walter J.; Folser, George R.; Pal, Uday B.; Singhal, Subhash C.

    1992-01-01

    A method to form an electrochemical cell (12) is characterized by the steps of thermal spraying stabilized zirconia over a doped lanthanum manganite air electrode tube (14) to provide an electrolyte layer (15), coating conductive particles over the electrolyte, pressurizing the outside of the electrolyte layer, feeding halide vapors of yttrium and zirconium to the outside of the electrolyte layer and feeding a source of oxygen to the inside of the electrolyte layer, heating to cause oxygen reaction with the halide vapors to close electrolyte pores if there are any and to form a metal oxide coating on and between the particles and provide a fuel electrode (16).

  3. ELECTROCHEMICAL ADVANCED OXIDATION PROCESS UTILIZING NB-DOPED TIO2 ELECTRODES

    EPA Science Inventory

    An electrochemical advanced oxidation process has been developed utilizing electrodes which generate hydroxyl free radical (HO) by oxidizing water. All substrates tested are oxidized, mostly with reaction rates proportional to the corresponding rate constants for reaction with hy...

  4. ELECTROCHEMICAL ADVANCED OXIDATION PROCESS UTILIZING NB-DOPED TIO2 ELECTRODES

    EPA Science Inventory

    An electrochemical advanced oxidation process has been developed, utilizing electrodes which generate hydroxyl free radical (HO) by oxidizing water. All substrates tested are oxidized, mostly with reaction rates proportional to the corresponding rate constants for reaction with h...

  5. Costs of the electrochemical oxidation of wastewaters: a comparison with ozonation and Fenton oxidation processes.

    PubMed

    Cañizares, Pablo; Paz, Rubén; Sáez, Cristina; Rodrigo, Manuel A

    2009-01-01

    In the work described here the technical and economic feasibilities of three Advanced Oxidation Processes (AOPs) have been studied: Conductive-Diamond Electrochemical Oxidation (CDEO), Ozonation and Fenton oxidation. The comparison was made by assessing the three technologies with synthetic wastewaters polluted with different types of organic compounds and also with actual wastes (from olive oil mills and from a fine-chemical manufacturing plant). All three technologies were able to treat the wastes, but very different results were obtained in terms of efficiency and mineralization. Only CDEO could achieve complete mineralization of the pollutants for all the wastes. However, the efficiencies were found to depend on the concentration of pollutant (mass transfer control of the oxidation rate). Results obtained in the oxidation with ozone (at pH 12) or by Fenton's reagent were found to depend on the nature of the pollutants, and significant concentrations of oxidation-refractory compounds were usually accumulated during the treatment. Within the discharge limits that all of the technologies can reach, the economic analysis shows that the operating cost of Fenton oxidation is lower than either CDEO or ozonation, although CD\\EO can compete satisfactorily with the Fenton process in the treatment of several kinds of wastes. Likewise, the investment cost for the ozonation process seems to be higher than either CDEO or Fenton oxidation, regardless of the pollutant treated. PMID:18082930

  6. STEP wastewater treatment: a solar thermal electrochemical process for pollutant oxidation.

    PubMed

    Wang, Baohui; Wu, Hongjun; Zhang, Guoxue; Licht, Stuart

    2012-10-01

    A solar thermal electrochemical production (STEP) pathway was established to utilize solar energy to drive useful chemical processes. In this paper, we use experimental chemistry for efficient STEP wastewater treatment, and suggest a theory based on the decreasing stability of organic pollutants (hydrocarbon oxidation potentials) with increasing temperature. Exemplified by the solar thermal electrochemical oxidation of phenol, the fundamental model and experimental system components of this process outline a general method for the oxidation of environmentally stable organic pollutants into carbon dioxide, which is easily removed. Using thermodynamic calculations we show a sharply decreasing phenol oxidation potential with increasing temperature. The experimental results demonstrate that this increased temperature can be supplied by solar thermal heating. In combination this drives electrochemical phenol removal with enhanced oxidation efficiency through (i) a thermodynamically driven decrease in the energy needed to fuel the process and (ii) improved kinetics to sustain high rates of phenol oxidation at low electrochemical overpotential. The STEP wastewater treatment process is synergistic in that it is performed with higher efficiency than either electrochemical or photovoltaic conversion process acting alone. STEP is a green, efficient, safe, and sustainable process for organic wastewater treatment driven solely by solar energy. PMID:22965739

  7. Remediation of a winery wastewater combining aerobic biological oxidation and electrochemical advanced oxidation processes.

    PubMed

    Moreira, Francisca C; Boaventura, Rui A R; Brillas, Enric; Vilar, Vítor J P

    2015-05-15

    Apart from a high biodegradable fraction consisting of organic acids, sugars and alcohols, winery wastewaters exhibit a recalcitrant fraction containing high-molecular-weight compounds as polyphenols, tannins and lignins. In this context, a winery wastewater was firstly subjected to a biological oxidation to mineralize the biodegradable fraction and afterwards an electrochemical advanced oxidation process (EAOP) was applied in order to mineralize the refractory molecules or transform them into simpler ones that can be further biodegraded. The biological oxidation led to above 97% removals of dissolved organic carbon (DOC), chemical oxygen demand (COD) and 5-day biochemical oxygen demand (BOD5), but was inefficient on the degradation of a bioresistant fraction corresponding to 130 mg L(-1) of DOC, 380 mg O2 L(-1) of COD and 8.2 mg caffeic acid equivalent L(-1) of total dissolved polyphenols. Various EAOPs such as anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF) and solar PEF (SPEF) were then applied to the recalcitrant effluent fraction using a 2.2 L lab-scale flow plant containing an electrochemical cell equipped with a boron-doped diamond (BDD) anode and a carbon-PTFE air-diffusion cathode and coupled to a photoreactor with compound parabolic collectors (CPCs). The influence of initial Fe(2+) concentration and current density on the PEF process was evaluated. The relative oxidative ability of EAOPs increased in the order AO-H2O2 < EF < PEF ≤ SPEF. The SPEF process using an initial Fe(2+) concentration of 35 mg L(-1), current density of 25 mA cm(-2), pH of 2.8 and 25 °C reached removals of 86% on DOC and 68% on COD after 240 min, regarding the biologically treated effluent, along with energy consumptions of 45 kWh (kg DOC)(-1) and 5.1 kWh m(-3). After this coupled treatment, color, odor, COD, BOD5, NH4(+), NO3(-) and SO4(2-) parameters complied with the legislation targets and, in addition, a total

  8. Electrochemical oxidation of cholesterol

    PubMed Central

    2015-01-01

    Summary Indirect cholesterol electrochemical oxidation in the presence of various mediators leads to electrophilic addition to the double bond, oxidation at the allylic position, oxidation of the hydroxy group, or functionalization of the side chain. Recent studies have proven that direct electrochemical oxidation of cholesterol is also possible and affords different products depending on the reaction conditions. PMID:25977713

  9. Occurrence and Removal of Organic Micropollutants in Landfill Leachates Treated by Electrochemical Advanced Oxidation Processes.

    PubMed

    Oturan, Nihal; van Hullebusch, Eric D; Zhang, Hui; Mazeas, Laurent; Budzinski, Hélène; Le Menach, Karyn; Oturan, Mehmet A

    2015-10-20

    In recent years, electrochemical advanced oxidation processes have been shown to be an effective alternative for the removal of refractory organic compounds from water. This study is focused on the effective removal of recalcitrant organic matter (micropollutants, humic substances, etc.) present in municipal solid waste landfill leachates. A mixture of eight landfill leachates has been studied by the electro-Fenton process using a Pt or boron-doped diamond (BDD) anode and a carbon felt cathode or by the anodic oxidation process with a BDD anode. These processes exhibit great oxidation ability due to the in situ production of hydroxyl radicals ((•)OH), a highly powerful oxidizing species. Both electrochemical processes were shown to be efficient in the removal of dissolved total organic carbon (TOC) from landfill leachates. Regarding the electro-Fenton process, the replacement of the classical anode Pt by the anode BDD allows better performance in terms of dissolved TOC removal. The occurrence and removal yield of 19 polycyclic aromatic hydrocarbons, 15 volatile organic compounds, 7 alkylphenols, 7 polychlorobiphenyls, 5 organochlorine pesticides, and 2 polybrominated diphenyl ethers in landfill leachate were also investigated. Both electrochemical processes allow one to reach a quasicomplete removal (about 98%) of these organic micropollutants. PMID:26378656

  10. Integrating electrochemical oxidation into forward osmosis process for removal of trace antibiotics in wastewater.

    PubMed

    Liu, Pengxiao; Zhang, Hanmin; Feng, Yujie; Shen, Chao; Yang, Fenglin

    2015-10-15

    During the rejection of trace pharmaceutical contaminants from wastewater by forward osmosis (FO), disposal of the FO concentrate was still an unsolved issue. In this study, by integrating the advantages of forward osmosis and electrochemical oxidation, a forward osmosis process with the function of electrochemical oxidation (FOwEO) was established for the first time to achieve the aim of rejection of trace antibiotics from wastewater and treatment of the concentrate at the same time. Results demonstrated that FOwEO (current density J=1 mA cm(-2)) exhibited excellent rejections of antibiotics (>98%) regardless of different operation conditions, and above all, antibiotics in the concentrate were well degraded (>99%) at the end of experiment (after 3h). A synergetic effect between forward osmosis and electrochemical oxidation was observed in FOwEO, which lies in that antibiotic rejections by FO were enhanced due to the degradation of antibiotics in the concentrate, while the electrochemical oxidation capacity was improved in the FOwEO channel, of which good mass transfer and the assist of indirect oxidation owing to the reverse NaCl from draw solution were supposed to be the mechanism. This study demonstrated that the FOwEO has the capability to thoroughly remove trace antibiotics from wastewater. PMID:25966924

  11. A comparison between conductive-diamond electrochemical oxidation and other advanced oxidation processes for the treatment of synthetic melanoidins.

    PubMed

    Cañizares, P; Hernández-Ortega, M; Rodrigo, M A; Barrera-Díaz, C E; Roa-Morales, G; Sáez, C

    2009-05-15

    In this study, three technologies classified as Advanced Oxidation Processes (Conductive-Diamond Electrochemical Oxidation (CDEO), ozonation and Fenton oxidation) have been compared to treat wastes produced in fermentation processes, and characterized by a significant color and a high organic load. Results of CDEO seem to strongly depend on the addition of an electrolyte salt, not only to decrease the energy cost but also to improve efficiency. The addition of sodium chloride as supporting electrolyte improves the removal percentages of organic load, indicating the important role of mediated oxidation processes carried out by the electrogenerated oxidants (hypochlorite). Fenton oxidation and ozonation seem to be less efficient, and mainly Fenton oxidation favors the accumulation of refractory compounds. The differences observed can be explained in terms of the contribution of hydroxyl radicals and other specific oxidation mechanisms involved in each technology. PMID:18789836

  12. Post-treatment of reclaimed waste water based on an electrochemical advanced oxidation process

    NASA Technical Reports Server (NTRS)

    Verostko, Charles E.; Murphy, Oliver J.; Hitchens, G. D.; Salinas, Carlos E.; Rogers, Tom D.

    1992-01-01

    The purification of reclaimed water is essential to water reclamation technology life-support systems in lunar/Mars habitats. An electrochemical UV reactor is being developed which generates oxidants, operates at low temperatures, and requires no chemical expendables. The reactor is the basis for an advanced oxidation process in which electrochemically generated ozone and hydrogen peroxide are used in combination with ultraviolet light irradiation to produce hydroxyl radicals. Results from this process are presented which demonstrate concept feasibility for removal of organic impurities and disinfection of water for potable and hygiene reuse. Power, size requirements, Faradaic efficiency, and process reaction kinetics are discussed. At the completion of this development effort the reactor system will be installed in JSC's regenerative water recovery test facility for evaluation to compare this technique with other candidate processes.

  13. Electrochemical oxide film formation at noble metals as a surface-chemical process

    NASA Astrophysics Data System (ADS)

    Conway, B. E.

    1995-08-01

    The mechanisms of electrochemical oxide film formation at noble metals are described and exemplified by the cases of Pt and Au, especially in the light of recent experimentation by means of cyclic voltammetry, ellipsometry and vacuum surface-science studies using LEED and AES. Unlike the mechanisms of base-metal oxidation, e.g., in corrosion processes, anodic oxide film formation at noble metals proceeds by surface chemical processes involving, initially, sub-monolayer, through monolayer, formation of 2-dimensional {OH}/{O} arrays. During such 2-d processes, place-exchange between electrosorbed OH or O species on the surface, and Pt or Au atoms within the surface lattice, takes place leading to a quasi-2-d compact film which then grows ultimately to a multilayer hydrous oxide film, probably by continuing injection of ions of the substrate metal and their migration through the growing film under the influence of the field. The initial, sub-monolayer stage of electrosorption of OH involves competitive chemisorption by anions, e.g. HSO 4-, ClO 4-, Cl -, which inhibits onset of the first stage of surface oxidation. These processes are demonstrable in experiments on single-crystal surfaces. The combination of such anion effects with place-exchange during the extension of the film, leads to a general mechanism of noble metal oxide film formation. The formation of the oxide films can be examined in detail by recording the distinguishable stages in the film's electrochemical reduction in linear-sweep voltammetry which is sensitive down to {OH}/{O} fractional coverages as low as 0.5% and over time-scales down to 50μs in experiments on time-evolution and transformation of the states of the oxide films. By means of LEED, AES and STM or AFM experiments, the reconstructions and perturbations (e.g. generation of stepped terraces) which oxide films cause on singlecrystal surfaces can be followed.

  14. [Degradation of aniline by a dual-electrode electrochemical oxidation process].

    PubMed

    Cen, Shi-Hong; Song, Xiao-Yan; Chu, Yan-Yang

    2011-08-01

    The efficiency and the mechanism of aniline degradation by an electrochemical oxidation process using a Ti/SnO2-Sb2O5 electrode as the anode and a graphite electrode as the cathode, were studied in two aqueous electrolytes with/without Fe2+. The results showed that the reasonable anodic potential was about 2.0 V +/- 0.1 V for Ti/SnO2-Sb2O5 electrode to oxidize organic compounds, while the optimum cathodic potential was -0.65 V for graphite electrode to reduce O2 generating H2O2. The oxidation degradation of aniline could not take place only by the single action of H2O2. Anodic oxidation was accounted for the degradation of aniline in the absence of Fe2+, while in the presence of Fe2+ both electro-Fenton oxidation and anodic oxidation (dual-electrode electrochemical oxidation) could degradate aniline effectively, and in this case the former was the main mechanism. Under the conditions of -0.65 V cathodic potential, pH 3.0 and 0.5 mmol x L(-1) Fe2+, the removal rate of COD was 77.5% after 10 h treatment and a current efficiency of 97.8% for COD removal could be obtained. This work indicates that the dual-electrode electrochemical oxidation is feasible for the degradation of organic compounds with a high current efficiency by using Ti/SnO2-Sb2O5 as anode as well as the reasonable anodic and cathodic potentials. PMID:22619954

  15. Efficient removal of insecticide "imidacloprid" from water by electrochemical advanced oxidation processes.

    PubMed

    Turabik, Meral; Oturan, Nihal; Gözmen, Belgin; Oturan, Mehmet A

    2014-01-01

    The oxidative degradation of imidacloprid (ICP) has been carried out by electrochemical advanced oxidation processes (EAOPs), anodic oxidation, and electro-Fenton, in which hydroxyl radicals are generated electrocatalytically. Carbon-felt cathode and platinum or boron-doped diamond (BDD) anodes were used in electrolysis cell. To determine optimum operating conditions, the effects of applied current and catalyst concentration were investigated. The decay of ICP during the oxidative degradation was well fitted to pseudo-first-order reaction kinetics and absolute rate constant of the oxidation of ICP by hydroxyl radicals was found to be k abs(ICP) = 1.23 × 10(9) L mol(-1) s(-1). The results showed that both anodic oxidation and electro-Fenton process with BDD anode exhibited high mineralization efficiency reaching 91 and 94% total organic carbon (TOC) removal at 2 h, respectively. For Pt-EF process, mineralization efficiency was also obtained as 71%. The degradation products of ICP were identified and a plausible general oxidation mechanism was proposed. Some of the main reaction intermediates such as 6-chloronicotinic acid, 6-chloronicotinaldehyde, and 6-hydroxynicotinic acid were determined by GC-MS analysis. Before complete mineralization, formic, acetic, oxalic, and glyoxylic acids were identified as end-products. The initial chlorine and organic nitrogen present in ICP were found to be converted to inorganic anions Cl(-), NO₃(-), and NH₄(+). PMID:24671401

  16. Electrochemical advanced oxidation and biological processes for wastewater treatment: a review of the combined approaches.

    PubMed

    Ganzenko, Oleksandra; Huguenot, David; van Hullebusch, Eric D; Esposito, Giovanni; Oturan, Mehmet A

    2014-01-01

    As pollution becomes one of the biggest environmental challenges of the twenty-first century, pollution of water threatens the very existence of humanity, making immediate action a priority. The most persistent and hazardous pollutants come from industrial and agricultural activities; therefore, effective treatment of this wastewater prior to discharge into the natural environment is the solution. Advanced oxidation processes (AOPs) have caused increased interest due to their ability to degrade hazardous substances in contrast to other methods, which mainly only transfer pollution from wastewater to sludge, a membrane filter, or an adsorbent. Among a great variety of different AOPs, a group of electrochemical advanced oxidation processes (EAOPs), including electro-Fenton, is emerging as an environmental-friendly and effective treatment process for the destruction of persistent hazardous contaminants. The only concern that slows down a large-scale implementation is energy consumption and related investment and operational costs. A combination of EAOPs with biological treatment is an interesting solution. In such a synergetic way, removal efficiency is maximized, while minimizing operational costs. The goal of this review is to present cutting-edge research for treatment of three common and problematic pollutants and effluents: dyes and textile wastewater, olive processing wastewater, and pharmaceuticals and hospital wastewater. Each of these types is regarded in terms of recent scientific research on individual electrochemical, individual biological and a combined synergetic treatment. PMID:24965093

  17. Application of electrochemical advanced oxidation processes to the mineralization of the herbicide diuron.

    PubMed

    Pipi, Angelo R F; Sirés, Ignasi; De Andrade, Adalgisa R; Brillas, Enric

    2014-08-01

    Here, solutions with 0.185mM of the herbicide diuron of pH 3.0 have been treated by electrochemical advanced oxidation processes (EAOPs) like electrochemical oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF) and UVA photoelectro-Fenton (PEF) or solar PEF (SPEF). Trials were performed in stirred tank reactors of 100mL and in a recirculation flow plant of 2.5L using a filter-press reactor with a Pt or boron-doped diamond (BDD) anode and an air-diffusion cathode for H2O2 electrogeneration. Oxidant hydroxyl radicals were formed from water oxidation at the anode and/or in the bulk from Fenton's reaction between added Fe(2+) and generated H2O2. In both systems, the relative oxidation ability of the EAOPs increased in the sequence EO-H2O2processes were more powerful due to the photolysis of intermediates by UV radiation. In the stirred tank reactor, the PEF treatment with BDD was the most potent method, yielding 93% mineralization after 360 min at 100 mA cm(-2). In the flow plant, the SPEF process attained a maximum mineralization of 70% at 100 mA cm(-2). Lower current densities slightly reduced the mineralization degree in SPEF, enhancing the current efficiency and dropping the energy consumption. The diuron decay always obeyed a pseudo-first-order kinetics, with a much greater apparent rate constant in EF and SPEF compared to EO-H2O2. Oxalic and oxamic acids were detected as final carboxylic acids. Ammonium and chloride ions were also released, the latter ion being partially converted into chlorate and perchlorate ions at the BDD surface. PMID:24873706

  18. Decolorization and mineralization of Allura Red AC aqueous solutions by electrochemical advanced oxidation processes.

    PubMed

    Thiam, Abdoulaye; Sirés, Ignasi; Garrido, José A; Rodríguez, Rosa M; Brillas, Enric

    2015-06-15

    The decolorization and mineralization of solutions containing 230 mg L(-1) of the food azo dye Allura Red AC at pH 3.0 have been studied upon treatment by electrochemical oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Experiments were performed with a stirred tank reactor containing a boron-doped diamond (BDD) or Pt anode and an air-diffusion cathode to generate H2O2. The main oxidants were hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between H2O2 and added Fe(2+). The oxidation ability increased in the sequence EO-H2O2 < EF < PEF and faster degradation was always obtained using BDD. PEF process with BDD yielded almost total mineralization following similar trends in SO4(2-), ClO4(-) and NO3(-) media, whereas in Cl(-) medium, mineralization was inhibited by the formation of recalcitrant chloroderivatives. GC-MS analysis confirmed the cleavage of the −N=N− bond with formation of two main aromatics in SO4(2-) medium and three chloroaromatics in Cl(-) solutions. The effective oxidation of final oxalic and oxamic acids by BDD along with the photolysis of Fe(III)-oxalate species by UVA light accounted for the superiority of PEF with BDD. NH4(+), NO3(-) and SO4(2-) ions were released during the mineralization. PMID:25734532

  19. Processing, microstructural evolution and electrochemical performance relationships in solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Sarikaya, Ayhan

    The relationships between the processing parameters, microstructures and electrochemical performance of solid oxide fuel cell (SOFC) components were investigated. The operating regimes (i.e., reducing vs. oxidizing) as well as the elevated temperatures (e.g. 800°C) for their operation introduce several material challenges. Therefore, composite materials are employed to withstand operating conditions while providing sufficient electrochemical performance for fuel cell operation. Analyses on lanthanum-strontium manganite (LSM) - yttria stabilized zirconia (YSZ) compositions (45 vol%-55 vol%) by impedance spectroscopy demonstrated that two competing polarization mechanisms (i.e. charge-exchange and surface adsorption-diffusion of oxygen) limit performance. Optimization of microstructures resulted in total resistances as low as 0.040 Ohm cm2. Studies on Ag composites revealed that incorporation of up to 25 vol% oxide particles (LSM and YSZ) with sizes comparable to the Ag grains (~0.5 microm) can minimize the densification and coarsening of the Ag matrix. While the powder based oxide additions increased the stability limit of porous Ag composites from <550°C to 800°C, the use of nanostructured coatings increased the stability limit to 900°C for cathodes and current collectors. Investigations of Ni-YSZ anode microstructures demonstrated that uniform distribution of percolating isometric pores (>5 microm) allows forming desired continuous percolation of all phases (Ni, YSZ and pores) lowering activation polarization below 0.100 Ohm cm2 and maintaining significant electrical conductivity (>1000 S/cm). Identification of polarization mechanisms by deconvolution of impedance spectra and tailoring the corresponding microstructures was demonstrated as an effective method for optimization of SOFC components.

  20. Incorporation of electrochemical advanced oxidation processes in a multistage treatment system for sanitary landfill leachate.

    PubMed

    Moreira, Francisca C; Soler, J; Fonseca, Amélia; Saraiva, Isabel; Boaventura, Rui A R; Brillas, Enric; Vilar, Vítor J P

    2015-09-15

    The current study has proved the technical feasibility of including electrochemical advanced oxidation processes (EAOPs) in a multistage strategy for the remediation of a sanitary landfill leachate that embraced: (i) first biological treatment to remove the biodegradable organic fraction, oxidize ammonium and reduce alkalinity, (ii) coagulation of the bio-treated leachate to precipitate humic acids and particles, followed by separation of the clarified effluent, and (iii) oxidation of the resulting effluent by an EAOP to degrade the recalcitrant organic matter and increase its biodegradability so that a second biological process for removal of biodegradable organics and nitrogen content could be applied. The influence of current density on an UVA photoelectro-Fenton (PEF) process was firstly assessed. The oxidation ability of various EAOPs such as electro-Fenton (EF) with two distinct initial total dissolved iron concentrations ([TDI]0), PEF and solar PEF (SPEF) was further evaluated and these processes were compared with their analogous chemical ones. A detailed assessment of the two first treatment stages was made and the biodegradability enhancement during the SPEF process was determined by a Zahn-Wellens test to define the ideal organics oxidation state to stop the EAOP and apply the second biological treatment. The best current density was 200 mA cm(-2) for a PEF process using a BDD anode, [TDI]0 of 60 mg L(-1), pH 2.8 and 20 °C. The relative oxidation ability of EAOPs increased in the order EF with 12 mg [TDI]0 L(-1) < EF with 60 mg [TDI]0 L(-1) < PEF with 60 mg [TDI]0 L(-1) ≤ SPEF with 60 mg [TDI]0 L(-1), using the abovementioned conditions. While EF process was much superior to the Fenton one, the superiority of PEF over photo-Fenton was less evident and SPEF attained similar degradation to solar photo-Fenton. To provide a final dissolved organic carbon (DOC) of 163 mg L(-1) to fulfill the discharge limits into the environment after

  1. Synthesis and characterization of zinc-molybdenum oxide photocatalysts using an electrochemical-thermal process

    NASA Astrophysics Data System (ADS)

    Goveas, J. J.; Gonsalves, R. A.; Rao, P.; Pinto, R.

    2016-05-01

    Dyes act as major pollutants in water and can be degraded by photocatalysis. This paper establishes the role of electrochemically generated nanostructures of Zinc-Molybdenum oxides (ZMO) as photocatalysts by degrading EBT (Eriochrome Black- T) taken as a model pollutant under UV light. A facile, rapid and low cost process to synthesize these nanostructures (ZMO) is presented. Various factors that affect the synthesis and photocatalytic activity of these nanostructures are discussed. The role of calcination temperature and pulverization on the photocatalytic action has also been established. Particles have been synthesized in pure form as well as using surfactants such as cetrimide (cetyl trimethyl ammonium bromide), polyethylene glycol (PEG) and SDS (sodium dodecyl sulphate) to enhance their photocatalytic action. This paper also discusses the characterization of these nanoparticles by powder XRD, SEM, FT-IR and UV-Visible spectroscopy. Decolourisation was achieved to completion under optimum experimental conditions at room temperature ascertaining the application of these nanostructures as effective photocatalysts.

  2. Inactivation of Pseudomonas aeruginosa in electrochemical advanced oxidation process with diamond electrodes.

    PubMed

    Griessler, M; Knetsch, S; Schimpf, E; Schmidhuber, A; Schrammel, B; Wesner, W; Sommer, R; Kirschner, A K T

    2011-01-01

    The electrochemical advanced oxidation process (EAOP) with diamond electrodes may serve as an additional technology to the currently approved methods for water disinfection. Only few data exist on the microbicidal effect of the EAOP. The aim of our study was to investigate the microbicidal effect of a flow-through oxidation cell with diamond electrodes, using Pseudomonas aeruginosa as the test organism. Without electrical current the EAOP had no measurable effect on investigated microbiological and chemical parameters. For direct electrical current a stronger impact was observed at low flow rate than at higher flow rate. Depending on the contact time of the oxidants and the type of quenching reagent added, inactivation of P. aeruginosa was in the range log 1.6-3.6 at the higher flow rate and log 2.4-4.4 at the lower rate. Direct electrical current showed a stronger microbicidal effect than alternating current (maximum reduction log 4.0 and log 2.9, respectively). The microbiological results of experiments with this EAOP prototype revealed higher standard deviations than expected, based on our experience with standard water disinfection methods. Safe use of an EAOP system requires operating parameters to be defined and used accurately, and thus specific monitoring tests must be developed. PMID:21902043

  3. Electrochemical oxidation of chemical weapons

    SciTech Connect

    Surma, J.E.

    1994-05-01

    Catalyzed electrochemical oxidation (CEO), a low-temperature electrochemical oxidation technique, is being examined for its potential use in destroying chemical warfare agents. The CEO process oxidizes organic compounds to form carbon dioxide and water. A bench-scale CEO system was used in three separate tests sponsored by the US Department of Energy`s (DOE) Office of Intelligence and National Security through the Advanced Concepts Program. The tests examined the effectiveness of CEO in destroying sarin (GB), a chemical nerve agent. The tests used 0.5 mL, 0.95 mL, and 1.0 mL of GB, corresponding to 544 mg, 816 mg, and 1,090 mg, respectively, of GB. Analysis of the off gas showed that, under continuous processing of the GB agent, destruction efficiencies of better than six 9s (99.9999% destroyed) could be achieved.

  4. Influence of electrochemical reduction and oxidation processes on the decolourisation and degradation of C.I. Reactive Orange 4 solutions.

    PubMed

    del Río, A I; Molina, J; Bonastre, J; Cases, F

    2009-06-01

    The electrochemical treatment of wastewaters from textile industry is a promising treatment technique for substances which are resistant to biodegradation. This paper presents the results of the electrochemical decolourisation and degradation of C.I. Reactive Orange 4 synthetic solutions (commercially known as Procion Orange MX2R). Electrolyses were carried out under galvanostatic conditions in a divided or undivided electrolytic cell. Therefore, oxidation, reduction or oxido-reduction experiences were tested. Ti/SnO(2)-Sb-Pt and stainless steel electrodes were used as anode and cathode, respectively. Degradation of the dye was followed by TOC, total nitrogen, COD and BOD(5) analyses. TOC removal after an oxidation process was higher than after oxido-reduction while COD removal after this last process was about 90%. Besides, the biodegradability of final samples after oxido-reduction process was studied and an improvement was observed. UV-Visible spectra revealed the presence of aromatic structures in solution when an electro-reduction was carried out while oxido-reduction process degraded both azo group and aromatic structures. HPLC analyses indicated the presence of a main intermediate after the reduction process with a chemical structure closely similar to 2-amine-1, 5-naphthalenedisulfonic acid. The lowest decolourisation rate corresponded to electrochemical oxidation. In these experiences a higher number of intermediates were generated as HPLC analysis demonstrated. The decolourisation process for the three electrochemical processes studied presented a pseudo-first order kinetics. PMID:19345978

  5. A Highly Controllable Electrochemical Anodization Process to Fabricate Porous Anodic Aluminum Oxide Membranes

    NASA Astrophysics Data System (ADS)

    Lin, Yuanjing; Lin, Qingfeng; Liu, Xue; Gao, Yuan; He, Jin; Wang, Wenli; Fan, Zhiyong

    2015-12-01

    Due to the broad applications of porous alumina nanostructures, research on fabrication of anodized aluminum oxide (AAO) with nanoporous structure has triggered enormous attention. While fabrication of highly ordered nanoporous AAO with tunable geometric features has been widely reported, it is known that its growth rate can be easily affected by the fluctuation of process conditions such as acid concentration and temperature during electrochemical anodization process. To fabricate AAO with various geometric parameters, particularly, to realize precise control over pore depth for scientific research and commercial applications, a controllable fabrication process is essential. In this work, we revealed a linear correlation between the integrated electric charge flow throughout the circuit in the stable anodization process and the growth thickness of AAO membranes. With this understanding, we developed a facile approach to precisely control the growth process of the membranes. It was found that this approach is applicable in a large voltage range, and it may be extended to anodization of other metal materials such as Ti as well.

  6. A Highly Controllable Electrochemical Anodization Process to Fabricate Porous Anodic Aluminum Oxide Membranes.

    PubMed

    Lin, Yuanjing; Lin, Qingfeng; Liu, Xue; Gao, Yuan; He, Jin; Wang, Wenli; Fan, Zhiyong

    2015-12-01

    Due to the broad applications of porous alumina nanostructures, research on fabrication of anodized aluminum oxide (AAO) with nanoporous structure has triggered enormous attention. While fabrication of highly ordered nanoporous AAO with tunable geometric features has been widely reported, it is known that its growth rate can be easily affected by the fluctuation of process conditions such as acid concentration and temperature during electrochemical anodization process. To fabricate AAO with various geometric parameters, particularly, to realize precise control over pore depth for scientific research and commercial applications, a controllable fabrication process is essential. In this work, we revealed a linear correlation between the integrated electric charge flow throughout the circuit in the stable anodization process and the growth thickness of AAO membranes. With this understanding, we developed a facile approach to precisely control the growth process of the membranes. It was found that this approach is applicable in a large voltage range, and it may be extended to anodization of other metal materials such as Ti as well. PMID:26706687

  7. [Toxicity of 4-Chlorophenol Solution Under Electrochemical Reduction-oxidation Process].

    PubMed

    Wang, Yan; Shi, Qin; Wang, Hui; Bian, Zhao-yong

    2016-04-15

    The Pd-Fe/graphene multi-functional catalytic cathode was prepared by UV-assisted photocatalytic reduction. The catalytic cathode and a Ti/IrO₂/RuO₂ anode consisting of both three-electrode system (two cathodes) and two-electrode system (one cathode) were designed for the degradation of 4-chlorophenol in aid of olectrochemical reducing and oxidizing processes. The concentrations of the intermediates and products were monitored by high performance liquid chromatography (HPLC), total organic carbon (TOC), and ion chromatography (IC). The theoretical toxicity was calculated according to the formula. The actual toxicity of the solution during the degradation process was detected using the luminescent bacteria. The comparison of the actual toxicity and theoretical toxicity was performed to analyze the trend of the two systems. The results showed that the toxicity of the solution in anode compartment first increased and then decreased, but the toxicity in cathode compartment decreased during the whole degradation for both systems. This trend could be attributed to the intermediate formed, benzoquinone. Through the analysis of correlation, the correlation coefficient was 1 of the theoretical toxicity and actual toxicity at the level of P = 0.01, which indicated the result of toxicity was reliable. The toxicity of three-electrode system was lower than that of two-electrode system after 120 mm. The three-electrode system was considered to be better than the two-electrode system. Therefore, the detection of actual toxicity in electrochemical reducing and oxidizing process for the degradation of chlorophenols in the actual industry has wide application prospect. PMID:27548966

  8. Electrochemical oxidation for landfill leachate treatment

    SciTech Connect

    Deng, Yang Englehardt, James D.

    2007-07-01

    This paper aims at providing an overview of electrochemical oxidation processes used for treatment of landfill leachate. The typical characteristics of landfill leachate are briefly reviewed, and the reactor designs used for electro-oxidation of leachate are summarized. Electrochemical oxidation can significantly reduce concentrations of organic contaminants, ammonia, and color in leachate. Pretreatment methods, anode materials, pH, current density, chloride concentration, and other additional electrolytes can considerably influence performance. Although high energy consumption and potential chlorinated organics formation may limit its application, electrochemical oxidation is a promising and powerful technology for treatment of landfill leachate.

  9. Oxidative electrochemical switching of photochromic diarylethene compounds

    NASA Astrophysics Data System (ADS)

    Fan, Congbin; Pu, Shouzhi; Liu, Weijun; Yang, Tianshe; Liu, Gang

    2008-12-01

    A series of photochromic diarylethenes compounds were synthesized and the electrochemistry and electrochemistry reaction mechanism properties were investigated. The cyclic voltammetry tests demonstrated that the colorless open-ring isomers were assigned to the unique oxidation process, but the color closed-ring isomers of these compounds were assigned to two oxidation processes. In addition, the electrochromism of diarylethene compound is observed in solution: The closed-ring reaction can be triggered by electrochemical oxidation, while the open-ring reaction must be photochemically driven. These oxidation processes properties can be useful as the oxidation processes electrochemical switching and the oxidation electrochemical switching properties of these different diarylethene isomers can be potential for electrochemistry data storages.

  10. Enriching distinctive microbial communities from marine sediments via an electrochemical-sulfide-oxidizing process on carbon electrodes

    PubMed Central

    Li, Shiue-Lin; Nealson, Kenneth H.

    2015-01-01

    Sulfide is a common product of marine anaerobic respiration, and a potent reactant biologically and geochemically. Here we demonstrate the impact on microbial communities with the removal of sulfide via electrochemical methods. The use of differential pulse voltammetry revealed that the oxidation of soluble sulfide was seen at +30 mV (vs. SHE) at all pH ranges tested (from pH = 4 to 8), while non-ionized sulfide, which dominated at pH = 4 was poorly oxidized via this process. Two mixed cultures (CAT and LA) were enriched from two different marine sediments (from Catalina Island, CAT; from the Port of Los Angeles, LA) in serum bottles using a seawater medium supplemented with lactate, sulfate, and yeast extract, to obtain abundant biomass. Both CAT and LA cultures were inoculated in electrochemical cells (using yeast-extract-free seawater medium as an electrolyte) equipped with carbon-felt electrodes. In both cases, when potentials of +630 or +130 mV (vs. SHE) were applied, currents were consistently higher at +630 then at +130 mV, indicating more sulfide being oxidized at the higher potential. In addition, higher organic-acid and sulfate conversion rates were found at +630 mV with CAT, while no significant differences were found with LA at different potentials. The results of microbial-community analyses revealed a decrease in diversity for both CAT and LA after electrochemical incubation. In addition, some bacteria (e.g., Clostridium and Arcobacter) not well-known to be capable of extracellular electron transfer, were found to be dominant in the electrochemical cells. Thus, even though the different mixed cultures have different tolerances for sulfide, electrochemical-sulfide removal can lead to major population changes. PMID:25741331

  11. Precious metal oxides for electrochemical energy converters: Pseudocapacitance and pH dependence of redox processes

    NASA Astrophysics Data System (ADS)

    Kurzweil, P.

    The mechanism of charge storage in hydrous platinum metal oxides is considered in more detail with respect to the pH dependence of redox capacitance for applications in double-layer capacitors, fuel cells, and pH sensors. An amorphous RuO 2 electrode is able to work like a pH glass electrode during the titration of hydrochloric acid with sodium hydroxide solution. It is shown that the proton exchange mechanism at a glass membrane can be reproduced by platinum metal oxide-hydrates bound in a polymer matrix. Hydrous RuO 2, obtained by alkaline precipitation or thermal decomposition from RuCl 3, as well as single crystal RuO 2, were characterized by TOF-SIMS, NMR spectroscopy, and electrochemical techniques. The proton conductivity of hydrous RuO 2 appears to be due to the dissociative adsorption of water and the formation of acidic OH groups in Ru(III,IV) cluster ions. Depending on the pH of the solution, the electrode potential is determined by the formal hydrogen oxidation or oxygen reduction in ruthenium cluster ions. During aging, the active Ru(III) surface sites are partially oxidized to Ru(IV).

  12. Direct electrochemical oxidation of polyacrylates.

    PubMed

    Bellagamba, Riccardo; Comninellis, Christos; Vatistas, Nicolaos

    2002-10-01

    A promising elimination treatment of non-biodegradable organic pollutants is the direct electro-oxidation. In this work has been proposed the electrochemical elimination of polyacrylates by using boron-doped diamond (BDD) as anodic material. The complete elimination of organic contaminants has been obtained and this is the first case of successful electrochemical treatment of polymeric and bio-refractory species. The tests of the electrochemical oxidation have been conducted at constant current conditions and a complete elimination of organic species has been reached. The decrease of the COD value with time follows the behaviour of an ideal anode as in the case of low molecular organic compounds. PMID:12489259

  13. Ductile mode electrochemical oxidation assisted micromachining for glassy carbon

    NASA Astrophysics Data System (ADS)

    Nam, Eunseok; Lee, Chan-Young; Jun, Martin B. G.; Min, Byung-Kwon

    2015-04-01

    Recently, a new mechanical machining process using electrochemical oxidation was reported. Electrochemical oxidation assisted micromachining was applied to the machining of glassy carbon. The material removal process of the electrochemical oxidation assisted micromachining consists of repeated cycles of oxidation followed by removal of the oxide layer. In this paper, we experimentally investigate and compare the critical chip thickness for ductile mode cutting in mechanical machining and electrochemical oxidation assisted micromachining of glassy carbon. The theoretical critical chip thickness is calculated for mechanical machining of glassy carbon and experimentally verified. The effect of electrochemical oxidation on the critical chip thickness for ductile mode micromachining is also studied for glassy carbon. It is found that the critical chip thickness is increased for the electrochemical oxidation assisted micromachining.

  14. Graphene-Based Hybrids with Manganese Oxide Polymorphs as Tailored Interfaces for Electrochemical Energy Storage: Synthesis, Processing, and Properties

    NASA Astrophysics Data System (ADS)

    Gupta, S.; van Meveren, M. M.; Jasinski, J.

    2015-01-01

    Technological progress is determined to a greater extent by developments of novel materials or new combinations of known materials with different dimensionality and diverse functionality. In this work, we report on the synthesis and characterization of graphene-based hybrid nanomaterials coupled with transition-metal oxide polymorphs (nano/micro-manganese oxides, i.e., β-MnO2 [Mn(IV)] and Mn3O4 [Mn(II, III)]). This lays the groundwork for high-performance electrochemical electrodes for alternative energy devices owing to their higher specific capacitance, wide operational potential window and stability through charge-discharge cycling, environmentally benignity, cost-effectiveness, easy processing, and reproducibility on a larger scale. To accomplish this, we strategically designed these hybrids by direct anchoring or physical adsorption of β-MnO2 and Mn3O4 on variants of graphene, namely graphene oxide and its reduced form, via mixing dispersions of the constituents under mild ultrasonication and drop-casting, resulting in four different combinations. This facile approach affords strong chemical/physical attachment and is expected to result in coupling between the pseudocapacitive transition-metal oxides and supercapacitive nanocarbons showing enhanced activity/reactivity and reasonable areal density of tailored interfaces. We used a range of complementary analytical characterization tools to determine the structure and physical properties, such as scanning electron microscopy combined with energy-dispersive x-ray spectroscopy, atomic force microscopy, x-ray diffraction, resonance Raman spectroscopy combined with elemental Raman mapping, and transmission electron microscopy in conjunction with selected-area electron diffraction. All of these techniques reveal surface morphology, local (lattice dynamical) and average structure, and local charge transfer due to the physically (or chemically) adsorbed manganese oxide of synthesized hybrids that helps to establish

  15. Electrochemical processing of solid waste

    NASA Technical Reports Server (NTRS)

    Bockris, J. OM.; Hitchens, G. D.; Kaba, L.

    1988-01-01

    The investigation into electrolysis as a means of waste treatment and recycling on manned space missions is described. The electrochemical reactions of an artificial fecal waste mixture was examined. Waste electrolysis experiments were performed in a single compartment reactor, on platinum electrodes, to determine conditions likely to maximize the efficiency of oxidation of fecal waste material to CO2. The maximum current efficiencies for artificial fecal waste electrolysis to CO2 was found to be around 50 percent in the test apparatus. Experiments involving fecal waste oxidation on platinum indicates that electrodes with a higher overvoltage for oxygen evolution such as lead dioxide will give a larger effective potential range for organic oxidation reactions. An electrochemical packed column reactor was constructed with lead dioxide as electrode material. Preliminary experiments were performed using a packed-bed reactor and continuous flow techniques showing this system may be effective in complete oxidation of fecal material. The addition of redox mediator Ce(3+)/Ce(4+) enhances the oxidation process of biomass components. Scientific literature relevant to biomass and fecal waste electrolysis were reviewed.

  16. Performance of electrochemical oxidation process for removal of di (2-ethylhexyl) phthalate.

    PubMed

    Espinoza, Josué Daniel García; Drogui, Patrick; Zolfaghari, Mehdi; Dirany, Ahmad; Ledesma, Maria Teresa Orta; Gortáres-Moroyoqui, Pablo; Buelna, Gerardo

    2016-06-01

    Di (2-ethylhexyl) phthalate (DEHP) is the most detected and concentrated plasticizer in environment and wastewaters, worldwide. In this study, different operating parameters such as current intensity, treatment time, type of anodes, and supporting electrolytes were tested to optimized the electro-oxidation process (EOP) for the removal of DEHP in the presence of methanol as a dissolved organic matter. Among the anodes, the Nb/BDD showed the best degradation rate of DEHP, at low current intensity of 0.2 A after 90 min of treatment time with a percentage of degradation recorded of 81 %, compared to 70 % obtained with the Ti/IrO2-RuO2. Furthermore, due to the combination of direct and indirect oxidation, the removal of DEHP in the presence of 1 g/L Na2SO4 was higher than NaBr, even though the oxidant production of NaBr was 11.7 mmol/L against 3.5 mmol/L recorded in the presence of sulfate at 0.5 A and after 60 min of electrolysis time. Under optimal condition (current intensity = 0.5 A, time = 120 min, using Nb/BDD anode and Na2SO4 as supporting electrolyte), the removal of 87.2 % of DEHP was achieved. The total cost of 0.106 US$/m(3) of treated water was achieved based on economical optimization of reactor with current intensity of 0.2 A and 1 g/L Na2SO4. PMID:26971515

  17. Graphene-Inorganic Hybrids with Cobalt Oxide Polymorphs for Electrochemical Energy Systems and Electrocatalysis: Synthesis, Processing and Properties

    NASA Astrophysics Data System (ADS)

    Gupta, Sanju; Carrizosa, Sara B.

    2015-11-01

    We report on the synthesis and physical property characterization of graphene-inorganic `hybrid' nanomaterials coupled with nano-/microscale transition metal oxide polymorphs namely, cobalt oxides, i.e. CoO [Co(II)] and Co3O4 [Co(II, III)]), for alternative energy storage and conversion devices. Their demand is owed to higher specific capacitance, wide operational potential window, stability through charge-discharge cycling, environmentally benignity, easily processability, reproducibility and manufacturability. To accomplish this, we strategically designed these hybrids by direct anchoring or physisorption of CoO and CO3O4 on two different variants of graphene: graphene oxide which is semiconducting, and its reduced form showing conducting behavior via mixing dispersions of the constituents under mild ultrasonication and drop-cast (or spray-cast) resulting in different combinations. This facile approach affords strong chemical/physical attachment and is expected to have coupling between the pseudocapacitive transition metal oxides and supercapacitive graphene showing enhanced surface activity/reactivity and reasonable areal density of tailored interfaces. We used a range of complementary tools to establish microscopic structure-property-function correlations including scanning electron microscopy combined with energy dispersive x-ray spectroscopy, atomic force microscopy, x-ray diffraction, transmission electron microscopy in conjunction with selected-area electron diffraction, and resonance Raman spectroscopy combined with elemental Raman mapping. They reveal surface morphology, local (lattice dynamical) and average structure and surface charge transfer/doping due to physically (or chemically) adsorbed cobalt oxide and highlight the surface structure and interfaces. This lays the groundwork to further investigate the electrochemical properties as high-performance supercapacitor cathodes, rechargeable secondary battery anodes and electrocatalytical platforms.

  18. A wind-powered BDD electrochemical oxidation process for the removal of herbicides.

    PubMed

    Souza, F L; Lanza, M R V; Llanos, J; Sáez, C; Rodrigo, M A; Cañizares, P

    2015-08-01

    In the search for greener treatment technologies, this work studies the coupling of a wind turbine energy supply with an electrolytic cell (CWTEC device) for the remediation of wastewater polluted with pesticide 2,4-dichlorophenoxyacetic acid (2,4-D). The discontinuous and unforeseeable supply of energy is the main challenge inspiring this new proposal, which aims at reducing the environmental impact of electrolytic treatment by using a green energy supply. The results obtained using the coupled technologies are compared with those obtained by powering the electrolyser with a traditional power supply with a similar current intensity. The mineralisation of wastewater can be accomplished independently of how the electrolytic cell is powered, although differences in performance are clearly observed in the total organic carbon (TOC) and 2,4-D decays. These changes can be explained in terms of the changing profile of the current intensity, which influences the concentrations of the oxidants produced and thereby the mediated electrolytic process. PMID:25950835

  19. Solid oxide electrochemical reactor science.

    SciTech Connect

    Sullivan, Neal P.; Stechel, Ellen Beth; Moyer, Connor J.; Ambrosini, Andrea; Key, Robert J.

    2010-09-01

    Solid-oxide electrochemical cells are an exciting new technology. Development of solid-oxide cells (SOCs) has advanced considerable in recent years and continues to progress rapidly. This thesis studies several aspects of SOCs and contributes useful information to their continued development. This LDRD involved a collaboration between Sandia and the Colorado School of Mines (CSM) ins solid-oxide electrochemical reactors targeted at solid oxide electrolyzer cells (SOEC), which are the reverse of solid-oxide fuel cells (SOFC). SOECs complement Sandia's efforts in thermochemical production of alternative fuels. An SOEC technology would co-electrolyze carbon dioxide (CO{sub 2}) with steam at temperatures around 800 C to form synthesis gas (H{sub 2} and CO), which forms the building blocks for a petrochemical substitutes that can be used to power vehicles or in distributed energy platforms. The effort described here concentrates on research concerning catalytic chemistry, charge-transfer chemistry, and optimal cell-architecture. technical scope included computational modeling, materials development, and experimental evaluation. The project engaged the Colorado Fuel Cell Center at CSM through the support of a graduate student (Connor Moyer) at CSM and his advisors (Profs. Robert Kee and Neal Sullivan) in collaboration with Sandia.

  20. Process for electrochemically gasifying coal

    DOEpatents

    Botts, T.E.; Powell, J.R.

    1985-10-25

    A process is claimed for electrochemically gasifying coal by establishing a flowing stream of coal particulate slurry, electrolyte and electrode members through a transverse magnetic field that has sufficient strength to polarize the electrode members, thereby causing them to operate in combination with the electrolyte to electrochemically reduce the coal particulate in the slurry. Such electrochemical reduction of the coal produces hydrogen and carbon dioxide at opposite ends of the polarized electrode members. Gas collection means are operated in conjunction with the process to collect the evolved gases as they rise from the slurry and electrolyte solution. 7 figs.

  1. Nano nickel oxide modified non-enzymatic glucose sensors with enhanced sensitivity through an electrochemical process strategy at high potential.

    PubMed

    Mu, Ying; Jia, Dongling; He, Yayun; Miao, Yuqing; Wu, Hai-Long

    2011-02-15

    Development of fast and sensitive sensors for glucose determination is important in food industry, clinic diagnostics, biotechnology and many other areas. In these years, considerable attention has been paid to develop non-enzymatic electrodes to solve the disadvantages of the enzyme-modified electrodes, such as instability, high cost, complicated immobilization procedure and critical operating situation et al. Nano nickel oxide (NiO) modified non-enzymatic glucose sensors with enhanced sensitivity were investigated. Potential scanning nano NiO modified carbon paste electrodes up to high potential in alkaline solution greatly increases the amount of redox couple Ni(OH)(2)/NiOOH derived from NiO, and thus improves their electrochemical properties and electrocatalytical performance toward the oxidation of glucose. The non-enzymatic sensors response quickly to glucose and the response time is less than 5s, demonstrating excellent electrocatalytical activity and assay performance. The calibration plot is linear over the wide concentration range of 1-110 μM with a sensitivity of 43.9 nA/μM and a correlation coefficient of 0.998. The detection limit of the electrode was found to be 0.16 μM at a signal-to-noise ratio of 3. The proposed non-enzymatic sensors can be used for the assay of glucose in real sample. PMID:21167705

  2. DEVELOPMENT OF ELECTROCHEMICAL REDUCTION TECHNOLOGY FOR SPENT OXIDE FUELS

    SciTech Connect

    Hur, Jin-Mok; Seo, Chung-Seok; Kim, Ik-Soo; Hong, Sun-Seok; Kang, Dae-Seung; Park, Seong-Won

    2003-02-27

    The Advanced Spent Fuel Conditioning Process (ACP) has been under development at Korea Atomic Energy Research Institute (KAERI) since 1997. The concept is to convert spent oxide fuel into metallic form and to remove high heat-load fission products such as Cs and Sr from the spent fuel. The heat power, volume, and radioactivity of spent fuel can decrease by a factor of a quarter via this process. For the realization of ACP, a concept of electrochemical reduction of spent oxide fuel in Li2O-LiCl molten salt was proposed and several cold tests using fresh uranium oxides have been carried out. In this new electrochemical reduction process, electrolysis of Li2O and reduction of uranium oxide are taking place simultaneously at the cathode part of electrolysis cell. The conversion of uranium oxide to uranium metal can reach more than 99% ensuring the feasibility of this process.

  3. Electrochemical oxidation of phenol using graphite anodes

    SciTech Connect

    Awad, Y.M.; Abuzaid, N.S.

    1999-02-01

    The effects of current and pH on the electrochemical oxidation of phenol on graphite electrodes is investigated in this study. There was no sign of deterioration of the graphite bed after 5 months of operation. Phenol removal efficiency was a function of the current applied and was around 70% at a current of 2.2 A. The increase of phenol removal efficiency with current is attributed to the increase of ionic transport which increases the rate of electrode reactions responsible for the removal process. The percentage of complete oxidation of phenol increases with current, with a maximum value of about 50%. However, at pH 0.2 it is slightly higher than that at pH 0.5 at all currents. The phenol removal rate increases with increases of current and pH. While the current (CO{sub 2}) efficiency reaches a maximum value in the current range of 1.0--1.2 A, it increases with an increase of acid concentration. The findings of this study have important implications: while anodic oxidation of phenol on graphite can achieve acceptable removal of phenol, the extent of oxidation should not be overlooked.

  4. Mineralization of salicylic acid in acidic aqueous medium by electrochemical advanced oxidation processes using platinum and boron-doped diamond as anode and cathodically generated hydrogen peroxide.

    PubMed

    Guinea, Elena; Arias, Conchita; Cabot, Pere Lluís; Garrido, José Antonio; Rodríguez, Rosa María; Centellas, Francesc; Brillas, Enric

    2008-01-01

    Solutions containing 164 mg L(-1) salicylic acid of pH 3.0 have been degraded by electrochemical advanced oxidation processes such as anodic oxidation, anodic oxidation with electrogenerated H(2)O(2), electro-Fenton, photoelectro-Fenton and solar photoelectro-Fenton at constant current density. Their oxidation power has been comparatively studied in a one-compartment cell with a Pt or boron-doped diamond (BDD) anode and a graphite or O(2)-diffusion cathode. In the three latter procedures, 0.5mM Fe(2+) is added to the solution to form hydroxyl radical (()OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the O(2)-diffusion cathode. Total mineralization is attained for all methods with BDD and for photoelectro-Fenton and solar photoelectro-Fenton with Pt. The poor decontamination achieved in anodic oxidation and electro-Fenton with Pt is explained by the slow removal of most pollutants by ()OH formed from water oxidation at the Pt anode in comparison to their quick destruction with ()OH produced at BDD. ()OH generated from Fenton's reaction oxidizes rapidly all aromatic pollutants, but it cannot destroy final Fe(III)-oxalate complexes. Solar photoelectro-Fenton treatments always yield quicker degradation rate due to the very fast photodecarboxylation of these complexes by UVA irradiation supplied by solar light. The effect of current density on the degradation rate, efficiency and energy cost of all methods is examined. The salicylic acid decay always follows a pseudo-first-order kinetics. 2,3-Dihydroxybenzoic, 2,5-dihydroxybenzoic, 2,6-dihydroxybenzoic, alpha-ketoglutaric, glycolic, glyoxylic, maleic, fumaric, malic, tartronic and oxalic acids are detected as oxidation products. A general reaction sequence for salicylic acid mineralization considering all these intermediates is proposed. PMID:17692891

  5. Characteristics of Fluorine-doped tin oxide thin films grown by Streaming process for Electrodeless Electrochemical Deposition

    NASA Astrophysics Data System (ADS)

    Yusuf, Gbadebo; Khalilzadeh-Rezaie, Farnood; Cleary, Justin W.; Oladeji, Isaiah O.; Suu, Koukou; Schoenfeld, Winston V.; Peale, Robert E.; Awodugba, Ayodeji O.

    2015-04-01

    This work investigated the characteristics of SnO2: F films grown by Streaming Process for Electrodeless Electrochemical Deposition (SPEED). Stannic chloride (SnCl4) and ammonium fluoride (NH4 F) was dissolved in a mixture of deionized water and organic solvents. The preheated substrate temperature was varied between 450 and 530° C. High quality SnO2: F films were grown at all the substrate temperatures studied. The typical film thickness was 250 nm. XRD shows that the grown films are polycrystalline SnO2 with a tetragonal crystal structure. The average optical transmission of the films was around 93% throughout the wavelength of 400 to 1000 nm. The lowest electrical resistivity achieved was 6 x 10-4 Ω cm. The Hall measurements showed that the film is an n-type semiconductor, with the highest carrier mobility of 8.3 cm2/V.s, and concentration of 1 x 1021 cm-3. The direct band gap was determined to be 4 eV from the transmittance spectrum.

  6. A comparison of corrosion, tribocorrosion and electrochemical impedance properties of pure Ti and Ti6Al4V alloy treated by micro-arc oxidation process

    NASA Astrophysics Data System (ADS)

    Fazel, M.; Salimijazi, H. R.; Golozar, M. A.; Garsivaz jazi, M. R.

    2015-01-01

    In this paper, the micro-arc oxidation (MAO) coatings were performed on pure Ti and Ti6Al4V samples at 180 V. The results indicated that unlike the volcanic morphology of oxide layer on pure Ti, a cortex-like morphology with irregular vermiform slots was seen on MAO/Ti6Al4V sample. According to polarization curves, the corrosion resistance of untreated samples was significantly increased by MAO process. The electrochemical impedance spectroscopy analysis showed a lower capacitance of barrier layer (led to higher resistance) for MAO/Ti specimens. This indicates that corrosive ions diffusion throughout the oxide film would be more difficult resulted in a higher corrosion resistance. Tribocorrosion results illustrated that the potential of untreated samples was dropped sharply to very low negative values. However, the lower wear volume loss was achieved for Ti6Al4V alloy. SEM images of worn surfaces demonstrated the local detachment of oxide layer within the wear track of MAO/Ti sample. Conversely, no delamination was detected in MAO/Ti6Al4V and a mild abrasive wear was the dominant mechanism.

  7. Corrosion and Electrochemical Oxidation of a Pyrite by Thiobacillus ferrooxidans

    PubMed Central

    Mustin, C.; Berthelin, J.; Marion, P.; de Donato, P.

    1992-01-01

    The oxidation of a pure pyrite by Thiobacillus ferrooxidans is not really a constant phenomenon; it must be considered to be more like a succession of different steps which need characterization. Electrochemical studies using a combination of a platinum electrode and a specific pyrite electrode (packed-ground-pyrite electrode) revealed four steps in the bioleaching process. Each step can be identified by the electrochemical behavior (redox potentials) of pyrite, which in turn can be related to chemical (leachate content), bacterial (growth), and physical (corrosion patterns) parameters of the leaching process. A comparison of the oxidation rates of iron and sulfur indicated the nonstoichiometric bacterial oxidation of a pure pyrite in which superficial phenomena, aqueous oxidation, and deep crystal dissolution are successively involved. Images PMID:16348688

  8. Corrosion and electrochemical oxidation of a pyrite by Thiobacillus ferrooxidans

    SciTech Connect

    Mustin, C.; Berthelin, J. ); Marion, P.; Donato, P. de )

    1992-04-01

    The oxidation of a pure pyrite by Thiobacillus Ferrooxidans is not really a constant phenomenon; it must be considered to be more like a succession of different steps which need characterization. Electrochemical studies using a combination of a platinum electrode and a specific pyrite electrode (packed-ground-pyrite electrode) revealed four steps in the bioleaching process. Each step can be identified by the electrochemical behavior (redox potentials) of pyrite, which in turn can be related to chemical (leachate content), bacterial (growth), and physical (corrosion patterns) parameters of the leaching process. A comparison of the oxidation rates of iron and sulfur indicated the nonstoichiometric bacterial oxidation of a pure pyrite in which superficial phenomena, aqueous oxidation, and deep crystal dissolution are successively involved.

  9. Electrochemical oxidation of perfluorinated compounds in water.

    PubMed

    Niu, Junfeng; Li, Yang; Shang, Enxiang; Xu, Zesheng; Liu, Jinzi

    2016-03-01

    Perfluorinated compounds (PFCs) are persistent and refractory organic pollutants that have been detected in various environmental matrices and municipal wastewater. Electrochemical oxidation (EO) is a promising remediation technique for wastewater contaminated with PFCs. A number of recent studies have demonstrated that the "non-active" anodes, including boron-doped diamond, tin oxide, and lead dioxide, are effective in PFCs elimination in wastewater due to their high oxygen evolution potential. Many researchers have conducted experiments to investigate the optimal conditions (i.e., potential, current density, pH value, plate distance, initial PFCs concentration, electrolyte, and other factors) for PFCs elimination to obtain the maximal elimination efficiency and current efficiency. The EO mechanism and pathways of PFCs have been clearly elucidated, which undergo electron transfer, Kolbe decarboxylation or desulfonation, hydrolysis, and radical reaction. In addition, the safety evaluation and energy consumption evaluation of the EO technology have also been summarized to decrease toxic ion release from electrode and reduce the cost of this technique. Although the ultrasonication and hydrothermal techniques combined with the EO process can improve the removal efficiency and current efficiency significantly, these coupled techniques have not been commercialized and applied in industrial wastewater treatment. Finally, key challenges facing EO technology are listed and the directions for further research are pointed out (such as combination with other techniques, treatment for natural waters contaminated by low levels of PFCs, and reactor design). PMID:26745381

  10. Method of electrode fabrication for solid oxide electrochemical cells

    DOEpatents

    Jensen, Russell R.

    1990-01-01

    A process for fabricating cermet electrodes for solid oxide electrochemical cells by sintering is disclosed. First, a porous metal electrode is fabricated on a solid oxide cell, such as a fuel cell by, for example, sintering, and is then infiltrated with a high volume fraction stabilized zirconia suspension. A second sintering step is used to sinter the infiltrated zirconia to a high density in order to more securely attach the electrode to the solid oxide electrolyte of the cell. High performance fuel electrodes can be obtained with this process. Further electrode performance enhancement may be achieved if stabilized zirconia doped with cerium oxide, chromium oxide, titanium oxide, and/or praseodymium oxide for electronic conduction is used.

  11. Method of electrode fabrication for solid oxide electrochemical cells

    DOEpatents

    Jensen, R.R.

    1990-11-20

    A process for fabricating cermet electrodes for solid oxide electrochemical cells by sintering is disclosed. First, a porous metal electrode is fabricated on a solid oxide cell, such as a fuel cell by, for example, sintering, and is then infiltrated with a high volume fraction stabilized zirconia suspension. A second sintering step is used to sinter the infiltrated zirconia to a high density in order to more securely attach the electrode to the solid oxide electrolyte of the cell. High performance fuel electrodes can be obtained with this process. Further electrode performance enhancement may be achieved if stabilized zirconia doped with cerium oxide, chromium oxide, titanium oxide, and/or praseodymium oxide for electronic conduction is used. 5 figs.

  12. Electrochemical processes in recovering metals from ores

    SciTech Connect

    Felker, D.L. ); Bautista, R.G. . Dept. of Chemical and Metallurgical Engineering)

    1990-04-01

    Chalcopyrite (CuFeS{sub 2}) is one of the most abundant copper-bearing minerals in the U.S. Oxidative leaching and smelting and refining are the most common methods used for recovering copper from chalcopyrite. One of the problems associated with oxidative leaching is the formation of an elemental sulfur product layer around the unreacted chalcopyrite core. The sulfur coating slows the reaction by inhibiting both the diffusion of the oxidant to the unreacted core, and the diffusion of the copper and iron species to the bulk solution. Another problem with leaching is that the iron and copper are oxidized simultaneously. Both appear in the bulk solution in their most oxidized states. The direct electrodissolution of copper sulfide ore slurries could reduce the number of steps involved in the copper recovery process, possibly leading to significant reductions in energy consumption and operating costs. The potential application of electrodissolution processes in hydrometallurgy has been reviewed. This paper reviews investigations of the electrochemical dissolution of chalcopyrite, digenite (Cu{sub 1.8}S), chalcocite (Cu{sub 2}S) and covellite (CuS).

  13. Electrochemical and partial oxidation of methane

    NASA Astrophysics Data System (ADS)

    Singh, Rahul

    2008-10-01

    Hydrogen has been the most common fuel used for the fuel cell research but there remains challenging technological hurdles and storage issues with hydrogen fuel. The direct electrochemical oxidation of CH4 (a major component of natural gas) in a solid oxide fuel cell (SOFC) to generate electricity has a potential of commercialization in the area of auxiliary and portable power units and battery chargers. They offer significant advantages over an external reformer based SOFC, namely, (i) simplicity in the overall system architecture and balance of plant, (ii) more efficient and (iii) availability of constant concentration of fuel in the anode compartment of SOFC providing stability factor. The extreme operational temperature of a SOFC at 700-1000°C provides a thermodynamically favorable pathway to deposit carbon on the most commonly used Ni anode from CH4 according to the following reaction (CH4 = C + 2H2), thus deteriorating the cell performance, stability and durability. The coking problem on the anode has been a serious and challenging issue faced by the catalyst research community worldwide. This dissertation presents (i) a novel fabricated bi-metallic Cu-Ni anode by electroless plating of Cu on Ni anode demonstrating significantly reduced or negligible coke deposition on the anode for CH4 and natural gas fuel after long term exposure, (ii) a thorough microstructural examination of Ni and Cu-Ni anode exposed to H2, CH4 and natural gas after long term exposure at 750°C by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction and (iii) in situ electrochemical analysis of Ni and Cu-Ni for H2, CH4 and natural gas during long term exposure at 750°C by impedance spectroscopy. A careful investigation of variation in the microstructure and performance characteristics (voltage-current curve and impedance) of Ni and Cu-Ni anode before and after a long term exposure of CH4 and natural gas would allow us to test the validation of a

  14. Air Force electrochemical impregnation process results

    NASA Technical Reports Server (NTRS)

    Miller, L. E.

    1978-01-01

    The status of the Air Force Electrochemical program was reviewed. The performance characteristics of the system was attributed to the use of an electrochemical impregnation process. The electrode improvements, the prototype equipment designs, and the actual construction of a production facility are discussed.

  15. Process for electrochemically gasifying coal using electromagnetism

    DOEpatents

    Botts, Thomas E.; Powell, James R.

    1987-01-01

    A process for electrochemically gasifying coal by establishing a flowing stream of coal particulate slurry, electrolyte and electrode members through a transverse magnetic field that has sufficient strength to polarize the electrode members, thereby causing them to operate in combination with the electrolyte to electrochemically reduce the coal particulate in the slurry. Such electrochemical reduction of the coal produces hydrogen and carbon dioxide at opposite ends of the polarized electrode members. Gas collection means are operated in conjunction with the process to collect the evolved gases as they rise from the slurry and electrolyte solution.

  16. Electrochemical processing of solid waste

    NASA Technical Reports Server (NTRS)

    Bockris, John OM.

    1987-01-01

    An investigation of electrochemical waste treatment methods suitable for closed, or partially closed, life support systems for manned space exploration is discussed. The technique being investigated involves the electrolysis of solid waste where the aim is to upgrade waste material (mainly fecal waste) to generate gases that can be recycled in a space station or planetary space environment.

  17. A robust and cost-effective integrated process for nitrogen and bio-refractory organics removal from landfill leachate via short-cut nitrification, anaerobic ammonium oxidation in tandem with electrochemical oxidation.

    PubMed

    Wu, Li-Na; Liang, Da-Wei; Xu, Ying-Ying; Liu, Ting; Peng, Yong-Zhen; Zhang, Jie

    2016-07-01

    A cost-effective process, consisting of a denitrifying upflow anaerobic sludge blanket (UASB), an oxygen-limited anoxic/aerobic (A/O) process for short-cut nitrification, and an anaerobic reactor (ANR) for anaerobic ammonia oxidation (anammox), followed by an electrochemical oxidation process with a Ti-based SnO2-Sb2O5 anode, was developed to remove organics and nitrogen in a sewage diluted leachate. The final chemical oxygen demand (COD), ammonia nitrogen (NH4(+)-N) and total nitrogen (TN) of 70, 11.3 and 39 (all in mg/L), respectively, were obtained. TN removal in UASB, A/O and ANR were 24.6%, 49.6% and 16.1%, respectively. According to the water quality and molecular biology analysis, a high degree of anammox besides short-cut nitrification and denitrification occurred in A/O. Counting for 16.1% of TN removal in ANR, at least 43.2-49% of TN was removed via anammox. The anammox bacteria in A/O and ANR, were in respective titers of (2.5-5.9)×10(9) and 2.01×10(10)copy numbers/(gSS). PMID:27115616

  18. Observable Electrochemical Oxidation of Carbon Promoted by Platinum Nanoparticles.

    PubMed

    Kou, Zongkui; Cheng, Kun; Wu, Hui; Sun, Ronghui; Guo, Beibei; Mu, Shichun

    2016-02-17

    The radical degradation of Pt-based catalysts toward oxygen reduction reaction (ORR), predominantly caused by the oxidation of carbon supports, heavily blocks the commercialization of polymer electrolyte membrane fuel cells (PEMFCs). As reported, the electrochemical oxidation of carbon could be accelerated by Pt catalysts; however, hitherto no direct evidence is present for the promotion of Pt catalysts. Herein, a unique ultrathin carbon layer (approximately 2.9 nm in thickness) covered Pt catalyst (Pt/C-GC) is designed and synthesized by a chemical vapor deposition (CVD) method. This magnifies the catalysis effect of Pt to carbon oxidation due to the greatly increased contact sites between the metal-support, making it easy to investigate the carbon oxidation process by observing the thinning of the carbon layer on Pt nanoparticles from TEM observations. Undoubtedly, this finding can better guide the structural design of the durable metal catalysts for PEMFCs and other applications. PMID:26788962

  19. Fabrication of solid oxide fuel cell by electrochemical vapor deposition

    DOEpatents

    Riley, B.; Szreders, B.E.

    1988-04-26

    In a high temperature solid oxide fuel cell (SOFC), the deposition of an impervious high density thin layer of electrically conductive interconnector material, such as magnesium doped lanthanum chromite, and of an electrolyte material, such as yttria stabilized zirconia, onto a porous support/air electrode substrate surface is carried out at high temperatures (/approximately/1100/degree/ /minus/ 1300/degree/C) by a process of electrochemical vapor deposition. In this process, the mixed chlorides of the specific metals involved react in the gaseous state with water vapor resulting in the deposit of an impervious thin oxide layer on the support tube/air electrode substrate of between 20--50 microns in thickness. An internal heater, such as a heat pipe, is placed within the support tube/air electrode substrate and induces a uniform temperature profile therein so as to afford precise and uniform oxide deposition kinetics in an arrangement which is particularly adapted for large scale, commercial fabrication of SOFCs.

  20. Fabrication of solid oxide fuel cell by electrochemical vapor deposition

    DOEpatents

    Brian, Riley; Szreders, Bernard E.

    1989-01-01

    In a high temperature solid oxide fuel cell (SOFC), the deposition of an impervious high density thin layer of electrically conductive interconnector material, such as magnesium doped lanthanum chromite, and of an electrolyte material, such as yttria stabilized zirconia, onto a porous support/air electrode substrate surface is carried out at high temperatures (approximately 1100.degree.-1300.degree. C.) by a process of electrochemical vapor deposition. In this process, the mixed chlorides of the specific metals involved react in the gaseous state with water vapor resulting in the deposit of an impervious thin oxide layer on the support tube/air electrode substrate of between 20-50 microns in thickness. An internal heater, such as a heat pipe, is placed within the support tube/air electrode substrate and induces a uniform temperature profile therein so as to afford precise and uniform oxide deposition kinetics in an arrangement which is particularly adapted for large scale, commercial fabrication of SOFCs.

  1. Fabrication of solid oxide fuel cell by electrochemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Riley, Brian; Szreders, Bernard E.

    1988-04-01

    In a high temperature solid oxide fuel cell (SOFC), the deposition of an impervious high density thin layer of electrically conductive interconnector material, such as magnesium doped lanthanum chromite, and of an electrolyte material, such as yttria stabilized zirconia, onto a porous support/air electrode substrate surface is carried out at high temperatures (approx. 1100 to 1300 C) by a process of electrochemical vapor deposition. In this process, the mixed chlorides of the specific metals involved react in the gaseous state with water vapor resulting in the deposit of an impervious thin oxide layer on the support tube/air electrode substrate of between 20 and 50 microns in thickness. An internal heater, such as a heat pipe, is placed within the support tube/air electrode substrate and induces a uniform temperature profile therein so as to afford precise and uniform oxide deposition kinetics in an arrangement which is particularly adapted for large scale, commercial fabrication of SOFCs.

  2. Selective Electrochemical versus Chemical Oxidation of Bulky Phenol.

    PubMed

    Zabik, Nicole L; Virca, Carolyn N; McCormick, Theresa M; Martic-Milne, Sanela

    2016-09-01

    The electrochemical oxidation of selected tert-butylated phenols 2,6-di-tert-butyl-4-methylphenol (1), 2,6-di-tert-butylphenol (2), 2,4,6-tri-tert-butylphenol (3), 2-tert-butylphenol (4), and 4-tert-butylphenol (5) was studied in an aprotic environment using cyclic voltammetry, square-wave voltammetry, and UV-vis spectroscopy. All compounds exhibited irreversible oxidation of the corresponding phenol or phenolate ion. Compound 2 was selectively electrochemically oxidized, while other phenol analogues underwent mostly chemical oxidation. The electrochemical oxidation of 2 produced a highly absorbing product, 3,5,3',5'-tetra-tert-butyl-4,4'-diphenoquinone, which was characterized by X-ray crystal diffraction. The electrochemical oxidation was monitored as a function of electrochemical parameters and concentration. Experimental and theoretical data indicated that the steric hindrance, phenoxyl radical stability, and hydrogen bonding influenced the outcome of the electrochemical oxidation. The absence of the substituent at the para position and the presence of the bulky substituents at ortho positions were structural and electrostatic requirements for the selective electrochemical oxidation. PMID:27454828

  3. Electrochemical formation of a composite polymer-aluminum oxide film

    NASA Astrophysics Data System (ADS)

    Runge-Marchese, Jude Mary

    1997-10-01

    The formation of polymer films through electrochemical techniques utilizing electrolytes which include conductive polymer is of great interest to the coatings and electronics industries as a means for creating electrically conductive and corrosion resistant finishes. One of these polymers, polyamino-benzene (polyaniline), has been studied for this purpose for over ten years. This material undergoes an insulator-to-metal transition upon doping with protonic acids in an acid/base type reaction. Review of prior studies dealing with polyaniline and working knowledge of aluminum anodization has led to the development of a unique process whereby composite polymer-aluminum oxide films are formed. The basis for the process is a modification of the anodizing electrolyte which results in the codeposition of polyaniline during aluminum anodization. A second process, which incorporates electrochemical sealing of the anodic layer with polyaniline was also developed. The formation of these composite films is documented through experimental processing, and characterized by way of scientific analysis and engineering tests. Analysis results revealed the formation of unique dual phase anodic films with fine microstructures which exhibited full intrusion of the columnar aluminum oxide structure with polyaniline, indicating the polymer was deposited as the metal oxidation proceeded. An aromatic amine derivative of polyaniline with aluminum sulfate was determined to be the reaction product within the aluminum oxide phase of the codeposited films. Scientific characterization determined the codeposition process yields completely chemically and metallurgically bound composite films. Engineering studies determined the films, obtained through a single step, exhibited superior wear and corrosion resistance to conventionally anodized and sealed films processed through two steps, demonstrating the increased manufacturing process efficiency that can be realized with the modification of the

  4. Exfoliated graphite-ruthenium oxide composite electrodes for electrochemical supercapacitors

    NASA Astrophysics Data System (ADS)

    Mitra, Sagar; Lokesh, K. S.; Sampath, S.

    The performance of exfoliated graphite (EG)-ruthenium oxide (RuO x) composites as binderless electrodes is evaluated for electrochemical capacitors (ECs). A composite of EG-RuO x is prepared by a modified sol-gel process. The material is characterized using X-ray diffraction and microscopy. Electrochemical capacitors with the composite electrodes in the presence of aqueous sulfuric acid (H 2SO 4) electrolyte are evaluated using voltammetry, impedance and charge-discharge studies. Cyclic voltammetry reveals very stable current-voltage behaviour up to several thousands of cycles, as well as high specific capacitances, e.g., a few hundreds of farads per gram for the composite that contains 16.5 wt.% RuO x.

  5. Electrochemical & Thermochemical Behavior of Cerium(IV) Oxide delta

    NASA Astrophysics Data System (ADS)

    Chueh, William C.

    The mixed-valent nature of nonstoichiometric ceria (CeO2-delta ) gives rise to a wide range of intriguing properties, such as mixed ionic and electronic conduction and oxygen storage. Surface and transport behavior in rare-earth (samaria) doped and undoped ceria were investigated, with particular emphasis on applications in electrochemical and thermochemical energy conversion processes such as fuel cells and solar fuel production. The electrochemical responses of bulk-processed ceria with porous Pt and Au electrodes were analyzed using 1-D and 2-D transport models to decouple surface reactions, near-surface transport and bulk transport. Combined experimental and numerical results indicate that hydrogen electro-oxidation and hydrolysis near open-circuit conditions occur preferentially over the ceria | gas interface rather than over the ceria | gas | metal interface, with the rate-limiting step likely to be either surface reaction or transport through the surface oxygen vacancy depletion layer. In addition, epitaxial thin films of ceria were grown on zirconia substrates using pulsed-laser deposition to examine electrocatalysis over well-defined microstructures. Physical models were derived to analyze the electrochemical impedance response. By varying the film thickness, interfacial and chemical capacitance were decoupled, with the latter shown to be proportional to the small polaron densities. The geometry of microfabricated metal current collectors (metal = Pt, Ni) was also systematically varied to investigate the relative activity of the ceria | gas and the ceria | metal | gas interfaces. The data suggests that the electrochemical activity of the metal-ceria composite is only weakly dependent on the metal due to the relatively high activity of the ceria | gas interface. In addition to electrochemical experiments, thermochemical reduction-oxidation studies were performed on ceria. It was shown that thermally-reduced ceria, upon exposure to H 2O and/or CO2, can be

  6. Electrochemical processing of nitrate waste solutions

    SciTech Connect

    Genders, D.; Weinberg, N.; Hartsough, D. )

    1992-10-07

    The second phase of research performed at The Electrosynthesis Co., Inc. has demonstrated the successful removal of nitrite and nitrate from a synthetic effluent stream via a direct electrochemical reduction at a cathode. It was shown that direct reduction occurs at good current efficiencies in 1,000 hour studies. The membrane separation process is not readily achievable for the removal of nitrites and nitrates due to poor current efficiencies and membrane stability problems. A direct reduction process was studied at various cathode materials in a flow cell using the complete synthetic mix. Lead was found to be the cathode material of choice, displaying good current efficiencies and stability in short and long term tests under conditions of high temperature and high current density. Several anode materials were studied in both undivided and divided cell configurations. A divided cell configuration was preferable because it would prevent re-oxidation of nitrite by the anode. The technical objective of eliminating electrode fouling and solids formation was achieved although anode materials which had demonstrated good stability in short term divided cell tests corroded in 1,000 hour experiments. The cause for corrosion is thought to be F[sup [minus

  7. Tutorial Review: Electrochemical Nitric Oxide Sensors for Physiological Measurements

    PubMed Central

    Privett, Benjamin J.; Shin, Jae Ho; Schoenfisch, Mark H.

    2013-01-01

    Summary The important biological roles of nitric oxide (NO) have prompted the development of analytical techniques capable of sensitive and selective detection of NO. Electrochemical sensing, more than any other NO-detection method, embodies the parameters necessary for quantifying NO in challenging physiological environments such as blood and the brain. Herein, we provide a broad overview of the field of electrochemical NO sensors, including design, fabrication, and analytical performance characteristics. Both electrochemical sensors and biological applications are detailed. PMID:20502795

  8. Electrode electrolyte interlayers containing cerium oxide for electrochemical fuel cells

    DOEpatents

    Borglum, Brian P.; Bessette, Norman F.

    2000-01-01

    An electrochemical cell is made having a porous fuel electrode (16) and a porous air electrode (13), with solid oxide electrolyte (15) therebetween, where the air electrode surface opposing the electrolyte has a separate, attached, dense, continuous layer (14) of a material containing cerium oxide, and where electrolyte (16) contacts the continuous oxide layer (14), without contacting the air electrode (13).

  9. Oxide modified air electrode surface for high temperature electrochemical cells

    DOEpatents

    Singh, Prabhakar; Ruka, Roswell J.

    1992-01-01

    An electrochemical cell is made having a porous cermet electrode (16) and a porous lanthanum manganite electrode (14), with solid oxide electrolyte (15) between them, where the lanthanum manganite surface next to the electrolyte contains a thin discontinuous layer of high surface area cerium oxide and/or praseodymium oxide, preferably as discrete particles (30) in contact with the air electrode and electrolyte.

  10. Simulation of the electrochemical machining process

    SciTech Connect

    Gray, L.J.; Serbin, C.A.; Dietrich, W.C.

    1984-11-01

    An algorithm for simulating a two-dimensional electrochemical machining process is presented. A major part of the calculation, the solution of Laplace's equation, is accomplished by a boundary element method based upon Green's formula. Polarization, in the form of the Tafel equation, is included in the model. The computer program is discussed in detail.

  11. Innovative oxide materials for electrochemical energy conversion

    NASA Astrophysics Data System (ADS)

    Wachsman, Eric D.

    2012-02-01

    Research in functional materials has progressed from those materials exhibiting structural to electronic functionality. The study of ion conducting ceramics ushers in a new era of ``chemically functional materials.'' This chemical functionality arises out of the defect equilibria of these materials, and results in the ability to transport chemical species and actively participate in chemical reactions at their surface. Moreover, this chemical functionality provides a promise for the future whereby the harnessing of our natural hydrocarbon energy resources can shift from inefficient and polluting combustion - mechanical methods to direct electrochemical conversion. The unique properties of these materials and their applications will be described. The focus will be on the application of ion conducting ceramics to energy conversion and storage, chemical sensors, chemical separation and conversion, and life support systems. Results presented will include development of record high power density (3 kW/kg) solid oxide fuel cells, NOx/CO species selective solid-state sensors, high yield membrane reactors, and regenerative life support systems that reduce CO2 to O2 and solid C.

  12. Electrochemical glucose oxidation on dendritic cuprous oxide film fabricated by PSS-assisted electrochemical deposition

    NASA Astrophysics Data System (ADS)

    Yang, Ming; Jin, Xiaoqi; Huang, Qiao

    2011-02-01

    Cuprous oxides (Cu 2O) with different morphologies were deposited on F-doped tin oxide (FTO) covered glass substrates by potentiostatic deposition. The as-deposited samples were characterized by XRD, BET surface area and SEM. The effects of Poly(styrene sulfonic acid) sodium salt (PSS) on the crystal morphologies of Cu 2O were studied. Different crystal morphologies of Cu 2O can be obtained by varying the concentrations of PSS in the electrolytes. The formation of dendritic microstructure in Cu 2O film depends on the concentration of PSS in the electrolyte. Dendritic Cu 2O crystals formed gradually with the increase of the concentration of PSS in the electrolyte from 0 to 4 g L -1. More symmetrical Cu 2O crystals appear when the concentration of PSS is changed from 4 to 8 g L -1. However, the Cu 2O nanoparticles formed instead of dendritic Cu 2O crystals if the concentration of PSS reaches to 12 g L -1, which is due to the slower diffusion rate of reactive species in high concentration of PSS. The as-deposited Cu 2O thin films with different morphologies all exhibit the electrochemical glucose oxidation properties. The improved performance of glucose oxidation is achieved on the dendritic Cu 2O film electrode. The result indicates that the dendritic microstructure is beneficial for decreasing the resistance and improving transportation and diffusion of reactants and products.

  13. Electrochemical oxidation of fluoroquinolone antibiotics: Mechanism, residual antibacterial activity and toxicity change.

    PubMed

    Zhu, Linyan; Santiago-Schübel, Beatrix; Xiao, Hongxia; Hollert, Henner; Kueppers, Stephan

    2016-10-01

    In this paper, we studied the electrochemical oxidation mechanisms of three typical fluoroquinolone antibiotics (FQs), and investigated residual antibacterial activity and toxicity changes after oxidation processes. Electrochemistry coupled to mass spectrometry (EC-MS) was used to study the oxidation processes of ciprofloxacin (CIP), norfloxacin (NOR) and ofloxacin (OFL). Eight oxidation products for each parent compound were identified and their chemical structures were elucidated. The transformation trend of each product, with the continuous increase of voltage from 0 to 3000 mV, was recorded by online EC-MS. The oxidation pathways were proposed based on the structural information and transformation trends of oxidation products. We found the oxidation mechanisms of FQs consisted of the hydroxylation and cleavage of piperazinyl ring via reactions with hydroxyl radicals, while the fluoroquinolone core remained intact. The antibacterial activity of the parent compounds and their oxidation mixtures was estimated using zone inhibition tests for gram-negative bacteria Salmonella typhimurium. It was found that the oxidation mixtures of CIP and NOR retained the antibacterial properties with lower activity compared to their parent compounds, while the antibacterial activity of OFL was almost eliminated after oxidation. Furthermore, the toxicity of the three FQs and their oxidation mixtures were evaluated using algal growth inhibition test (Desmodesmus subspicatus). The median effective concentration (EC50) values for the algal inhibition tests were calculated for the end point of growth rate. The toxicity of CIP and NOR to green algae after electrochemical oxidation, remained unchanged, while that of OFL significantly increased. The results presented in this paper contribute to an understanding of the electrochemical oxidation mechanisms of FQs, and highlight the potential environmental risks of FQs after electrochemical oxidation processes. PMID:27318447

  14. Enhanced photocatalytic activity of electrochemically synthesized aluminum oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Pathania, Deepak; Katwal, Rishu; Kaur, Harpreet

    2016-03-01

    In this study, aluminum oxide (Al2O3) nanoparticles (NPs) were synthesized via an electrochemical method. The effects of reaction parameters such as supporting electrolytes, solvent, current and electrolysis time on the shape and size of the resulting NPs were investigated. The Al2O3 NPs were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, thermogravimetric analysis/differential thermal analysis, energy-dispersive X-ray analysis, and ultraviolet-visible spectroscopy. Moreover, the Al2O3 NPs were explored for photocatalytic degradation of malachite green (MG) dye under sunlight irradiation via two processes: adsorption followed by photocatalysis; coupled adsorption and photocatalysis. The coupled process exhibited a higher photodegradation efficiency (45%) compared to adsorption followed by photocatalysis (32%). The obtained kinetic data was well fitted using a pseudo-first-order model for MG degradation.

  15. Solution Processed PEDOT Analogues in Electrochemical Supercapacitors.

    PubMed

    Österholm, Anna M; Ponder, James F; Kerszulis, Justin A; Reynolds, John R

    2016-06-01

    We have designed fully soluble ProDOTx-EDOTy copolymers that are electrochemically equivalent to electropolymerized PEDOT without using any surfactants or dispersants. We show that these copolymers can be incorporated as active layers in solution processed thin film supercapacitors to demonstrate capacitance, stability, and voltage similar to the values of those that use electrodeposited PEDOT as the active material with the added advantage of the possibility for large scale, high-throughput processing. These Type I supercapacitors provide exceptional cell voltages (up to 1.6 V), highly symmetrical charge/discharge behavior, promising long-term stability exceeding 50 000 charge/discharge cycles, as well as energy (4-18 Wh/kg) and power densities (0.8-3.3 kW/kg) that are comparable to those of electrochemically synthesized analogues. PMID:27195798

  16. In Situ Electrochemical Oxidation Tuning of Transition Metal Disulfides to Oxides for Enhanced Water Oxidation.

    PubMed

    Chen, Wei; Wang, Haotian; Li, Yuzhang; Liu, Yayuan; Sun, Jie; Lee, Sanghan; Lee, Jang-Soo; Cui, Yi

    2015-08-26

    The development of catalysts with earth-abundant elements for efficient oxygen evolution reactions is of paramount significance for clean and sustainable energy storage and conversion devices. Our group demonstrated recently that the electrochemical tuning of catalysts via lithium insertion and extraction has emerged as a powerful approach to improve catalytic activity. Here we report a novel in situ electrochemical oxidation tuning approach to develop a series of binary, ternary, and quaternary transition metal (e.g., Co, Ni, Fe) oxides from their corresponding sulfides as highly active catalysts for much enhanced water oxidation. The electrochemically tuned cobalt-nickel-iron oxides grown directly on the three-dimensional carbon fiber electrodes exhibit a low overpotential of 232 mV at current density of 10 mA cm(-2), small Tafel slope of 37.6 mV dec(-1), and exceptional long-term stability of electrolysis for over 100 h in 1 M KOH alkaline medium, superior to most non-noble oxygen evolution catalysts reported so far. The materials evolution associated with the electrochemical oxidation tuning is systematically investigated by various characterizations, manifesting that the improved activities are attributed to the significant grain size reduction and increase of surface area and electroactive sites. This work provides a promising strategy to develop electrocatalysts for large-scale water-splitting systems and many other applications. PMID:27162978

  17. In Situ Electrochemical Oxidation Tuning of Transition Metal Disulfides to Oxides for Enhanced Water Oxidation

    PubMed Central

    2015-01-01

    The development of catalysts with earth-abundant elements for efficient oxygen evolution reactions is of paramount significance for clean and sustainable energy storage and conversion devices. Our group demonstrated recently that the electrochemical tuning of catalysts via lithium insertion and extraction has emerged as a powerful approach to improve catalytic activity. Here we report a novel in situ electrochemical oxidation tuning approach to develop a series of binary, ternary, and quaternary transition metal (e.g., Co, Ni, Fe) oxides from their corresponding sulfides as highly active catalysts for much enhanced water oxidation. The electrochemically tuned cobalt–nickel–iron oxides grown directly on the three-dimensional carbon fiber electrodes exhibit a low overpotential of 232 mV at current density of 10 mA cm–2, small Tafel slope of 37.6 mV dec–1, and exceptional long-term stability of electrolysis for over 100 h in 1 M KOH alkaline medium, superior to most non-noble oxygen evolution catalysts reported so far. The materials evolution associated with the electrochemical oxidation tuning is systematically investigated by various characterizations, manifesting that the improved activities are attributed to the significant grain size reduction and increase of surface area and electroactive sites. This work provides a promising strategy to develop electrocatalysts for large-scale water-splitting systems and many other applications. PMID:27162978

  18. Vanadium oxides nanostructures: Hydrothermal synthesis and electrochemical properties

    SciTech Connect

    Mjejri, I.; Etteyeb, N.; Sediri, F.

    2014-12-15

    Highlights: • Vanadium oxides nanostructures were synthesized hydrothermally. • Reversible redox behavior with doping/dedoping process. • Doping/dedoping is easier for Li{sup +} to Na{sup +}. • Energy-related applications such as cathodes in lithium batteries. - Abstract: A facile and template-free one-pot strategy is applied to synthesize nanostructured vanadium oxide particles via a hydrothermal methodology. X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transforms infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) have been used to characterize the structure and morphology of the samples. The products are gradually changed from sheet-shaped VO{sub 2}(B) to rod-like V{sub 3}O{sub 7}·H{sub 2}O with decreasing cyclohexanediol as both protective and reducing agent. The specific surface area of the VO{sub 2}(B) nanosheets and V{sub 3}O{sub 7}·H{sub 2}O nanorods was found to be 22 and 16 m{sup 2} g{sup −1}, respectively. Thin films of VO{sub 2}(B) and V{sub 3}O{sub 7}·H{sub 2}O deposited on ITO substrates were electrochemically characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The voltammograms show reversible redox behavior with doping/dedoping process corresponding to reversible cation intercalation/de-intercalation into the crystal lattice of the nanorods/nanosheets. This process is easier for the small Li{sup +} cation than larger ones Na{sup +}.

  19. Electrochemical oxidation and reuse of tannery saline wastewater.

    PubMed

    Sundarapandiyan, S; Chandrasekar, R; Ramanaiah, B; Krishnan, S; Saravanan, P

    2010-08-15

    In this present work, electrochemical treatment of saline wastewater with organic (protein) load was studied. The influence of the critical parameters of electro-oxidation such as pH, period, salt concentration and current density on the reduction of organic load was studied using graphite electrodes. It was found that current density of 0.024 A/cm(2) for a period of 2 h at pH 9.0 rendered best results in terms of reduction in COD and TKN. The energy requirement for the reduction of 1 kg of TKN and 1 kg of COD are 22.45 kWh and 0.80 kWh respectively at pH 9 and 0.024 A/cm(2). Reuse experiments were conducted at commercial scale. One of the saline waste streams in leather manufacturing process, pickling was treated and reused continuously thrice. The characteristics of the waste stream and the quality of the leathers indicate that the reuse of saline streams with intermittent electrochemical treatment is feasible. PMID:20435417

  20. Design of electrochemical processes for treatment of unusual waste streams

    SciTech Connect

    Farmer, J.C.

    1998-01-01

    UCRL- JC- 129438 PREPRINT This document was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor the University of California nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or the University of California. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or the University of California, and shall not be used for advertising or product endorsement purposes. Introduction. An overview of work done on the development of three electrochemical processes that meet the specific needs of low- level waste treatment is presented. These technologies include: mediated electrochemical oxidation [I- 4]; bipolar membrane electrodialysis [5]; and electrosorption of carbon aerogel electrodes [6- 9]. Design strategies are presented to assess the suitability of these electrochemical processes for Mediated electrochemical oxidation. Mixed wastes include both hazardous and radioactive components. It is desirable to reduce the overall volume of the waste before immobilization and disposal in repositories. While incineration is an attractive technique for the destruction of organic fractions of mixed wastes, such high-temperature thermal processes pose the threat of volatilizing various radionuclides. By destroying organics in the aqueous phase at low temperature and ambient pressure, the risk of volatilization can be reduced. One approach that is

  1. The electrochemical reduction processes of solid compounds in high temperature molten salts.

    PubMed

    Xiao, Wei; Wang, Dihua

    2014-05-21

    Solid electrode processes fall in the central focus of electrochemistry due to their broad-based applications in electrochemical energy storage/conversion devices, sensors and electrochemical preparation. The electrolytic production of metals, alloys, semiconductors and oxides via the electrochemical reduction of solid compounds (especially solid oxides) in high temperature molten salts has been well demonstrated to be an effective and environmentally friendly process for refractory metal extraction, functional materials preparation as well as spent fuel reprocessing. The (electro)chemical reduction of solid compounds under cathodic polarizations generally accompanies a variety of changes at the cathode/melt electrochemical interface which result in diverse electrolytic products with different compositions, morphologies and microstructures. This report summarizes various (electro)chemical reactions taking place at the compound cathode/melt interface during the electrochemical reduction of solid compounds in molten salts, which mainly include: (1) the direct electro-deoxidation of solid oxides; (2) the deposition of the active metal together with the electrochemical reduction of solid oxides; (3) the electro-inclusion of cations from molten salts; (4) the dissolution-electrodeposition process, and (5) the electron hopping process and carbon deposition with the utilization of carbon-based anodes. The implications of the forenamed cathodic reactions on the energy efficiency, chemical compositions and microstructures of the electrolytic products are also discussed. We hope that a comprehensive understanding of the cathodic processes during the electrochemical reduction of solid compounds in molten salts could form a basis for developing a clean, energy efficient and affordable production process for advanced/engineering materials. PMID:24535552

  2. Sensitive electrochemical detection of nitric oxide based on AuPt and reduced graphene oxide nanocomposites.

    PubMed

    Liu, Zhonggang; Forsyth, Heidi; Khaper, Neelam; Chen, Aicheng

    2016-06-20

    Since nitric oxide (NO) plays a critical role in many biological processes, its precise detection is essential toward an understanding of its specific functions. Here we report on a facile and environmentally compatible strategy for the construction of an electrochemical sensor based on reduced graphene oxide (rGO) and AuPt bimetallic nanoparticles. The prepared nanocomposites were further employed for the electroanalysis of NO using differential pulse voltammetry (DPV) and amperometric methods. The dependence of AuPt molar ratios on the electrochemical performance was investigated. Through the combination of the advantages of the high conductivity from rGO and highly electrocatalytic activity from AuPt bimetallic nanoparticles, the AuPt-rGO based NO sensor exhibited a high sensitivity of 7.35 μA μM(-1) and a low detection limit of 2.88 nM. Additionally, negligible interference from common ions or organic molecules was observed, and the AuPt-rGO modified electrode demonstrated excellent stability. Moreover, this optimized electrochemical sensor was practicable for efficiently monitoring the NO released from rat cardiac cells, which were stimulated by l-arginine (l-arg), showing that stressed cells generated over 10 times more NO than normal cells. The novel sensor developed in this study may have significant medical diagnostic applications for the prevention and monitoring of disease. PMID:27143513

  3. Electrochemical oxidation of butein at glassy carbon electrodes.

    PubMed

    Tesio, Alvaro Yamil; Robledo, Sebastián Noel; Fernández, Héctor; Zon, María Alicia

    2013-06-01

    The electrochemical oxidation of flavonoid butein is studied at glassy carbon electrodes in phosphate and citrate buffer solutions of different pH values, and 1M perchloric acid aqueous solutions by cyclic and square wave voltammetries. The oxidation peak corresponds to the 2e(-), 2H(+) oxidation of the 3,4-dihydroxy group in B ring of butein, given the corresponding quinone species. The overall electrode process shows a quasi-reversible behavior and an adsorption/diffusion mixed control at high butein bulk concentrations. At low butein concentrations, the electrode process shows mainly an adsorption control. Butein surface concentration values were obtained from the charge associated with the adsorbed butein oxidation peaks, which are in agreement with those values expected for the formation of a monolayer of adsorbate in the concentration range from 1 to 5μM. Square wave voltammetry was used to perform a full thermodynamic and kinetics characterization of the butein surface redox couple. Therefore, from the combination of the "quasi-reversible maximum" and the "splitting of the net square wave voltammetric peak" methods, values of (0.386±0.003) V, (0.46±0.04), and 2.7×10(2)s(-1) were calculated for the formal potential, the anodic transfer coefficient, and the formal rate constant, respectively, of the butein overall surface redox process in pH4.00 citrate buffer solutions. These results will be then used to study the interaction of butein, and other flavonoids with the deoxyribonucleic acid, in order to better understand the potential therapeutic applications of these compounds. PMID:23434740

  4. Synthesis of hollow cobalt oxide nanopowders by a salt-assisted spray pyrolysis process applying nanoscale Kirkendall diffusion and their electrochemical properties.

    PubMed

    Ju, Hyeon Seok; Cho, Jung Sang; Kim, Jong Hwa; Choi, Yun Ju; Kang, Yun Chan

    2015-12-21

    A new concept for preparing hollow metal oxide nanopowders by salt-assisted spray pyrolysis applying nanoscale Kirkendall diffusion is introduced. The composite powders of metal oxide and indecomposable metal salt are prepared by spray pyrolysis. Post-treatment under a reducing atmosphere and subsequent washing using distilled water produce aggregation-free metal nanopowders. The metal nanopowders are then transformed into metal oxide hollow nanopowders by nanoscale Kirkendall diffusion. Co3O4 hollow nanopowders are prepared as first target materials. A cobalt oxide-NaCl composite powder prepared by spray pyrolysis transforms into several Co3O4 hollow nanopowders by several treatment processes. The discharge capacities of the Co3O4 nanopowders with filled and hollow structures at a current density of 1 A g(-1) for the 150th cycle are 605 and 775 mA h g(-1), respectively. The hollow structure formed by nanoscale Kirkendall diffusion improves the lithium-ion storage properties of Co3O4 nanopowders. PMID:26571144

  5. Ultrasonically enhanced electrochemical oxidation of ibuprofen.

    PubMed

    Thokchom, Binota; Kim, Kyungho; Park, Jeonghyuk; Khim, Jeehyeong

    2015-01-01

    A hybrid advanced oxidation process combining sonochemistry (US) and electrochemistry (EC) for the batch scale degradation of ibuprofen was developed. The performance of this hybrid reactor system was evaluated by quantifying on the degradation of ibuprofen under the variation in electrolytes, frequency, applied voltage, ultrasonic power density and temperature in aqueous solutions with a platinum electrode. Among the methods examined (US, EC and US/EC), the hybrid method US/EC resulted 89.32%, 81.85% and 88.7% degradations while using NaOH, H2SO4 and deionized water (DI), respectively, with a constant electrical voltages of 30V, an ultrasound frequency of 1000kHz, and a power density of 100WL(-1) at 298K in 1h. The degradation was established to follow pseudo first order kinetics. In addition, energy consumption and energy efficiencies were also calculated. The probable mechanism for the anodic oxidation of ibuprofen at a platinum electrode was also postulated. PMID:24844440

  6. Thermally Reduced Graphene Oxide Electrochemically Activated by Bis-Spiro Quaternary Alkyl Ammonium for Capacitors.

    PubMed

    He, Tieshi; Meng, Xiangling; Nie, Junping; Tong, Yujin; Cai, Kedi

    2016-06-01

    Thermally reduced graphene oxide (RGO) electrochemically activated by a quaternary alkyl ammonium-based organic electrolytes/activated carbon (AC) electrode asymmetric capacitor is proposed. The electrochemical activation process includes adsorption of anions into the pores of AC in the positive electrode and the interlayer intercalation of cations into RGO in the negative electrode under high potential (4.0 V). The EA process of RGO by quaternary alkyl ammonium was investigated by X-ray diffraction and electrochemical measurements, and the effects of cation size and structure were extensively evaluated. Intercalation by quaternary alkyl ammonium demonstrates a small degree of expansion of the whole crystal lattice (d002) and a large degree of expansion of the partial crystal lattice (d002) of RGO. RGO electrochemically activated by bis-spiro quaternary alkyl ammonium in propylene carbonate/AC asymmetric capacitor exhibits good activated efficiency, high specific capacity, and stable cyclability. PMID:27180820

  7. Electrochemical decontamination of actinide processing gloveboxes

    SciTech Connect

    Lugo, J.L.; Wedman, D.E.; Nelson, T.O.

    1997-12-31

    Electrochemical technology for the decontamination of metallic surfaces has been successfully demonstrated. Highly enriched uranium and stainless steel surfaces are readily decontaminated to Low Level Waste (LLW) criteria using this process. This process is similar to electropolishing and utilizes the anodic dissolution of the substrate material to generate a clean surface. The surface contaminants are thus removed and collected along with the stripped substrate material as a compact precipitate. This separation allows the electrolyte to be recycled indefinitely. Using an alkaline Sodium Sulfate electrolyte solution, we are able to decontaminate to low levels of alpha activity, gloveboxes previously used in Actinide processing. Surfaces with contamination levels > 1,000,000 cpm alpha activity have been decontaminated to levels as low as 7,000. The process is rapid with decontamination occurring at a rate of over 3 square cm/sec.

  8. Surface Morphology of Si(111) during Electrochemical Oxidation

    NASA Astrophysics Data System (ADS)

    Ando, A.; Miki, K.; Sakamoto, K.; Matsumoto, K.; Morita, Y.; Tokumoto, H.

    1997-03-01

    Topographical changes of hydrogen terminated Si(111) during electrochemical oxidation in a 0.2 M H_2SO4 aqueous solution have been investigated using atomic force microscopy (AFM). The hydrogen terminated surface with atomically flat terraces was prepared by dipping into a NH_4F aqueous solution. Electrochemical oxidation has been performed by a potentiostatic (constant potential) or a galvanostatic (constant current) method. AFM images show that the oxidation occured on the terraces and proceeded homogeneously. The surface became rough as the oxidation proceeded. However, step edges were still observed even after the charge of 50 mC/cm^2 was applied. Quantitative analysis of a relation between the charge and surface morphology will be discussed. the address below:

  9. Evaluation of the formation of oxidants and by-products using Pt/Ti, RuO2/Ti, and IrO2/Ti electrodes in the electrochemical process.

    PubMed

    Yoon, Yeojoon; Cho, Eunha; Jung, Youmi; Kwon, Minhwan; Yoon, Jaekyung; Kang, Joon-Wun

    2015-01-01

    The aim of this study was to evaluate the formation of oxidants and by-products by using different electrode materials, such as Pt/Ti, RuO2/Ti, and IrO2/Ti, in the electrochemical process. The harmful by-products ClO3- and ClO4- were formed during the electrolysis of a Cl- electrolyte solution, as well as active chlorine, which is the most common water disinfectant. With regard to drinking water treatment, the most efficient electrode was defined as that leading to a higher formation of active chlorine and a lower formation of hazardous by-products. Overall, it was found that the Pt/Ti electrode should not be used for drinking water treatment applications, while the IrO2/Ti and RuO2/Ti electrodes are ideal for use. PMID:25514133

  10. Graphene oxide nanocapsules within silanized hydrogels suitable for electrochemical pseudocapacitors.

    PubMed

    Kataky, R; Hadden, J H L; Coleman, K S; Ntola, C N M; Chowdhury, M; Duckworth, A R; Dobson, B P; Campos, R; Pyner, S; Shenton, F

    2015-06-28

    Soft biocompatible gels comprised of rolled up graphene oxide nanocapsules within the pores of silanized hydrogels may be used as electrochemical pseudocapacitors with physiological glucose or KOH as a reducing agent, affording a material suitable for devices requiring pulses with characteristic time less than a second. PMID:25977943

  11. Electrochemical oxidation of imazapyr with BDD electrode in titanium substrate.

    PubMed

    Souza, F L; Teodoro, T Q; Vasconcelos, V M; Migliorini, F L; Lima Gomes, P C F; Ferreira, N G; Baldan, M R; Haiduke, R L A; Lanza, M R V

    2014-12-01

    In this work we have studied the treatment of imazapyr by electrochemical oxidation with boron-doped diamond anode. Electrochemical degradation experiments were performed in a one-compartment cell containing 0.45 L of commercial formulations of herbicide in the pH range 3.0-10.0 by applying a density current between 10 and 150 mA cm(-2) and in the temperature range 25-45 °C. The maximum current efficiencies were obtained at lower current densities since the electrochemical system is under mass transfer control. The mineralization rate increased in acid medium and at higher temperatures. The treatment was able to completely degrade imazapyr in the range 4.6-100.0 mg L(-1), although the current charge required rises along with the increasing initial concentration of the herbicide. Toxicity analysis with the bioluminescent bacterium Vibrio fischeri showed that at higher pollutant concentrations the toxicity was reduced after the electrochemical treatment. To clarify the reaction pathway for imazapyr mineralization by OH radicals, LC-MS/MS analyses we performed together with a theoretical study. Ions analysis showed the formation of high levels of ammonium in the cathode. The main final products of the electrochemical oxidation of imazapyr with diamond thin film electrodes are formic, acetic and butyric acids. PMID:25461923

  12. Decolorization of landfill leachate using electrochemical oxidation technique

    NASA Astrophysics Data System (ADS)

    Jumaah, Majd Ahmed; Othman, Mohamed Rozali

    2015-09-01

    The study was carried out to investigate the electrochemical oxidation of landfill leachate from the Jeram sanitary landfill leachate using charcoal base metallic composite electrodes. The control parameters used were applied voltage, Cl- concentration (as supporting electrolyte) and pH of the solution. The optimum conditions obtained were NaCl concentration of 1.5 % (w/v), applied voltage of 10 V, operating time 180 min and C60CG Co10PVC15 electrode as an anode.15 Electrochemical treatment using charcoal base metallic composite electrode was able to remove color up to 79%.

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

    NASA Astrophysics Data System (ADS)

    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. Solid oxide materials research accelerated electrochemical testing

    SciTech Connect

    Windisch, C.; Arey, B.

    1995-08-01

    The objectives of this work were to develop methods for accelerated testing of cathode materials for solid oxide fuel cells under selected operating conditions. The methods would be used to evaluate the performance of LSM cathode material.

  15. NEPTUNIUM OXIDE PROCESSING

    SciTech Connect

    Jordan, J; Watkins, R; Hensel, S

    2009-05-27

    The Savannah River Site's HB-Line Facility completed a campaign in which fifty nine cans of neptunium oxide were produced and shipped to the Idaho National Laboratory in the 9975 shipping container. The neptunium campaign was divided into two parts: Part 1 which consisted of oxide made from H-Canyon neptunium solution which did not require any processing prior to conversion into an oxide, and Part 2 which consisted of oxide made from additional H-Canyon neptunium solutions which required processing to purify the solution prior to conversion into an oxide. The neptunium was received as a nitrate solution and converted to oxide through ion-exchange column extraction, precipitation, and calcination. Numerous processing challenges were encountered in order make a final neptunium oxide product that could be shipped in a 9975 shipping container. Among the challenges overcome was the issue of scale: translating lab scale production into full facility production. The balance between processing efficiency and product quality assurance was addressed during this campaign. Lessons learned from these challenges are applicable to other processing projects.

  16. Electrochemical phase diagrams for Ti oxides from density functional calculations

    NASA Astrophysics Data System (ADS)

    Huang, Liang-Feng; Rondinelli, James M.

    2015-12-01

    Developing an accurate simulation method for the electrochemical stability of solids, as well as understanding the physics related with its accuracy, is critically important for improving the performance of compounds and predicting the stability of new materials in aqueous environments. Herein we propose a workflow for the accurate calculation of first-principles electrochemical phase (Pourbaix) diagrams. With this scheme, we study the electrochemical stabilities of Ti and Ti oxides using density-functional theory. First, we find the accuracy of an exchange-correlation functional in predicting formation energies and electrochemical stabilities is closely related with the electronic exchange interaction therein. Second, the metaGGA and hybrid functionals with a more precise description of the electronic exchange interaction lead to a systematic improvement in the accuracy of the Pourbaix diagrams. Furthermore, we show that accurate Ti Pourbaix diagrams also require that thermal effects are included through vibrational contributions to the free energy. We then use these diagrams to explain various experimental electrochemical phenomena for the Ti-O system, and show that if experimental formation energies for Ti oxides, which contain contributions from defects owing to their generation at high (combustion) temperatures, are directly used to predict room temperature Pourbaix diagrams then significant inaccuracies result. In contrast, the formation energies from accurate first-principles calculations, e.g., using metaGGA and hybrid functionals, are found to be more reliable. Finally, to facilitate the future application of our accurate electrochemical phase equilibria diagrams, the variation of the Ti Pourbaix diagrams with aqueous ion concentration is also provided.

  17. Electrochemical reduction of CO 2 in solid oxide electrolysis cells

    NASA Astrophysics Data System (ADS)

    Zhan, Zhongliang; Zhao, Lin

    This paper describes results on the electrochemical reduction of carbon dioxide using the same device as the typical planar nickel-YSZ cermet electrode supported solid oxide fuel cells (H 2-CO 2, Ni-YSZ|YSZ|LSCF-GDC, LSCF, air). Operation in both the fuel cell and the electrolysis mode indicates that the electrodes could work reversibly for the charge transfer processes. An electrolysis current density of ≈1 A cm -2 is observed at 800 °C and 1.3 V for an inlet mixtures of 25% H 2-75% CO 2. Mass spectra measurement suggests that the nickel-YSZ cermet electrode is highly effective for reduction of CO 2 to CO. Analysis of the gas transport in the porous electrode and the adsorption/desorption process over the nickel surface indicates that the cathodic reactions are probably dominated by the reduction of steam to hydrogen, whereas carbon monoxide is mainly produced via the reverse water gas shift reaction.

  18. Electrochemical deposition of conducting ruthenium oxide films from solution

    SciTech Connect

    Anderson, D.P.; Warren, L.F.

    1984-02-01

    In the last decade, ruthenium oxide, RuO /sub x/ (x less than or equal to 2), has been used extensively as the active anode electrocatalyst constituent for Cl/sub 2/ and O/sub 2/ evolution reactions, in chlorate production, and in metal electrowinning from mixed chloride-sulfate solutions. More recently, this material has been incorporated in several light-induced water electrolysis schemes and apparently possesses the ability to inhibit CdS photocorrosion by acting as a hole scavenger. The numerous applications for this catalyst material certainly warrant further studies of its electrochemical properties on a variety of substrates, e.g., semiconductors. The lack of a simple technique for controlled deposition of ruthenium oxide onto conducting substrates prompted us to investigate an electrochemical approach to this problem. We describe here a new way to electrochemically deposit conducting films of hydrated ruthenium oxide from an aqueous solution of the benzeneruthenium (II)aqua complex. The films slowly dissolve in aqueous electrolytes upon potential cycling, yet appear to be catalytic with regards to water oxidation.

  19. Direct electrochemical reduction of metal-oxides

    DOEpatents

    Redey, Laszlo I.; Gourishankar, Karthick

    2003-01-01

    A method of controlling the direct electrolytic reduction of a metal oxide or mixtures of metal oxides to the corresponding metal or metals. A non-consumable anode and a cathode and a salt electrolyte with a first reference electrode near the non-consumable anode and a second reference electrode near the cathode are used. Oxygen gas is produced and removed from the cell. The anode potential is compared to the first reference electrode to prevent anode dissolution and gas evolution other than oxygen, and the cathode potential is compared to the second reference electrode to prevent production of reductant metal from ions in the electrolyte.

  20. An Electrochemical Glucose Sensor Based on Zinc Oxide Nanorods.

    PubMed

    Marie, Mohammed; Mandal, Sanghamitra; Manasreh, Omar

    2015-01-01

    A glucose electrochemical sensor based on zinc oxide (ZnO) nanorods was investigated. The hydrothermal sol-gel growth method was utilized to grow ZnO nanorods on indium tin oxide-coated glass substrates. The total active area of the working electrode was 0.3 × 0.3 cm2 where titanium metal was deposited to enhance the contact. Well aligned hexagonal structured ZnO nanorods with a diameter from 68 to 116 nm were obtained. The excitonic peak obtained from the absorbance spectroscopy was observed at ~370 nm. The dominant peak of Raman spectroscopy measurement was at 440 cm(-1), matching with the lattice vibration of ZnO. The uniform distribution of the GOx and Nafion membrane that has been done using spin coating technique at 4000 rotations per minute helps in enhancing the ion exchange and increasing the sensitivity of the fabricated electrochemical sensor. The amperometric response of the fabricated electrochemical sensor was 3 s. The obtained sensitivity of the fabricated ZnO electrochemical sensor was 10.911 mA/mM·cm2 and the lower limit of detection was 0.22 µM. PMID:26263988

  1. Treatment of papermaking tobacco sheet wastewater by electrocoagulation combined with electrochemical oxidation.

    PubMed

    Ma, Xiangjuan; Gao, Yang; Huang, Hanping

    2015-01-01

    Attempts were made in this study to examine the efficiency of electrocoagulation (EC) using aluminum (Al) anode and stainless steel net cathode combined with electrochemical oxidation with a β-PbO₂anode or a mixed metal oxide (MMO) anode for treatment of papermaking tobacco sheet wastewater, which has the characteristics of high content of suspended solids (SS), intensive color, and low biodegradability. The wastewater was first subjected to the EC process under 40 mA/cm² of current density, 2.5 g/L of NaCl, and maintaining the original pH of wastewater. After 6 minutes of EC process, the effluent was further treated by electrochemical oxidation. The results revealed that the removal of SS during the EC process was very beneficial to mass transfer of organics during electrochemical oxidation. After the combined process, 83.9% and 82.8% of chemical oxygen demand (COD) removal could be achieved on the β-PbO₂and MMO anodes, respectively. The main components of the final effluent were biodegradable organic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, and hexahyl carbonic acid; the 5-day biochemical oxygen demand/chemical oxygen demand (BOD₅/COD) ratio increased from 0.06 to 0.85 (Al + β-PbO₂) or 0.80 (Al + MMO). Therefore, this integrated process is a promising alternative for pretreatment of papermaking tobacco sheet wastewater prior to biological treatment. PMID:25909726

  2. Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy.

    PubMed

    Huang, Yi-Fan; Kooyman, Patricia J; Koper, Marc T M

    2016-01-01

    Understanding the atomistic details of how platinum surfaces are oxidized under electrochemical conditions is of importance for many electrochemical devices such as fuel cells and electrolysers. Here we use in situ shell-isolated nanoparticle-enhanced Raman spectroscopy to identify the intermediate stages of the electrochemical oxidation of Pt(111) and Pt(100) single crystals in perchloric acid. Density functional theory calculations were carried out to assist in assigning the experimental Raman bands by simulating the vibrational frequencies of possible intermediates and products. The perchlorate anion is suggested to interact with hydroxyl phase formed on the surface. Peroxo-like and superoxo-like two-dimensional (2D) surface oxides and amorphous 3D α-PtO2 are sequentially formed during the anodic polarization. Our measurements elucidate the process of the electrochemical oxidation of platinum single crystals by providing evidence for the structure-sensitive formation of a 2D platinum-(su)peroxide phase. These results may contribute towards a fundamental understanding of the mechanism of degradation of platinum electrocatalysts. PMID:27514695

  3. Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy

    PubMed Central

    Huang, Yi-Fan; Kooyman, Patricia J.; Koper, Marc T. M.

    2016-01-01

    Understanding the atomistic details of how platinum surfaces are oxidized under electrochemical conditions is of importance for many electrochemical devices such as fuel cells and electrolysers. Here we use in situ shell-isolated nanoparticle-enhanced Raman spectroscopy to identify the intermediate stages of the electrochemical oxidation of Pt(111) and Pt(100) single crystals in perchloric acid. Density functional theory calculations were carried out to assist in assigning the experimental Raman bands by simulating the vibrational frequencies of possible intermediates and products. The perchlorate anion is suggested to interact with hydroxyl phase formed on the surface. Peroxo-like and superoxo-like two-dimensional (2D) surface oxides and amorphous 3D α-PtO2 are sequentially formed during the anodic polarization. Our measurements elucidate the process of the electrochemical oxidation of platinum single crystals by providing evidence for the structure-sensitive formation of a 2D platinum-(su)peroxide phase. These results may contribute towards a fundamental understanding of the mechanism of degradation of platinum electrocatalysts. PMID:27514695

  4. Playing peekaboo with graphene oxide: a scanning electrochemical microscopy investigation.

    PubMed

    Rapino, Stefania; Treossi, Emanuele; Palermo, Vincenzo; Marcaccio, Massimo; Paolucci, Francesco; Zerbetto, Francesco

    2014-11-01

    Scanning electrochemical microscopy (SECM) can image graphene oxide (GO) flakes on insulating and conducting substrates. The contrast between GO and the substrate is controlled by the electrostatic interactions that are established between the charges of the molecular redox mediator and the charges present in the sheet/substrate. SECM also allows quantitative measurement - at the nano/microscale - of the charge transfer kinetics between single monolayer sheets and agent molecules. PMID:25224581

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

    PubMed

    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. PMID:24418938

  6. Electrochemical and electrochromic behavior of reactively sputtered nickel oxide

    SciTech Connect

    Miller, E.L.; Rocheleau, R.E.

    1997-06-01

    Nickel oxide thin films were deposited by reactive sputtering in a 20% oxygen/argon atmosphere for use as oxygen evolution catalysts in the photoelectrochemical production of hydrogen. The optical properties of the films were also characterized to evaluate their application as window layers. The polycrystalline films deposited at residual gas pressures of 6 or 10 mTorr exhibited moderate activity for oxygen evolution in 1 N KOH and pronounced coloration and bleaching during alternating anodic/cathodic bias. Properties of these films were not sensitive to growth rate over the range studied, 0.5 to 4 {angstrom}/s. In contrast, films deposited at 2 mTorr exhibited poor activity for oxygen evolution and severely limited electrochromic behavior which the authors attribute to marked changes in the morphology and crystallinity in the low-pressure films. The films grown at 6 mTorr and higher tended to be more oriented, to have a higher degree of crystallinity, and higher oxygen content. Strong linkages between the electrochemical and optical behaviors observed in this work provide new insights into the processes involved in oxygen evolution reaction catalysis and electrochromism in reactively sputtered NiO{sub x} films. The results presented indicate that reactive sites located on or near grain boundaries are responsible for both behaviors.

  7. Route of electrochemical oxidation of the antibiotic sulfamethoxazole on a mixed oxide anode.

    PubMed

    Hussain, Sajjad; Gul, Saima; Steter, Juliana R; Miwa, Douglas W; Motheo, Artur J

    2015-10-01

    The appearance of pharmaceutical compounds and their bioactive transformation products in aquatic environments is becoming an issue of increasing concern. In this study, the electrochemical oxidation of the widely used antibiotic sulfamethoxazole (SMX) was investigated using a commercial mixed oxide anode (Ti/Ru0.3Ti0.7O2) and a single compartment filter press-type flow reactor. The kinetics of SMX degradation was determined as a function of electrolyte composition, applied current density, and initial pH. Almost complete (98 %) degradation of SMX could be achieved within 30 min of electrolysis in 0.1 mol L(-1) NaCl solution at pH 3 with applied current densities ≥20 mA cm(-2). Nine major intermediates of the reaction were identified by LC-ESI-Q-TOF-MS (e.g., C6H9NO2S (m/z = 179), C6H4NOCl (m/z = 141), and C6H6O2 (m/z = 110)). The degradation followed various routes involving cleavage of the oxazole and benzene rings by hydroxyl and/or chlorine radicals, processes that could occur before or after rupture of the N-S bond, followed by oxidation of the remaining moieties. Analysis of the total organic carbon content revealed that the antibiotic was partially mineralized under the conditions employed and some inorganic ions, including NO3 (-) and SO4 (2-), could be identified. The results presented herein demonstrate the efficacy of the electrochemical process using a Ti/Ru0.3Ti0.7O2 anode for the remediation of wastewater containing the antibiotic SMX. PMID:26002364

  8. Electrochemical processes at interfaces and mixed conductor development

    SciTech Connect

    Youngblood, G.E.; Bates, J.L.; Kingsley, J.J.; Pederson, L.R.; Rupaal, A.S.; Weber, W.J.; Windisch, C.F. Jr.

    1993-07-01

    Rates of oxygen reduction at the cathode/electrolyte interface of an electrochemical cell that simulated an operating solid oxide fuel cell were assessed for a variety of cathode materials. Using complex impedance with an unbonded interface cell design and dc polarization methods, the relative contributions of charge transfer, oxygen dissociation and diffusional processes could be distinguished. This experimental approach yielded intrinsic electrocatalytic activities for cathode materials as a function of temperature and oxygen partial pressure, independent of interfacial morphology. Electrocatalytic activities for substituted lanthanum manganites and yttrium manganites varied considerably depending on composition, but all showed intrinsic activities substantially higher than platinum. Ceramics that conduct both ions and electrons (mixed conductors) are technologically important materials, with applications as semipermeable membranes in gas separation, as electrodes in solid oxide fuel cells, and as electrocatalysts. Oxygen transport can occur under open circuit conditions in such materials, driven only by a gradient in the chemical potential of oxygen. An increase in the rate of charge transfer reactions and a reduction in polarization effects are among the advantages of the use of mixed conductors as electrode materials in solid oxide fuel cells. Predominantly ionically-conducting ceria-zirconia compositions were doped with multivalent rare earth oxides to introduce extrinsic electronic conductivity. Electronic conduction was further enhanced by partial reduction.

  9. Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

    DOEpatents

    Isenberg, Arnold O.

    1987-01-01

    An electrochemical apparatus is made containing an exterior electrode bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

  10. Electrochemically active species and multielectron processes in ionic melts

    NASA Astrophysics Data System (ADS)

    Shapoval, Viktor I.; Solov'ev, Veniamin V.; Malyshev, Viktor V.

    2001-02-01

    The model concepts for the mechanisms of formation of electrochemically active species and multielectron processes in ionic nitrate-, carbonate-, boron- and titanium-containing fluoride melts are generalised. The fundamental importance of the acid-base properties of a melt in the mechanism of formation of electrochemically active species is shown for nitrate- and carbonate-containing melts. This fact is confirmed by electrochemical measurements and by calculations of force constants for oxyanions. The optimum form of electrochemically active species has been established; their reduction abilities depend on the cationic composition of a melt, the adsorption properties of the electrode surface and the electric field strength. The bibliography includes 218 references.

  11. Mineralization of 2-chlorophenol by sequential electrochemical reductive dechlorination and biological processes.

    PubMed

    Arellano-González, Miguel Ángel; González, Ignacio; Texier, Anne-Claire

    2016-08-15

    In this work, a novel approach was applied to obtain the mineralization of 2-chlorophenol (2-CP) in an electrochemical-biological combined system where an electrocatalytic dehydrogenation process (reductive dechlorination) was coupled to a biological denitrification process. Reductive dechlorination of 2-CP was conducted in an ECCOCEL-type reactor on a Pd-Ni/Ti electrode at a potential of -0.40V vs Ag/AgCl(s)/KCl(sat), achieving 100 percent transformation of 2-CP into phenol. The electrochemically pretreated effluent was fed to a rotating cylinder denitrifying bioreactor where the totality of phenol was mineralized by denitrification, obtaining CO2 and N2 as the end products. The total time required for 2-CP mineralization in the combined electrochemical-biological process was 7.5h. This value is close to those previously reported for electrochemical and advanced oxidation processes but in this case, an efficient process was obtained without accumulation of by-products or generation of excessive energy costs due to the selective electrochemical pretreatment. This study showed that the use of electrochemical reductive pretreatment combined with biological processes could be a promising technology for the removal of recalcitrant molecules, such as chlorophenols, from wastewaters by more efficient, rapid, and environmentally friendly processes. PMID:27131458

  12. Electrochemical oxidation as a final treatment of synthetic tannery wastewater.

    PubMed

    Panizza, Marco; Cerisola, Giacomo

    2004-10-15

    Vegetable tannery wastewaters contain high concentrations of organics and other chemicals that inhibit the activity of microorganisms during biological oxidations, so biorefractory organics that are not removed by biological treatment must be eliminated by a tertiary or advanced wastewater treatment. In this paper, the applicability of electrochemical oxidation as a tertiary treatment of a vegetable tannery wastewater was investigated by performing galvanostatic electrolysis using lead dioxide (Ti/PbO2) and mixed titanium and ruthenium oxide (Ti/TiRuO2) as anodes under different experimental conditions. The experimental results showed that both the electrodes performed complete mineralization of the wastewater. In particular, the oxidation took place on the PbO2 anode by direct electron transfer and indirect oxidation mediated by active chlorine, while it occurred on the Ti/TiRuO2 anode only by indirect oxidation. Furthermore, the Ti/PbO2 gave a somewhat higher oxidation rate than that observed for the Ti/TiRuO2 anode. Although the Ti/TiRuO2 required almost the same energy consumption for complete COD removal, it was more stable and did not release toxic ions, so it was the best candidate for industrial applications. With the Ti/TiRuO2 anode, the rate of tannery wastewater oxidation increased with the current density, pH, and temperature of the solution. These results strongly indicate that electrochemical methods can be applied effectively as a final treatment of vegetable tannery wastewater allowing the complete removal of COD, tannin, and ammonium and decolorization. PMID:15543753

  13. Fabrication of advanced electrochemical energy materials using sol-gel processing techniques

    NASA Technical Reports Server (NTRS)

    Chu, C. T.; Chu, Jay; Zheng, Haixing

    1995-01-01

    Advanced materials play an important role in electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. They are being used as both electrodes and electrolytes. Sol-gel processing is a versatile solution technique used in fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. The application of sol-gel processing in the fabrication of advanced electrochemical energy materials will be presented. The potentials of sol-gel derived materials for electrochemical energy applications will be discussed along with some examples of successful applications. Sol-gel derived metal oxide electrode materials such as V2O5 cathodes have been demonstrated in solid-slate thin film batteries; solid electrolytes materials such as beta-alumina for advanced secondary batteries had been prepared by the sol-gel technique long time ago; and high surface area transition metal compounds for capacitive energy storage applications can also be synthesized with this method.

  14. Electrically Conductive Diamond Membrane for Electrochemical Separation Processes.

    PubMed

    Gao, Fang; Nebel, Christoph E

    2016-07-20

    Electrochemically switchable selective membranes play an important role in selective filtration processes such as water desalination, industrial waste treatment, and hemodialysis. Currently, membranes for these purposes need to be optimized in terms of electrical conductivity and stability against fouling and corrosion. In this paper, we report the fabrication of boron-doped diamond membrane by template diamond growth on quartz fiber filters. The morphology and quality of the diamond coating are characterized via SEM and Raman spectroscopy. The membrane is heavily boron doped (>10(21) cm(-3)) with >3 V potential window in aqueous electrolyte. By applying a membrane potential against the electrolyte, the redox active species can be removed via flow-through electrolysis. Compared to planar diamond electrodes, the ∼250 times surface enlargement provided by such a membrane ensures an effective removal of target chemicals from the input electrolyte. The high stability of diamond enables the membrane to not only work at high membrane bias but also to be self-cleaning via in situ electrochemical oxidation. Therefore, we believe that the diamond membrane presented in this paper will provide a solution to future selective filtration applications especially in extreme conditions. PMID:27396448

  15. Simultaneous Electrochemical Reduction and Delamination of Graphene Oxide Films.

    PubMed

    Wang, Xiaohan; Kholmanov, Iskandar; Chou, Harry; Ruoff, Rodney S

    2015-09-22

    Here we report an electrochemical method to simultaneously reduce and delaminate graphene oxide (G-O) thin films deposited on metal (Al and Au) substrates. During the electrochemical reaction, interface charge transfer between the G-O thin film and the electrode surface was found to be important in eliminating oxygen-containing groups, yielding highly reduced graphene oxide (rG-O). In the meantime, hydrogen bubbles were electrochemically generated at the rG-O film/electrode interface, propagating the film delamination. Unlike other metal-based G-O reduction methods, the metal used here was either not etched at all (for Au) or etched a small amount (for Al), thus making it possible to reuse the substrate and lower production costs. The delaminated rG-O film exhibits a thickness-dependent degree of reduction: greater reduction is achieved in thinner films. The thin rG-O films having an optical transmittance of 90% (λ = 550 nm) had a sheet resistance of 6390 ± 447 Ω/□ (ohms per square). rG-O-based stretchable transparent conducting films were also demonstrated. PMID:26257072

  16. ADVANCED OXIDATION PROCESS

    SciTech Connect

    Dr. Colin P. Horwitz; Dr. Terrence J. Collins

    2003-11-04

    The removal of recalcitrant sulfur species, dibenzothiophene and its derivatives, from automotive fuels is an integral component in the development of cleaner burning and more efficient automobile engines. Oxidative desulfurization (ODS) wherein the dibenzothiophene derivative is converted to its corresponding sulfoxide and sulfone is an attractive approach to sulfur removal because the oxidized species are easily extracted or precipitated and filtered from the hydrocarbon phase. Fe-TAML{reg_sign} activators of hydrogen peroxide (TAML is Tetra-Amido-Macrocyclic-Ligand) catalytically convert dibenzothiophene and its derivatives rapidly and effectively at moderate temperatures (50-60 C) and ambient pressure to the corresponding sulfoxides and sulfones. The oxidation process can be performed in both aqueous systems containing alcohols such as methanol, ethanol, or t-butanol, and in a two-phase hydrocarbon/aqueous system containing tert-butanol or acetonitrile. In the biphasic system, essentially complete conversion of the DBT to its oxidized products can be achieved using slightly longer reaction times than in homogeneous solution. Among the key features of the technology are the mild reaction conditions, the very high selectivity where no over oxidation of the sulfur compounds occurs, the near stoichiometric use of hydrogen peroxide, the apparent lack of degradation of sensitive fuel components, and the ease of separation of oxidized products.

  17. Mapping Electrochemical Heterogeneity at Iron Oxide Surfaces: A Local Electrochemical Impedance Study.

    PubMed

    Lucas, Marie; Boily, Jean-François

    2015-12-22

    Alternating current scanning electrochemical microscopy (AC-SECM) was used for the first time to map key electrochemical attributes of oriented hematite (α-Fe2O3) single crystal surfaces at the micron-scale. Localized electrochemical impedance spectra (LEIS) of the (001) and (012) faces provided insight into the spatial variations of local double layer capacitance (C(dl)) and charge transfer resistance (R(ad)). These parameters were extracted by LEIS measurements in the 0.4-8000 Hz range to probe the impedance response generated by the redistribution of water molecules and charge carriers (ions) under an applied AC. These were attributed to local variations in the local conductivity of the sample surfaces. Comparison with global EIS measurements on the same samples uncovered highly comparable frequency-resolved processes, that were broken down into contributions from the bulk hematite, the interface as well as the microelectrode/tip assembly. This work paves the way for new studies aimed at mapping electrochemical processes at the mesoscale on this environmentally and technologically important material. PMID:26625255

  18. Electrochemical/Pyrometallurgical Waste Stream Processing and Waste Form Fabrication

    SciTech Connect

    Steven Frank; Hwan Seo Park; Yung Zun Cho; William Ebert; Brian Riley

    2015-07-01

    This report summarizes treatment and waste form options being evaluated for waste streams resulting from the electrochemical/pyrometallurgical (pyro ) processing of used oxide nuclear fuel. The technologies that are described are South Korean (Republic of Korea – ROK) and United States of America (US) ‘centric’ in the approach to treating pyroprocessing wastes and are based on the decade long collaborations between US and ROK researchers. Some of the general and advanced technologies described in this report will be demonstrated during the Integrated Recycle Test (IRT) to be conducted as a part of the Joint Fuel Cycle Study (JFCS) collaboration between US Department of Energy (DOE) and ROK national laboratories. The JFCS means to specifically address and evaluated the technological, economic, and safe guard issues associated with the treatment of used nuclear fuel by pyroprocessing. The IRT will involve the processing of commercial, used oxide fuel to recover uranium and transuranics. The recovered transuranics will then be fabricated into metallic fuel and irradiated to transmutate, or burn the transuranic elements to shorter lived radionuclides. In addition, the various process streams will be evaluated and tested for fission product removal, electrolytic salt recycle, minimization of actinide loss to waste streams and waste form fabrication and characterization. This report specifically addresses the production and testing of those waste forms to demonstrate their compatibility with treatment options and suitability for disposal.

  19. Advanced materials and electrochemical processes in high-temperature solid electrolytes

    SciTech Connect

    Bates, J.L.; Chick, L.A.; Youngblood, G.E.; Weber, W.J.

    1990-10-01

    Fuel cells for the direct conversion of fossil fuels to electric energy necessitates the use of high-temperature solid electrodes. This study has included: (1) determination of electrical transport, thermal and electrical properties to illucidate the effects of microstructure, phase equilibria, oxygen partial pressure, additives, synthesis and fabrication on these properties; (2) investigation of synthesis and fabrication of advanced oxide materials, such as La{sub 0.9}Sn{sub 0.1}MnO{sub 3}; and (3) application of new analytical techniques using complex impedance coupled with conventional electrochemical methods to study the electrochemical processes and behavior of materials for solid oxide fuel cells and other high-temperature electrolyte electrochemical process. 15 refs., 10 figs., 2 tabs. (BM)

  20. Electrochemical processing of nitrate waste solutions. Phase 2, Final report

    SciTech Connect

    Genders, D.; Weinberg, N.; Hartsough, D.

    1992-10-07

    The second phase of research performed at The Electrosynthesis Co., Inc. has demonstrated the successful removal of nitrite and nitrate from a synthetic effluent stream via a direct electrochemical reduction at a cathode. It was shown that direct reduction occurs at good current efficiencies in 1,000 hour studies. The membrane separation process is not readily achievable for the removal of nitrites and nitrates due to poor current efficiencies and membrane stability problems. A direct reduction process was studied at various cathode materials in a flow cell using the complete synthetic mix. Lead was found to be the cathode material of choice, displaying good current efficiencies and stability in short and long term tests under conditions of high temperature and high current density. Several anode materials were studied in both undivided and divided cell configurations. A divided cell configuration was preferable because it would prevent re-oxidation of nitrite by the anode. The technical objective of eliminating electrode fouling and solids formation was achieved although anode materials which had demonstrated good stability in short term divided cell tests corroded in 1,000 hour experiments. The cause for corrosion is thought to be F{sup {minus}} ions from the synthetic mix migrating across the cation exchange membrane and forming HF in the acid anolyte. Other possibilities for anode materials were explored. A membrane separation process was investigated which employs an anion and cation exchange membrane to remove nitrite and nitrate, recovering caustic and nitric acid. Present research has shown poor current efficiencies for nitrite and nitrate transport across the anion exchange membrane due to co-migration of hydroxide anions. Precipitates form within the anion exchange membranes which would eventually result in the failure of the membranes. Electrochemical processing offers a highly promising and viable method for the treatment of nitrate waste solutions.

  1. Scalable and sustainable electrochemical allylic C-H oxidation.

    PubMed

    Horn, Evan J; Rosen, Brandon R; Chen, Yong; Tang, Jiaze; Chen, Ke; Eastgate, Martin D; Baran, Phil S

    2016-05-01

    New methods and strategies for the direct functionalization of C-H bonds are beginning to reshape the field of retrosynthetic analysis, affecting the synthesis of natural products, medicines and materials. The oxidation of allylic systems has played a prominent role in this context as possibly the most widely applied C-H functionalization, owing to the utility of enones and allylic alcohols as versatile intermediates, and their prevalence in natural and unnatural materials. Allylic oxidations have featured in hundreds of syntheses, including some natural product syntheses regarded as "classics". Despite many attempts to improve the efficiency and practicality of this transformation, the majority of conditions still use highly toxic reagents (based around toxic elements such as chromium or selenium) or expensive catalysts (such as palladium or rhodium). These requirements are problematic in industrial settings; currently, no scalable and sustainable solution to allylic oxidation exists. This oxidation strategy is therefore rarely used for large-scale synthetic applications, limiting the adoption of this retrosynthetic strategy by industrial scientists. Here we describe an electrochemical C-H oxidation strategy that exhibits broad substrate scope, operational simplicity and high chemoselectivity. It uses inexpensive and readily available materials, and represents a scalable allylic C-H oxidation (demonstrated on 100 grams), enabling the adoption of this C-H oxidation strategy in large-scale industrial settings without substantial environmental impact. PMID:27096371

  2. Scalable and sustainable electrochemical allylic C–H oxidation

    NASA Astrophysics Data System (ADS)

    Horn, Evan J.; Rosen, Brandon R.; Chen, Yong; Tang, Jiaze; Chen, Ke; Eastgate, Martin D.; Baran, Phil S.

    2016-05-01

    New methods and strategies for the direct functionalization of C–H bonds are beginning to reshape the field of retrosynthetic analysis, affecting the synthesis of natural products, medicines and materials. The oxidation of allylic systems has played a prominent role in this context as possibly the most widely applied C–H functionalization, owing to the utility of enones and allylic alcohols as versatile intermediates, and their prevalence in natural and unnatural materials. Allylic oxidations have featured in hundreds of syntheses, including some natural product syntheses regarded as “classics”. Despite many attempts to improve the efficiency and practicality of this transformation, the majority of conditions still use highly toxic reagents (based around toxic elements such as chromium or selenium) or expensive catalysts (such as palladium or rhodium). These requirements are problematic in industrial settings; currently, no scalable and sustainable solution to allylic oxidation exists. This oxidation strategy is therefore rarely used for large-scale synthetic applications, limiting the adoption of this retrosynthetic strategy by industrial scientists. Here we describe an electrochemical C–H oxidation strategy that exhibits broad substrate scope, operational simplicity and high chemoselectivity. It uses inexpensive and readily available materials, and represents a scalable allylic C–H oxidation (demonstrated on 100 grams), enabling the adoption of this C–H oxidation strategy in large-scale industrial settings without substantial environmental impact.

  3. ENHANCED ELECTROCHEMICAL PROCESSES IN SUBCRITICAL WATER

    SciTech Connect

    Steven B. Hawthorne

    2000-07-01

    This project involved designing and performing preliminary electrochemical experiments in subcritical water. An electrochemical cell with substantially better performance characteristics than presently available was designed, built, and tested successfully. The electrochemical conductivity of subcritical water increased substantially with temperature, e.g., conductivities increased by a factor of 120 when the temperature was increased from 25 to 250 C. Cyclic voltammograms obtained with platinum and nickel demonstrated that the voltage required to produce hydrogen and oxygen from water can be dropped by a factor of three in subcritical water compared to the voltages required at ambient temperatures. However, no enhancement in the degradation of 1,2-dichlorobenzene and the polychlorinated biphenyl 3,3',4,4'-tetrachlorobiphenyl was observed with applied potential in subcritical water.

  4. Treatment of methyl orange dye wastewater by cooperative electrochemical oxidation in anodic-cathodic compartment.

    PubMed

    Pang, L; Wang, H; Bian, Z Y

    2013-01-01

    Electrochemical oxidation of methyl orange wastewater was studied using Ti/IrO(2)/RuO(2) anode and a self-made Pd/C O(2)-fed cathode in the divided cell with a terylene diaphragm. The result indicated that the appropriate rate of feeding air improved the methyl orange removal efficiency. The discoloration efficiency of methyl orange in the divided cell increased with increasing current density. The initial pH value had some effect on the discoloration of methyl orange, which became not obvious when the pH ranged from 2 to 10. However, the average removal efficiency of methyl orange wastewater in terms of total organic carbon (TOC) can reach 89.3%. The methyl orange structure had changed in the electrolytic process, and the characteristic absorption peak of methyl orange was about 470 nm. With the extension of electrolysis time, the concentration of methyl orange gradually reduced; wastewater discoloration rate increased gradually. The degradation of methyl orange was assumed to be cooperative oxidation by direct or indirect electrochemical oxidation at the anode and H(2)O(2), ·OH, O(2)(-)· produced by oxygen reduction at the cathode in the divided cell. Therefore, the cooperative electrochemical oxidation of methyl orange wastewater in the anodic-cathodic compartment had better degradation effects. PMID:23202555

  5. Corner heating in rectangular solid oxide electrochemical cell generators

    DOEpatents

    Reichner, Philip

    1989-01-01

    Disclosed is an improvement in a solid oxide electrochemical cell generator 1 having a rectangular design with four sides that meet at corners, and containing multiplicity of electrically connected fuel cells 11, where a fuel gas is passed over one side of said cells and an oxygen containing gas is passed into said cells, and said fuel is burned to form heat, electricity, and an exhaust gas. The improvement comprises passing the exhaust gases over the multiplicity of cells 11 in such a way that more of the heat in said exhaust gases flows at the corners of the generator, such as through channels 19.

  6. Synthesis and electrochemical performance of hierarchical nano-vanadium oxide.

    PubMed

    Mjejri, I; Sediri, F

    2016-10-15

    Hierarchically structured nano-vanadium oxides with different morphologies have been synthesized via a template-free hydrothermal route by adjusting the organic precursor quantities. The effects of molar ratio on structure, morphology and crystallite sized were investigated. The possible growth mechanism is also proposed. When evaluated as a cathode material for lithium-ion batteries, the vanadium oxyhydroxide H2V3O8 samples deliver very high charging capacity, good reversibility and a better cycling stability. The excellent electrochemical performance is attributed to multiple advantageous structural features. PMID:27442146

  7. Moisture effects on the electrochemical reaction and resistance switching at Ag/molybdenum oxide interfaces.

    PubMed

    Yang, Chuan-Sen; Shang, Da-Shan; Chai, Yi-Sheng; Yan, Li-Qin; Shen, Bao-Gen; Sun, Young

    2016-05-14

    An important potential application of solid state electrochemical reactions is in redox-based resistive switching memory devices. Based on the fundamental switching mechanisms, the memory has been classified into two modes, electrochemical metallization memory (ECM) and valence change memory (VCM). In this work, we have investigated a solid state electrochemical cell with a simple Ag/MoO3-x/fluorine-doped tin oxide (FTO) sandwich structure, which shows a normal ECM switching mode after an electroforming process. While in the lower voltage sweep range, the switching behavior changes to VCM-like mode with the opposite switching polarity to the ECM mode. By current-voltage measurements under different ambient atmospheres and X-ray photoemission spectroscopy analysis, electrochemical anodic passivation of the Ag electrode and valence change of molybdenum ions during resistance switching have been demonstrated. The crucial role of moisture adsorption in the switching mode transition has been clarified based on the Pourbaix diagram for the Ag-H2O system for the first time. These results provide a fundamental insight into the resistance switching mechanism model in solid state electrochemical cells. PMID:26996952

  8. Electroless deposition of conformal nanoscale iron oxide on carbon nanoarchitectures for electrochemical charge storage.

    PubMed

    Sassin, Megan B; Mansour, Azzam N; Pettigrew, Katherine A; Rolison, Debra R; Long, Jeffrey W

    2010-08-24

    We describe a simple self-limiting electroless deposition process whereby conformal, nanoscale iron oxide (FeO(x)) coatings are generated at the interior and exterior surfaces of macroscopically thick ( approximately 90 microm) carbon nanofoam paper substrates via redox reaction with aqueous K(2)FeO(4). The resulting FeO(x)-carbon nanofoams are characterized as device-ready electrode structures for aqueous electrochemical capacitors and they demonstrate a 3-to-7 fold increase in charge-storage capacity relative to the native carbon nanofoam when cycled in a mild aqueous electrolyte (2.5 M Li(2)SO(4)), yielding mass-, volume-, and footprint-normalized capacitances of 84 F g(-1), 121 F cm(-3), and 0.85 F cm(-2), respectively, even at modest FeO(x) loadings (27 wt %). The additional charge-storage capacity arises from faradaic pseudocapacitance of the FeO(x) coating, delivering specific capacitance >300 F g(-1) normalized to the content of FeO(x) as FeOOH, as verified by electrochemical measurements and in situ X-ray absorption spectroscopy. The additional capacitance is electrochemically addressable within tens of seconds, a time scale of relevance for high-rate electrochemical charge storage. We also demonstrate that the addition of borate to buffer the Li(2)SO(4) electrolyte effectively suppresses the electrochemical dissolution of the FeO(x) coating, resulting in <20% capacitance fade over 1000 consecutive cycles. PMID:20731433

  9. Control of disinfection and halogenated disinfection byproducts by the electrochemical process.

    PubMed

    Jung, Y J; Oh, B S; Kang, J W; Page, M A; Phillips, M J; Mariñas, B J

    2007-01-01

    The aim of this study was to investigate some aspects of the performance of electrochemical process as an alternative disinfection strategy, while minimising DBPs, for water purification. The study of electrochemical processes has shown free chlorine to be produced, but smaller amounts of stronger oxidants, such as ozone, hydrogen peroxide and OH radicals (*OH), were also generated. The formation of mixed oxidants increased with increasing electric conductivity, but was limited at conductivities greater than 0.6 mS/cm. Using several microorganisms, such as E. coli and MS2 bacteriophage, inactivation kinetic studies were performed. With the exception of free chlorine, the role of mixed oxidants, especially OH radicals, was investigated for enhancement of the inactivation rate. Additionally, the formation and reduction of DBPs was studied by monitoring the concentration of haloacetic acids (HAAs) during the process. PMID:17674851

  10. Optimization and electrochemical characterization of RF-sputtered iridium oxide microelectrodes for electrical stimulation

    NASA Astrophysics Data System (ADS)

    Kang, Xiaoyang; Liu, Jingquan; Tian, Hongchang; Yang, Bin; NuLi, Yanna; Yang, Chunsheng

    2014-02-01

    A reactively sputtered iridium oxide (IrOx) thin film has been developed as electrochemical modification material for microelectrodes to obtain high stability and charge storage capacity (CSC) in functional electrical stimulation. The effect of the oxygen flow and oxygen to argon ratio during sputtering process on the microstructure and electrochemical properties of the IrOx film is characterized. After optimization, the activated IrOx microelectrode shows the highest CSC of 36.15 mC cm-2 at oxygen flow of 25 sccm and oxygen to argon ratio of (2.5:1). Because the deposition process of the reactively sputtered iridium oxide is an exothermic reaction, it is difficult to form film patterning by the lift-off process. The lift-off process was focused on the partially carbonized photoresist (PR) and normal PR. The higher of the carbonization degree of PR reaches, the longer the immersion duration. However, the patterning process of the iridium oxide film becomes feasible when the sputtering pressure is increasing. The experimental results show that the iridium oxide films forms the pattern with the lowest duration of ultrasonic agitation when the deposition pressure is 4.2 Pa and pressure ratio between O2 and Ar pressure is 3:4.

  11. Mediated electrochemical oxidation of Rocky Flats combustible low level mixed wastes

    SciTech Connect

    Chiba, Z.

    1992-12-01

    Mediated Electrochemical Oxidation (MEO) was originally developed for dissolution of difficult to dissolve forms of plutonium oxide. It was also found to be effective for oxidizing non-polymerized organic materials. MEO is an inherently safe process since the hazardous and radioactive materials are completely contained in the aqueous phase, and operating temperatures and pressures of the system are low (well below 100 {degree}C and 30 psig). The most commonly used mediator-electrolyte combination is silver in nitric acid. The process produces divalent silver ion, a strong oxidizing agent, which dissolves the radioactive components of mixed wastes and destroys the organic components. In the past, work at LLNL has been focused on understanding the basic science and modeling the dissolution and destruction mechanisms. Reaction rates of water with Ag(H) were measured using spectrophotometric methods, and the diffusivity of silver ions in nitric acid was estimated using a rotating disk electrode.

  12. Functionalizing Aluminum Oxide by Ag Dendrite Deposition at the Anode during Simultaneous Electrochemical Oxidation of Al.

    PubMed

    Rafailović, Lidija D; Gammer, Christoph; Rentenberger, Christian; Trišović, Tomislav; Kleber, Christoph; Karnthaler, Hans Peter

    2015-11-01

    A novel synthesis strategy is presented for depositing metallic Ag at the anode during simultaneous electrochemical oxidation of Al. This unexpected result is achieved based on galvanic coupling. Metallic dendritic nanostructures well-anchored in a high surface area supporting matrix are envisioned to open up a new avenue of applications. PMID:26398487

  13. Mechanistic studies of water electrolysis and hydrogen electro-oxidation on high temperature ceria-based solid oxide electrochemical cells.

    PubMed

    Zhang, Chunjuan; Yu, Yi; Grass, Michael E; Dejoie, Catherine; Ding, Wuchen; Gaskell, Karen; Jabeen, Naila; Hong, Young Pyo; Shavorskiy, Andrey; Bluhm, Hendrik; Li, Wei-Xue; Jackson, Gregory S; Hussain, Zahid; Liu, Zhi; Eichhorn, Bryan W

    2013-08-01

    Through the use of ambient pressure X-ray photoelectron spectroscopy (APXPS) and a single-sided solid oxide electrochemical cell (SOC), we have studied the mechanism of electrocatalytic splitting of water (H2O + 2e(-) → H2 + O(2-)) and electro-oxidation of hydrogen (H2 + O(2-) → H2O + 2e(-)) at ∼700 °C in 0.5 Torr of H2/H2O on ceria (CeO2-x) electrodes. The experiments reveal a transient build-up of surface intermediates (OH(-) and Ce(3+)) and show the separation of charge at the gas-solid interface exclusively in the electrochemically active region of the SOC. During water electrolysis on ceria, the increase in surface potentials of the adsorbed OH(-) and incorporated O(2-) differ by 0.25 eV in the active regions. For hydrogen electro-oxidation on ceria, the surface concentrations of OH(-) and O(2-) shift significantly from their equilibrium values. These data suggest that the same charge transfer step (H2O + Ce(3+) <-> Ce(4+) + OH(-) + H(•)) is rate limiting in both the forward (water electrolysis) and reverse (H2 electro-oxidation) reactions. This separation of potentials reflects an induced surface dipole layer on the ceria surface and represents the effective electrochemical double layer at a gas-solid interface. The in situ XPS data and DFT calculations show that the chemical origin of the OH(-)/O(2-) potential separation resides in the reduced polarization of the Ce-OH bond due to the increase of Ce(3+) on the electrode surface. These results provide a graphical illustration of the electrochemically driven surface charge transfer processes under relevant and nonultrahigh vacuum conditions. PMID:23822749

  14. Electrochemically tunable thermal conductivity of lithium cobalt oxide

    NASA Astrophysics Data System (ADS)

    Cho, Jiung; Losego, Mark D.; Zhang, Hui Gang; Kim, Honggyu; Zuo, Jianmin; Petrov, Ivan; Cahill, David G.; Braun, Paul V.

    2014-06-01

    Using time-domain thermoreflectance, the thermal conductivity and elastic properties of a sputter deposited LiCoO2 film, a common lithium-ion cathode material, are measured as a function of the degree of lithiation. Here we report that via in situ measurements during cycling, the thermal conductivity of a LiCoO2 cathode reversibly decreases from ~5.4 to 3.7 W m-1 K-1, and its elastic modulus decreases from 325 to 225 GPa, as it is delithiated from Li1.0CoO2 to Li0.6CoO2. The dependence of the thermal conductivity on lithiation appears correlated with the lithiation-dependent phase behaviour. The oxidation-state-dependent thermal conductivity of electrolytically active transition metal oxides provides opportunities for dynamic control of thermal conductivity and is important to understand for thermal management in electrochemical energy storage devices.

  15. Electrochemically tunable thermal conductivity of lithium cobalt oxide.

    PubMed

    Cho, Jiung; Losego, Mark D; Zhang, Hui Gang; Kim, Honggyu; Zuo, Jianmin; Petrov, Ivan; Cahill, David G; Braun, Paul V

    2014-01-01

    Using time-domain thermoreflectance, the thermal conductivity and elastic properties of a sputter deposited LiCoO2 film, a common lithium-ion cathode material, are measured as a function of the degree of lithiation. Here we report that via in situ measurements during cycling, the thermal conductivity of a LiCoO2 cathode reversibly decreases from ~5.4 to 3.7 W m(-1) K(-1), and its elastic modulus decreases from 325 to 225 GPa, as it is delithiated from Li1.0CoO2 to Li0.6CoO2. The dependence of the thermal conductivity on lithiation appears correlated with the lithiation-dependent phase behaviour. The oxidation-state-dependent thermal conductivity of electrolytically active transition metal oxides provides opportunities for dynamic control of thermal conductivity and is important to understand for thermal management in electrochemical energy storage devices. PMID:24892640

  16. ADVANCED OXIDATION PROCESS

    SciTech Connect

    Colin P. Horwitz; Terrence J. Collins

    2003-10-22

    The design of new, high efficiency and cleaner burning engines is strongly coupled with the removal of recalcitrant sulfur species, dibenzothiophene and its derivatives, from fuels. Oxidative desulfurization (ODS) wherein these dibenzothiophene derivatives are oxidized to their corresponding sulfoxides and sulfones is an approach that has gained significant attention. Fe-TAML{reg_sign} activators of hydrogen peroxide (TAML is Tetra-Amido-Macrocyclic-Ligand) convert in a catalytic process dibenzothiophene and its derivatives to the corresponding sulfoxides and sulfones rapidly at moderate temperatures (60 C) and ambient pressure. The reaction can be performed in both an aqueous system containing an alcohol (methanol, ethanol, or t-butanol) to solubilize the DBT and in a two-phase hydrocarbon/aqueous system where the alcohol is present in both phases and facilitates the oxidation. Under a consistent set of conditions using the FeBF{sub 2} TAML activator, the degree of conversion was found to be t-butanol > methanol > ethanol. In the cases of methanol and ethanol, both the sulfoxide and sulfone were observed while for t-butanol only the sulfone was detected. In the two-phase system, the alcohol may function as an inverse phase transfer agent. The oxidation was carried out using two different TAML activators. In homogeneous solution, approximately 90% oxidation of the DBT could be achieved using the prototype TAML activator, FeB*, by sonicating the solution at near room temperature. In bi-phasic systems conversions as high as 50% were achieved using the FeB* TAML activator and hydrogen peroxide at 100 C. The sonication method yielded only {approx}6% conversion but this may have been due to mixing.

  17. Electrodeposition and electrochemical reduction of epitaxial metal oxide thin films and superlattices

    NASA Astrophysics Data System (ADS)

    He, Zhen

    The focus of this dissertation is the electrodeposition and electrochemical reduction of epitaxial metal oxide thin films and superlattices. The electrochemical reduction of metal oxides to metals has been studied for decades as an alternative to pyrometallurgical processes for the metallurgy industry. However, the previous work was conducted on bulk polycrystalline metal oxides. Paper I in this dissertation shows that epitaxial face-centered cubic magnetite (Fe3O4 ) thin films can be electrochemically reduced to epitaxial body-centered cubic iron (Fe) thin films in aqueous solution on single-crystalline Au substrates at room temperature. This technique opens new possibilities to produce special epitaxial metal/metal oxide heterojunctions and a wide range of epitaxial metallic alloy films from the corresponding mixed metal oxides. Electrodeposition, like biomineralization, is a soft solution processing method which can produce functional materials with special properties onto conducting or semiconducting solid surfaces. Paper II in this dissertation presents the electrodeposition of cobalt-substituted magnetite (CoxFe3-xO4, 0 of cobalt-substituted magnetite (CoxFe3-xO4, 0oxide (Co3O4) thin films on stainless steel and Au single-crystalline substrates. The crystalline Co3O4 thin films exhibit high catalytic activity towards the oxygen evolution reaction in an alkaline solution. A possible application of the electrodeposited Co 3O4 is the fabrication of highly active and low-cost photoanodes for photoelectrochemical water-splitting cells.

  18. Selective electrochemical generation of hydrogen peroxide from water oxidation

    SciTech Connect

    Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

    2015-10-08

    Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e– water oxidation to H2O2 and the 4e– oxidation to O2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively.

  19. Selective electrochemical generation of hydrogen peroxide from water oxidation

    DOE PAGESBeta

    Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

    2015-10-08

    Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, wemore » show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e– water oxidation to H2O2 and the 4e– oxidation to O2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively.« less

  20. Electrochemical Aspects of the ESR Process

    NASA Astrophysics Data System (ADS)

    Mitchell, Alec

    2016-07-01

    Current passage in the ESR process is accomplished by at least two Faradaic reaction systems, one at the electrode/slag interface and another at the slag/ingot interface. The nature of these reactions has been investigated and is reported to be a function of the alloy composition, current density and slag composition. In this report, data generated from both DC and line- frequency AC ESR operations is used to relate laboratory investigations on these reactions to results obtained in industrial practice. The operating reaction in the line frequency AC melting of simple alloy steels is found to be principally the reversible anodic oxidation of iron (Fe/Fe2+). In the equivalent DC process there is in addition the cathodic deposition of aluminium, resulting in the formation of substantial amounts of D-type alumina inclusions in the ingot. The Faradaic reactions involve energy exchange which should be taken into account in the process energy balance. They also are likely to change the interface physical characteristics such as interfacial tension. The data is extended to the case of low frequency ESR furnaces in which it is found that the extent of the reactions is strongly dependent on current density. It is concluded that the presence of Faradaic reactions in low frequency furnaces is unlikely to lead to quality problems in the alloys and applications for which these processes are used. This conclusion appears to be supported by industrial practice and leads to a further conclusion that low frequency practices in large ESR furnaces could potentially be replaced by simpler DC systems.

  1. Controlling and Measuring Electrochemical Processes at the Nanoscale

    NASA Astrophysics Data System (ADS)

    Lipson, Albert Leonard

    New applications for electrochemistry require an improved ability to characterize and influence processes at the nanoscale. For instance, the ability to create controllable nanostructures in a scalable manner can enable the wide use of nanotechnology. Furthermore, batteries that are used in electric vehicles and other mobile applications need to be lighter, safer and last longer. The performance of batteries is often controlled by nanoscale phenomena such as the breakdown of the electrolyte into a solid electrolyte interphase layer (SEI). In this thesis, a variety of techniques are discussed that address these deficiencies in our abilities to understand and control nanoscale phenomena. In particular, the use of nanosphere lithography to pattern thin films of aluminum prior to anodization is described, which allows for nearly arbitrary control of the pore size, interpore spacing and aspect ratio. Next, the ability to enhance the lithiation capacity of crystalline SiC via high temperature graphitization is explored. In particular, it is shown that if the SiC is doped and has the native oxide removed that the lithiation capacity of the SiC can be approximately double that of graphite. Characterization of nanoscale electrochemical phenomena can be performed by a wide variety of in situ and ex situ techniques. For instance, the same graphitized SiC can be exploited as a model system that mimics the basal planes of graphite, which is amenable to in situ X-ray characterization. By this method crystalline and textured LiF was found to grow on this surface during cycling along with other amorphous solid electrolyte interphase (SEI) components. Scanning probe microscopy can also be employed to study Li-ion battery electrodes and the formation of SEI. In particular, the development of scanning ion conductance microscopy (SICM) as a technique for mapping both the topography and local ion current is examined. The application of SICM to study the inhibition of SEI formation via

  2. Catalytic process for formaldehyde oxidation

    NASA Technical Reports Server (NTRS)

    Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); D'Ambrosia, Christine M. (Inventor)

    1996-01-01

    Disclosed is a process for oxidizing formaldehyde to carbon dioxide and water without the addition of energy. A mixture of formaldehyde and an oxidizing agent (e.g., ambient air containing formaldehyde) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

  3. A novel method for photodegradation of high-chroma dye wastewater via electrochemical pre-oxidation.

    PubMed

    Zhao, Kunjiao; Zhao, Guohua; Li, Peiqiang; Gao, Junxia; Lv, Baoying; Li, Dongming

    2010-06-01

    A new two-step process involving the electrocatalytic (EC) pre-oxidation and the following photoelectrocatalytic synergistic (PEC) oxidation is proposed to treat the high concentration and high-chroma methyl orange dye wastewater, which cannot be degraded by photocatalytic oxidation (PC) directly. The SnO(2)/TiO(2)-NTs/Ti electrode simultaneously possessing the outstanding PC oxidation properties of TiO(2)-NTs and the excellent EC oxidation abilities of the Sb doped SnO(2) was synthesized by impregnating Sb doped SnO(2) nanoparticles into TiO(2)-NTs. In the pre-oxidation process as the first stage, the high-color dye wastewater is decolorized with electrochemical method to some extent. Then, the wastewater becomes a light transmission system. It provides a suitable condition for PC oxidation reaction in the second stage. The synergistic effects of PC and EC oxidation led to the high PEC efficiency and the complete mineralization of dye wastewater is achieved. This two-step process is fast and efficient, which is worthy to study and explore in the practical environmental treatment. PMID:20434754

  4. Microfluidic electrochemical device and process for chemical imaging and electrochemical analysis at the electrode-liquid interface in-situ

    DOEpatents

    Yu, Xiao-Ying; Liu, Bingwen; Yang, Li; Zhu, Zihua; Marshall, Matthew J.

    2016-03-01

    A microfluidic electrochemical device and process are detailed that provide chemical imaging and electrochemical analysis under vacuum at the surface of the electrode-sample or electrode-liquid interface in-situ. The electrochemical device allows investigation of various surface layers including diffuse layers at selected depths populated with, e.g., adsorbed molecules in which chemical transformation in electrolyte solutions occurs.

  5. Electrochemical oxidation of the poultry manure anaerobic digested effluents for enhancing pollutants removal by Chlorella vulgaris.

    PubMed

    Wang, Mengzi; Cao, Wei; Wu, Yu; Lu, Haifeng; Li, Baoming

    2016-01-01

    The mechanisms and pseudo-kinetics of the electrochemical oxidation for wastewater treatment and the synergistic effect of combining algal biological treatment were investigated. NaCl, Na2SO4 and HCl were applied to compare the effect of electrolyte species on nutrients removal. NaCl was proved to be more efficient in removing ammonia ([Formula: see text]), total phosphorus (TP), total organic carbon (TOC) and inorganic carbon (IC). [Formula: see text] oxidation by using Ti/Pt-IrO2 electrodes was modelled, which indicates that the [Formula: see text] removal followed the zero-order kinetic with sufficient Cl(-) and the first-order kinetic with insufficient Cl(-), respectively. The feasibility of combining electrochemical oxidation with microalgae cultivation for wastewater treatment was also determined. A 2 h electrochemical pretreatment reduced 57% [Formula: see text], 76% TP, 72% TOC and 77% IC from the digested effluent, which is applied as feedstock for algae cultivation, and resulted in increasing both the biomass production and pollutants removal efficiencies of the algal biological process. PMID:26853507

  6. Simultaneous hydrogen production and electrochemical oxidation of organics using boron-doped diamond electrodes.

    PubMed

    Jiang, Juyuan; Chang, Ming; Pan, Peng

    2008-04-15

    This paper presents advantages of using a boron-doped diamond (BDD) electrode for hydrogen production and wastewater treatment in a single electrochemical cell. Results indicated that the BDD electrode possessed the widest known electrochemical window, allowing new possibilities for both anodic and cathodic reactions to simultaneously take place. The BDD electrode exhibited high anodic potential, generating high oxidation state radicals that facilitated oxidation of toxic waste organic compounds such as 4-nitrophenols. In contrast, because of widening of potential windows, the rate of hydrogen evolution at the cathode was significantly increased. Time-on-stream concentrations of reaction intermediates were monitored to elucidate mechanism involved in 4-nitrophenol oxidation. Spalling, fouling, or reduction in the thickness of thin-film diamond coating was not observed. Overall, the BDD electrode exhibits unique properties including chemical inertness, anticorrosion, and extended service life. These properties are especially important in wastewater treatment. Economic advantages were attributed to the low cost and long duration BDD electrode and the valuable hydrogen byproduct produced. Analysis has shown that technology associated with the BDD electrode could be effectively implemented with minimum energy input and capital requirements. When combined with solar energy and fuel cells, electrochemical wastewater processing can become energy efficient and cost-effective. PMID:18497166

  7. Cross-flow electrochemical reactor cells, cross-flow reactors, and use of cross-flow reactors for oxidation reactions

    DOEpatents

    Balachandran, Uthamalingam; Poeppel, Roger B.; Kleefisch, Mark S.; Kobylinski, Thaddeus P.; Udovich, Carl A.

    1994-01-01

    This invention discloses cross-flow electrochemical reactor cells containing oxygen permeable materials which have both electron conductivity and oxygen ion conductivity, cross-flow reactors, and electrochemical processes using cross-flow reactor cells having oxygen permeable monolithic cores to control and facilitate transport of oxygen from an oxygen-containing gas stream to oxidation reactions of organic compounds in another gas stream. These cross-flow electrochemical reactors comprise a hollow ceramic blade positioned across a gas stream flow or a stack of crossed hollow ceramic blades containing a channel or channels for flow of gas streams. Each channel has at least one channel wall disposed between a channel and a portion of an outer surface of the ceramic blade, or a common wall with adjacent blades in a stack comprising a gas-impervious mixed metal oxide material of a perovskite structure having electron conductivity and oxygen ion conductivity. The invention includes reactors comprising first and second zones seprated by gas-impervious mixed metal oxide material material having electron conductivity and oxygen ion conductivity. Prefered gas-impervious materials comprise at least one mixed metal oxide having a perovskite structure or perovskite-like structure. The invention includes, also, oxidation processes controlled by using these electrochemical reactors, and these reactions do not require an external source of electrical potential or any external electric circuit for oxidation to proceed.

  8. Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

    NASA Astrophysics Data System (ADS)

    Dang-Long, T.; Quang-Tuyen, T.; Shiratori, Y.

    2016-06-01

    Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH4 and CO2 and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidate for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO2 reforming of CH4 and electrochemical oxidation of the produced syngas (H2-CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH4-CO2 mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO2 had strong influences on both reaction processes. The increase in CO2 partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH4-CO2 mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

  9. Removal of caffeine from aqueous solution by indirect electrochemical oxidation using a graphite-PVC composite electrode: A role of hypochlorite ion as an oxidising agent.

    PubMed

    Al-Qaim, Fouad F; Mussa, Zainab H; Othman, Mohamed R; Abdullah, Md P

    2015-12-30

    The electrochemical oxidation of caffeine, a widely over-the-counter stimulant drug, has been investigated in effluent wastewater and deionized water (DIW) using graphite-poly vinyl chloride (PVC) composite electrode as anode. Effects of initial concentration of caffeine, chloride ion (Cl(-)) loading, presence of hydrogen peroxide (H2O2), sample volume, type of sample and applied voltage were determined to test and to validate a kinetic model for the oxidation of caffeine by the electrochemical oxidation process. The results revealed that the electrochemical oxidation rates of caffeine followed pseudo first-order kinetics, with rate constant values ranged from 0.006 to 0.23 min(-1) depending on the operating parameters. The removal efficiency of caffeine increases with applied voltage very significantly, suggesting a very important role of mediated oxidation process. However, the consumption energy was considered during electrochemical oxidation process. In chloride media, removal of caffeine is faster and more efficiently, although occurrence of more intermediates takes place. The study found that the adding H2O2 to the NaCl solution will inhibit slightly the electrochemical oxidation rate in comparison with only NaCl in solution. Liquid chromatography-time of flight-mass spectrometry (LC-TOF-MS) technique was applied to the identification of the by-products generated during electrochemical oxidation, which allowed to construct the proposed structure of by-products. PMID:26218306

  10. SERS speciation of the electrochemical oxidation-reduction of riboflavin.

    PubMed

    Bailey, Matthew R; Schultz, Zachary D

    2016-08-15

    The reduction and oxidation of the flavin system is an important electron transfer reaction in biological systems. Several reaction pathways exist to connect oxidized to fully reduced riboflavin, each with unique intermediates including a semi-quinone radical. By performing surface-enhanced Raman scattering (SERS) with simultaneous electrochemical detection of riboflavin at different pH values, we are able to correlate reversible changes in spectral features to the current changes observed in the cyclic voltammetry. Multivariate curve resolution analysis of the SERS spectra indicates that three distinct components were present at the SERS electrode at each pH during the potential sweep. To verify and better understand the variations in Raman bands across the voltammogram, density functional theory (DFT) calculations were performed to model the effect of pH and oxidation state on the riboflavin Raman spectrum. The calculated spectra show qualitative agreement with the species identified in the chemometric analysis. This combination of results indicates the presence of the oxidized, semi-quinone, and reduced forms of riboflavin and provides insight into the mechanism of the flavin redox system. PMID:27297697

  11. Electrochemical production of hydrogen coupled with the oxidation of arsenite.

    PubMed

    Kim, Jungwon; Kwon, Daejung; Kim, Kitae; Hoffmann, Michael R

    2014-01-01

    The production of hydrogen accompanied by the simultaneous oxidation of arsenite (As(III)) was achieved using an electrochemical system that employed a BiOx-TiO2 semiconductor anode and a stainless steel (SS) cathode in the presence of sodium chloride (NaCl) electrolyte. The production of H2 was enhanced by the addition of As(III) during the course of water electrolysis. The synergistic effect of As(III) on H2 production can be explained in terms of (1) the scavenging of reactive chlorine species (RCS), which inhibit the production of H2 by competing with water molecules (or protons) for the electrons on the cathode, by As(III) and (2) the generation of protons, which are more favorably reduced on the cathode than water molecules, through the oxidation of As(III). The addition of 1.0 mM As(III) to the electrolyte at a constant cell voltage (E cell) of 3.0 V enhanced the production of H2 by 12% even though the cell current (I cell) was reduced by 5%. The net effect results in an increase in the energy efficiency (EE) for H2 production (ΔEE) by 17.5%. Furthermore, the value ΔEE, which depended on As(III) concentration, also depended on the applied E cell. For example, the ΔEE increased with increasing As(III) concentration in the micromolar range but decreased as a function of E cell. This is attributed to the fact that the reactions between RCS and As(III) are influenced by both RCS concentration depending on E cell and As(III) concentration in the solution. On the other hand, the ΔEE decreased with increasing As(III) concentration in the millimolar range due to the adsorption of As(V) generated from the oxidation of As(III) on the semiconductor anode. In comparison to the electrochemical oxidation of certain organic compounds (e.g., phenol, 4-chlorophenol, 2-chlorophenol, salicylic acid, catechol, maleic acid, oxalate, and urea), the ΔEE obtained during As(III) oxidation (17.5%) was higher than that observed during the oxidation of the above organic compounds

  12. Physical and electrochemical study of cobalt oxide nano- and microparticles

    SciTech Connect

    Alburquenque, D.; Vargas, E.; Denardin, J.C.; Escrig, J.; Marco, J.F.; Gautier, J.L.

    2014-07-01

    Cobalt oxide nanocrystals of size 17–21 nm were synthesized by a simple reaction between cobalt acetate (II) and dodecylamine. On the other hand, micrometric Co{sub 3}O{sub 4} was prepared using the ceramic method. The structural examination of these materials was performed using powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM and HRTEM). XRD studies showed that the oxides were pure, well-crystallized, spinel cubic phases with a-cell parameter of 0.8049 nm and 0.8069 nm for the nano and micro-oxide, respectively. The average particle size was 19 nm (nano-oxide) and 1250 μm (micro-oxide). Morphological studies carried out by SEM and TEM analyses have shown the presence of octahedral particles in both cases. Bulk and surface properties investigated by X-ray photoelectron spectroscopy (XPS), point zero charge (pzc), FTIR and cyclic voltammetry indicated that there were no significant differences in the composition on both materials. The magnetic behavior of the samples was determined using a vibrating sample magnetometer. The compounds showed paramagnetic character and no coercivity and remanence in all cases. Galvanostatic measurements of electrodes formed with nanocrystals showed better performance than those built with micrometric particles. - Highlights: • Spinel Co{sub 3}O{sub 4} nanoparticles and microparticles with same structure but with different cell parameters, particle size and surface area were synthesized. • Oxide nanoparticles showed better electrochemical behavior than micrometric ones due to area effect.

  13. Advances toward industrialization of novel molten salt electrochemical processes.

    PubMed

    Ito, Yasuhiko; Nishikiori, Tokujiro; Tsujimura, Hiroyuki

    2016-08-15

    We have invented various novel molten salt electrochemical processes, that can be put to practical use in the fields of energy and materials. These processes are promising from both technological and commercial viewpoints, and they are currently under development for industrial application. To showcase current developments in work toward industrialization, we focus here on three of these processes: (1) electrolytic synthesis of ammonia from water and nitrogen under atmospheric pressure, (2) electrochemical formation of carbon film, and (3) plasma-induced discharge electrolysis to produce nanoparticles. PMID:27265244

  14. Electrochemical process and production of novel complex hydrides

    DOEpatents

    Zidan, Ragaiy

    2013-06-25

    A process of using an electrochemical cell to generate aluminum hydride (AlH.sub.3) is provided. The electrolytic cell uses a polar solvent to solubilize NaAlH.sub.4. The resulting electrochemical process results in the formation of AlH.sub.3. The AlH.sub.3 can be recovered and used as a source of hydrogen for the automotive industry. The resulting spent aluminum can be regenerated into NaAlH.sub.4 as part of a closed loop process of AlH.sub.3 generation.

  15. Effect of surfactant on the electrochemical performance of graphene/iron oxide electrode for supercapacitor

    NASA Astrophysics Data System (ADS)

    Ghasemi, Shahram; Ahmadi, Fatemeh

    2015-09-01

    In this study, reduced graphene oxide- Fe3O4 (RGO-Fe3O4) nanocomposite is fabricated using simple electrophoretic deposition (EPD) method followed by an electrochemical reduction process. It is characterized using atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and scanning electron microscopy. Fe3O4 nanoparticles with 20-50 nm in diameter are uniformly formed on RGO. Electrochemical properties of nanocomposite are characterized by cyclic voltammetery, galvanostatic charge/discharge and electrochemical impedance spectroscopy. According to the galvanostatic charge/discharge analysis, RGO-Fe3O4/SS presents specific capacitance (Cs) of 154 F g-1 at current density of 1 A g-1, which is higher than that of RGO/SS (81 F g-1) in Na2SO4 electrolyte. Also, the electrochemical behaviors show that addition of three kind of surfactant, i.e. sodium dodecyl sulphate, cetyltrimethylammonium bromide, t-octyl phenoxy polyethoxyethanol (Triton X-100) to Na2SO4 aqueous solution can improve the Cs of RGO-Fe3O4/SS electrodes. RGO-Fe3O4/SS in Na2SO4 electrolyte containing Triton X-100 shows maximum Cs of 236 F g-1 at 1 A g-1 which retains 97% of initial capacitance after 500 cycles.

  16. Direct electrochemical reduction of graphene oxide on ionic liquid doped screen-printed electrode and its electrochemical biosensing application.

    PubMed

    Ping, Jianfeng; Wang, Yixian; Fan, Kai; Wu, Jian; Ying, Yibin

    2011-10-15

    A novel electrochemical biosensing platform using electrochemically reduced graphene oxide (ER-GNO) modified electrode was proposed. This modified electrode was prepared by one-step electrodeposition of the exfoliated GNO sheets onto the ionic liquid doped screen-printed electrode (IL-SPE). The resulting ER-GNO/IL-SPE brought new capabilities for electrochemical devices by combining the advantages of ER-GNO and disposable electrode. Two important biomolecules, nicotinamide adenine dinucleotide (NADH) and hydrogen peroxide (H(2)O(2)), were employed to study the electrochemical performance of the ER-GNO/IL-SPE, which exhibited more favorable electron transfer kinetics than the bare IL-SPE. On the basis of the greatly enhanced electrochemical reactivity of H(2)O(2) at the developed electrode, ER-GNO and glucose oxidase constructed disposable biosensor showed better analytical performance for the glucose detection compared with the IL-SPE based biosensor. The linear range for the detection of glucose was from 5.0 μM to 12.0 mM with a detection limit of 1.0 μM. This work provides a useful avenue for implementing ER-GNO as a new generation of electrochemical transducer in disposable electrode, which could expand the scope of graphene constructed electrochemical biosensing devices and hold great promise for routine sensing applications. PMID:21807494

  17. Electrochemical oxidation of biological pretreated and membrane separated landfill leachate concentrates on boron doped diamond anode

    NASA Astrophysics Data System (ADS)

    Zhou, Bo; Yu, Zhiming; Wei, Qiuping; Long, HangYu; Xie, Youneng; Wang, Yijia

    2016-07-01

    In the present study, the high quality boron-doped diamond (BDD) electrodes with excellent electrochemical properties were deposited on niobium (Nb) substrates by hot filament chemical vapor deposition (HFCVD) method. The electrochemical oxidation of landfill leachate concentrates from disc tube reverse osmosis (DTRO) process over a BDD anode was investigated. The effects of varying operating parameters, such as current density, initial pH, flow velocity and cathode material on degradation efficiency were also evaluated following changes in chemical oxygen demand (COD) and ammonium nitrogen (NH3sbnd N). The instantaneous current efficiency (ICE) was used to appraise different operating conditions. As a result, the best conditions obtained were as follows, current density 50 mA cm-2, pH 5.16, flow velocity 6 L h-1. Under these conditions, 87.5% COD and 74.06% NH3sbnd N removal were achieved after 6 h treatment, with specific energy consumption of 223.2 kWh m-3. In short, these results indicated that the electrochemical oxidation with BDD/Nb anode is an effective method for the treatment of landfill leachate concentrates.

  18. Boron doped ZnO embedded into reduced graphene oxide for electrochemical supercapacitors

    NASA Astrophysics Data System (ADS)

    Alver, Ü.; Tanrıverdi, A.

    2016-08-01

    In this work, reduced graphene oxide/boron doped zinc oxide (RGO/ZnO:B) composites were fabricated by a hydrothermal process and their electrochemical properties were investigated as a function of dopant concentration. First, boron doped ZnO (ZnO:B) particles was fabricated with different boron concentrations (5, 10, 15 and 20 wt%) and then ZnO:B particles were embedded into RGO sheets. The physical properties of sensitized composites were characterized by XRD and SEM. Characterization indicated that the ZnO:B particles with plate-like structure in the composite were dispersed on graphene sheets. The electrochemical properties of the RGO/ZnO:B composite were investigated through cyclic voltammetry, galvanostatic charge/discharge measurements in a 6 M KOH electrolyte. Electrochemical measurements show that the specific capacitance values of RGO/ZnO:B electrodes increase with increasing boron concentration. RGO/ZnO:B composite electrodes (20 wt% B) display the specific capacitance as high as 230.50 F/g at 5 mV/s, which is almost five times higher than that of RGO/ZnO (52.71 F/g).

  19. Reduced graphene oxide anchored Cu(OH)2 as a high performance electrochemical supercapacitor.

    PubMed

    Pramanik, Atin; Maiti, Sandipan; Mahanty, Sourindra

    2015-09-01

    Developing new materials for electrochemical supercapacitors with higher energy density has recently gained tremendous impetus in the context of effective utilization of renewable energy. Herein, we report a simple one-pot synthesis of bundled nanorods of Cu(OH)2 embedded in a matrix of reduced graphene oxide (Cu(OH)2@RGO) under mild hydrothermal conditions of 80 °C for 1 h. The synthesized material shows a high BET surface area of 78.7 m(2) g(-1) and a mesoporous nature with a broad pore-size distribution consisting of structural pores as well as inter-particle pores. Raman spectroscopy suggests an intimate interaction between Cu(OH)2 and reduced graphene oxide (RGO) creating more defects by destruction of sp(2) domains which would help the defect-assisted charge transport during electrochemical processes. When investigated as an electrochemical supercapacitor, Cu(OH)2@RGO shows a high capacitance of 602 F g(-1) at 0.2 A g(-1) in 1 M KOH in a three-electrode cell configuration. Detailed electrochemical studies indicate that the Faradic processes are diffusion controlled and follow a quasi-reversible kinetics. Further, a two-electrode symmetric cell shows good energy density and power density (84.5 Wh kg(-1) at 0.55 kW kg(-1) and 20.5 Wh kg(-1) at 5.5 kW kg(-1)) characteristics demonstrating superior application potential of this common low-cost transition metal hydroxide for high performance energy storage devices. PMID:26208312

  20. The cooperative electrochemical oxidation of chlorophenols in anode-cathode compartments.

    PubMed

    Wang, Hui; Wang, Jian Long

    2008-06-15

    By using a self-made carbon/polytetrafluoroethylene (C/PTFE) O2-fed as the cathode and Ti/IrO2/RuO2 as the anode, the degradation of three organic compounds (phenol, 4-chlorophenol, and 2,4-dichlorophenol) was investigated in the diaphragm (with terylene as diaphragm material) electrolysis device by electrochemical oxidation process. The result indicated that the concentration of hydrogen peroxide (H2O2) was 8.3 mg/L, and hydroxyl radical (HO) was determined in the cathodic compartment by electron spin resonance spectrum (ESR). The removal efficiency for organic compounds reached about 90% after 120 min, conforming to the sequence of phenol, 4-chlorophenol, and 2,4-dichlorophenol. And the dechlorination degree of 4-chlorophenol exceeded 90% after 80 min. For H2O2, HO existed in the catholyte and reduction dechlorination at the cathode, the mineralization of organics in the cathodic compartment was better than that in the anodic compartment. The degradation of organics was supposed to be cooperative oxidation by direct or indirect electrochemical oxidation at the anode and H2O2, HO produced by oxygen reduction at the cathode. High-performance liquid chromatography (HPLC) allowed identifying phenol as the dechlorination product of 4-chlorophenol in the cathodic compartment, and hydroquinone, 4-chlorocatechol, benzoquinone, maleic, fumaric, oxalic, and formic acids as the main oxidation intermediates in the cathodic and anodic compartments. A reaction scheme involving all these intermediates was proposed. PMID:17996367

  1. Electrochemical capacitor

    DOEpatents

    Anderson, Marc A.; Liu, Kuo -Chuan; Mohr, Charles M.

    1999-10-05

    An inexpensive porous metal oxide material having high surface area, good conductivity and high specific capacitance is advantageously used in an electrochemical capacitor. The materials are formed in a sol-gel process which affords control over the properties of the resultant metal oxide materials.

  2. Electrochemical, H2O2-Boosted Catalytic Oxidation System

    NASA Technical Reports Server (NTRS)

    Akse, James R.; Thompson, John O.; Schussel, Leonard J.

    2004-01-01

    An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

  3. Electrochemically Reduced Water Protects Neural Cells from Oxidative Damage

    PubMed Central

    Hamasaki, Takeki; Kinjo, Tomoya; Nakamichi, Noboru; Teruya, Kiichiro; Kabayama, Shigeru

    2014-01-01

    Aging-related neurodegenerative disorders are closely associated with mitochondrial dysfunction and oxidative stresses and their incidence tends to increase with aging. Brain is the most vulnerable to reactive species generated by a higher rate of oxygen consumption and glucose utilization compared to other organs. Electrochemically reduced water (ERW) was demonstrated to scavenge reactive oxygen species (ROS) in several cell types. In the present study, the protective effect of ERW against hydrogen peroxide (H2O2) and nitric oxide (NO) was investigated in several rodent neuronal cell lines and primary cells. ERW was found to significantly suppress H2O2 (50–200 μM) induced PC12 and SFME cell deaths. ERW scavenged intracellular ROS and exhibited a protective effect against neuronal network damage caused by 200 μM H2O2 in N1E-115 cells. ERW significantly suppressed NO-induced cytotoxicity in PC12 cells despite the fact that it did not have the ability to scavenge intracellular NO. ERW significantly suppressed both glutamate induced Ca2+ influx and the resulting cytotoxicity in primary cells. These results collectively demonstrated for the first time that ERW protects several types of neuronal cells by scavenging ROS because of the presence of hydrogen and platinum nanoparticles dissolved in ERW. PMID:25383141

  4. Electrochemically reduced water protects neural cells from oxidative damage.

    PubMed

    Kashiwagi, Taichi; Yan, Hanxu; Hamasaki, Takeki; Kinjo, Tomoya; Nakamichi, Noboru; Teruya, Kiichiro; Kabayama, Shigeru; Shirahata, Sanetaka

    2014-01-01

    Aging-related neurodegenerative disorders are closely associated with mitochondrial dysfunction and oxidative stresses and their incidence tends to increase with aging. Brain is the most vulnerable to reactive species generated by a higher rate of oxygen consumption and glucose utilization compared to other organs. Electrochemically reduced water (ERW) was demonstrated to scavenge reactive oxygen species (ROS) in several cell types. In the present study, the protective effect of ERW against hydrogen peroxide (H2O2) and nitric oxide (NO) was investigated in several rodent neuronal cell lines and primary cells. ERW was found to significantly suppress H2O2 (50-200 μM) induced PC12 and SFME cell deaths. ERW scavenged intracellular ROS and exhibited a protective effect against neuronal network damage caused by 200 μM H2O2 in N1E-115 cells. ERW significantly suppressed NO-induced cytotoxicity in PC12 cells despite the fact that it did not have the ability to scavenge intracellular NO. ERW significantly suppressed both glutamate induced Ca(2+) influx and the resulting cytotoxicity in primary cells. These results collectively demonstrated for the first time that ERW protects several types of neuronal cells by scavenging ROS because of the presence of hydrogen and platinum nanoparticles dissolved in ERW. PMID:25383141

  5. Morphological, rheological and electrochemical studies ofpoly(ethylene oxide) electrolytes containing fumed silicananoparticles

    SciTech Connect

    Xie, Jiangbing; Kerr, John B.; Duan, Robert G.; Han, Yongbong

    2003-06-01

    In this paper, the rheology and crystallization of composite Poly(Ethylene Oxide) (PEO) electrolytes were studied by dynamic mechanical analysis, DSC and polarized light microscopy. The effects of fumed silica nanoparticles on the conductivities of the polymer electrolytes at temperatures above and below their melting point were measured and related to their rheology and crystallization behavior, respectively. The electrolyte/electrode interfacial properties and cycling performances of the composite polymer electrolytes in Li/Li cells are also discussed. The measured electrochemical properties were found to depend heavily on the operational environments and sample processing history.

  6. Treatment of ink effluents from flexographic printing by lime precipitation and boron-doped diamond (BDD) electrochemical oxidation.

    PubMed

    Diamadopoulos, Evan; Barndõk, Helen; Xekoukoulotakis, Nikolaos P; Mantzavinos, Dionissios

    2009-01-01

    Effluent treatment from flexographic printing was investigated by precipitation/coagulation and electrochemical oxidation over boron-doped diamond electrodes. Precipitation with 3 g/L of lime led to complete removal of effluent turbidity (initial value of about 410 NTU) but only about 20% chemical oxygen demand (COD) decrease (initial value of about 1,900 mg/L). Higher lime dosages (up to 15 g/L) had no effect on separation. On the other hand, coagulation with alum in the range 0.05-1 mM failed to enhance the extent of solids separation achieved by gravity settling alone (i.e. about 60%). Preliminary electrochemical oxidation experiments in the presence of sulphuric acid as supporting electrolyte showed that treatment performance (in terms of COD removal and decrease in sample absorbance at 300 nm) increased with increasing applied current. The latter was more efficiently utilized at shorter treatment times and lower currents with efficiency reaching 30%. Following lime precipitation, the effluent was electrochemically oxidized at alkaline conditions for 360 min yielding 64% absorbance reduction and 50% COD removal (this corresponds to 60% overall COD removal for the combined process). The rather low electrochemical treatment performance may be attributed to limestone deposition and fouling of electrodes and other electrochemical reactor components as evidenced by the gradual drop in conductivity/current throughout the operation. PMID:19923752

  7. Electrochemical degradation of the antihypertensive losartan in aqueous medium by electro-oxidation with boron-doped diamond electrode.

    PubMed

    Salazar, Claudio; Contreras, Nicole; Mansilla, Héctor D; Yáñez, Jorge; Salazar, Ricardo

    2016-12-01

    In this work the electrochemical oxidation of losartan, an emerging pharmaceutical pollutant, was studied. Electrochemical oxidation was carried out in batch mode, in an open and undivided cell of 100cm(3) using a boron-doped diamond (BDD)/stainless steel system. With Cl(-) medium 56% of mineralization was registered, while with the trials containing SO4(2-) as supporting electrolyte a higher mineralization yield of 67% was reached, even obtaining a total removal of losartan potassium at 80mAcm(-2) and 180min of reaction time at pH 7.0. Higher losartan potassium concentrations enhanced the mineralization degree and the efficiency of the electrochemical oxidation process. During the mineralization up to 4 aromatic intermediates were identified by ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Moreover, short-linear carboxylic acids, like oxalic, succinic and oxamic were detected and quantified by ion-exclusion HPLC. Finally, the ability of the electrochemical oxidation process to mineralize dissolved commercial tablets containing losartan was achieved, obtaining TOC removal up to 71% under optimized conditions (10mAcm(-2), 0.05M Na2SO4, pH 7.0 and 25°C and 360min of electrolysis). PMID:27180209

  8. ELECTROCHEMICAL PROCESSES FOR IN-SITU TREATMENT OF CONTAMINATED SOILS

    EPA Science Inventory

    This project will study electrochemical processes for the in situ treatment of soils contaminated by mixed wastes, i.e., organic and inorganic. Soil samples collected from selected DOE waste sites will be characterized for specific organic and metal contaminants and hydraulic per...

  9. Electrochemically Deposited Ceria Structures for Advanced Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Brown, Evan C.

    As the pursuit towards emissions reduction intensifies with growing interest and nascent technologies, solid oxide fuel cells (SOFCs) remain an illustrious candidate for achieving our goals. Despite myriad advantages, SOFCs are still too costly for widespread deployment, even as unprecedented materials developments have recently emerged. This suggests that, in addition to informed materials selection, the necessary power output--and, thereby, cost-savings--gains must come from the fuel cell architecture. The work presented in this manuscript primarily investigates cathodic electrochemical deposition (CELD) as a scalable micro-/nanoscale fabrication tool for engineering ceria-based components in a SOFC assembly. Also, polymer sphere lithography was utilized to deposit fully connected, yet fully porous anti-dot metal films on yttira-stabilized zirconia (YSZ) with specific and knowable geometries, useful for mechanistic studies. Particular attention was given to anode structures, for which anti-dot metal films on YSZ served as composite substrates for subsequent CELD of doped ceria. By tuning the applied potential, a wide range of microstructures from high surface area coatings to planar, thin films was possible. In addition, definitive deposition was shown to occur on the electronically insulating YSZ surfaces, producing quality YSZ|ceria interfaces. These CELD ceria deposits exhibited promising electrochemical activity, as probed by A.C. Impedance Spectroscopy. In an effort to extend its usefulness as a SOFC fabrication tool, the CELD of ceria directly onto common SOFC cathode materials without a metallic phase was developed, as well as templated deposition schemes producing ceria nanowires and inverse opals.

  10. Electrochemical and microstructural study of oxide films formed electrochemically at microcrystalline Al-Fe-V-Si alloys.

    PubMed

    Thomas, S C; Birss, V I; Steele, D; Tessier, D

    1995-07-01

    A recent advance in metallurgical technology has been the application of rapid solidification techniques to Al alloy production. FVS0812 is the designation given to a microcrystalline Al-based alloy consisting of 8 wt% Fe, 1 wt% V and 2 wt% Si. It is a two-phase alloy, consisting of ca. 27 vol percent of approximately spherical Fe-V-Si-rich dispersoids in an essentially pure Al matrix. The high strength, low density properties of this advanced material, and other related alloys, have not yet been realized, however, due, in part, to the inability of the alloy to form a thick, adherent, abrasion-resistant outer surface oxide film, a feature readily achieved at conventional Al alloys by normal anodizing methods. The present research has involved an electro-chemical study of oxide film growth at the 812 alloy, with the specific goals being to seek an understanding of the origin of the oxide film growth problem and ultimately to propose alternative approaches to the formation of a thick, stable oxide film at this material. The techniques used in this research have included electrochemical methodologies such as cyclic voltammetry and electrochemical impedance spectroscopy. Crucial information has been obtained through transmission electron microscopy (TEM) of ultramicrotomed specimens. Experiments were carried out initially in neutral borate solutions to characterize the compact barrier oxide film formed in this environment and expected to be present beneath the porous oxide film formed in the normal sulfuric acid anodizing medium.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7549001

  11. Mechanism of enhanced removal of quinonic intermediates during electrochemical oxidation of Orange II under ultraviolet irradiation.

    PubMed

    Li, Fazhan; Li, Guoting; Zhang, Xiwang

    2014-03-01

    The effect of ultraviolet irradiation on generation of radicals and formation of intermediates was investigated in electrochemical oxidation of the azo-dye Orange II using a TiO2-modified β-PbO2 electrode. It was found that a characteristic absorbance of quinonic compounds at 255 nm, which is responsible for the rate-determining step during aromatics degradation, was formed only in electrocatalytic oxidation. The dye can be oxidized by either HO radicals or direct electron transfer. Quinonic compounds were produced concurrently. The removal of TOC by photo-assisted electrocatalytic oxidation was 1.56 times that of the sum of the other two processes, indicating a significant synergetic effect. In addition, once the ultraviolet irradiation was introduced into the process of electrocatalytic oxidation, the degradation rate of quinonic compounds was enhanced by as much as a factor of two. The more efficient generation of HO radicals resulted from the introduction of ultraviolet irradiation in electrocatalytic oxidation led to the significant synergetic effect as well as the inhibiting effect on the accumulation of quinonic compounds. PMID:25079285

  12. PROCESS OF OXIDIZING PLUTONIUM

    DOEpatents

    Coryell, C.D.

    1959-08-25

    The oxidation of plutonium to the plus six valence state is described. The oxidation is accomplished by treating the plutonium in aqueous solution with a solution above 0.01 molar in argentic ion, above 1.1 molar in nitric acid, and above 0.02 molar in argentous ion.

  13. DEVELOPMENT OF A SCALABLE, LOW-COST, ULTRANANOCRYSTALLINE DIAMOND ELECTROCHEMICAL PROCESS FOR THE DESTRUCTION OF CONTAMINANTS OF EMERGING CONCERN (CECS) - PHASE II

    EPA Science Inventory

    This Small Business Innovation Research (SBIR) Phase II project will employ the large scale; highly reliable boron-doped ultrananocrystalline diamond (BD-UNCD®) electrodes developed during Phase I project to build and test Electrochemical Anodic Oxidation process (EAOP)...

  14. Mass spectrometric methods for monitoring redox processes in electrochemical cells

    PubMed Central

    Oberacher, Herbert; Pitterl, Florian; Erb, Robert; Plattner, Sabine

    2015-01-01

    Electrochemistry (EC) is a mature scientific discipline aimed to study the movement of electrons in an oxidation–reduction reaction. EC covers techniques that use a measurement of potential, charge, or current to determine the concentration or the chemical reactivity of analytes. The electrical signal is directly converted into chemical information. For in-depth characterization of complex electrochemical reactions involving the formation of diverse intermediates, products and byproducts, EC is usually combined with other analytical techniques, and particularly the hyphenation of EC with mass spectrometry (MS) has found broad applicability. The analysis of gases and volatile intermediates and products formed at electrode surfaces is enabled by differential electrochemical mass spectrometry (DEMS). In DEMS an electrochemical cell is sampled with a membrane interface for electron ionization (EI)-MS. The chemical space amenable to EC/MS (i.e., bioorganic molecules including proteins, peptides, nucleic acids, and drugs) was significantly increased by employing electrospray ionization (ESI)-MS. In the simplest setup, the EC of the ESI process is used to analytical advantage. A limitation of this approach is, however, its inability to precisely control the electrochemical potential at the emitter electrode. Thus, particularly for studying mechanistic aspects of electrochemical processes, the hyphenation of discrete electrochemical cells with ESI-MS was found to be more appropriate. The analytical power of EC/ESI-MS can further be increased by integrating liquid chromatography (LC) as an additional dimension of separation. Chromatographic separation was found to be particularly useful to reduce the complexity of the sample submitted either to the EC cell or to ESI-MS. Thus, both EC/LC/ESI-MS and LC/EC/ESI-MS are common. PMID:24338642

  15. Study of the electrochemical oxidation and reduction of C.I. Reactive Orange 4 in sodium sulphate alkaline solutions.

    PubMed

    del Río, A I; Molina, J; Bonastre, J; Cases, F

    2009-12-15

    Synthetic solutions of hydrolysed C.I. Reactive Orange 4, a monoazo textile dye commercially named Procion Orange MX-2R (PMX2R) and colour index number C.I. 18260, was exposed to electrochemical treatment under galvanostatic conditions and Na2SO4 as electrolyte. The influence of the electrochemical process as well as the applied current density was evaluated. Ti/SnO2-Sb-Pt and stainless steel electrodes were used as anode and cathode, respectively, and the intermediates generated on the cathode during electrochemical reduction were investigated. Aliquots of the solutions treated were analysed by UV-visible and FTIR-ATR spectroscopy confirming the presence of aromatic structures in solution when an electro-reduction was carried out. Electro-oxidation degraded both the azo group and aromatic structures. HPLC measures revealed that all processes followed pseudo-first order kinetics and decolourisation rates showed a considerable dependency on the applied current density. CV experiments and XPS analyses were carried out to study the behaviour of both PMX2R and intermediates and to analyse the state of the cathode after the electrochemical reduction, respectively. It was observed the presence of a main intermediate in solution after an electrochemical reduction whose chemical structure is similar to 2-amino-1,5-naphthalenedisulphonic acid. Moreover, the analysis of the cathode surface after electrochemical reduction reveals the presence of a coating layer with organic nature. PMID:19647934

  16. Effect of hydrothermal reaction time and alkaline conditions on the electrochemical properties of reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Vermisoglou, E. C.; Giannakopoulou, T.; Romanos, G.; Giannouri, M.; Boukos, N.; Lei, C.; Lekakou, C.; Trapalis, C.

    2015-12-01

    Reduced graphene oxide sheets (rGO) were prepared by hydrothermal treatment of aqueous dispersions of graphite oxide (GtO) applied for short (4 h) and prolonged reaction times (19-24 h). The effect of process duration as well as the alkaline conditions (pH ∼10) by addition of K2CO3 on the quality characteristics of the produced rGO materials was investigated. Both reduction and exfoliation occurred during this process as it was evidenced by FTIR and XRD data. SEM, TEM and HRTEM microscopy displayed highly exfoliated rGO materials. XPS verified that the re-establishment of the conjugated graphene network is more extensive for prolonged times of hydrothermal processing in accordance to Raman spectroscopy measurements. The sample produced under alkaline conditions bore fewer defects and almost 5 times higher BET surface area (∼181 m2/g) than the sample with no pH adjustment (∼34 m2/g) for the same hydrothermal reaction time (19 h), attributed to the developed microporosity. The specific capacitance of this material estimated by electrochemical impedance using three-electrode cell and KCl aqueous solution as an electrolyte was ∼400-500 F/g. When EDLC capacitors were fabricated from rGO materials the electrochemical testing in organic electrolyte i.e. TEABF4 in PC, revealed that the shortest hydrothermal reaction time (4 h) was more efficient resulting in capacitance around 60 F/g.

  17. Electrochemically Formed Ultrafine Metal Oxide Nanocatalysts for High-Performance Lithium-Oxygen Batteries.

    PubMed

    Liu, Bin; Yan, Pengfei; Xu, Wu; Zheng, Jianming; He, Yang; Luo, Langli; Bowden, Mark E; Wang, Chong-Min; Zhang, Ji-Guang

    2016-08-10

    Lithium-oxygen (Li-O2) batteries have an extremely high theoretical specific energy density when compared with conventional energy-storage systems. However, practical application of the Li-O2 battery system still faces significant challenges. In this work, we report a new approach for synthesis of ultrafine metal oxide nanocatalysts through an electrochemical prelithiation process. This process reduces the size of NiCo2O4 (NCO) particles from 20-30 nm to a uniformly distributed domain of ∼2 nm and significantly improves their catalytic activity. Structurally, the prelithiated NCO nanowires feature ultrafine NiO/CoO nanoparticles that are highly stable during prolonged cycles in terms of morphology and particle size, thus maintaining an excellent catalytic effect to oxygen reduction and evolution reactions. A Li-O2 battery using this catalyst demonstrated an initial capacity of 29 280 mAh g(-1) and retained a capacity of >1000 mAh g(-1) after 100 cycles based on the weight of the NCO active material. Direct in situ transmission electron microscopy observations conclusively revealed the lithiation/delithiation process of as-prepared NCO nanowires and provided in-depth understanding for both catalyst and battery chemistries of transition-metal oxides. This unique electrochemical approach could also be used to form ultrafine nanoparticles of a broad range of materials for catalyst and other applications. PMID:27380300

  18. Novel quasi-symmetric solid oxide fuel cells with enhanced electrochemical performance

    NASA Astrophysics Data System (ADS)

    Chen, Yonghong; Cheng, Zhuanxia; Yang, Yang; Gu, Qingwen; Tian, Dong; Lu, Xiaoyong; Yu, Weili; Lin, Bin

    2016-04-01

    Symmetrical solid oxide fuel cell (SSOFC) using same materials as both anode and cathode simultaneously has gained extensively attentions, which can simplify fabrication process, minimize inter-diffusion between components, enhance sulfur and coking tolerance by operating the anode as the cathode in turn. With keeping the SSOFC's advantages, a novel quasi-symmetrical solid oxide fuel cell (Q-SSOFC) is proposed to further improve the performance, which optimally combines two different SSOFC electrode materials as both anode and cathode simultaneously. PrBaFe2O5+δ (PBFO) and PrBaFe1.6Ni0.4O5+δ (PBFNO, Fe is partially substituted by Ni.) are prepared and applied as both cathode and anode for SSOFC, which exhibit desirable chemical and thermal compatibility with Sm0.8Ce0.2O1.9 (SDC) electrolyte. PBFO cathode exhibits higher oxygen reduction reaction (ORR) activity than PBFNO cathode in air, whereas PBFNO anode exhibits higher hydrogen oxidation reaction (HOR) activity than PBFO anode in H2. The as-designed Q-SSOFC of PBFNO/SDC/PBFO exhibits higher electrochemical performance than the conventional SSOFCs of both PBFO/SDC/PBFO and PBFNO/SDC/PBFNO. The superior performance of Q-SSOFC is attributed to the lowest polarization resistance (Rp). The newly developed Q-SSOFCs open doors for further improvement of electrochemical performance in SSOFC, which hold more promise for various potential applications.

  19. Retarding of electrochemical oxidation of formate on the platinum anode by a coat of Nafion membrane

    NASA Astrophysics Data System (ADS)

    Zhang, Rui; Lv, Weixin; Li, Guanghua; Mezaal, Mohammed Adnan; Li, Xiaojing; Lei, Lixu

    2014-12-01

    It has been found that the faradaic efficiency is decreasing with the electrolysis time for electrochemical reduction of CO2 to formate on a Sn cathode with a Pt anode in an undivided electrolytic cell, because the oxidation of formed formate takes place on the Pt anode, which also limits seriously the highest concentration of formate in the system. Here, we report that a coat of Nafion membrane on the Pt anode can retard the oxidation of formate: even if the concentration of the formate in the electrolyte reaches to 0.12 mol L-1, the faradaic efficiency still maintains above 61.3%; in contrast, the oxidation reaction of the formate on the naked Pt electrode is very fast, when the concentration of the formate in the electrolyte reaches to 0.023 mol L-1, the faradaic efficiency decreases to 35.3%. This is very important because the separation of formic acid could not be economical when its concentration is not high enough, and it is also costly if the depleted solution allows too less of its concentration because the solution has to be reused in the electrochemical process.

  20. Destination of organic pollutants during electrochemical oxidation of biologically-pretreated dye wastewater using boron-doped diamond anode.

    PubMed

    Zhu, Xiuping; Ni, Jinren; Wei, Junjun; Xing, Xuan; Li, Hongna

    2011-05-15

    Electrochemical oxidation of biologically-pretreated dye wastewater was performed in a boron-doped diamond (BDD) anode system. After electrolysis of 12h, the COD was decreased from 532 to 99 mg L(-1) (<100 mg L(-1), the National Discharge Standard of China). More importantly, the destination of organic pollutants during electrochemical oxidation process was carefully investigated by molecular weight distribution measurement, resin fractionation, ultraviolet-visible spectroscopy, HPLC and GC-MS analysis, and toxicity test. As results, most organic pollutants were completely removed by electrochemical oxidation and the rest was primarily degraded to simpler compounds (e.g., carboxylic acids and short-chain alkanes) with less toxicity, which demonstrated that electrochemical oxidation of biologically-pretreated dye wastewater with BDD anode was very effective and safe. Especially, the performance of BDD anode system in degradation of large molecular organics such as humic substances makes it very promising in practical applications as an advanced treatment of biologically-pretreated wastewaters. PMID:21377794

  1. Enhanced electrochemical supercapacitance of binder-free nanoporous ternary metal oxides/metal electrode.

    PubMed

    Gao, J J; Qiu, H-J; Wen, Y R; Chiang, F-K; Wang, Y

    2016-07-15

    Free-standing nanoporous Ni-Cu-Mn mixed metal oxides on metal with a high surface area was fabricated by chemically dealloying a Ni8Cu12Mn80 single-phase precursor, followed by electrochemical oxidation in an alkaline solution. Electrochemical analysis shows that first Cu and Mn-based metal oxides formed by the electrochemical oxidation. Ni-based oxides grow later with the increase of electrochemical CV cycles and mix with the Cu/Mn oxides, forming a relatively stable mixed metal oxides thin film on metal ligament network. Due to the different electrochemical properties of each metal and the synergetic effect between them, the mixed ternary metal oxides formed on metal nano-ligament can operate stably between a wide potential window (1.5V) in 1.0M KOH aqueous solution when tested as a free-standing supercapacitor electrode. Due to the high volumetric surface area, wide operating potential window and excellent conductivity, the nanoporous metal oxides@metal composite exhibits a high volumetric capacitance (∼500Fcm(-3)), high energy density (∼38mWhcm(-3)) and good cycling stability. PMID:27089016

  2. Electrochemical treatment of the pollutants generated in an ink-manufacturing process.

    PubMed

    Cañizares, P; Louhichi, B; Gadri, A; Nasr, B; Paz, R; Rodrigo, M A; Saez, C

    2007-07-31

    The effluents of ink-manufacturing processes contain a large variety of pollutants such as dyes, surfactants, biocides, water soluble solvents, etc. In this work, the electrochemical oxidation of several dyes (methylene blue and rhodamine B), solvents (monoethylene glycol, diethylene glycol and glycerol) and surfactants (sodium dodecylbenzenesulfonate) has been studied. To carry out the electrolyses, a bench-scale plant with a single-compartment electrochemical flow-cell was used. Boron doped diamond (BDD) was used as anode and stainless steel (AISI 304) as cathode. For all the compounds tested, the conductive diamond electrooxidation allows achieving the almost complete removal of COD of the waste with a very high current efficiency. The efficiencies of the electrochemical processes seem to depend on the current density and on the nature of the anions contained in the waste (chlorine, sulphate, phosphate). Thus, it has been observed that the use of chloride media favours the treatment of dyes. On the contrary, the use of sulphate- or phosphate-containing solutions improves the removal of the aliphatic compounds studied (solvents). These results suggest an important role of the mediated electrochemical processes on the overall performance of the reaction system. PMID:17532123

  3. Electrochemical chlorine evolution at rutile oxide (110) surfaces.

    PubMed

    Hansen, Heine A; Man, Isabela C; Studt, Felix; Abild-Pedersen, Frank; Bligaard, Thomas; Rossmeisl, Jan

    2010-01-01

    Based on density functional theory (DFT) calculations we study the electrochemical chlorine evolution reaction on rutile (110) oxide surfaces. First we construct the Pourbaix surface diagram for IrO(2) and RuO(2), and from this we find the chlorine evolution reaction intermediates and identify the lowest overpotential at which all elementary reaction steps in the chlorine evolution reaction are downhill in free energy. This condition is then used as a measure for catalytic activity. Linear scaling relations between the binding energies of the intermediates and the oxygen binding energies at cus-sites are established for MO(2) (M being Ir, Ru, Pt, Ti). The linear relations form the basis for constructing a generalized surface phase diagram where two parameters, the potential and the binding energy of oxygen, are needed to determine the surface composition. We calculate the catalytic activity as function of the oxygen binding energy, giving rise to a Sabatier volcano. By combining the surface phase diagram and the volcano describing the catalytic activity, we find that the reaction mechanism differs depending on catalyst material. The flexibility in reaction path means that the chlorine evolution activity is high for a wide range of oxygen binding energies. We find that the required overpotential for chlorine evolution is lower than the overpotential necessary for oxygen evolution. PMID:20024470

  4. Eliminating degradation in solid oxide electrochemical cells by reversible operation

    NASA Astrophysics Data System (ADS)

    Graves, Christopher; Ebbesen, Sune Dalgaard; Jensen, Søren Højgaard; Simonsen, Søren Bredmose; Mogensen, Mogens Bjerg

    2015-02-01

    One promising energy storage technology is the solid oxide electrochemical cell (SOC), which can both store electricity as chemical fuels (electrolysis mode) and convert fuels to electricity (fuel-cell mode). The widespread use of SOCs has been hindered by insufficient long-term stability, in particular at high current densities. Here we demonstrate that severe electrolysis-induced degradation, which was previously believed to be irreversible, can be completely eliminated by reversibly cycling between electrolysis and fuel-cell modes, similar to a rechargeable battery. Performing steam electrolysis continuously at high current density (1 A cm-2), initially at 1.33 V (97% energy efficiency), led to severe microstructure deterioration near the oxygen-electrode/electrolyte interface and a corresponding large increase in ohmic resistance. After 4,000 h of reversible cycling, however, no microstructural damage was observed and the ohmic resistance even slightly improved. The results demonstrate the viability of applying SOCs for renewable electricity storage at previously unattainable reaction rates, and have implications for our fundamental understanding of degradation mechanisms that are usually assumed to be irreversible.

  5. Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors.

    PubMed

    Lang, Xingyou; Hirata, Akihiko; Fujita, Takeshi; Chen, Mingwei

    2011-04-01

    Electrochemical supercapacitors can deliver high levels of electrical power and offer long operating lifetimes, but their energy storage density is too low for many important applications. Pseudocapacitive transition-metal oxides such as MnO(2) could be used to make electrodes in such supercapacitors, because they are predicted to have a high capacitance for storing electrical charge while also being inexpensive and not harmful to the environment. However, the poor conductivity of MnO(2) (10(-5)-10(-6) S cm(-1)) limits the charge/discharge rate for high-power applications. Here, we show that hybrid structures made of nanoporous gold and nanocrystalline MnO(2) have enhanced conductivity, resulting in a specific capacitance of the constituent MnO(2) (~1,145 F g(-1)) that is close to the theoretical value. The nanoporous gold allows electron transport through the MnO(2), and facilitates fast ion diffusion between the MnO(2) and the electrolytes while also acting as a double-layer capacitor. The high specific capacitances and charge/discharge rates offered by such hybrid structures make them promising candidates as electrodes in supercapacitors, combining high-energy storage densities with high levels of power delivery. PMID:21336267

  6. Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors

    NASA Astrophysics Data System (ADS)

    Lang, Xingyou; Hirata, Akihiko; Fujita, Takeshi; Chen, Mingwei

    2011-04-01

    Electrochemical supercapacitors can deliver high levels of electrical power and offer long operating lifetimes, but their energy storage density is too low for many important applications. Pseudocapacitive transition-metal oxides such as MnO2 could be used to make electrodes in such supercapacitors, because they are predicted to have a high capacitance for storing electrical charge while also being inexpensive and not harmful to the environment. However, the poor conductivity of MnO2 (10-5-10-6 S cm-1) limits the charge/discharge rate for high-power applications. Here, we show that hybrid structures made of nanoporous gold and nanocrystalline MnO2 have enhanced conductivity, resulting in a specific capacitance of the constituent MnO2 (~1,145 F g-1) that is close to the theoretical value. The nanoporous gold allows electron transport through the MnO2, and facilitates fast ion diffusion between the MnO2 and the electrolytes while also acting as a double-layer capacitor. The high specific capacitances and charge/discharge rates offered by such hybrid structures make them promising candidates as electrodes in supercapacitors, combining high-energy storage densities with high levels of power delivery.

  7. Porous structured vanadium oxide electrode material for electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Reddy, Ravinder N.; Reddy, Ramana G.

    A nano porous vanadium oxide (V 2O 5) was prepared by sol-gel method. The preparation involved elutriation of aqueous sodium meta vanadate over a cation exchange resin. The product was characterized using X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, surface area analysis and thermogravimetric analysis. Electrochemical characterization was done using cyclic voltammetry in a three electrode system consisting of a saturated calomel electrode as reference electrode, platinum mesh as a counter electrode, and V 2O 5 mounted on Ti mesh as the working electrode. Two molars of aqueous KCl, NaCl and LiCl were used as electrolytes. A maximum capacitance of 214 F g -1 was obtained at a scan rate of 5 mV s -1 in 2 M KCl. The effect of different electrolytes and the effect of concentration of KCl on the specific capacitance of V 2O 5 were studied. Specific capacitance faded rapidly over 100 cycles in 2 M KCl at a 5 mV s -1 scan rate.

  8. Decolourisation of simulated reactive dyebath effluents by electrochemical oxidation assisted by UV light.

    PubMed

    López-Grimau, V; Gutiérrez, M C

    2006-01-01

    This study is focused on the optimisation of the electrochemical decolourisation of textile effluents containing reactive dyes with the aim of making feasible-technically and economically-this method at industrial scale. Coloured waters were treated in continuous at low current density, to reduce the electrical consumption. Ti/PtO(x) electrodes were used to oxidize simulated dyebaths prepared with an azo/dichlorotriazine reactive dye (C.I. Reactive Orange 4). The decolourisation yield was dependent on the dyeing electrolyte (NaCl or Na(2)SO(4)). Dyeing effluents which contained from 0.5 to 20 gl(-1) of NaCl reached a high decolourisation yield, depending on the current density, immediately after the electrochemical process. These results were improved when the effluents were stored for several hours under solar light. After the electrochemical treatment the effluents were stored in a tank and exposed under different lighting conditions: UV light, solar light and darkness. The evolution of the decolourisation versus the time of storage was reported and kinetic constants were calculated. The time of storage was significantly reduced by the application of UV light. A dye mineralization study was also carried out on a concentrated dyebath. A TOC removal of 81% was obtained when high current density was applied for a prolonged treatment with recirculation. This treatment required a high electrical consumption. PMID:15893798

  9. Electrochemical tuning of layered lithium transition metal oxides for improvement of oxygen evolution reaction.

    PubMed

    Lu, Zhiyi; Wang, Haotian; Kong, Desheng; Yan, Kai; Hsu, Po-Chun; Zheng, Guangyuan; Yao, Hongbin; Liang, Zheng; Sun, Xiaoming; Cui, Yi

    2014-01-01

    Searching for low-cost and efficient catalysts for the oxygen evolution reaction has been actively pursued owing to its importance in clean energy generation and storage. While developing new catalysts is important, tuning the electronic structure of existing catalysts over a wide electrochemical potential range can also offer a new direction. Here we demonstrate a method for electrochemical lithium tuning of catalytic materials in organic electrolyte for subsequent enhancement of the catalytic activity in aqueous solution. By continuously extracting lithium ions out of LiCoO2, a popular cathode material in lithium ion batteries, to Li0.5CoO2 in organic electrolyte, the catalytic activity is significantly improved. This enhancement is ascribed to the unique electronic structure after the delithiation process. The general efficacy of this methodology is demonstrated in several mixed metal oxides with similar improvements. The electrochemically delithiated LiCo0.33Ni0.33Fe0.33O2 exhibits a notable performance, better than the benchmark iridium/carbon catalyst. PMID:24993836

  10. Flexible conducting polymer/reduced graphene oxide films: synthesis, characterization, and electrochemical performance

    NASA Astrophysics Data System (ADS)

    Yang, Wenyao; Zhao, Yuetao; He, Xin; Chen, Yan; Xu, Jianhua; Li, Shibin; Yang, Yajie; Jiang, Yadong

    2015-05-01

    In this paper, we demonstrate the preparation of a flexible poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate)/reduced graphene oxide (PEDOT-PSS/RGO) film with a layered structure via a simple vacuum filtered method as a high performance electrochemical electrode. The PEDOT-PSS/RGO films are characterized by scanning electron microscopy (SEM), X-ray diffraction, Raman spectroscopy, and Fourier transform infrared (FT-IR) spectrometry. The results indicate that a layer-ordered structure is constructed in this nanocomposite during the vacuum filtering process. The electrochemical performances of the flexible films are characterized by electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic charge/discharge. The results reveal that a 193.7 F/g highly specific capacitance of nanocomposite film is achieved at a current density of 500 mA/g. This flexible and self-supporting nanocomposite film exhibits excellent cycling stability, and the capacity retention is 90.6 % after 1000 cycles, which shows promising application as high-performance electrode materials for flexible energy-storage devices.

  11. Electrochemical tuning of layered lithium transition metal oxides for improvement of oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Lu, Zhiyi; Wang, Haotian; Kong, Desheng; Yan, Kai; Hsu, Po-Chun; Zheng, Guangyuan; Yao, Hongbin; Liang, Zheng; Sun, Xiaoming; Cui, Yi

    2014-07-01

    Searching for low-cost and efficient catalysts for the oxygen evolution reaction has been actively pursued owing to its importance in clean energy generation and storage. While developing new catalysts is important, tuning the electronic structure of existing catalysts over a wide electrochemical potential range can also offer a new direction. Here we demonstrate a method for electrochemical lithium tuning of catalytic materials in organic electrolyte for subsequent enhancement of the catalytic activity in aqueous solution. By continuously extracting lithium ions out of LiCoO2, a popular cathode material in lithium ion batteries, to Li0.5CoO2 in organic electrolyte, the catalytic activity is significantly improved. This enhancement is ascribed to the unique electronic structure after the delithiation process. The general efficacy of this methodology is demonstrated in several mixed metal oxides with similar improvements. The electrochemically delithiated LiCo0.33Ni0.33Fe0.33O2 exhibits a notable performance, better than the benchmark iridium/carbon catalyst.

  12. Facile preparation and electrochemical characterization of cobalt oxide/multi-walled carbon nanotube composites for supercapacitors

    NASA Astrophysics Data System (ADS)

    Lang, Junwei; Yan, Xingbin; Xue, Qunji

    A series of cobalt oxide/multi-walled carbon nanotube (Co 3O 4/MWCNT) composites are successfully synthesized by a facile chemical co-precipitation method followed by a simple thermal treatment process. The morphology and structure of as-obtained composites are characterized by X-ray diffraction, scanning electron microscopy, and N 2-adsorption/desorption measurements, and the electrochemical properties are investigated by cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS). For all Co 3O 4/MWCNT composites, MWCNTs are well dispersed in the loosely packed Co 3O 4 nanoparticles. Among them, the Co 3O 4-5%MWCNT composite exhibits the highest specific surface area of 137 m 2 g -1 and a mesoporous structure with a narrow distribution of pore size from 2 to 10 nm. Because of the synergistic effects coming from Co 3O 4 nanoparticles and MWCNTs, the electrochemical performances of pure Co 3O 4 material are significantly improved after adding MWCNTs. The Co 3O 4-5%MWCNT composite shows the largest specific capacitance of 418 F g -1 at a current density of 0.625 A g -1 in 2 M KOH electrolyte. Furthermore, this composite exhibits good cycling stability and lifetime. Therefore, based on the above investigation, such Co 3O 4/MWCNT composite could be a potential candidate for supercapacitors.

  13. Electrochemical decontamination system for actinide processing gloveboxes

    SciTech Connect

    Wedman, D.E.; Lugo, J.L.; Ford, D.K.; Nelson, T.O.; Trujillo, V.L.; Martinez, H.E.

    1998-03-01

    An electrolytic decontamination technology has been developed and successfully demonstrated at Los Alamos National Laboratory (LANL) for the decontamination of actinide processing gloveboxes. The technique decontaminates the interior surfaces of stainless steel gloveboxes utilizing a process similar to electropolishing. The decontamination device is compact and transportable allowing it to be placed entirely within the glovebox line. In this way, decontamination does not require the operator to wear any additional personal protective equipment and there is no need for additional air handling or containment systems. Decontamination prior to glovebox decommissioning reduces the potential for worker exposure and environmental releases during the decommissioning, transport, and size reduction procedures which follow. The goal of this effort is to reduce contamination levels of alpha emitting nuclides for a resultant reduction in waste level category from High Level Transuranic (TRU) to low Specific Activity (LSA, less than or equal 100 nCi/g). This reduction in category results in a 95% reduction in disposal and disposition costs for the decontaminated gloveboxes. The resulting contamination levels following decontamination by this method are generally five orders of magnitude below the LSA specification. Additionally, the sodium sulfate based electrolyte utilized in the process is fully recyclable which results in the minimum of secondary waste. The process bas been implemented on seven gloveboxes within LANL`s Plutonium Facility at Technical Area 55. Of these gloveboxes, two have been discarded as low level waste items and the remaining five have been reused.

  14. Electrochemical characterization of transition metal oxide aerogels for secondary lithium batteries

    NASA Astrophysics Data System (ADS)

    Dong, Winny

    The ability of transition metals to exist in multiple valence states, along with the fact that many transition metal oxides have a layered structure, has made transition metal oxides prime candidates as electrodes for the emerging technology of secondary lithium batteries. Traditionally, the electrochemical behavior of these materials is considered to be intrinsic to the material. In order to obtain different electrochemical performance needs, different materials need to be selected. The principal objective of this dissertation is to correlate electrochemical behavior with the microstructure of a material, allowing a material to meet different application requirements through the control of its microstructure. In this research, three different studies are used to explore the interrelationship between microstructure and electrochemical behavior. Sol-gel chemistry is used exclusively to prepare the electrochemically active materials as this process enables one to control the resulting microstructure and morphology. The first study looks at the influence of the degree of crystallinity in MoO3 aerogels on lithium capacity. The degree of crystallinity is controlled through heat treatment and observed to affect the lithium capacity. The nanocrystalline MoO3 aerogel exhibited higher lithium capacity (1.5 Li/Mo) compared to both the amorphous (1.1 Li/Mo) and crystalline (1.1 Li/Mo) samples. The second study involves the synthesis of organic/inorganic hybrids, achieved by simultaneously polymerizing the polypyrrole network within the Mo-O-Mo network. The addition of the conducting polymer phase increases both the electrical conductivity (4 x 10-3 S/cm) and the lithium capacity (1.7 Li/Mo) compared to that of MoO3 aerogels. The third study emphasizes the use of the "sticky carbon" electrode to study the effects of high surface area and pore size on the lithium intercalation properties of V2O5 aerogels. A series of V2O 5 aerogels with varying surface areas (10 to 280 m2/g) is

  15. Physics-based model for electro-chemical process

    SciTech Connect

    Zhang, Jinsuo

    2013-07-01

    Considering the kinetics of electrochemical reactions and mass transfer at the surface and near-surface of the electrode, a physics-based separation model for separating actinides from fission products in an electro-refiner is developed. The model, taking into account the physical, chemical and electrochemical processes at the electrode surface, can be applied to study electrorefining kinetics. One of the methods used for validation has been to apply the developed model to the computation of the cyclic voltammetry process of PuCl{sub 3} and UCl{sub 3} at a solid electrode in molten KCl-LiCl. The computed results appear to be similar to experimental measures. The separation model can be applied to predict materials flows under normal and abnormal operation conditions. Parametric studies can be conducted based on the model to identify the most important factors that affect the electrorefining processes.

  16. Facile and controllable electrochemical reduction of graphene oxide and its applications

    SciTech Connect

    Shao, Yuyan; Wang, Jun; Engelhard, Mark H.; Wang, Chong M.; Lin, Yuehe

    2010-01-01

    Graphene oxide is electrochemically reduced which is called electrochemically reduced graphene oxide (ER-G). ER-G is characterized with scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The oxygen content is significantly decreased and the sp 2 carbon is restored after electrochemical reduction. ER-G exhibits much higher electrochemical capacitance and cycling durability than carbon nanotubes (CNTs) and chemically reduced graphene; the specific capacitance measured with cyclic voltammetry (20 mV/s) is ~165 F/g, ~86 F/g, and ~100 F/g for ER-G, CNTs, and chemically reduced graphene,1 respectively. The electrochemical reduction of oxygen and hydrogen peroxide was greatly enhanced on ER-G electrodes as compared with CNTs. ER-G has shown a good potential for applications in energy storage, biosensors, and electrocatalysis.

  17. Electrochemical synthesis of hydrogen with depolarization of the anodic process

    NASA Astrophysics Data System (ADS)

    Tulskiy, Gennadiy; Tulskaya, Alena; Skatkov, Leonid; Gomozov, Valeriy; Deribo, Svetlana

    2016-05-01

    A new active composite coating for graphite gas diffusion electrode for hybrid sulfur cycle was proposed. The kinetics of oxidation of SO2 were studied on porous graphite anodes with different catalytic coatings. It was shown that the most efficient composite coating is based on activated carbon and platinum supported on graphite gas diffusion substrate. The voltage drop in the laboratory electrochemical cell was 1.3 V at a current density of 1000 A·m-2. This corresponds to a specific consumption of 3.1 kWh electric energy per 1 m3 of hydrogen.

  18. Electrochemical Processes Enhanced by Acoustic Liquid Manipulation

    NASA Technical Reports Server (NTRS)

    Oeftering, Richard C.

    2004-01-01

    Acoustic liquid manipulation is a family of techniques that employ the nonlinear acoustic effects of acoustic radiation pressure and acoustic streaming to manipulate the behavior of liquids. Researchers at the NASA Glenn Research Center are exploring new methods of manipulating liquids for a variety of space applications, and we have found that acoustic techniques may also be used in the normal Earth gravity environment to enhance the performance of existing fluid processes. Working in concert with the NASA Commercial Technology Office, the Great Lakes Industrial Technology Center, and Alchemitron Corporation (Elgin, IL), researchers at Glenn have applied nonlinear acoustic principles to industrial applications. Collaborating with Alchemitron Corporation, we have adapted the devices to create acoustic streaming in a conventional electroplating process.

  19. Solid-phase electrochemical reduction of graphene oxide films in alkaline solution

    PubMed Central

    2013-01-01

    Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO. PMID:24059434

  20. Ruthenium Oxide Electrochemical Super Capacitor Optimization for Pulse Power Applications

    NASA Technical Reports Server (NTRS)

    Merryman, Stephen A.; Chen, Zheng

    2000-01-01

    Electrical actuator systems are being pursued as alternatives to hydraulic systems to reduce maintenance time, weight and costs while increasing reliability. Additionally, safety and environmental hazards associated with the hydraulic fluids can be eliminated. For most actuation systems, the actuation process is typically pulsed with high peak power requirements but with relatively modest average power levels. The power-time requirements for electrical actuators are characteristic of pulsed power technologies where the source can be sized for the average power levels while providing the capability to achieve the peak requirements. Among the options for the power source are battery systems, capacitor systems or battery-capacitor hybrid systems. Battery technologies are energy dense but deficient in power density; capacitor technologies are power dense but limited by energy density. The battery-capacitor hybrid system uses the battery to supply the average power and the capacitor to meet the peak demands. It has been demonstrated in previous work that the hybrid electrical power source can potentially provide a weight savings of approximately 59% over a battery-only source. Electrochemical capacitors have many properties that make them well-suited for electrical actuator applications. They have the highest demonstrated energy density for capacitive storage (up to 100 J/g), have power densities much greater than most battery technologies (greater than 30kW/kg), are capable of greater than one million charge-discharge cycles, can be charged at extremely high rates, and have non-explosive failure modes. Thus, electrochemical capacitors exhibit a combination of desirable battery and capacitor characteristics.

  1. Effect of electrochemical redox reaction on biochemical ammonium oxidation and chemical nitrite oxidation.

    PubMed

    Jeon, Bo Young; Seo, Ha Na; Kang, Seung Won; Park, Doo Hyun

    2010-03-01

    A modified graphite felt electrode with neutral red (NRelectrode) was shown to catalyze the chemical oxidation of nitrite to nitrate under aerobic conditions. The electrochemically oxidized NR-electrode (EO-NR-electrode) and reduced NR-electrode (ER-NR-electrode) catalyzed the oxidation of 1,094+/-39 mg/l and 382+/-45 mg/l of nitrite, respectively, for 24 h. The electrically uncharged NRelectrode (EU-NR-electrode) catalyzed the oxidation of 345+/-47 mg/l of nitrite for 24 h. The aerobic bacterial community immobilized in the EO-NR-electrode did not oxidize ammonium to nitrite; however, the aerobic bacterial community immobilized in the ER-NR-electrode bioelectrochemically oxidized 1,412+/-39 mg/l of ammonium for 48 h. Meanwhile, the aerobic bacterial community immobilized on the EU-NR-electrode biochemically oxidized 449+/-22 mg/l of ammonium for 48 h. In the continuous culture system, the aerobic bacterial community immobilized on the ER-NR-electrode bioelectrochemically oxidized a minimal 1,337+/-38 mg/l to a maximal 1,480+/-38 mg/l of ammonium to nitrate, and the community immobilized on the EU-NR-electrode biochemically oxidized a minimal 327+/-23 mg/l to a maximal 412+/-26 mg/l of ammonium to nitrate every two days. The bacterial communities cultivated in the ER-NR-electrode and EU-NR-electrode in the continuous culture system were analyzed by TGGE on the 20th and 50th days of incubation. Some ammoniumoxidizing bacteria were enriched on the ER-NR-electrode, but not on the EU-NR-electrode. PMID:20372016

  2. Hydrogen production aided solid oxide electrochemical reformer fed with octane: A theoretical analysis

    NASA Astrophysics Data System (ADS)

    Murashkina, A. A.; Maragou, V. I.; Demin, A. K.; Pikalova, E. Yu.; Tsiakaras, P. E.

    In the present work the possibility of pure hydrogen production by a solid oxide electrochemical reformer (SOER) is examined. Initial reagents are water steam, flowing into the cathode channel and octane flowing into the anode channel. Three modes of reforming are considered: (i) steam reforming (SR-mode), (ii) preliminary octane partial oxidation (PO-mode) and (iii) preliminary octane reforming by exhaust anode gas recycling (EAGR-mode). A parametric analysis is carried out that can be easily applied for various hydrocarbons. It was found that the electromotive force (EMF) value depends mainly on the ratio of steam moles' number supplied to the cathode space to the number of hydrogen output moles (k-parameter). It was also found that EMF increases with k increase, while is weakly affected from the temperature and the heat losses amount. Moreover, the EMF average value under the PO-mode is lower than that under the SR-mode. Finally, it is shown that the SOER optimum characteristics can be reached under the EAGR-mode, since it provides the most favorable combination of the reforming efficiency and the rate of the electrochemical process.

  3. Modeling of Electrochemical Process for the Treatment of Wastewater Containing Organic Pollutants

    NASA Astrophysics Data System (ADS)

    Rodrigo, Manuel A.; Cañizares, Pablo; Lobato, Justo; Sáez, Cristina

    Electrocoagulation and electrooxidation are promising electrochemical technologies that can be used to remove organic pollutants contained in wastewaters. To make these technologies competitive with the conventional technologies that are in use today, a better understanding of the processes involved must be achieved. In this context, the development of mathematical models that are consistent with the processes occurring in a physical system is a relevant advance, because such models can help to understand what is happening in the treatment process. In turn, a more detailed knowledge of the physical system can be obtained, and tools for a proper design of the processes, or for the analysis of operating problems, are attained. The modeling of these technologies can be carried out using single-variable or multivariable models. Likewise, the position dependence of the model species can be described with different approaches. In this work, a review of the basics of the modeling of these processes and a description of several representative models for electrochemical oxidation and coagulation are carried out. Regarding electrooxidation, two models are described: one which summarizes the pollution of a wastewater in only one model species and that considers a macroscopic approach to formulate the mass balances and other that considers more detailed profile of concentration to describe the time course of pollutants and intermediates through a mixed maximum gradient/macroscopic approach. On the topic of electrochemical coagulation, two different approaches are also described in this work: one that considers the hydrodynamic conditions as the main factor responsible for the electrochemical coagulation processes and the other that considers the chemical interaction of the reagents and the pollutants as the more significant processes in the description of the electrochemical coagulation of organic compounds. In addition, in this work it is also described a multivariable model

  4. Electrochemical oxidation of drug residues in water by the example of tetracycline, gentamicine and aspirin.

    PubMed

    Weichgrebe, D; Danilova, E; Rosenwinkel, K H; Vedenjapin, A A; Baturova, M

    2004-01-01

    Electro-chemical oxidation as a method to destroy drug residues like aspirin, tetracycline or gentamicine in water was investigated with C-anodes (modified by manganese oxides) and Pt anodes. The mechanism of aspirin and tetracycline oxidation and the influence of the biocide effect was observed using GC-MS and three different microbiological tests. In general, the biological availability increases with progressive oxidation of the antibiotics. PMID:15077972

  5. Towards a carbon independent and CO2-free electrochemical membrane process for NH3 synthesis.

    PubMed

    Kugler, K; Ohs, B; Scholz, M; Wessling, M

    2014-04-01

    Ammonia is exclusively synthesized by the Haber-Bosch process starting from precious carbon resources such as coal or CH4. With H2O, H2 is produced and with N2, NH3 can be synthesized at high pressures and temperatures. Regrettably, the carbon is not incorporated into NH3 but emitted as CO2. Valuable carbon sources are consumed which could be used otherwise when carbon sources become scarce. We suggest an alternative process concept using an electrochemical membrane reactor (ecMR). A complete synthesis process with N2 production and downstream product separation is presented and evaluated in a multi-scale model to quantify its energy consumption. A new micro-scale ecMR model integrates mass, species, heat and energy balances with electrochemical conversions allowing further integration into a macro-scale process flow sheet. For the anodic oxidation reaction H2O was chosen as a ubiquitous H2 source. Nitrogen was obtained by air separation which combines with protons from H2O to give NH3 using a hypothetical catalyst recently suggested from DFT calculations. The energy demand of the whole electrochemical process is up to 20% lower than the Haber-Bosch process using coal as a H2 source. In the case of natural gas, the ecMR process is not competitive under today's energy and resource conditions. In future however, the electrochemical NH3 synthesis might be the technology-of-choice when coal is easily accessible over natural gas or limited carbon sources have to be used otherwise but for the synthesis of the carbon free product NH3. PMID:24557153

  6. Electrochemically deposited gallium oxide nanostructures on silicon substrates

    PubMed Central

    2014-01-01

    We report a synthesis of β-Ga2O3 nanostructures on Si substrate by electrochemical deposition using a mixture of Ga2O3, HCl, NH4OH, and H2O. The presence of Ga3+ ions contributed to the deposition of Ga2O3 nanostructures on the Si surface with the assistance of applied potentials. The morphologies of the grown structures strongly depended on the molarity of Ga2O3 and pH level of electrolyte. β-Ga2O3 nanodot-like structures were grown on Si substrate at a condition with low molarity of Ga2O3. However, Ga2O3 nanodot structures covered with nanorods on top of their surfaces were obtained at higher molarity, and the densities of nanorods seem to increase with the decrease of pH level. High concentration of Ga3+ and OH- ions may promote the reaction of each other to produce Ga2O3 nanorods in the electrolyte. Such similar nature of Ga2O3 nanorods was also obtained by using hydrothermal process. The grown structures seem to be interesting for application in electronic and optoelectronic devices as well as to be used as a seed structure for subsequent chemical synthesis of GaN by thermal transformation method. PMID:24629107

  7. Nanocrystals of Uranium Oxide: Controlled Synthesis and Enhanced Electrochemical Performance of Hydrogen Evolution by Ce Doping.

    PubMed

    Hu, Shi; Li, Haoyi; Liu, Huiling; He, Peilei; Wang, Xun

    2015-06-10

    A preliminary study of the growth of 0D, 1D, and 2D nanostructures of uranium oxides with feature sizes from several nanometers down to 1 nm are presented. Cerium is successfully doped into these oxides and its influence on the growth dynamics and electrochemical performance investigated. PMID:25627103

  8. Optimization of Electrochemical Treatment Process Conditions for Distillery Effluent Using Response Surface Methodology

    PubMed Central

    Arulmathi, P.; Elangovan, G.; Begum, A. Farjana

    2015-01-01

    Distillery industry is recognized as one of the most polluting industries in India with a large amount of annual effluent production. In this present study, the optimization of electrochemical treatment process variables was reported to treat the color and COD of distillery spent wash using Ti/Pt as an anode in a batch mode. Process variables such as pH, current density, electrolysis time, and electrolyte dose were selected as operation variables and chemical oxygen demand (COD) and color removal efficiency were considered as response variable for optimization using response surface methodology. Indirect electrochemical-oxidation process variables were optimized using Box-Behnken response surface design (BBD). The results showed that electrochemical treatment process effectively removed the COD (89.5%) and color (95.1%) of the distillery industry spent wash under the optimum conditions: pH of 4.12, current density of 25.02 mA/cm2, electrolysis time of 103.27 min, and electrolyte (NaCl) concentration of 1.67 g/L, respectively. PMID:26491716

  9. Hydrothermally Oxidized Single-Walled Carbon Nanotube Networks for High Volumetric Electrochemical Energy Storage.

    PubMed

    Liu, Tianyuan; Davijani, Amir A Bakhtiary; Sun, Jingying; Chen, Shuo; Kumar, Satish; Lee, Seung Woo

    2016-07-01

    Improving volumetric energy density is one of the major challenges in nanostructured carbon electrodes for electrochemical energy storage device applications. Herein, a simple hydrothermal oxidation process of single-walled carbon nanotube (SWNT) networks in dilute nitric acid is reported, enabling simultaneous physical densification and chemical functionalization of the as-assembled randomly-packed SWNT films. After the hydrothermal oxidation process, the density of the SWNT films increases from 0.63 to 1.02 g cm(-3) and a considerable amount of redox-active oxygen functional groups are introduced on the surface of the SWNTs. The functionalized SWNT films are used as positive electrodes against Li metal negative electrodes for potential Li-ion capacitors or Li-ion battery applications. The functionalized SWNT electrodes deliver high volumetric as well as gravimetric capacities, 154 Ah L(-1) and 152 mAh g(-1) , respectively, owing to the surface redox reactions between the introduced oxygen functional groups and Li ions. In addition, these electrodes exhibit a remarkable rate-capability by retaining its high capacity of 94 Ah L(-1) (92 mAh g(-1) ) at a high discharge rate of 10 A g(-1) . These results demonstrate the simple hydrothermal oxidation process as an attractive strategy for improving the volumetric performance of nanostructured carbon electrodes. PMID:27200509

  10. Introduction to Electrochemical Process Integration for Cu Interconnects

    NASA Astrophysics Data System (ADS)

    Ohba, Takayuki

    This chapter focuses on advanced multilevel interconnects, contributed by distinguished authors in the following sections: Damascene Concept and Process Steps (Nobuyoshi Kobayashi), Advanced BEOL Technology Overview (Takashi Yoda and Hideshi Miyajima), Lithography for Cu Damascene fabrication (Yoshihiro Hayashi), Physical Vapor Deposition Barriers for Cu metallization PVD Barriers (Junichi Koike), Low-k dielectrics (Yoshihiro Hayashi), CMP for Cu Processing (Manabu Tsujimura), Electrochemical View of Copper Chemical Mechanical Polishing (CMP) (D. Starosvetsky and Y. Ein-Eli), and Copper Post-CMP Cleaning (D. Starosvetsky and Y. Ein-Eli).

  11. Electrochemical determination of activation energies for methanol oxidation on polycrystalline platinum in acidic and alkaline electrolytes.

    PubMed

    Cohen, Jamie L; Volpe, David J; Abruña, Héctor D

    2007-01-01

    The oxidation pathways of methanol (MeOH) have been the subject of intense research due to its possible application as a liquid fuel in polyelectrolyte membrane (PEM) fuel cells. The design of improved catalysts for MeOH oxidation requires a deep understanding of these complex oxidation pathways. This paper will provide a discussion of the literature concerning the extensive research carried out in acidic and alkaline electrolytes. It will highlight techniques that have proven useful in the determination of product ratios, analysis of surface poisoning, anion adsorption, and oxide formation processes, in addition to the effects of temperature on the MeOH oxidation pathways at bulk polycrystalline platinum (Pt(poly)) electrodes. This discussion will provide a framework with which to begin the analysis of activation energy (E(a)) values. This kinetic parameter may prove useful in characterizing the rate-limiting step of the MeOH oxidation at an electrode surface. This paper will present a procedure for the determination of E(a) values for MeOH oxidation at a Pt(poly) electrode in acidic and alkaline media. Values from 24-76 kJ mol(-1) in acidic media and from 36-86 kJ mol(-1) in alkaline media were calculated and found to be a function of applied potential and direction of the potential sweep in a voltammetric experiment. Factors that influence the magnitude of the calculated E(a) include surface poisoning from MeOH oxidation intermediates, anion adsorption from the electrolyte, pH effects, and oxide formation processes. These factors are all potential, and temperature, dependent and must clearly be addressed when citing E(a) values in the literature. Comparison of E(a) values must be between systems of comparable electrochemical environment and at the same potential. E(a) values obtained on bulk Pt(poly), compared with other catalysts, may give insight into the superiority of other Pt-based catalysts for MeOH oxidation and lead to the development of new catalysts

  12. Writing nanopatterns with electrochemical oxidation on redox responsive organometallic multilayers by AFM

    NASA Astrophysics Data System (ADS)

    Song, Jing; Hempenius, Mark A.; Jing Chung, Hong; Julius Vancso, G.

    2015-05-01

    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 structure generation. The influence of applied bias potential, tip velocity, and multilayer thickness on the pattern height and width were investigated.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 structure generation. The influence of applied bias potential, tip velocity, and multilayer thickness on the pattern height and width were investigated. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01206f

  13. A non-oxidative electrochemical approach to online measurements of dopamine release through laccase-catalyzed oxidation and intramolecular cyclization of dopamine.

    PubMed

    Lin, Yuqing; Zhang, Zipin; Zhao, Lingzhi; Wang, Xiang; Yu, Ping; Su, Lei; Mao, Lanqun

    2010-02-15

    A new electrochemical approach to selective online measurements of dopamine (DA) release in the cerebral microdialysate is demonstrated with a non-oxidative mechanism based on the distinct reaction properties of DA and the excellent biocatalytic activity of laccase. To make the successful transition of the distinct sequential reaction properties of DA from a conceptual determination protocol to a practical online analytical system, laccase enzyme is immobilized onto magnetite nanoparticles and the nanoparticles are confined into a fused-silica capillary through an external magnetic field to fabricate a magnetic microreactor. The microreactor is placed in the upstream of the thin-layer electrochemical flow cell to efficiently catalyze the oxidation of DA into its quinonoid form and thereby initialize the sequential reactions including deprotonation, intramolecular cyclization, disproportionation and/or oxidation to finally give 5,6-dihydroxyindoline quinone. The electrochemical reduction of the produced 5,6-dihydroxyindoline quinone at bare glassy carbon electrode is used as the readout for the DA measurement. The laccase-immobilized microreactor is also found to catalyze the oxidation of ascorbic acid (AA) and 3,4-dihydroxyphenylacetic acid (DOPAC) into electroinactive species and, as such, to eliminate the great interference from both species. Moreover, the successful transition of the mechanism for DA detection from the conventional oxidative electrochemical approach to the non-oxidative one substantially enables the measurements virtually interference-free from physiological levels of uric acid, 5-hydroxytryptamine, norepinephrine, and epinephrine. The current response is linear with DA concentration within a concentration range from 1 to 20 microM with a sensitivity of 3.97 nA/microM. The detection limit, based on a signal-to-noise ratio of 3, is calculated to be 0.3 microM. The high selectivity and the good linearity as well as the high stability of the online

  14. Catalytic oxidative dehydrogenation process

    DOEpatents

    Schmidt, Lanny D.; Huff, Marylin

    2002-01-01

    A process for the production of a mono-olefin from a gaseous paraffinic hydrocarbon having at least two carbon atoms or mixtures thereof comprising reacting said hydrocarbons and molecular oxygen in the presence of a platinum catalyst. The catalyst consist essentially of platinum supported on alumina or zirconia monolith, preferably zirconia and more preferably in the absence of palladium, rhodium and gold.

  15. Chemical and Electrochemical Processing of Aluminum Dross Using Molten Salts

    NASA Astrophysics Data System (ADS)

    Yan, Xiao Y.

    2008-04-01

    A novel molten salt process was investigated, where Al, as metal or contained in Al2O3 and AlN, was recovered from Al dross by chemical or direct electrochemical reduction in electrolytic cells. Electrolysis experiments were carried out under argon at temperatures from 1123 to 1243 K. In order to better understand the reduction behavior, the as-received Al dross was simulated using simplified systems, including pure Al2O3, pure AlN, an Al2O3/AlN binary mixture, and an Al2O3/AlN/Al ternary mixture. The reduction of the as-received dross was also studied experimentally. The studies showed that solid Al2O3 was chemically reduced by the Ca in a Ca-saturated Ca-CaCl2 melt to form Al2Ca or electrochemically reduced to Al-rich Al-Ca alloys and that the Al value in the Al2O3 was easily recovered from the Al drosses. It was found experimentally that solid AlN in the drosses could not be calciothermically reduced to any extent, consistent with thermodynamic evaluations. It was also found that the direct electrochemical reduction of the AlN in the drosses was confined to three phase boundaries (3PBs) between the AlN, the electrolyte, and the current collector and could not be enhanced by using the LiCl-containing chloride melt or the chloride-fluoride melts studied. The presence of Al powder in the Al2O3/AlN mixture facilitated the direct electrochemical reduction of both Al2O3 and AlN. The reduction mechanisms are discussed based upon the present experimental observations. Flow sheets for recovering the metallic Al and the Al in the Al2O3 and AlN from Al dross are finally proposed.

  16. Nanoporous zeolite and solid-state electrochemical devices for nitrogen-oxide sensing

    NASA Astrophysics Data System (ADS)

    Yang, Jiun-Chan

    Solid-state electrochemical gas sensing devices composed of stabilized-zirconia electrolyte have used extensively in the automobile and chemical industry. Two types of electrochemical devices, potentiometric and amperometric, were developed in this thesis for total NOx (NO + NO2) detection in harsh environments. In potentiometric devices, Pt covered with Pt containing zeolite Y (PtY) and WO3 were examined as the two electrode materials. Significant reactivity differences toward NOx between PtY and WO 3 led to the difference in non-electrochemical reactions and resulted in a electrode potential. With gases passing through a PtY filter, it was possible to remove interferences from 2000 ppm CO, 800 ppm propane, 10 ppm NH3, as well as to minimize effects of 1˜13% O2, CO2, and H2O. Total NOx concentration was measured by maintaining a temperature difference between the filter and the sensor. The sensitivity was significantly improved by connecting sensors in series. Amperometic devices were also developed to detect NOx passing through the PtY filter. By applying a low anodic potential of 80 mV, NO in the NOx equilibrated mixture can be oxidized at a Pt working electrode on the YSZ electrolyte at 500°C. The PtY can be held separate from the YSZ or coated onto the YSZ as a film. This design was demonstrated to exhibit total-NOx detection capability, a low NOx detection limit (< 1 ppm), high NOx selectivity relative to CO and oxygen, and linear dependence on NOx concentration. The non-electrochemical reactions around the triple-phase boundary were studied to understand the origin of the superior performance of WO3 on potentiometric NOx sensing. From TPD, DRIFTS, XRD, Raman, and catalytic activity measurements, the interfacial reactions between WO 3 and YSZ were found to dramatically reduce the NOx catalytic activity of YSZ. WO3 reacted with surface Y2O3 on YSZ and formed less catalytically active yttrium tungsten oxides and monoclinic ZrO2, which suppressed the non-electrochemical

  17. Virtual electrochemical nitric oxide analyzer using copper, zinc superoxide dismutase immobilized on carbon nanotubes in polypyrrole matrix.

    PubMed

    Madasamy, Thangamuthu; Pandiaraj, Manickam; Balamurugan, Murugesan; Karnewar, Santosh; Benjamin, Alby Robson; Venkatesh, Krishna Arun; Vairamani, Kanagavel; Kotamraju, Srigiridhar; Karunakaran, Chandran

    2012-10-15

    In this work, we have designed and developed a novel and cost effective virtual electrochemical analyzer for the measurement of NO in exhaled breath and from hydrogen peroxide stimulated endothelial cells using home-made potentiostat. Here, data acquisition system (NI MyDAQ) was used to acquire the data from the electrochemical oxidation of NO mediated by copper, zinc superoxide dismutase (Cu,ZnSOD). The electrochemical control programs (graphical user-interface software) were developed using LabVIEW 10.0 to sweep the potential, acquire the current response and process the acquired current signal. The Cu,ZnSOD (SOD1) immobilized on the carbon nanotubes in polypyrrole modified platinum electrode was used as the NO biosensor. The electrochemical behavior of the SOD1 modified electrode exhibited the characteristic quasi-reversible redox peak at the potential, +0.06 V vs. Ag/AgCl. The biological interferences were eliminated by nafion coated SOD1 electrode and then NO was measured selectively. Further, this biosensor showed a wide linear range of response over the concentration of NO from 0.1 μM to 1 mM with a detection limit of 0.1 μM and high sensitivity of 1.1 μA μM(-1). The electroanalytical results obtained here using the developed virtual electrochemical instrument were also compared with the standard cyclic voltammetry instrument and found in agreement with each other. PMID:23141325

  18. Kinetics of the electrochemical oxidation of 1,1-bis-hydroperoxy-4-methylcyclohexane on platinum

    NASA Astrophysics Data System (ADS)

    Vedenyapina, M. D.; Simakova, A. P.; Platonov, M. M.; Terent'ev, A. O.; Skundin, A. M.; Vedenyapin, A. A.

    2013-03-01

    The electrochemical synthesis of 3,12-dimethyl-7,8,15,16-tetraoxadispiro[5.2.5.2]hexadecane (1,2,4,5-tetraoxane) from 1,1-bis-hydroperoxy-4-methylcyclohexane on platinum electrode in a cell with separated and unseparated cathode and anode space in an aprotic solvent is conducted. The kinetics of electrochemical oxidation of 1,1-bis(hydroperoxy)-4-methylcyclohexane is studied. The current yield of the reaction is determined.

  19. Hydroxyapatite/gelatin functionalized graphene oxide composite coatings deposited on TiO2 nanotube by electrochemical deposition for biomedical applications

    NASA Astrophysics Data System (ADS)

    Yan, Yajing; Zhang, Xuejiao; Mao, Huanhuan; Huang, Yong; Ding, Qiongqiong; Pang, Xiaofeng

    2015-02-01

    Graphene oxide cross-linked gelatin was employed as reinforcement fillers in hydroxyapatite coatings by electrochemical deposition process on TiO2 nanotube arrays (TNs). The TNs were grown on titanium by electrochemical anodization in hydrofluoric electrolyte using constant voltage. Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Field emission scanning electron microscopy equipped with energy dispersive X-ray analysis and biological studies were used to characterize the coatings. The corrosion resistance of the coatings was also investigated by electrochemical method in simulated body fluid solution.

  20. Colour and organic removal of biologically treated coffee curing wastewater by electrochemical oxidation method.

    PubMed

    Bejankiwar, Rajesh S; Lokesh, K S; Gowda, T P Halappa

    2003-05-01

    The treatment of biologically treated wastewater of coffee-curing industry by the electrochemical oxidation using steel anode was investigated. Bench-scale experiments were conducted for activated sludge process on raw wastewater and the treated effluents were further treated by electrochemical oxidation method for its colour and organic content removal. The efficiency of the process was determined in terms of removal percentage of COD, BOD and colour during the course of reaction. Several operating parameters like time, pH and current density were examined to ascertain their effects on the treatment efficiency. Steel anode was found to be effective for the COD and colour removal with anode efficiency of 0.118 kgCOD x h(-1) x A(-1) x m(-2) and energy consumption 20.61 kWh x kg(-1) of COD at pH 9. The decrease in pH from 9 to 3 found to increase the anode efficiency from 0.118 kgCOD x h(-1) x A(-1) x m(-2) to 0.144 kWh x kg(-1) of COD while decrease the energy consumption from 20.61 kWh x kg(-1) of COD to 12.86 kWh x kg(-1) of COD. The pH of 5 was considered an ideal from the present treatment process as it avoids the addition of chemicals for neutralization of treated effluents and also economical with respect to energy consumption. An empirical relation developed for relationship between applied current density and COD removal efficiency showed strong predictive capability with coefficient of determination of 96.5%. PMID:12938980

  1. Electrochemical Characterization of a Solid Oxide Membrane Electrolyzer for Production of High-Purity Hydrogen

    NASA Astrophysics Data System (ADS)

    Pati, Soobhankar; Yoon, Kyung Joong; Gopalan, Srikanth; Pal, Uday B.

    2009-12-01

    A laboratory-scale solid oxide membrane (SOM) steam electrolyzer that can potentially use energy value in waste or any source of carbon or hydrocarbon to produce high-purity hydrogen has been fabricated and evaluated. The SOM electrolyzer comprises an oxygen-ion-conducting yttria-stabilized zirconia (YSZ) electrolyte with a Ni-YSZ cermet cathode coated on one side and liquid-metal anode on the other side. The SOM electrolyzer is operated at 1000 °C by providing a steam-rich gas feed to the Ni-YSZ cermet cathode and feeding a reductant source into the liquid-metal anode. The steam is reduced over the cathode, and oxygen ions are transported through the YSZ electrolyte and are oxidized at the molten metal electrode by the reductant feed. The advantage of SOM electrolyzer over the state-of-the-art solid oxide electrolyzer is its ability to use solid, liquid, and gaseous reductant feed in the liquid-metal anode to reduce the oxygen chemical potential and drive the reaction for hydrogen production. In this study, an electrochemical process model for a SOM electrolyzer was developed. The condition of the liquid-metal anode with reductant was simulated by bubbling humidified hydrogen (3 pct H2O) in the liquid metal, and the electrochemical performance of the SOM electrolyzer was modeled. The experimental data were curve-fitted into the model to identify the various polarization losses. It showed that the performance of the SOM electrolyzer was dominated by the ohmic resistance of the YSZ membrane. Based on the results of this study, future work is needed toward increasing the performance efficiency of the SOM electrolyzer.

  2. Study and characterization of porous copper oxide produced by electrochemical anodization for radiometric heat absorber

    PubMed Central

    2014-01-01

    The aim of this work is to optimize the different parameters for realization of an absorbing cavity to measure the incident absolute laser energy. Electrochemical oxidation is the background process that allowed the copper blackening. A study of the blackened surface quality was undertaken using atomic force microscopy (AFM) analysis and ultraviolet-visible-infrared spectrophotometry using a Shimadzu spectrophotometer. A two-dimensional and three-dimensional visualization by AFM of the formed oxide coating showed that the copper surfaces became porous after electrochemical etching with different roughness. This aspect is becoming more and more important with decreasing current density anodization. In a 2 mol L -1 of NaOH solution, at a temperature of 90°C, and using a 16 mA cm2 constant density current, the copper oxide formed has a reflectivity of around 3% in the spectral range between 300 and 1,800 nm. Using the ‘mirage effect’ technique, the obtained Cu2O diffusivity and thermal conductivity are respectively equal to (11.5 ± 0.5) 10 to 7 m2 s-1 and (370 ± 20) Wm-1 K-1. This allows us to consider that our Cu2O coating is a good thermal conductor. The results of the optical and thermal studies dictate the choice of the cavity design. The absorbing cavity is a hollow cylinder machined to its base at an angle of 30°. If the included angle of the plane is 30° and the interior surface gives specular reflection, an incoming ray parallel to the axis will undergo five reflections before exit. So the absorption of the surface becomes closely near 0.999999. PMID:25349555

  3. Study and characterization of porous copper oxide produced by electrochemical anodization for radiometric heat absorber.

    PubMed

    Ben Salem, Sonia; Achour, Zahra Ben; Thamri, Kamel; Touayar, Oualid

    2014-01-01

    The aim of this work is to optimize the different parameters for realization of an absorbing cavity to measure the incident absolute laser energy. Electrochemical oxidation is the background process that allowed the copper blackening. A study of the blackened surface quality was undertaken using atomic force microscopy (AFM) analysis and ultraviolet-visible-infrared spectrophotometry using a Shimadzu spectrophotometer. A two-dimensional and three-dimensional visualization by AFM of the formed oxide coating showed that the copper surfaces became porous after electrochemical etching with different roughness. This aspect is becoming more and more important with decreasing current density anodization. In a 2 mol L(-1) of NaOH solution, at a temperature of 90°C, and using a 16 mA cm(2) constant density current, the copper oxide formed has a reflectivity of around 3% in the spectral range between 300 and 1,800 nm. Using the 'mirage effect' technique, the obtained Cu2O diffusivity and thermal conductivity are respectively equal to (11.5 ± 0.5) 10 to 7 m(2) s(-1) and (370 ± 20) Wm(-1) K(-1). This allows us to consider that our Cu2O coating is a good thermal conductor. The results of the optical and thermal studies dictate the choice of the cavity design. The absorbing cavity is a hollow cylinder machined to its base at an angle of 30°. If the included angle of the plane is 30° and the interior surface gives specular reflection, an incoming ray parallel to the axis will undergo five reflections before exit. So the absorption of the surface becomes closely near 0.999999. PMID:25349555

  4. Study and characterization of porous copper oxide produced by electrochemical anodization for radiometric heat absorber

    NASA Astrophysics Data System (ADS)

    Ben Salem, Sonia; Achour, Zahra Ben; Thamri, Kamel; Touayar, Oualid

    2014-10-01

    The aim of this work is to optimize the different parameters for realization of an absorbing cavity to measure the incident absolute laser energy. Electrochemical oxidation is the background process that allowed the copper blackening. A study of the blackened surface quality was undertaken using atomic force microscopy (AFM) analysis and ultraviolet-visible-infrared spectrophotometry using a Shimadzu spectrophotometer. A two-dimensional and three-dimensional visualization by AFM of the formed oxide coating showed that the copper surfaces became porous after electrochemical etching with different roughness. This aspect is becoming more and more important with decreasing current density anodization. In a 2 mol L -1 of NaOH solution, at a temperature of 90°C, and using a 16 mA cm2 constant density current, the copper oxide formed has a reflectivity of around 3% in the spectral range between 300 and 1,800 nm. Using the `mirage effect' technique, the obtained Cu2O diffusivity and thermal conductivity are respectively equal to (11.5 ± 0.5) 10 to 7 m2 s-1 and (370 ± 20) Wm-1 K-1. This allows us to consider that our Cu2O coating is a good thermal conductor. The results of the optical and thermal studies dictate the choice of the cavity design. The absorbing cavity is a hollow cylinder machined to its base at an angle of 30°. If the included angle of the plane is 30° and the interior surface gives specular reflection, an incoming ray parallel to the axis will undergo five reflections before exit. So the absorption of the surface becomes closely near 0.999999.

  5. Single and Coupled Electrochemical Processes and Reactors for the Abatement of Organic Water Pollutants: A Critical Review.

    PubMed

    Martínez-Huitle, Carlos A; Rodrigo, Manuel A; Sirés, Ignasi; Scialdone, Onofrio

    2015-12-23

    Traditional physicochemical and biological techniques, as well as advanced oxidation processes (AOPs), are often inadequate, ineffective, or expensive for industrial water reclamation. Within this context, the electrochemical technologies have found a niche where they can become dominant in the near future, especially for the abatement of biorefractory substances. In this critical review, some of the most promising electrochemical tools for the treatment of wastewater contaminated by organic pollutants are discussed in detail with the following goals: (1) to present the fundamental aspects of the selected processes; (2) to discuss the effect of both the main operating parameters and the reactor design on their performance; (3) to critically evaluate their advantages and disadvantages; and (4) to forecast the prospect of their utilization on an applicable scale by identifying the key points to be further investigated. The review is focused on the direct electrochemical oxidation, the indirect electrochemical oxidation mediated by electrogenerated active chlorine, and the coupling between anodic and cathodic processes. The last part of the review is devoted to the critical assessment of the reactors that can be used to put these technologies into practice. PMID:26654466

  6. Solid oxide electrolysis cell analysis by means of electrochemical impedance spectroscopy: A review

    NASA Astrophysics Data System (ADS)

    Nechache, A.; Cassir, M.; Ringuedé, A.

    2014-07-01

    High temperature water electrolysis based on Solid Oxide Electrolysis Cell (SOEC) is a very promising solution to produce directly pure hydrogen. However, degradation issues occurring during operation still represent a scientific and technological barrier in view of its development at an industrial scale. Electrochemical Impedance Spectroscopy (EIS) is a powerful in-situ fundamental tool adapted to the study of SOEC systems. Hence, after a quick presentation of EIS principle and data analysis methods, this review demonstrates how EIS can be used: (i) to characterize the performance and mechanisms of SOEC electrodes; (ii) as a complementary tool to study SOEC degradation processes for different cell configurations, in addition to post-test tools such as scanning electron microscopy (SEM) or X-ray diffraction (XRD). The use of EIS to establish a systematic SOEC analysis is introduced as well.

  7. Spontaneous electrochemical treatment for sulfur recovery by a sulfide oxidation/vanadium(V) reduction galvanic cell.

    PubMed

    Kijjanapanich, Pimluck; Kijjanapanich, Pairoje; Annachhatre, Ajit P; Esposito, Giovanni; Lens, Piet N L

    2015-02-01

    Sulfide is the product of the biological sulfate reduction process which gives toxicity and odor problems. Wastewaters or bioreactor effluents containing sulfide can cause severe environmental impacts. Electrochemical treatment can be an alternative approach for sulfide removal and sulfur recovery from such sulfide rich solutions. This study aims to develop a spontaneous electrochemical sulfide oxidation/vanadium(V) reduction cell with a graphite electrode system to recover sulfide as elemental sulfur. The effects of the internal and external resistance on the sulfide removal efficiency and electrical current produced were investigated at different pH. A high surface area of the graphite electrode is required in order to have as less internal resistance as possible. In this study, graphite powder was added (contact area >633 cm(2)) in order to reduce the internal resistance. A sulfide removal efficiency up to 91% and electrical charge of more than 400 C were achieved when using five graphite rods supplemented with graphite powder as the electrode at an external resistance of 30 Ω and a sulfide concentration of 250 mg L(-1). PMID:25463589

  8. Electrochemical oxidation of 2,4,5-trichlorophenoxyacetic acid by metal-oxide-coated Ti electrodes.

    PubMed

    Maharana, Dusmant; Xu, Zesheng; Niu, Junfeng; Rao, Neti Nageswara

    2015-10-01

    Electrochemical oxidation of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) over metal-oxide-coated Ti anodes, i.e., Ti/SnO2-Sb/Ce-PbO2, Ti/SnO2-Sb and Ti/RuO2, was examined. The degradation efficiency of over 90% was attained at 20 min at different initial concentrations (0.5-20 mg L(-1)) and initial pH values (3.1-11.2). The degradation efficiencies of 2,4,5-T on Ti/SnO2-Sb/Ce-PbO2, Ti/SnO2-Sb and Ti/RuO2 anodes were higher than 99.9%, 97.2% and 91.5% at 30 min, respectively, and the respective total organic carbon removal ratios were 65.7%, 54.6% and 37.2%. The electrochemical degradation of 2,4,5-T in aqueous solution followed pseudo-first-order kinetics. The compounds, i.e., 2,5-dichlorohydroquinone and 2,5-dihydroxy-p-benzoquinone, have been identified as the main aromatic intermediates by liquid chromatography-mass spectrometry. The results showed that the energy efficiencies of 2,4,5-T (20 mg L(-1)) degradation with Ti/SnO2-Sb/Ce-PbO2 anode at the optimal current densities from 2 to 16 mA cm(-2) ranged from 8.21 to 18.73 kWh m(-3). PMID:25981800

  9. Nanostructured Metal Oxide Coatings for Electrochemical Energy Conversion and Storage Electrodes

    NASA Astrophysics Data System (ADS)

    Cordova, Isvar Abraxas

    The realization of an energy future based on safe, clean, sustainable, and economically viable technologies is one of the grand challenges facing modern society. Electrochemical energy technologies underpin the potential success of this effort to divert energy sources away from fossil fuels, whether one considers alternative energy conversion strategies through photoelectrochemical (PEC) production of chemical fuels or fuel cells run with sustainable hydrogen, or energy storage strategies, such as in batteries and supercapacitors. This dissertation builds on recent advances in nanomaterials design, synthesis, and characterization to develop novel electrodes that can electrochemically convert and store energy. Chapter 2 of this dissertation focuses on refining the properties of TiO2-based PEC water-splitting photoanodes used for the direct electrochemical conversion of solar energy into hydrogen fuel. The approach utilized atomic layer deposition (ALD); a growth process uniquely suited for the conformal and uniform deposition of thin films with angstrom-level thickness precision. ALD's thickness control enabled a better understanding of how the effects of nitrogen doping via NH3 annealing treatments, used to reduce TiO2's bandgap, can have a strong dependence on TiO2's thickness and crystalline quality. In addition, it was found that some of the negative effects on the PEC performance typically associated with N-doped TiO2 could be mitigated if the NH 3-annealing was directly preceded by an air-annealing step, especially for ultrathin (i.e., < 10 nm) TiO2 films. ALD was also used to conformally coat an ultraporous conductive fluorine-doped tin oxide nanoparticle (nanoFTO) scaffold with an ultrathin layer of TiO2. The integration of these ultrathin films and the oxide nanoparticles resulted in a heteronanostructure design with excellent PEC water oxidation photocurrents (0.7 mA/cm2 at 0 V vs. Ag/AgCl) and charge transfer efficiency. In Chapter 3, two innovative

  10. High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes.

    PubMed

    Aquino, José Mario; Rocha-Filho, Romeu C; Sáez, Cristina; Cañizares, Pablo; Rodrigo, Manuel A

    2014-01-01

    Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at

  11. Mediated electrochemical oxidation of organic wastes without electrode separators

    DOEpatents

    Farmer, Joseph C.; Wang, Francis T.; Hickman, Robert G.; Lewis, Patricia R.

    1996-01-01

    An electrochemical cell/electrolyte/mediator combination for the efficient destruction of organic contaminants using metal salt mediators in a sulfuric acid electrolyte, wherein the electrodes and mediator are chosen such that hydrogen gas is produced at the cathode and no cell membrane is required.

  12. Mediated electrochemical oxidation of organic wastes without electrode separators

    DOEpatents

    Farmer, J.C.; Wang, F.T.; Hickman, R.G.; Lewis, P.R.

    1996-05-14

    An electrochemical cell/electrolyte/mediator combination is described for the efficient destruction of organic contaminants using metal salt mediators in a sulfuric acid electrolyte, wherein the electrodes and mediator are chosen such that hydrogen gas is produced at the cathode and no cell membrane is required. 3 figs.

  13. Synthesis and electrochemical behavior of nanostructured cauliflower-shape Co-Ni/Co-Ni oxides composites

    SciTech Connect

    Gupta, Vinay Kawaguchi, Toshikazu; Miura, Norio

    2009-01-08

    Nanostructured Co-Ni/Co-Ni oxides were electrochemically deposited onto stainless steel electrode by electrochemical method and characterized for their structural and supercapacitive properties. The SEM images indicated that the obtained Co-Ni/Co-Ni oxides had cauliflower-type nanostructure. The X-ray diffraction pattern showed the formation of Co{sub 3}O{sub 4}, NiO, Co and Ni. The EDX elemental mapping images indicated that Ni, Co and O are distributed uniformly. The deposited Co-Ni/Co-Ni oxides showed good supercapacitive characteristics with a specific capacitance of 331 F/g at 1 mA/cm{sup 2} current density in 1 M KOH electrolyte. A mechanism of the formation of cauliflower-shape Co-Ni/Co-Ni oxides was proposed. A variety of promising applications in the fields such as energy storage devices and sensors can be envisioned from Co-Ni/Co-Ni oxides.

  14. Toxicological and chemical assessment of arsenic-contaminated groundwater after electrochemical and advanced oxidation treatments.

    PubMed

    Radić, Sandra; Crnojević, Helena; Vujčić, Valerija; Gajski, Goran; Gerić, Marko; Cvetković, Želimira; Petra, Cvjetko; Garaj-Vrhovac, Vera; Oreščanin, Višnja

    2016-02-01

    Owing to its proven toxicity and mutagenicity, arsenic is regarded a principal pollutant in water used for drinking. The objective of this study was the toxicological and chemical evaluation of groundwater samples obtained from arsenic enriched drinking water wells before and after electrochemical and ozone-UV-H2O2-based advanced oxidation processes (EAOP). For this purpose, acute toxicity test with Daphnia magna and chronic toxicity test with Lemna minor L. were employed as well as in vitro bioassays using human peripheral blood lymphocytes (HPBLs). Several oxidative stress parameters were estimated in L.minor. Physicochemical analysis showed that EAOP treatment was highly efficient in arsenic but also in ammonia and organic compound removal from contaminated groundwater. Untreated groundwater caused only slight toxicity to HPBLs and D. magna in acute experiments. However, 7-day exposure of L. minor to raw groundwater elicited genotoxicity, a significant growth inhibition and oxidative stress injury. The observed genotoxicity and toxicity of raw groundwater samples was almost completely eliminated by EAOP treatment. Generally, the results obtained with L. minor were in agreement with those obtained in the chemical analysis suggesting the sensitivity of the model organism in monitoring of arsenic-contaminated groundwater. In parallel to chemical analysis, the implementation of chronic toxicity bioassays in a battery is recommended in the assessment of the toxic and genotoxic potential of such complex mixtures. PMID:26580737

  15. Porous nanoarchitectures of spinel-type transition metal oxides for electrochemical energy storage systems.

    PubMed

    Park, Min-Sik; Kim, Jeonghun; Kim, Ki Jae; Lee, Jong-Won; Kim, Jung Ho; Yamauchi, Yusuke

    2015-12-14

    Transition metal oxides possessing two kinds of metals (denoted as AxB3-xO4, which is generally defined as a spinel structure; A, B = Co, Ni, Zn, Mn, Fe, etc.), with stoichiometric or even non-stoichiometric compositions, have recently attracted great interest in electrochemical energy storage systems (ESSs). The spinel-type transition metal oxides exhibit outstanding electrochemical activity and stability, and thus, they can play a key role in realising cost-effective and environmentally friendly ESSs. Moreover, porous nanoarchitectures can offer a large number of electrochemically active sites and, at the same time, facilitate transport of charge carriers (electrons and ions) during energy storage reactions. In the design of spinel-type transition metal oxides for energy storage applications, therefore, nanostructural engineering is one of the most essential approaches to achieving high electrochemical performance in ESSs. In this perspective, we introduce spinel-type transition metal oxides with various transition metals and present recent research advances in material design of spinel-type transition metal oxides with tunable architectures (shape, porosity, and size) and compositions on the micro- and nano-scale. Furthermore, their technological applications as electrode materials for next-generation ESSs, including metal-air batteries, lithium-ion batteries, and supercapacitors, are discussed. PMID:26549729

  16. Synthesis and characterization of a nanocomposite of goethite nanorods and reduced graphene oxide for electrochemical capacitors

    SciTech Connect

    Shou Qingliang; Cheng Jipeng; Zhang Li; Nelson, Bradley J.; Zhang Xiaobin

    2012-01-15

    We report a one-step synthesis of a nanocomposite of goethite ({alpha}-FeOOH) nanorods and reduced graphene oxide (RGO) using a solution method in which ferrous cations serve as a reducing agent of graphite oxide (GO) to graphene and a precursor to grow goethite nanorods. As-prepared goethite nanorods have an average length of 200 nm and a diameter of 30 nm and are densely attached on both sides of the RGO sheets. The electrochemical properties of the nanocomposite were characterized by cyclic voltammetry (CV) and chronopotentiometry (CP) charge-discharge tests. The results showed that goethite/RGO composites have a high electrochemical capacitance of 165.5 F g{sup -1} with an excellent recycling capability making the material promising for electrochemical capacitors. - Graphical abstract: The reduced graphene oxide sheets are decorated with goethite nanorods. The as-prepared composite exhibits a high electrochemical capacitance with good recycling capability, which is promising for supercapacitor applications. Higlights: Black-Right-Pointing-Pointer Ferrous ions act as reductant of graphite oxide and precursor of goethite nanorods. Black-Right-Pointing-Pointer Goethite nanorods are attached on both sides of the reduced graphene oxide sheets. Black-Right-Pointing-Pointer Composite exhibits a high specific capacitance and a good recycling capability. Black-Right-Pointing-Pointer Composite is promising for supercapacitor applications.

  17. Electrochemical processes for in-situ treatment of contaminated soils. 1998 annual progress report

    SciTech Connect

    Huang, C.P.

    1998-06-01

    'This research project is to develop electrochemical processes for in-situ treatment of contaminated soils. Specifically, it is to study electrokinetic (EK) and electro-Fento (EF) processes and to integrate these processes for the treatment of soils containing mixed contaminants. The objectives are: (1) To study important parameters controlling the mobilization and the transport of selected organics and metals in soils by the electrokinetic (EK) process. Factors to be studied include field strength, pH, ionic strength, soil washing agents, types of organic and metal contaminants, and soil surface properties such as cation exchange capacity(CEC), soil organic content, soil moisture content, soil composition, and surface charge. (2) To study the important factors governing the oxidation of selected organic contaminants by the electro-Fenton (EF) process. Parameters such as pH, surface area and the configuration of working electrode, oxygen concentration, ferrous ion, and temperature that may affect the performance of the EF process will be investigated. (3) To understand the mechanism of the oxidation of selected organic contaminants by the electro-Fenton oxidation process.'

  18. Challenges and Opportunities for Electrochemical Processes as Next-Generation Technologies for the Treatment of Contaminated Water.

    PubMed

    Radjenovic, Jelena; Sedlak, David L

    2015-10-01

    Electrochemical processes have been extensively investigated for the removal of a range of organic and inorganic contaminants. The great majority of these studies were conducted using nitrate-, perchlorate-, sulfate-, and chloride-based electrolyte solutions. In actual treatment applications, organic and inorganic constituents may have substantial effects on the performance of electrochemical treatment. In particular, the outcome of electrochemical oxidation will depend on the concentration of chloride and bromide. Formation of chlorate, perchlorate, chlorinated, and brominated organics may compromise the quality of the treated effluent. A critical review of recent research identifies future opportunities and research needed to overcome major challenges that currently limit the application of electrochemical water treatment systems for industrial and municipal water and wastewater treatment. Given the increasing interest in decentralized wastewater treatment, applications of electrolytic systems for treatment of domestic wastewater, greywater, and source-separated urine are also included. To support future adoption of electrochemical treatment, new approaches are needed to minimize the formation of toxic byproducts and the loss of efficiency caused by mass transfer limitations and undesired side reactions. Prior to realizing these improvements, recognition of the situations where these limitations pose potential health risks is a necessary step in the design and operation of electrochemical treatment systems. PMID:26370517

  19. Electrochemical capacitance of iron oxide nanotube (Fe-NT): effect of annealing atmospheres

    NASA Astrophysics Data System (ADS)

    Sarma, Biplab; Jurovitzki, Abraham L.; Ray, Rupashree S.; Smith, York R.; Mohanty, Swomitra K.; Misra, Mano

    2015-07-01

    The effect of annealing atmosphere on the supercapacitance behavior of iron oxide nanotube (Fe-NT) electrodes has been explored and reported here. Iron oxide nanotubes were synthesized on a pure iron substrate through an electrochemical anodization process in an ethylene glycol solution containing 3% H2O and 0.5 wt.% NH4F. Subsequently, the annealing of the nanotubes was carried out at 500 °C for 2 h in various gas atmospheres such as air, oxygen (O2), nitrogen (N2), and argon (Ar). The morphology and crystal phases evolved after the annealing processes were examined via field emission scanning electron microscopy, x-ray diffraction, Raman spectroscopy, and x-ray photoelectron spectroscopy. The electrochemical capacitance properties of the annealed Fe-NT electrodes were evaluated by conducting cyclic voltammetry (CV), galvanostatic charge-discharge, and electrochemical impedance spectroscopy tests in the Li2SO4 electrolyte. Based on these experiments, it was found that the capacitance of the Fe-NT electrodes annealed in air and O2 atmospheres shows mixed behavior comprising both the electric double layer and pseudocapacitance. However, annealing in N2 and Ar environments resulted in well-defined redox peaks in the CV profiles of the Fe-NT electrodes, which are therefore attributed to the relatively higher pseudonature of the capacitance in these electrodes. Based on the galvanostatic charge-discharge studies, the specific capacitance achieved in the Fe-NT electrode after annealing in Ar was about 300 mF cm-2, which was about twice the value obtained for N2-annealed Fe-NTs and three times higher than those annealed in air and O2. The experiments also demonstrated excellent cycle stability for the Fe-NT electrodes with 83%-85% capacitance retention, even after many charge-discharge cycles, irrespective of the gas atmospheres used during annealing. The increase in the specific capacitance was discussed in terms of increased oxygen vacancies as a result of the

  20. Ultra-thin films on transparent conductor oxides for the development of spectro-electrochemical transducers

    NASA Astrophysics Data System (ADS)

    Grigore, E.; Delacôte, C.; Thobie-Gautier, C.; Boujtita, M.; Tessier, P. Y.

    2013-07-01

    Transparent C, Au and Pt films with thickness in the 5-10 nm range have been deposited by a DC magnetron sputtering system on commercial ITO (indium tin oxide) coated glass substrate for evaluation as electrode of spectro-electrochemical transducer. The transmission, over the investigated spectral range, is superior to 55% with the best transmission values obtained for C films (higher than 80%). The deposited films have been characterized by AFM, XPS and electrochemical methods. Results showed a low roughness, improved in comparison with uncoated electrodes. Electrochemical properties of the Au and Pt films evidenced a metallic behavior, which allowed qualifying them as conductive optically transparent electrodes for spectro-electrochemical devices.

  1. Direct reduction processes for titanium oxide in molten salt

    NASA Astrophysics Data System (ADS)

    Suzuki, Ryosuke O.

    2007-02-01

    Molten salt electrolysis using CaCl2 is employed to produce pure titanium and its alloys directly from TiO2 and a mixture of elemental oxides, respectively, as an alternate to the Kroll process. This is because CaO, which is a reduction by-product, is highly soluble in CaCl2. Good-quality titanium containing only a small amount of residual oxygen has been successfully produced and scaled to industrial levels. Thermochemical and electrochemical bases are reviewed to optimize the process conditions. Several processes using molten salt are being examined for future progress in titanium processing.

  2. 3D CFD ELECTROCHEMICAL AND HEAT TRANSFER MODEL OF AN INTERNALLY MANIFOLDED SOLID OXIDE ELECTROLYSIS CELL

    SciTech Connect

    Grant L. Hawkes; James E. O'Brien; Greg Tao

    2011-11-01

    A three-dimensional computational fluid dynamics (CFD) electrochemical model has been created to model high-temperature electrolysis cell performance and steam electrolysis in an internally manifolded planar solid oxide electrolysis cell (SOEC) stack. This design is being evaluated at the Idaho National Laboratory for hydrogen production from nuclear power and process heat. Mass, momentum, energy, and species conservation and transport are provided via the core features of the commercial CFD code FLUENT. A solid-oxide fuel cell (SOFC) model adds the electrochemical reactions and loss mechanisms and computation of the electric field throughout the cell. The FLUENT SOFC user-defined subroutine was modified for this work to allow for operation in the SOEC mode. Model results provide detailed profiles of temperature, operating potential, steam-electrode gas composition, oxygen-electrode gas composition, current density and hydrogen production over a range of stack operating conditions. Single-cell and five-cell results will be presented. Flow distribution through both models is discussed. Flow enters from the bottom, distributes through the inlet plenum, flows across the cells, gathers in the outlet plenum and flows downward making an upside-down ''U'' shaped flow pattern. Flow and concentration variations exist downstream of the inlet holes. Predicted mean outlet hydrogen and steam concentrations vary linearly with current density, as expected. Effects of variations in operating temperature, gas flow rate, oxygen-electrode and steam-electrode current density, and contact resistance from the base case are presented. Contour plots of local electrolyte temperature, current density, and Nernst potential indicate the effects of heat transfer, reaction cooling/heating, and change in local gas composition. Results are discussed for using this design in the electrolysis mode. Discussion of thermal neutral voltage, enthalpy of reaction, hydrogen production, cell thermal

  3. Electrochemical functionalization of polypyrrole through amine oxidation of poly(amidoamine) dendrimers: Application to DNA biosensor.

    PubMed

    Miodek, Anna; Mejri-Omrani, Nawel; Khoder, Rabih; Korri-Youssoufi, Hafsa

    2016-07-01

    Electrochemical patterning method has been developed to fabricate composite based on polypyrrole (PPy) film and poly(amidoamine) dendrimers of fourth generation (PAMAM G4). PPy layer was generated using electrochemical polymerization of pyrrole on a gold electrode. PPy film was then modified with PAMAM G4 using amines electro-oxidation method. Covalent bonding of PAMAM G4 and the formation of PPy-PAMAM composite was characterized using Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). Ferrocenyl groups were then attached to such surface as a redox marker. Electrochemical properties of the modified nanomaterial (PPy-PAMAM-Fc) were studied using both amperometric and impedimetric methods to demonstrate the efficiency of electron transfer through the modified PPy layer. The obtained electrical and electrochemical properties were compared to a composite where PPy bearing carboxylic acid functions was chemically modified with PAMAM G4 by covalent attachment through formation of amid bond (PPy-CONH-PAMAM). The above mentioned studies showed that electrochemical patterning does not disturb the electronic properties of PPy. The effect of the number of functional groups introduced by the electrochemical patterning was demonstrated through the association of various compounds (ethylenediamine, PAMAM G2 and PAMAM G6). We demonstrated that such compounds could be applied in the biosensors technology. The modified PPy-PAMAM-Fc was evaluated as a platform for DNA sensing. High performance in the DNA detection by variation of the electrochemical signal of ferrocene was obtained with detection limit of 0.4 fM. Furthermore, such approach of electrochemical patterning by oxidation of amines could be applied for chemical modification of PPy and open a new way in various biosensing application involving functionalized PPy. PMID:27154698

  4. Electrochemical investigation of Mn4O4-cubane water-oxidizing clusters.

    PubMed

    Brimblecombe, Robin; Bond, Alan M; Dismukes, G Charles; Swiegers, Gerhard F; Spiccia, Leone

    2009-08-14

    High valence states in manganese clusters are a key feature of the function of one of the most important catalysts found in nature, the water-oxidizing complex of photosystem II. We describe a detailed electrochemical investigation of two bio-inspired manganese-oxo complexes, [Mn(4)O(4)L(6)] (L = diphenylphosphinate (1) and bis(p-methoxyphenyl)phosphinate (2)), in solution, attached to an electrode surface and suspended within a Nafion film. These complexes contain a cubic [Mn(4)O(4)](6+) core stabilized by phosphinate ligands. They have previously been shown to be active and durable photocatalysts for the oxidation of water to dioxygen. A comparison of catalytic photocurrent generated by films deposited by two methods of electrode immobilization reveals that doping of the catalyst in Nafion results in higher photocurrent than was observed for a solid layer of cubane on an electrode surface. In dichloromethane solution, and under conditions of cyclic voltammetry, the one-electron oxidation processes 1/1(+) and 2/2(+) were found to be reversible and quasi-reversible, respectively. Some decomposition of 1(+) and 2(+) was detected on the longer timescale of bulk electrolysis. Both compounds also undergo a two-electron, chemically irreversible reduction in dichloromethane, with a mechanism that is dependent on scan rate and influenced by the presence of a proton donor. When immersed in aqueous electrolyte, the reduction process exhibits a limited level of chemical reversibility. These data provide insights into the catalytic operation of these molecules during photo-assisted electrolysis of water and highlight the importance of the strongly electron-donating ligand environment about the manganese ions in the ability of the cubanes to photocatalyze water oxidation at low overpotentials. PMID:19809676

  5. Electrochemical protection of zirconium in oxidizing hydrochloric acid solutions

    SciTech Connect

    Yuu, T-L.; Maguire, M.

    1984-06-01

    An electrochemical protection technique using cathodic polarization to maintain zirconium below its critical repassivation potential was used to avoid pitting and stress corrosion cracking (SCC) in hydrochloric acid (HCI) containing ferric ions (Fe/sup +3/). Corrosion and pit penetration rates are reported for pickled, abraded, and as-received surface conditions in 10, 20, and 37% HCI containing 50, 100, or 500 ppm Fe/sup +3/ at temperatures to boiling. The pickled surface was the least susceptible to pitting in the 64 day tests. Electrochemical protection is then evaluated for total immersion, partial immersion, U-bend, and constant strain rate tensile tests. Protection is effective in eliminating pitting and SCC in 10 and 20% HCI containing Fe/sup +3/.

  6. Electrochemical protection of Zr against SCC by oxidizing HCl solutions

    SciTech Connect

    Yaiu, T.; Maguire, M.

    1985-07-01

    Results are reported for electrochemical protection of zirconium in HCl containing 500 ppm ferric ions. Corrosion rate and pit propagation rate data as a function of acid concentration (10 to 37%) and temperature (25 to 107 C) are presented first as a basis for observations of SCC and/or intergranular attack associated with weld metals. U-bend, C-ring, sustained load tensile, and slow strain-rate tests were used and compared to define conditions where SCC occurs. Along with electrochemical protection, heat treatment and reducing the ferric ion concentration are presented as ways to alleviate local attack. Metallography was used both to define the mode of attack and to show the benefits of protection techniques.

  7. Electrochemical oxidation of bisphenol-A from aqueous solution using graphite electrodes.

    PubMed

    Govindaraj, M; Rathinam, R; Sukumar, C; Uthayasankar, M; Pattabhi, S

    2013-01-01

    Electrochemical oxidation of bisphenol-A (BPA) from aqueous solution using graphite electrodes has been investigated. The effect of the types and concentration of supporting electrolytes, initial pH and applied current density on the performance of the process were examined. During electrolysis, concentration of BPA has been monitored and determined using UV-vis spectra, chemical oxygen demand (COD) and energy consumption. NaCl has been considered as the best supporting electrolyte among the electrolytes used in the present study. Initial pH 5.0, higher concentration (0.01 to 0.1 M) of supporting electrolyte and higher applied current density (4 to 20 mA cm(-2)) facilitate the treatment process. The maximum COD removal of 78.3% has been achieved under the optimal experimental conditions such as NaCl concentration of 0.05 M, applied current density of 12 mA cm(-2), initial pH 5.0 and electrolysis time of 120 min. When the energy consumption has been found to be decreasing with increasing NaCl concentration, it has increased with increasing applied current density. SEM-EDAX analysis has confirmed that the gases such as oxygen and chlorine are produced during the anodic oxidation in graphite anode. The result of UV-vis spectrum analysis confirms the degradation of BPA from aqueous solution at the end of the treatment. PMID:23530365

  8. Preparation, characterization, and electrochemical application of mesoporous copper oxide

    SciTech Connect

    Cheng, Liang; Shao, Mingwang; Chen, Dayan; Zhang, Yuzhong

    2010-02-15

    Mesoporous CuO was successfully synthesized via thermal decomposition of CuC{sub 2}O{sub 4} precursors. These products had ring-like morphology, which was made up of nanoparticles with the average diameter of 40 nm. The electrochemical experiments showed that the mesoporous CuO decreased the overvoltage of the electrode and increased electron transference in the measurement of dopamine.

  9. CO2 decomposition using electrochemical process in molten salts

    NASA Astrophysics Data System (ADS)

    Otake, Koya; Kinoshita, Hiroshi; Kikuchi, Tatsuya; Suzuki, Ryosuke O.

    2012-08-01

    The electrochemical decomposition of CO2 gas to carbon and oxygen gas in LiCl-Li2O and CaCl2-CaO molten salts was studied. This process consists of electrochemical reduction of Li2O and CaO, as well as the thermal reduction of CO2 gas by the respective metallic Li and Ca. Two kinds of ZrO2 solid electrolytes were tested as an oxygen ion conductor, and the electrolytes removed oxygen ions from the molten salts to the outside of the reactor. After electrolysis in both salts, the aggregations of nanometer-scale amorphous carbon and rod-like graphite crystals were observed by transmission electron microscopy. When 9.7 %CO2-Ar mixed gas was blown into LiCl-Li2O and CaCl2-CaO molten salts, the current efficiency was evaluated to be 89.7 % and 78.5 %, respectively, by the exhaust gas analysis and the supplied charge. When a solid electrolyte with higher ionic conductivity was used, the current and carbon production became larger. It was found that the rate determining step is the diffusion of oxygen ions into the ZrO2 solid electrolyte.

  10. Analysis of electrochemical noise by the stochastic process detector method

    SciTech Connect

    Roberge, P.R. . Dept. of Chemistry and Chemical Engineering)

    1994-07-01

    Electrochemical noise (EN) generated during the corrosion of metal specimens can be analyzed for its stochastic nature. Voltage fluctuations observed during the exposure of commercial aluminum (Al) sheet material were analyzed using a new technique based on randomness of these fluctuations. The stochastic process detector (SPD) technique was found to be very sensitive to the presence of deterministic features that are sometimes present in noise records. Results obtained with three orthogonal faces of Aluminum Association (AA) 7075-T6 Al alloy (UNS A97075) exposed to a saline solution were compared to electrochemical impedance spectroscopy (EIS) measurements and micrographs of exposed specimens. Some fundamental characteristics of voltage fluctuations revealed by SPD appeared to be related directly to the degree of localized corrosion in progress on the metal surfaces. The noise fluctuations' voltage rise times (RT) seemed to be related directly to the propensity of the AA 7075-T6 alloy tested to suffer from localized forms of corrosion visible under optical microscopy (OM). These findings agreed with variations observed in the constant-phase element (CPE) exponents, as calculated from EIS measurements, which also have been related to the degree of localized attack on corroding specimens.

  11. Electrochemical and structural properties of radio frequency sputtered cobalt oxide electrodes for thin-film supercapacitors

    NASA Astrophysics Data System (ADS)

    Kim, Han-Ki; Seong, Tae-Yeon; Lim, Jae-Hong; Cho, Won, Ii; Soo Yoon, Young

    The electrochemical and structural properties of cobalt oxide films which are deposited at different sputtering gas-ratios of O 2/(Ar+O 2) are investigated. In order to examine the electrochemical properties of the as-deposited films, all solid-state thin-film supercapacitors (TFSCs) are fabricated. There consist of Co 3O 4 electrodes and an amorphous LiPON thin-film electrolyte. It is shown that the capacitance behaviour of the Co 3O 4/LiPON/Co 3O 4 TFSCs is similar to bulk-type supercapacitor behaviour. It is further shown that the electrochemical behaviour of the TFSCs is dependent on the sputtering gas-ratios. The gas-ratio dependence of the capacitance of the oxide electrode films is discussed based on X-ray diffraction (XRD) and electrical results for the Co 3O 4 films.

  12. Photo-electrochemical Oxidation of Organic C1 Molecules over WO3 Films in Aqueous Electrolyte: Competition Between Water Oxidation and C1 Oxidation.

    PubMed

    Reichert, Robert; Zambrzycki, Christian; Jusys, Zenonas; Behm, R Jürgen

    2015-11-01

    To better understand organic-molecule-assisted photo-electrochemical water splitting, photo-electrochemistry and on-line mass spectrometry measurements are used to investigate the photo-electrochemical oxidation of the C1 molecules methanol, formaldehyde, and formic acid over WO3 film anodes in aqueous solution and its competition with O2 evolution from water oxidation O2 (+) and CO2 (+) ion currents show that water oxidation is strongly suppressed by the organic species. Photo-electro-oxidation of formic acid is dominated by formation of CO2 , whereas incomplete oxidation of formaldehyde and methanol prevails, with the selectivity for CO2 formation increasing with increasing potential and light intensity. The mechanistic implications for the photo-electro-oxidation of the organic molecules and its competition with water oxidation, which could be derived from this novel approach, are discussed. PMID:26382643

  13. Phenolic compounds as enhancers in enzymatic and electrochemical oxidation of veratryl alcohol and lignins.

    PubMed

    Díaz-González, María; Vidal, Teresa; Tzanov, Tzanko

    2011-03-01

    Sixteen phenolic compounds, 14 of which naturally occurring, were compared to the synthetic 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) and violuric acid (VA) in terms of their ability to act as mediators/enhancers in: (1) laccase oxidation of veratryl alcohol as a lignin model compound, and (2) electrochemical oxidation of kraft and flax lignins. HPLC analysis revealed that the syringyl-type phenols methyl syringate and acetosyringone were the most efficient natural enhancers in the laccase oxidation of veratryl alcohol. Both compounds, though far from the performance of ABTS were able to generate veratraldehyde in amount similar to that obtained with VA. By contrast, the best performing phenolic enhancers for the electrochemical oxidation of lignins were sinapinaldehyde, vanillin, acetovanillone, and syringic acid. Catalytic efficiencies close to those achieved with ABTS and VA were calculated for these phenolic compounds. PMID:21110019

  14. Electrochemical detection of nitric oxide production in perfused pig coronary artery: comparison of the performances of two electrochemical sensors.

    PubMed

    Villeneuve, N; Bedioui, F; Voituriez, K; Avaro, S; Vilaine, J P

    1998-08-01

    In situ direct measurement of nitric oxide (NO) in biological media is now possible by means of electrochemical detection. In the literature, there are principally two amperometric approaches based on the direct oxidation of NO either on a sensor made from platinum/ iridium (Pt/Ir) alloy coated with a three-layered membrane or on a nickel porphyrin and Nafion-coated carbon fiber electrode. Nonetheless, the exact nature of the experimental amperometric signal obtained with the Pt/Ir system was never authenticated as being related to NO. This study compared responses of two sensors to the inhibition effect of Nomega-nitro-L-arginine (L-NA) as the amperometric signals produced by 5-hydroxytryptamine (5-HT) on isolated pig coronary preparations. These amperometric signals could be attributed to NO only for the nickel porphyrin and Nafion-coated carbon fiber electrode. Indeed, voltammetric characterization of the electrochemical response demonstrated only variations of the baseline current upon additions of either SNAP or NO on the Pt/Ir electrode instead of anodic peak current displayed at 0.63-0.75 V for the other system. Nitrites induced baseline current variations with the Pt/Ir electrode, similar to those obtained with S-nitroso-N-acetyl-dl-penicillamine (SNAP) or NO. This study highlights the potential hazards and pitfalls that may be associated with the use of a Pt/Ir sensor calibrated with SNAP solutions for the detection of NO production in various biological systems. PMID:10100498

  15. Synthesis, optical and electrochemical properties of ZnO nanowires/graphene oxide heterostructures

    PubMed Central

    2013-01-01

    Large-scale vertically aligned ZnO nanowires with high crystal qualities were fabricated on thin graphene oxide films via a low temperature hydrothermal method. Room temperature photoluminescence results show that the ultraviolet emission of nanowires grown on graphene oxide films was greatly enhanced and the defect-related visible emission was suppressed, which can be attributed to the improved crystal quality and possible electron transfer between ZnO and graphene oxide. Electrochemical property measurement results demonstrated that the ZnO nanowires/graphene oxide have large integral area of cyclic voltammetry loop, indicating that such heterostructure is promising for application in supercapacitors. PMID:23522184

  16. Chemical and electrochemical oxidation of C8-arylamine adducts of 2′-deoxyguanosine

    PubMed Central

    Stover, James S.; Ciobanu, Madalina; Cliffel, David E.; Rizzo, Carmelo J.

    2008-01-01

    The electrochemical and chemical oxidation of a series of C8-arylamine adducts of 2′-deoxyguanosine has been examined. The oxidations were found to be reversible by cyclic and square-wave voltammetry in both aqueous buffer and aprotic organic solvent. The mechanism of the oxidation in protic media was either one- or two-electron depending on the aryl group. The chemical oxidation resulted in guanidinohydantoin and spiroiminodihydantoin rearrangement products similar to those observed for 8-oxo-7,8-dihydro-2′-deoxyguanosine. PMID:17256856

  17. Synthesis, optical and electrochemical properties of ZnO nanowires/graphene oxide heterostructures

    NASA Astrophysics Data System (ADS)

    Zeng, Huidan; Cao, Ying; Xie, Shufan; Yang, Junhe; Tang, Zhihong; Wang, Xianying; Sun, Luyi

    2013-03-01

    Large-scale vertically aligned ZnO nanowires with high crystal qualities were fabricated on thin graphene oxide films via a low temperature hydrothermal method. Room temperature photoluminescence results show that the ultraviolet emission of nanowires grown on graphene oxide films was greatly enhanced and the defect-related visible emission was suppressed, which can be attributed to the improved crystal quality and possible electron transfer between ZnO and graphene oxide. Electrochemical property measurement results demonstrated that the ZnO nanowires/graphene oxide have large integral area of cyclic voltammetry loop, indicating that such heterostructure is promising for application in supercapacitors.

  18. Electrochemical oxidation stability of anions for modern battery electrolytes: a CBS and DFT study.

    PubMed

    Jónsson, Erlendur; Johansson, Patrik

    2015-02-01

    The electrochemical stability vs. oxidation is a crucial property of anions in order to be suitable as components in lithium-ion batteries. Here the applicability of a number of computational approaches and methods to assess this property, employing a wide selection of DFT functionals, has been studied using the CCSD(T)/CBS method as the reference. In all, the vertical anion oxidation potential, ΔEv, is a fair way to calculate the stability vs. oxidation, however, a functional of at least hybrid quality is recommended. In addition, the chemical hardness, η, is identified as a novel approach to calculate the stability vs. oxidation. PMID:25557392

  19. Nitrogen doped holey graphene as an efficient metal-free multifunctional electrochemical catalyst for hydrazine oxidation and oxygen reduction

    NASA Astrophysics Data System (ADS)

    Yu, Dingshan; Wei, Li; Jiang, Wenchao; Wang, Hong; Sun, Bo; Zhang, Qiang; Goh, Kunli; Si, Rongmei; Chen, Yuan

    2013-03-01

    Electrocatalysts for anode or cathode reactions are at the heart of electrochemical energy conversion and storage devices. Molecular design of carbon based nanomaterials may create the next generation electrochemical catalysts for broad applications. Herein, we present the synthesis of a three-dimensional (3D) nanostructure with a large surface area (784 m2 g-1) composed of nitrogen doped (up to 8.6 at.%) holey graphene. The holey structure of graphene sheets (~25% of surface area is attributed to pores) engenders more exposed catalytic active edge sites. Nitrogen doping further improves catalytic activity, while the formation of the 3D porous nanostructure significantly reduces graphene nanosheet stacking and facilitates the diffusion of reactants/electrolytes. The three factors work together, leading to superb electrochemical catalytic activities for both hydrazine oxidation (its current generation ability is comparable to that of 10 wt% Pt-C catalyst) and oxygen reduction (its limiting current is comparable to that of 20 wt% Pt-C catalyst) with four-electron transfer processes and excellent durability.Electrocatalysts for anode or cathode reactions are at the heart of electrochemical energy conversion and storage devices. Molecular design of carbon based nanomaterials may create the next generation electrochemical catalysts for broad applications. Herein, we present the synthesis of a three-dimensional (3D) nanostructure with a large surface area (784 m2 g-1) composed of nitrogen doped (up to 8.6 at.%) holey graphene. The holey structure of graphene sheets (~25% of surface area is attributed to pores) engenders more exposed catalytic active edge sites. Nitrogen doping further improves catalytic activity, while the formation of the 3D porous nanostructure significantly reduces graphene nanosheet stacking and facilitates the diffusion of reactants/electrolytes. The three factors work together, leading to superb electrochemical catalytic activities for both

  20. A hydrophobic three-dimensionally networked boron-doped diamond electrode towards electrochemical oxidation.

    PubMed

    He, Yapeng; Lin, Haibo; Wang, Xue; Huang, Weimin; Chen, Rongling; Li, Hongdong

    2016-06-28

    A boron-doped diamond electrode with a three-dimensional network was fabricated on a mesh titanium substrate. Properties such as higher surface area, enhanced mass transfer and a hydrophobic surface endowed the prepared electrode with excellent electrochemical oxidation ability towards contaminants. PMID:27264247

  1. Electrochemically triggered release of human insulin from an insulin-impregnated reduced graphene oxide modified electrode.

    PubMed

    Teodorescu, Florina; Rolland, Laure; Ramarao, Viswanatha; Abderrahmani, Amar; Mandler, Daniel; Boukherroub, Rabah; Szunerits, Sabine

    2015-09-28

    An electrochemical insulin-delivery system based on reduced graphene oxide impregnated with insulin is described. Upon application of a potential pulse of -0.8 V for 30 min, up to 70 ± 4% of human insulin was released into a physiological medium while preserving its biological activity. PMID:26257079

  2. CO oxidation on stepped-Pt(111) under electrochemical conditions: insights from theory and experiment.

    PubMed

    Busó-Rogero, C; Herrero, E; Bandlow, J; Comas-Vives, A; Jacob, Timo

    2013-11-14

    The co-adsorption of CO and OH on two Pt stepped surfaces vicinal to the (111) orientation has been evaluated by means of density functional theory (DFT) calculations. Focusing on Pt(533) and Pt(221), which contain (100) and (111)-steps, respectively, we find that (111)-steps should be more reactive towards CO oxidation than surfaces containing (100)-steps. The DFT results are compared with electrochemical experiments on the CO adsorption and oxidation on these vicinal surfaces. PMID:24072258

  3. Oxygen vacancy diffusion across cathode/electrolyte interface in solid oxide fuel cells: An electrochemical phase-field model

    NASA Astrophysics Data System (ADS)

    Hong, Liang; Hu, Jia-Mian; Gerdes, Kirk; Chen, Long-Qing

    2015-08-01

    An electrochemical phase-field model is developed to study electronic and ionic transport across the cathode/electrolyte interface in solid oxide fuel cells. The influences of local current density and interfacial electrochemical reactions on the transport behaviors are incorporated. This model reproduces two electrochemical features. Nernst equation is satisfied through the thermodynamic equilibriums of the electron and oxygen vacancy. The distributions of charged species around the interface induce charge double layer. Moreover, we verify the nonlinear current/overpotential relationship. This model facilitates the exploration of problems in solid oxide fuel cells, which are associated with transport of species and electrochemical reactions at high operating temperature.

  4. Thermoelectric microdevice fabricated by a MEMS-like electrochemical process

    NASA Technical Reports Server (NTRS)

    Snyder, G. Jeffrey; Lim, James R.; Huang, Chen-Kuo; Fleurial, Jean-Pierre

    2003-01-01

    Microelectromechanical systems (MEMS) are the basis of many rapidly growing technologies, because they combine miniature sensors and actuators with communications and electronics at low cost. Commercial MEMS fabrication processes are limited to silicon-based materials or two-dimensional structures. Here we show an inexpensive, electrochemical technique to build MEMS-like structures that contain several different metals and semiconductors with three-dimensional bridging structures. We demonstrate this technique by building a working microthermoelectric device. Using repeated exposure and development of multiple photoresist layers, several different metals and thermoelectric materials are fabricated in a three-dimensional structure. A device containing 126 n-type and p-type (Bi, Sb)2Te3 thermoelectric elements, 20 microm tall and 60 microm in diameter with bridging metal interconnects, was fabricated and cooling demonstrated. Such a device should be of technological importance for precise thermal control when operating as a cooler, and for portable power when operating as a micro power generator.

  5. Electrochemical machining of super-hydrophobic Al surfaces and effect of processing parameters on wettability

    NASA Astrophysics Data System (ADS)

    Song, Jin-long; Xu, Wen-ji; Liu, Xin; Lu, Yao; Sun, Jing

    2012-09-01

    Super-hydrophobic aluminum (Al) surfaces were successfully fabricated via electrochemical machining in neutral NaClO3 electrolyte and subsequent fluoroalkylsilane (FAS) modification. The effects of the processing time, processing current density, and electrolyte concentration on the wettability, morphology, and roughness were studied. The surface morphology, chemical composition, and wettability of the Al surfaces were investigated using scanning electron microscopy (SEM) equipped with energy-dispersive spectroscopy (EDS), white-light interferometry, roughness measurements, X-ray diffraction (XRD), Fourier-transform infrared spectrometry (FTIR), and optical contact angle measurements. The results show that hierarchical rough structures and low surface energy films were present on the Al surfaces after electrochemical machining and FAS modification. The combination of the rough structures and the low surface energy materials plays a crucial role in achieving super-hydrophobicity. Compared with the anodic oxidation and chemical etching method, the method proposed in our work does not require strong acid or alkali, and causes less harm to the environment and operators but with high processing efficiency. The rough structures required by the super-hydrophobic surfaces were obtained at 30-s processing time and the best super-hydrophobicity with 164.6∘ water contact angle and 2∘ tilting angle was obtained at 360 s. The resulting super-hydrophobic Al surfaces have a long-time stability in air and an excellent resistance to corrosive liquids.

  6. Chemical and electrochemical study of fabrics coated with reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Molina, J.; Fernández, J.; del Río, A. I.; Bonastre, J.; Cases, F.

    2013-08-01

    Polyester fabrics coated with reduced graphene oxide (RGO) have been obtained and later characterized by means of chemical and electrochemical techniques. X-ray photoelectron spectroscopy showed a decrease of the oxygen content as well as an increase of the sp2 fraction after chemical reduction of graphene oxide (GO). The electrical conductivity was measured by electrochemical impedance spectroscopy (EIS) and showed a decrease of 5 orders of magnitude in the resistance (Ω) when GO was reduced to RGO. The phase angle also changed from 90° for PES-GO (capacitative behavior) to 0° for RGO coated fabrics (resistive behavior). In general an increase in the number of RGO layers produced an increase of the conductivity of the fabrics. EIS measurements in metal/sample/electrolyte configuration showed better electrocatalytic properties and faster diffusion rate for RGO specimens. Scanning electrochemical microscopy was employed to test the electroactivity of the different fabrics obtained. The sample coated with GO was not conductive since negative feedback was obtained. When GO was reduced to RGO the sample behaved like a conducting material since positive feedback was obtained. Approach curves indicated that the redox mediator had influence on the electrochemical response. The Fe(CN)63-/4- redox mediator produced a higher electrochemical response than Ru(NH3)63+/2+ one.

  7. Electrochemical Urea Biosensor Based on Sol-gel Derived Nanostructured Cerium Oxide

    NASA Astrophysics Data System (ADS)

    Ansari, Anees A.; Azahar, Md; Malhotra, B. D.

    2012-04-01

    Urease (Urs) and glutamate dehydrogenase (GLDH) have been co-immobilized onto a nanostructured-cerium oxide (Nano-CeO2) film deposited onto a indium-tin-oxide (ITO) coated glass substrate by dip-coating via sol-gel process for urea detection. This nanostructured film has characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR), Scanning electron microscope (SEM) and electrochemical techniques, respectively. The particle size of the Nano-CeO2 film has been found to be 23 nm. Electrochemcial response (CV) studies show that Ur-GLDH/Nano-CeO2/ITO bioelectrode is found to be sensitive in the 10-80 mg/dL urea concentration range and can detect urea concentration upto 0.1 mg/dL level. The value of Michaelis-Menten constant (Km) estimated using Lineweaver-Burke plot found as 6.09 mg/dL indicates enhancement in the affinity and/or activity of enzyme attached to their nanobiocomposite. This bioelectrode retained 95% of enzyme activity after 6 months at 4°C.

  8. Ferrate(VI) as a greener oxidant: Electrochemical generation and treatment of phenol.

    PubMed

    Sun, Xuhui; Zhang, Qi; Liang, He; Ying, Li; Xiangxu, Meng; Sharma, Virender K

    2016-12-01

    Ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) is a greener oxidant in the treatment of drinking water and wastewater. The electrochemical synthesis of Fe(VI) may be considered environmentally friendly because it involves one-step process to convert Fe(0) to Fe(VI) without using harmful chemicals. Electrolysis was performed by using a sponge iron as an anode in NaOH solution at different ionic strengths. The cyclic voltammetric (CV) curves showed that the sponge iron had higher electrical activity than the grey cast iron. The optimum current density was 0.054mAcm(-2) in 10M NaOH solution, which is much lower than the electrolyte concentrations used in other electrode materials. A comparison of current efficiency and energy consumption was conducted and is briefly discussed. The generated ferrate solution was applied to degrade phenol in water at two levels (2mgL(-1) and 5mgL(-1)). The maximum removal efficiency was ∼70% and the optimum pH for phenol treatment was 9.0. Experiments on phenol removal using conventional coagulants (ferric chloride (FeCl3) and polyaluminium chloride (PAC)) were performed independently to demonstrate that removal of phenol by Fe(VI) occurred mainly by oxidative transformation. A combination of Fe(VI) and coagulant may be advantageous in enhancing removal efficiency, adjusting pH, and facilitating flocculation. PMID:26738940

  9. Comparative studies on single-layer reduced graphene oxide films obtained by electrochemical reduction and hydrazine vapor reduction

    PubMed Central

    2012-01-01

    The comparison between two kinds of single-layer reduced graphene oxide (rGO) sheets, obtained by reduction of graphene oxide (GO) with the electrochemical method and hydrazine vapor reduction, referred to as E-rGO and C-rGO, respectively, is systematically studied. Although there is no morphology difference between the E-rGO and C-rGO films adsorbed on solid substrates observed by AFM, the reduction process to obtain the E-rGO and C-rGO films is quite different. In the hydrazine vapor reduction, the nitrogen element is incorporated into the obtained C-rGO film, while no additional element is introduced to the E-rGO film during the electrochemical reduction. Moreover, Raman spectra show that the electrochemical method is more effective than the hydrazine vapor reduction method to reduce the GO films. In addition, E-rGO shows better electrocatalysis towards dopamine than does C-rGO. This study is helpful for researchers to understand these two different reduction methods and choose a suitable one to reduce GO based on their experimental requirements. PMID:22373422

  10. Synthesis and Microstructural Characterization of Manganese Oxide Electrodes for Application as Electrochemical Supercapacitors

    NASA Astrophysics Data System (ADS)

    Babakhani, Banafsheh

    The aim of this thesis work was to synthesize Mn-based oxide electrodes with high surface area structures by anodic electrodeposition for application as electrochemical capacitors. Rod-like structures provide large surface areas leading to high specific capacitances. Since templated electrosynthesis of rods is not easy to use in practical applications, it is more desirable to form rod-like structures without using any templates. In this work, Mn oxide electrodes with rod-like structures (˜1.5 µm in diameter) were synthesized from a solution of 0.01 M Mn acetate under galvanostatic control without any templates, on Au coated Si substrates. The electrochemical properties of the synthesized nanocrystalline electrodes were investigated to determine the effect of morphology, chemistry and crystal structure on the corresponding electrochemical behavior of Mn oxide electrodes. Mn oxides prepared at different current densities showed a defective antifluoritetype crystal structure. The rod-like Mn oxide electrodes synthesized at low current densities (5 mAcm.2) exhibited a high specific capacitance due to their large surface areas. Also, specific capacity retention after 250 cycles in an aqueous solution of 0.5 M Na2SO4 at 100 mVs -1 was about 78% of the initial capacity (203 Fg-1 ). To improve the electrochemical capacitive behavior of Mn oxide electrodes, a sequential approach and a one-step method were adopted to synthesize Mn oxide/PEDOT electrodes through anodic deposition on Au coated Si substrates from aqueous solutions. In the former case, free standing Mn oxide rods (about 10 µm long and less than 1.5 µm in diameter) were first synthesized, then coated by electro-polymerization of a conducting polymer (PEDOT) giving coaxial rods. The one-step, co-electrodeposition method produced agglomerated Mn oxide/PEDOT particles. The electrochemical behavior of the deposits depended on the morphology and crystal structure of the fabricated electrodes, which were affected

  11. Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

    DOEpatents

    Rieke, Peter C.; Coffey, Gregory W.; Pederson, Larry R.; Marina, Olga A.; Hardy, John S.; Singh, Prabhaker; Thomsen, Edwin C.

    2010-07-20

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

  12. Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

    DOEpatents

    Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

    2010-03-02

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

  13. Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

    DOEpatents

    Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

    2010-11-23

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

  14. Radio frequency sputtered cobalt oxide coating: Structural, optical, and electrochemical characterization

    NASA Astrophysics Data System (ADS)

    Estrada, W.; Fantini, M. C. A.; de Castro, S. C.; Polo da Fonseca, C. N.; Gorenstein, A.

    1993-11-01

    Cobalt oxide thin films (thickness 2000 Å) with different stoichiometries were deposited by reactive rf sputtering. The variation of the oxygen partial pressure lead to films with compositions varying from metallic cobalt to CO3O4, as determined by x-ray diffraction and x-ray photoelectron spectroscopy. The electrochromic properties of the films were investigated in aqueous electrolytes (0.1 M KOH). The initial electrochemical behavior of the films is strongly dependent on the film deposition conditions, but after cycling the electrochemical/electrochromic characteristics of the different deposits were quite similar. Transmittance changes and electrochromic efficiency are discussed.

  15. Towards electrochemical purification of chemically reduced graphene oxide from redox accessible impurities.

    PubMed

    Tan, Shu Min; Ambrosi, Adriano; Khezri, Bahareh; Webster, Richard D; Pumera, Martin

    2014-04-21

    The electrochemical properties of graphene are highly sensitive to residual metallic impurities that persist despite various purification efforts. To accurately evaluate the electrochemical performance of graphene, highly purified materials free of metallic impurities are required. In this study, the partial purification of chemically reduced graphene oxides prepared via Hummers (CRGO-HU) and Staudenmaier (CRGO-ST) oxidation methods was performed through cyclic voltammetric (CV) scans executed in nitric acid, followed by CV measurements of cumene hydroperoxide (CHP). The purification of graphene was monitored by the changes in the peak current and potential of CHP which is sensitive to iron impurities. The CRGOs were characterised by inductively coupled plasma-mass spectrometry (ICP-MS), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and CV. The micrographs revealed CRGOs of similar morphologies, but with greater defects in CRGO-HU. The dependencies of CHP peak current and peak potential on the number of purification cycles exhibit greater efficiency of removing iron impurities from CRGO-HU than CRGO-ST. This can be attributed to the oxidative method that is used in CRGO-HU production, which exposes more defect sites for iron impurities to reside in. This facile electrochemical purification of graphenes can be utilised as a routine preparation and cleaning method of graphene before electrochemical measurements for analytes that show exceptional sensitivity towards electrocatalytic metallic impurities in sp(2) nanocarbon materials. PMID:24615543

  16. Modified cermet fuel electrodes for solid oxide electrochemical cells

    DOEpatents

    Ruka, Roswell J.; Spengler, Charles J.

    1991-01-01

    An exterior porous electrode (10), bonded to a solid oxygen ion conducting electrolyte (13) which is in contact with an interior electrode (14), contains coarse metal particles (12) of nickel and/or cobalt, having diameters from 3 micrometers to 35 micrometers, where the coarse particles are coated with a separate, porous, multiphase layer (17) containing fine metal particles of nickel and/or cobalt (18), having diameters from 0.05 micrometers to 1.75 micrometers and conductive oxide (19) selected from cerium oxide, doped cerium oxide, strontium titanate, doped strontium titanate and mixtures thereof.

  17. Graphene Oxide Modified TiO2 Micro Whiskers and Their Photo Electrochemical Performance.

    PubMed

    Rambabu, Y; Jaiswal, Manu; Roy, Somnath C

    2016-05-01

    Harnessing the solar energy and producing clean fuel hydrogen through efficient photo-electrochemical water splitting has remained one of the most challenging endeavors in materials science. The core problem is to develop a suitable photo-catalyst material that absorbs a significant part of the solar spectrum and produces electron-hole pairs that can be easily separated without recombination. In the recent times, the composite of Titanium dioxide with graphene have been investigated to explore the advantages of both class of materials. Here we report on the photo-electrochemical properties of reduced graphene oxide functionalised TiO2 whiskers. The TiO2 whiskers are obtained from potassium titanium oxide (KTi8O16) synthesized through hydrothermal technique followed by ion exchange method and heat treatment. Graphene oxide was deposited on the as prepared TiO2 whiskers using hydrothermal method. As formed samples were characterized by Raman spectroscopy to confirm the presence of reduced graphene oxide (RGO) attached to TiO2 whiskers. Comparative photo electrochemical studies were carried out for TiO2 and reduced graphene oxide modified TiO2 whiskers. Among these, RGO modified TiO2 whiskers show significantly higher photo current density possibly due to enhancement in charge separation ability and longer electron life times. PMID:27483830

  18. Recent advances in nanostructured Nb-based oxides for electrochemical energy storage

    NASA Astrophysics Data System (ADS)

    Yan, Litao; Rui, Xianhong; Chen, Gen; Xu, Weichuan; Zou, Guifu; Luo, Hongmei

    2016-04-01

    For the past five years, nanostructured niobium-based oxides have emerged as one of the most prominent materials for batteries, supercapacitors, and fuel cell technologies, for instance, TiNb2O7 as an anode for lithium-ion batteries (LIBs), Nb2O5 as an electrode for supercapacitors (SCs), and niobium-based oxides as chemically stable electrochemical supports for fuel cells. Their high potential window can prevent the formation of lithium dendrites, and their rich redox chemistry (Nb5+/Nb4+, Nb4+/Nb3+) makes them very promising electrode materials. Their unique chemical stability under acid conditions is favorable for practical fuel-cell operation. In this review, we summarized recent progress made concerning the use of niobium-based oxides as electrodes for batteries (LIBs, sodium-ion batteries (SIBs), and vanadium redox flow batteries (VRBs)), SCs, and fuel cell applications. Moreover, crystal structures, charge storage mechanisms in different crystal structures, and electrochemical performances in terms of the specific capacitance/capacity, rate capability, and cycling stability of niobium-based oxides are discussed. Insights into the future research and development of niobium-based oxide compounds for next-generation electrochemical devices are also presented. We believe that this review will be beneficial for research scientists and graduate students who are searching for promising electrode materials for batteries, SCs, and fuel cells.

  19. Recent advances in nanostructured Nb-based oxides for electrochemical energy storage.

    PubMed

    Yan, Litao; Rui, Xianhong; Chen, Gen; Xu, Weichuan; Zou, Guifu; Luo, Hongmei

    2016-04-28

    For the past five years, nanostructured niobium-based oxides have emerged as one of the most prominent materials for batteries, supercapacitors, and fuel cell technologies, for instance, TiNb2O7 as an anode for lithium-ion batteries (LIBs), Nb2O5 as an electrode for supercapacitors (SCs), and niobium-based oxides as chemically stable electrochemical supports for fuel cells. Their high potential window can prevent the formation of lithium dendrites, and their rich redox chemistry (Nb(5+)/Nb(4+), Nb(4+)/Nb(3+)) makes them very promising electrode materials. Their unique chemical stability under acid conditions is favorable for practical fuel-cell operation. In this review, we summarized recent progress made concerning the use of niobium-based oxides as electrodes for batteries (LIBs, sodium-ion batteries (SIBs), and vanadium redox flow batteries (VRBs)), SCs, and fuel cell applications. Moreover, crystal structures, charge storage mechanisms in different crystal structures, and electrochemical performances in terms of the specific capacitance/capacity, rate capability, and cycling stability of niobium-based oxides are discussed. Insights into the future research and development of niobium-based oxide compounds for next-generation electrochemical devices are also presented. We believe that this review will be beneficial for research scientists and graduate students who are searching for promising electrode materials for batteries, SCs, and fuel cells. PMID:27074412

  20. Electron transfer of Pseudomonas aeruginosa CP1 in electrochemical reduction of nitric oxide.

    PubMed

    Zhou, Shaofeng; Huang, Shaobin; He, Jiaxin; Li, Han; Zhang, Yongqing

    2016-10-01

    This study reports catalytic electro-chemical reduction of nitric oxide (NO) enhanced by Pseudomonas aeruginosa strain CP1. The current generated in the presence of bacteria was 4.36times that in the absence of the bacteria. The strain was able to catalyze electro-chemical reduction of NO via indirect electron transfer with an electrode, revealed by a series of cyclic voltammetry experiments. Soluble electron shuttles secreted into solution by live bacteria were responsible for the catalytic effects. The enhancement of NO reduction was also confirmed by detection of nitrous oxide; the level of this intermediate was 46.4% higher in the presence of bacteria than in controls, illustrated that the electron transfer pathway did not directly reduce nitric oxide to N2. The findings of this study may offer a new model for bioelectrochemical research in the field of NO removal by biocatalysts. PMID:27426634

  1. Development of graphene-nanometre-sized cerium oxide-incorporated aluminium and its electrochemical evaluation

    NASA Astrophysics Data System (ADS)

    Ashraf, P. Muhamed; Thomas, Saly N.; Edwin, Leela

    2016-02-01

    Graphene-nanometre-sized cerium oxide-incorporated aluminium was prepared and its electrochemical and surface morphological characteristics were studied. The atomic force micrographs and scanning electron micrographs evaluation highlighted that the graphene and nanometre-sized cerium oxide in aluminium had decreased the surface roughness and improved the surface morphological characteristics. The graphene: nanometre-sized cerium oxide (ratios 1:2 or 2:1) with lesser amounts of particle in the matrix showed excellent corrosion resistance in the marine environment as evidenced by linear polarization, electrochemical impedance and weight loss studies. Introduction of graphene in the aluminium matrix showed a barrier separation between the outermost layer and inner layer, increased roughness and increased corrosion. The material is found to be a potential candidate for use in marine environment.

  2. The electrochemical oxidation of toluene catalysed by Co(II) in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide.

    PubMed

    Balaji, S; Kannan, K; Moon, I S

    2015-12-14

    The electrochemical oxidation of toluene in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([bmpyr](+)[Ntf2](-)) was investigated by using cyclic voltammetry and galvanostatic electrolysis in the presence of Co(II) at a Pt disc working electrode. Cyclic voltammetry (CV) investigations revealed that Co(II)-Co(III) oxidation is a diffusion controlled electron transfer process. The diffusion coefficient values of Co(II) were found to increase from 0.38 × 10(-7) to 1.9 × 10(-7) cm(2) s(-1) as the temperature was increased from 25 °C to 80 °C. The CV peak current for toluene electro-oxidation increased by nearly 7 fold in the presence of Co(II) demonstrating a good catalytic effect. Co(II) catalysed galvanostatic electrolysis of toluene at room temperature has shown that benzaldehyde was formed along with a small quantity of 3-methyl-1-hexanol. PMID:26538114

  3. Polyaniline-grafted reduced graphene oxide for efficient electrochemical supercapacitors.

    PubMed

    Kumar, Nanjundan Ashok; Choi, Hyun-Jung; Shin, Yeon Ran; Chang, Dong Wook; Dai, Liming; Baek, Jong-Beom

    2012-02-28

    An alternative and effective route to prepare conducting polyaniline-grafted reduced graphene oxide (PANi-g-rGO) composite with highly enhanced properties is reported. In order to prepare PANi-g-rGO, amine-protected 4-aminophenol was initially grafted to graphite oxide (GO) via acyl chemistry where a concomitant partial reduction of GO occurred due to the refluxing and exposure of GO to thionyl chloride vapors and heating. Following the deprotection of amine groups, an in situ chemical oxidative grafting of aniline in the presence of an oxidizing agent was carried out to yield highly conducting PANi-g-rGO. Electron microscopic studies demonstrated that the resultant composite has fibrillar morphology with a room-temperature electrical conductivity as high as 8.66 S/cm and capacitance of 250 F/g with good cycling stability. PMID:22276770

  4. Morphological and electrochemical properties of crystalline praseodymium oxide nanorods.

    PubMed

    Shamshi Hassan, M; Shaheer Akhtar, M; Shim, Kyung-Bo; Yang, O-Bong

    2010-01-01

    Highly crystalline Pr6O11 nanorods were prepared by a simple precipitation method of triethylamine complex at 500°C. Synthesized Pr6O11 nanorods were uniformly grown with the diameter of 12-15 nm and the length of 100-150 nm without any impurities of unstable PrO2 phase. The Pr6O11 nanorod electrodes attained a high electrical conductivity of 0.954 Scm-1 with low activation energy of 0.594 eV at 850°C. The electrochemical impedance study showed that the resistance of electrode was significantly decreased at high temperature, which resulted from its high conductivity and low activation energy. The reduced impedance and high electrical conductivity of Pr6O11 nanorod electrodes are attributed to the reduction of grain boundaries and high space charge width. PMID:20672103

  5. Electrochemical iron generation: The ideal process for simultaneous removal of heavy metals from contaminated groundwater

    SciTech Connect

    Brewster, M.D.

    1993-12-31

    At most Superfund sites, many heavy metals must be removed from contaminated groundwater. Simultaneous extraction is complicated due to the various chemical properties that metals exhibit. A comprehensive understanding of solubilities, oxidation states, and adsorptive mechanisms is needed to accomplish treatment objectives. This paper uses data from treatability tests conducted on groundwater from the King of Prussia Technical Corporation Site to discuss the electrochemical iron generation process developed by Andco Environmental Processes, Inc. Electrical current and sacrificial steel electrodes were used to put ferrous ions into solution. The chemistry was properly manipulated to provide adsorption and coprecipitation conditions capable of simultaneously removing beryllium, cadmium, chromium, copper, iron, manganese, mercury, nickel, and zinc. Strict cleanup levels were required since the site is located within Pinelands National Reserve and adjacent to New Jersey`s Winslow Wildlife Refuge. System design, operating costs, and sludge production rate are also discussed.

  6. Effect of processing on structural features of anodic aluminum oxides

    NASA Astrophysics Data System (ADS)

    Erdogan, Pembe; Birol, Yucel

    2012-09-01

    Morphological features of the anodic aluminum oxide (AAO) templates fabricated by electrochemical oxidation under different processing conditions were investigated. The selection of the polishing parameters does not appear to be critical as long as the aluminum substrate is polished adequately prior to the anodization process. AAO layers with a highly ordered pore distribution are obtained after anodizing in 0.6 M oxalic acid at 20 °C under 40 V for 5 minutes suggesting that the desired pore features are attained once an oxide layer develops on the surface. While the pore features are not affected much, the thickness of the AAO template increases with increasing anodization treatment time. Pore features are better and the AAO growth rate is higher at 20 °C than at 5 °C; higher under 45 V than under 40 V; higher with 0.6 M than with 0.3 M oxalic acid.

  7. Enhancing electrochemical detection on graphene oxide-CNT nanostructured electrodes using magneto-nanobioprobes.

    PubMed

    Sharma, Priyanka; Bhalla, Vijayender; Dravid, Vinayak; Shekhawat, Gajendera; Jinsong-Wu; Prasad, E Senthil; Suri, C Raman

    2012-01-01

    Graphene and related materials have come to the forefront of research in electrochemical sensors during recent years due to the promising properties of these nanomaterials. Further applications of these nanomaterials have been hampered by insufficient sensitivity offered by these nanohybrids for the type of molecules requiring lower detection ranges. Here, we report a signal amplification strategy based on magneto-electrochemical immunoassay which combines the advantages of carbon nanotube and reduced graphene oxide together with electrochemical bursting of magnetic nanoparticles into a large number of metal ions. Sensitive detection was achieved by precisely designing the nanohybrid and correlating the available metal ions with analyte concentration. We confirmed the ultrahigh sensitivity of this method for a new generation herbicide diuron and its analogues up to sub-picomolar concentration in standard water samples. The novel immune-detection platform showed the excellent potential applicability in rapid and sensitive screening of environmental pollutants or toxins in samples. PMID:23166860

  8. Enhancing electrochemical detection on graphene oxide-CNT nanostructured electrodes using magneto-nanobioprobes

    PubMed Central

    Sharma, Priyanka; Bhalla, Vijayender; Dravid, Vinayak; Shekhawat, Gajendera; Jinsong-Wu, J W; Prasad, E. Senthil; Suri, C. Raman

    2012-01-01

    Graphene and related materials have come to the forefront of research in electrochemical sensors during recent years due to the promising properties of these nanomaterials. Further applications of these nanomaterials have been hampered by insufficient sensitivity offered by these nanohybrids for the type of molecules requiring lower detection ranges. Here, we report a signal amplification strategy based on magneto-electrochemical immunoassay which combines the advantages of carbon nanotube and reduced graphene oxide together with electrochemical bursting of magnetic nanoparticles into a large number of metal ions. Sensitive detection was achieved by precisely designing the nanohybrid and correlating the available metal ions with analyte concentration. We confirmed the ultrahigh sensitivity of this method for a new generation herbicide diuron and its analogues up to sub-picomolar concentration in standard water samples. The novel immune-detection platform showed the excellent potential applicability in rapid and sensitive screening of environmental pollutants or toxins in samples. PMID:23166860

  9. Mechanistic Study for Facile Electrochemical Patterning of Surfaces with Metal Oxides.

    PubMed

    Jones, Evan C; Liu, Qihan; Suo, Zhigang; Nocera, Daniel G

    2016-05-24

    Reactive interface patterning promoted by lithographic electrochemistry serves as a method for generating submicrometer scale structures. We use a binary-potential step on a metallic overlayer on silicon to fabricate radial patterns of cobalt oxide on the nanoscale. The mechanism for pattern formation has heretofore been ill-defined. The binary potential step allows the electrochemical boundary conditions to be controlled such that initial conditions for a scaling analysis are afforded. With the use of the scaling analysis, a mechanism for producing the observed pattern geometry is correlated to the sequence of electrochemical steps involved in the formation of the submicrometer structures. The patterning method is facile and adds to electrochemical micromachining techniques employing a silicon substrate. PMID:27072117

  10. Microgravity Processing of Oxide Superconductors

    NASA Technical Reports Server (NTRS)

    Olive, James R.; Hofmeister, William H.; Bayuzick, Robert J.; Vlasse, Marcus

    1999-01-01

    Considerable effort has been concentrated on the synthesis and characterization of high T(sub c) oxide superconducting materials. The YBaCuO system has received the most intense study, as this material has shown promise for the application of both thin film and bulk materials. There are many problems with the application of bulk materials- weak links, poor connectivity, small coherence length, oxygen content and control, environmental reactivity, phase stability, incongruent melting behavior, grain boundary contamination, brittle mechanical behavior, and flux creep. The extent to which these problems are intrinsic or associated with processing is the subject of controversy. This study seeks to understand solidification processing of these materials, and to use this knowledge for alternative processing strategies, which, at the very least, will improve the understanding of bulk material properties and deficiencies. In general, the phase diagram studies of the YBaCuO system have concentrated on solid state reactions and on the Y2BaCuO(x) + liquid yields YBa2Cu3O(7-delta) peritectic reaction. Little information is available on the complete melting relations, undercooling, and solidification behavior of these materials. In addition, rare earth substitutions such as Nd and Gd affect the liquidus and phase relations. These materials have promising applications, but lack of information on the high temperature phase relations has hampered research. In general, the understanding of undercooling and solidification of high temperature oxide systems lags behind the science of these phenomena in metallic systems. Therefore, this research investigates the fundamental melting relations, undercooling, and solidification behavior of oxide superconductors with an emphasis on improving ground based synthesis of these materials.

  11. Degradation of 1-hydroxy-2,4-dinitrobenzene from aqueous solutions by electrochemical oxidation: role of anodic material.

    PubMed

    Quiroz, Marco A; Sánchez-Salas, José L; Reyna, Silvia; Bandala, Erick R; Peralta-Hernández, Juan M; Martínez-Huitle, Carlos A

    2014-03-15

    Electrochemical oxidation (ECOx) of 1-hydroxy-2,4-dinitrobenzene (or 2,4-dinitrophenol: 2,4-DNP) in aqueous solutions by electrolysis under galvanostatic control was studied at Pb/PbO2, Ti/SnO2, Ti/IrxRuySnO2 and Si/BDD anodes as a function of current density applied. Oxidative degradation of 2,4-DNP has clearly shown that electrode material and the current density applied were important parameters to optimize the oxidation process. It was observed that 2,4-DNP was oxidized at few substrates to CO2 with different results, obtaining good removal efficiencies at Pb/PbO2, Ti/SnO2 and Si/BDD anodes. Trends in degradation way depend on the production of hydroxyl radicals (OH) on these anodic materials, as confirmed in this study. Furthermore, HPLC results suggested that two kinds of intermediates were generated, polyhydroxylated intermediates and carboxylic acids. The formation of these polyhydroxylated intermediates seems to be associated with the denitration step and substitution by OH radicals on aromatic rings, this being the first proposed step in the reaction mechanism. These compounds were successively oxidized, followed by the opening of aromatic rings and the formation of a series of carboxylic acids which were at the end oxidized into CO2 and H2O. On the basis of these information, a reaction scheme was proposed for each type of anode used for 2,4-D oxidation. PMID:24462986

  12. Electrochemical modification of the passive oxide layer on a Ti film observed by in situ neutron reflectometry

    SciTech Connect

    Tun, Z.; Noeel, J.J.; Shoesmith, D.W.

    1999-03-01

    Anodization and the effect of subsequently applying cathodic potential to a thin-film Ti electrode in an aqueous NaCl solution have been studied with in situ neutron reflectometry. This new technique provides further insight into the processes underlying anodic oxide formation and hydrogen absorption under cathodic polarization. The results (Pilling-Bedworth ratio, anodization ratio, the onset of fluctuations in electrode current under cathodic potential, etc.) are generally in agreement with the literature, but this new technique provides further insight into the electrochemical processes. The anodized oxide is observed to be not porous, and has the density of the rutile structure for its entire thickness. However, it comprises two distinct regions: an inner region similar in thickness and composition to the original air-grown oxide, and an outer region containing a significant amount of hydrogen. The similarity of the inner region to the original oxide suggests that the underlying oxide growth mechanism for Ti is the point-defect model. Under applied cathodic potentials the overall oxide thickness remains constant, but the inner region is gradually converted to a material similar in hydrogen content to the outer region. The onset of massive hydrogen penetration seems to occur when the conversion is complete, or when the inner region has been reduced to only a few atomic layers.

  13. Microgravity Processing of Oxide Superconductors

    NASA Technical Reports Server (NTRS)

    Hofmeister, William H.; Bayuzick, Robert J.; Vlasse, Marcus; McCallum, William; Peters, Palmer (Technical Monitor)

    2000-01-01

    The primary goal is to understand the microstructures which develop under the nonequilibrium solidification conditions achieved by melt processing in copper oxide superconductor systems. More specifically, to define the liquidus at the Y- 1:2:3 composition, the Nd-1:2:3 composition, and several intermediate partial substitution points between pure Y-1:2:3 and Nd-1:2:3. A secondary goal has been to understand resultant solidification morphologies and pathways under a variety of experimental conditions and to use this knowledge to better characterize solidification phenomena in these systems.

  14. Microfluidic Electrochemical Sensor for On-line Monitoring of Aerosol Oxidative Activity

    PubMed Central

    Sameenoi, Yupaporn; Koehler, Kirsten; Shapiro, Jeff; Boonsong, Kanokporn; Sun, Yele; Collett, Jeffrey; Volckens, John; Henry, Charles S.

    2012-01-01

    Particulate matter (PM) air pollution has a significant impact on human morbidity and mortality; however, the mechanisms of PM-induced toxicity are poorly defined. A leading hypothesis states that airborne PM induces harm by generating reactive oxygen species (ROS) in and around human tissues, leading to oxidative stress. We report here, a system employing a microfluidic electrochemical sensor coupled directly to a Particle-into-Liquid-Sampler (PILS) system to measure aerosol oxidative activity in an on-line format. The oxidative activity measurement is based on the dithiothreitol assay (DTT assay) where after oxidized by PM, the remaining reduced DTT was analyzed by the microfluidic sensor. The sensor consists of an array of working, reference, and auxiliary electrodes fabricated in a poly(dimethylsiloxane) (PDMS)-based microfluidic device. Cobalt (II) phthalocyanine (CoPC)-modified carbon paste was used as the working electrode material allowing selective detection of reduced DTT. The electrochemical sensor was validated off-line against the traditional DTT assay using filter samples taken from urban environments and biomass burning events. After off-line characterization, the sensor was coupled to a PILS to enable on-line sampling/analysis of aerosol oxidative activity. Urban dust and industrial incinerator ash samples were aerosolized in an aerosol chamber and analyzed for their oxidative activity. The on-line sensor reported DTT consumption rates (oxidative activity) in good correlation with aerosol concentration (R2 from 0.86–.97) with a time-resolution of approximately 3 minutes. PMID:22651886

  15. Inactivation of Microcystis aeruginosa by continuous electrochemical cycling process in tube using Ti/RuO2 electrodes.

    PubMed

    Liang, Wenyan; Qu, Jiuhui; Chen, Libin; Liu, Huijuan; Lei, Pengju

    2005-06-15

    Algae in waters often bring about influence in drinking water supplies. In this study, an electrochemical tube employing titanium coated with RuO2 as anode was constructed for inactivation of cyanobacteria (often called bluegreen algae) Microcystis aeruginosa. Suspensions containing M. aeruginosa (2-4 x 10(9) L(-1)) were exposed to current densities ranging from 1 to 10 mA cm(-2) in a detention time of 52 min. The variations of cell density, chlorophyll-a, optical density, pH, and conductivity were examined during the treatment. After 3.5 min the population of M. aeruginosa dropped rapidly and was reduced from 3 x 10(9) to 0.6 x 10(9) L(-1) after 52 min at current densities from 5 to 10 mA cm(-2). The cell density and optical density of M. aeruginosa decreased proportionally to the current density and the detention time. Scanning electron microscopy investigation of algae revealed surface damage and apparent leakage of intracellular contents after electrochemical cycling process. Due to the damage of cells, the chlorophyll-a released from the cells was degraded by electrochemical oxidation. The removal rate of chlorophyll-a could reach 96% at the current density of 10 mA cm(-2). Electrochemical treatment caused minor variation of pH values and conductivity of the suspensions. After electrochemical cycling processes, the optical density at 680 nm of algal cell suspensions remained below 0.1 after 6 days, and it showed that cells had no potential to survive and grow. The results implicated that the inactivation of M. aeruginosa was successfully performed by the electrochemical treatment, and it made the algal cells lose ability to survive, demonstrating the potential of such an alternative process for efficient water purification. PMID:16047803

  16. Melatonin involvement in oxidative processes.

    PubMed

    Ianăş, O; Olinescu, R; Bădescu, I

    1991-01-01

    The fact that the pineal gland, by its melatonin (MT) production, responds to environmental light variations (the day-night cycle), being also a modulator of the body adaptation to these conditions, may lead to the assumption of its involvement in the body oxidative processes. The redox capacity of melatonin was followed-up in vitro by the chemiluminescence phenomenon. The system generating chemiluminescence as well as free radicals was made up of luminol and H2O2. Incubation of melatonin in doses of 0.08-0.5 microM/ml with the generating system showed that in doses under 0.25 microM/ml melatonin has a pro-oxidative effect while in doses above this value it has an antioxidative effect. The diagram of the results shows the answer specific to a modulator. The study of the correlation between the dose of melatonin with highest pro-oxidative properties and the various peroxide concentrations in the generating system showed that melatonin gets antioxidative properties with the increase in peroxide concentrations (less than 8 mM/ml). In the presence of a hypothalamic homogenate, which is a stimulant of the chemiluminescence-generating system (PXI = 16), melatonin has a dose-dependent antioxidative effect. Similar results were also obtained by adding tryptophan--a free radicals acceptor (PXI = 0.1) and the substrate in melatonin synthesis to the reaction medium. Melatonin in low concentrations (greater than 0.1 microM/ml) has an antioxidative effect while in higher doses it has a dose-dependent pro-oxidative effect.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:1821072

  17. Effect of additives on electrochemical performance of lithium nickel cobalt manganese oxide at high temperature

    NASA Astrophysics Data System (ADS)

    Kang, Kyoung Seok; Choi, Suneui; Song, JunHo; Woo, Sang-Gil; Jo, Yong Nam; Choi, Jungkyu; Yim, Taeeun; Yu, Ji-Sang; Kim, Young-Jun

    2014-05-01

    Lithium-nickel-cobalt-manganese oxide, Li[NixCoyMnz]O2 (NCM) is a low-cost cathode material with a high capacity and a moderately high rate capability, however, it still suffers from poor electrochemical performance. In this study, several types of additives are attempted to enhance the surface stability of high-Ni-content (Ni ≥ 60%) cathodes and the most effective additive turns out to be PS. The cycle performance in the presence of 2% PS is much improved at a high temperature of 60 °C: (1) 98.9% of its initial capacity is preserved, (2) the increase in thickness is only 17.9%, preventing undesired swellings, and (3) gases are not generated in large amounts with the internal pressure being 56.4 kPa. The FT-IR spectroscopy results suggest that the surface of the cathode in the presence of 2% PS is covered with a film of alkyl sulfone components (RSOSR and RSO2SR), which is possibly formed by the electrochemical oxidation of PS. The current results confirm that the electrochemical performance of Ni-rich cathodes can be improved via the appropriate use of additives. They also indicate that among the tested additive candidates in this study, PS is highly desirable for enhancing the electrochemical performance of Ni-rich cathodes.

  18. Development of the chemical and electrochemical coal cleaning (CECC) process

    SciTech Connect

    Yoon, Roe-Hoan; Basilio, C.I.

    1992-05-01

    The Chemical and Electrochemical Coal Cleaning (CECC) process developed at Virginia Polytechnic Institute and State University was studied further in this project. This process offers a new method of physically cleaning both low- and high-rank coals without requiring fine grinding. The CECC process is based on liberating mineral matter from coal by osmotic pressure. The majority of the work was conducted on Middle Wyodak, Pittsburgh No. 8 and Elkhorn No. 3 coals. The coal samples were characterized for a variety of physical and chemical properties. Parametric studies were then conducted to identify the important operating parameters and to establish the optimum conditions. In addition, fundamental mechanisms of the process were studied, including mineral matter liberation, kinetics of mineral matter and pyrite dissolution, ferric ion regeneration schemes and alternative methods of separating the cleaned coal from the liberated mineral matter. The information gathered from the parametric and fundamental studies was used in the design, construction and testing of a bench-scale continuous CECC unit. Using this unit, the ash content of a Middle Wyodak coal was reduced from 6.96 to 1.61% at a 2 lbs/hr throughput. With an Elkhorn No. 3 sample, the ash content was reduced from 9.43 to 1.8%, while the sulfur content was reduced from 1.57 to 0.9%. The mass balance and liberation studies showed that liberation played a more dominant role than the chemical dissolution in removing mineral matter and inorganic sulfur from the different bituminous coals tested. However, the opposite was found to be the case for the Wyodak coal since this coal contained a significant amount of acid-soluble minerals.

  19. Design of a visible light driven photo-electrochemical/electro-Fenton coupling oxidation system for wastewater treatment.

    PubMed

    Ding, Xing; Ai, Zhihui; Zhang, Lizhi

    2012-11-15

    In this study, we report on a photo-electrochemical/electro-Fenton oxidation (PEC/EF) system by coupling visible light driven photo-electrochemical oxidation (PEC) and electro-Fenton oxidation (EF) in an undivided cell. Bi2WO6 nanoplates deposited on FTO glass (Bi2WO6/FTO) and Fe@Fe2O3 core-shell nanowires supported on activated carbon fiber (Fe@Fe2O3/ACF) were used as the anode and the cathode in the PEC/EF system, respectively. This novel PEC/EF system showed much higher activity than the single PEC and EF systems on degradation of rhodamine B in aqueous solution at natural pH. Moreover, the degradation and the instantaneous current efficiencies of the PEC/EF system were increased by 154% and 26% in comparison with the sum of those of single PEC and EF systems, respectively. These significant enhancements could be attributed to the synergetic effect from better separation of photo-generated carriers in the photo-anode and the transfer of photo-electrons to the oxygen diffusion cathode to generate more electro-generated H2O2 and hydroxyl radicals on the Fenton cathode. The better separation of photo-generated carriers contribute more to the overall degradation enhancement than the photo-electrons generated H2O2 and the subsequent Fenton reaction on the cathode during the PEC/EF process. PMID:23017238

  20. Technology advancement of the electrochemical CO2 concentrating process

    NASA Technical Reports Server (NTRS)

    Schubert, F. H.; Woods, R. R.; Hallick, T. M.; Heppner, D. B.

    1978-01-01

    The overall objectives of the present program are to: (1) improve the performance of the electrochemical CO2 removal technique by increasing CO2 removal efficiencies at pCO2 levels below 400 Pa, increasing cell power output and broadening the tolerance of electrochemical cells for operation over wide ranges of cabin relative humidity; (2) design, fabricate, and assemble development hardware to continue the evolution of the electrochemical concentrating technique from the existing level to an advanced level able to efficiently meet the CO2 removal needs of a spacecraft air revitalization system (ARS); (3) develop and incorporate into the EDC the components and concepts that allow for the efficient integration of the electrochemical technique with other subsystems to form a spacecraft ARS; (4) combine ARS functions to enable the elimination of subsystem components and interfaces; and (5) demonstrate the integration concepts through actual operation of a functionally integrated ARS.

  1. Strongly improved electrochemical cycling durability by adding iridium to electrochromic nickel oxide films.

    PubMed

    Wen, Rui-Tao; Niklasson, Gunnar A; Granqvist, Claes G

    2015-05-13

    Anodically colored nickel oxide (NiO) thin films are of much interest as counter electrodes in tungsten oxide based electrochromic devices such as "smart windows" for energy-efficient buildings. However, NiO films are prone to suffering severe charge density degradation upon prolonged electrochemical cycling, which can lead to insufficient device lifetime. Therefore, a means to improve the durability of NiO-based films is an important challenge at present. Here we report that the incorporation of a modest amount of iridium into NiO films [Ir/(Ir + Ni) = 7.6 atom %] leads to remarkable durability, exceeding 10000 cycles in a lithium-conducting electrolyte, along with significantly improved optical modulation during extended cycling. Structure characterization showed that the face-centered-cubic-type NiO structure remained after iridium addition. Moreover, the crystallinity of these films was enhanced upon electrochemical cycling. PMID:25919917

  2. Electrochemical sensing of glucose by reduced graphene oxide-zinc ferrospinels

    NASA Astrophysics Data System (ADS)

    Shahnavaz, Zohreh; Woi, Pei Meng; Alias, Yatimah

    2016-08-01

    We have developed ZnFe2O4 magnetic nanoparticles/reduced graphene oxide nanosheets modified glassy carbon (ZnFe2O4/rGO/GCE) electrode as a novel system for the electrochemical glucose sensing. Via a facile in situ hydrothermal route, the reduction of GO and the formation of ZnFe2O4 nanoparticles occurred simultaneously. This enables the ZnFe2O4 nanoparticles dispersed on the reduced graphene sheet. Characterization of nanocomposite by X-ray diffraction (XRD) and transmission electron microscopy (TEM) clearly demonstrate the successful attachment of ZnFe2O4 nanoparticles to graphene sheets. Electrochemical studies revealed that the ZnFe2O4/rGO/GCE possess excellent electrocatalytic activities toward the oxidation of glucose and the performance of sensor is enhanced by integration of graphene nanosheets with ZnFe2O4 nanoparticles.

  3. Electrochemical impedance spectroscopy studies of lithium diffusion in doped manganese oxide

    SciTech Connect

    Johnson, B.J.; Doughty, D.H.; Voigt, J.A.; Boyle, T.J.

    1996-06-01

    Cathode performance is critical to lithium ion rechargeable battery performance; effects of doping lithium manganese oxide cathode materials on cathode performance are being investigated. In this paper, Li diffusion in Al-doped LiMn{sub 2}O{sub 4} was studied and found to be controlled by the quantity of Al dopant. Electrochemical cycling was conducted at 0.5mA/cm{sub 2}; electrochemical impedance spectra were taken at open circuit potential, with impedance being measured at 65 kHz-0.01 Hz. As the Al dopant level was increased, the Li diffusion rate decreased; this was attributed to the decreased lattice parameter of the doped oxide.

  4. An electrochemical approach to graphene oxide coated sulfur for long cycle life

    NASA Astrophysics Data System (ADS)

    Moon, Joonhee; Park, Jungjin; Jeon, Cheolho; Lee, Jouhahn; Jo, Insu; Yu, Seung-Ho; Cho, Sung-Pyo; Sung, Yung-Eun; Hong, Byung Hee

    2015-07-01

    Owing to the possibilities of achieving high theoretical energy density and gravimetric capacity, sulfur has been considered as a promising cathode material for rechargeable lithium batteries. However, sulfur shows rapid capacity fading due to the irreversible loss of soluble polysulfides and the decrease in active sites needed for conducting agents. Furthermore, the low electrical conductivity of sulfur hampers the full utilization of active materials. Here we report that graphene oxide coated sulfur composites (GO-S/CB) exhibit improved electrochemical stability as well as enhanced rate performance, evidenced by various electrochemical analyses. The cyclic voltammetry and the galvanostatic cycling analysis revealed that the GO plays key roles in homogenizing the nanocomposite structures of the electrodes, in improving the electrochemical contact, and in minimizing the loss of soluble polysulfide intermediates. An electrochemical impedance spectroscopy analysis also confirms the enhanced structural stability of the GO-S/CB composites after battery operation. As a result, the GO-S/CB exhibited excellent cycle stability and specific capacity as high as ~723.7 mA h g-1 even after 100 cycles at 0.5 C.Owing to the possibilities of achieving high theoretical energy density and gravimetric capacity, sulfur has been considered as a promising cathode material for rechargeable lithium batteries. However, sulfur shows rapid capacity fading due to the irreversible loss of soluble polysulfides and the decrease in active sites needed for conducting agents. Furthermore, the low electrical conductivity of sulfur hampers the full utilization of active materials. Here we report that graphene oxide coated sulfur composites (GO-S/CB) exhibit improved electrochemical stability as well as enhanced rate performance, evidenced by various electrochemical analyses. The cyclic voltammetry and the galvanostatic cycling analysis revealed that the GO plays key roles in homogenizing the

  5. Thermoelectric microdevice fabricated by a MEMS-like electrochemical process.

    PubMed

    Snyder, G Jeffrey; Lim, James R; Huang, Chen-Kuo; Fleurial, Jean-Pierre

    2003-08-01

    Microelectromechanical systems (MEMS) are the basis of many rapidly growing technologies, because they combine miniature sensors and actuators with communications and electronics at low cost. Commercial MEMS fabrication processes are limited to silicon-based materials or two-dimensional structures. Here we show an inexpensive, electrochemical technique to build MEMS-like structures that contain several different metals and semiconductors with three-dimensional bridging structures. We demonstrate this technique by building a working microthermoelectric device. Using repeated exposure and development of multiple photoresist layers, several different metals and thermoelectric materials are fabricated in a three-dimensional structure. A device containing 126 n-type and p-type (Bi, Sb)2Te3 thermoelectric elements, 20 microm tall and 60 microm in diameter with bridging metal interconnects, was fabricated and cooling demonstrated. Such a device should be of technological importance for precise thermal control when operating as a cooler, and for portable power when operating as a micro power generator. PMID:12883550

  6. Studies of electrochemical oxidation of Zircaloy nuclear reactor fuel cladding using time-of-flight-energy elastic recoil detection analysis

    NASA Astrophysics Data System (ADS)

    Whitlow, H. J.; Zhang, Y.; Wang, Y.; Winzell, T.; Simic, N.; Ahlberg, E.; Limbäck, M.; Wikmark, G.

    2000-03-01

    The trend towards increased fuel burn-up and higher operating temperatures in order to achieve more economic operation of nuclear power plants places demands on a better understanding of oxidative corrosion of Zircaloy (Zry) fuel rod cladding. As part of a programme to study these processes we have applied time-of-flight-energy elastic recoil detection (ToF-E ERD), electrochemical impedance measurements and scanning electron microscopy to quantitatively characterise thin-oxide films corresponding to the pre-transition oxidation regime. Oxide films of different nominal thickness in the 9-300 nm range were grown on a series of rolled Zr and Zry-2 plates by anodisation in dilute H 2SO 4 with applied voltages. The dielectric thickness of the oxide layer was determined from the electrochemical impedance measurements and the surface topography characterised by scanning electron microscopy. ToF-E ERD with a 60 MeV 127I 11+ ion beam was used to determine the oxygen content and chemical composition of the oxide layer. In the Zr samples, the oxygen content (O atom cm -2) that was determined by ERD was closely similar to the O content derived from impedance measurements from the dielectric film. The absolute agreement was well within the uncertainty associated with the stopping powers. Moreover, the measured composition of the thick oxide layers corresponded to ZrO 2 for the films thicker than 65 nm where the oxide layer was resolved in the ERD depth profile. Zry-2 samples exhibited a similar behaviour for small thickness ( ⩽130 nm) but had an enhanced O content at larger thicknesses that could be associated either with enhanced rough surface topography or porous oxide formation that was correlated with the presence of Second Phase Particles (SPP) in Zry-2. The concentration of SPP elements (Fe, Cr, Ni) in relation to Zr was the same in the outer 9×10 17 atom cm -2 of oxide as in the same thickness of metal. The results also revealed the presence of about 1 at.% 32S in the

  7. Voltage equilibration for reactive atomistic simulations of electrochemical processes

    SciTech Connect

    Onofrio, Nicolas; Strachan, Alejandro

    2015-08-07

    We introduce electrochemical dynamics with implicit degrees of freedom (EChemDID), a model to describe electrochemical driving force in reactive molecular dynamics simulations. The method describes the equilibration of external electrochemical potentials (voltage) within metallic structures and their effect on the self-consistent partial atomic charges used in reactive molecular dynamics. An additional variable assigned to each atom denotes the local potential in its vicinity and we use fictitious, but computationally convenient, dynamics to describe its equilibration within connected metallic structures on-the-fly during the molecular dynamics simulation. This local electrostatic potential is used to dynamically modify the atomic electronegativities used to compute partial atomic changes via charge equilibration. Validation tests show that the method provides an accurate description of the electric fields generated by the applied voltage and the driving force for electrochemical reactions. We demonstrate EChemDID via simulations of the operation of electrochemical metallization cells. The simulations predict the switching of the device between a high-resistance to a low-resistance state as a conductive metallic bridge is formed and resistive currents that can be compared with experimental measurements. In addition to applications in nanoelectronics, EChemDID could be useful to model electrochemical energy conversion devices.

  8. Mediated electrochemical oxidation of organic wastes using a Co(III) mediator in a neutral electrolyte

    DOEpatents

    Balazs, G. Bryan; Lewis, Patricia R.

    1999-01-01

    An electrochemical cell with a Co(III) mediator and neutral pH anolyte provides efficient destruction of organic and mixed wastes. The organic waste is concentrated in the anolyte reservoir, where the cobalt mediator oxidizes the organics and insoluble radioactive species and is regenerated at the anode until all organics are converted to carbon dioxide and destroyed. The neutral electrolyte is non-corrosive, and thus extends the lifetime of the cell and its components.

  9. Mediated electrochemical oxidation of organic wastes using a Co(III) mediator in a neutral electrolyte

    DOEpatents

    Balazs, G.B.; Lewis, P.R.

    1999-07-06

    An electrochemical cell with a Co(III) mediator and neutral pH anolyte provides efficient destruction of organic and mixed wastes. The organic waste is concentrated in the anolyte reservoir, where the cobalt mediator oxidizes the organics and insoluble radioactive species and is regenerated at the anode until all organics are converted to carbon dioxide and destroyed. The neutral electrolyte is non-corrosive, and thus extends the lifetime of the cell and its components. 2 figs.

  10. One step hydrothermal synthesis of a carbon nanotube/cerium oxide nanocomposite and its electrochemical properties

    NASA Astrophysics Data System (ADS)

    Kalubarme, Ramchandra S.; Kim, Yong-Han; Park, Chan-Jin

    2013-09-01

    A carbon nanotube (CNT)/cerium oxide composite was prepared by a one-pot hydrothermal reaction in the presence of KOH and capping agent polyvinylpyrrolidone. The nanocomposite displayed pronounced capacitive behaviour with very small diffusion resistance. The electrochemical performance of the composite electrode in a symmetric supercapacitor displayed a high energy density of 35.9 Wh kg-1 corresponding to a specific capacitance of 289 F g-1. These composite electrodes also demonstrated a long cycle life with better capacity retention.

  11. An Investigation into the Effect of a Post-electroplating Electrochemical Oxidation Treatment on Tin Whisker Formation

    NASA Astrophysics Data System (ADS)

    Ashworth, M. A.; Haspel, D.; Wu, L.; Wilcox, G. D.; Mortimer, R. J.

    2015-01-01

    Since the `cracked oxide theory' was proposed by Tu in 1994,1 there has only been a limited number of studies that have sought to investigate the effect of the Sn oxide on whisker growth. The current study has used electrochemical oxidation to produce oxide films, which has enabled the effect of the surface oxide thickness on whisker growth to be established. The effect of oxide thickness on whisker growth has been investigated for tin electrodeposits on both Cu and brass substrates. The influence of applied oxidation potential on the thickness of the Sn oxide film has been investigated using x-ray photoelectron spectroscopy (XPS) for potassium bicarbonate-carbonate and borate buffer electrolyte solutions. Whisker growth from electrochemically oxidised Sn-Cu deposits on Cu and Sn deposits on brass has been investigated and compared with samples left to develop a native air-formed oxide. XPS studies show that the thickness of the electrochemically formed Sn oxide film is dependent on the applied oxidation potential and the total charge passed. Subsequent whisker growth studies demonstrate that electrochemically oxidised Sn-Cu deposits on Cu and Sn deposits on brass are significantly less susceptible to whisker growth than those having a native oxide film. For Sn deposits on brass, the electrochemically formed Sn oxide greatly reduces Zn oxide formation at the surface of the tin deposit, which results in whisker mitigation. For Sn-Cu deposits on Cu, the reduction in whisker growth must simply derive from the increased thickness of the Sn oxide, i.e. the Sn oxide film has an important role in stemming the development of whiskers.

  12. Synthesis of gallium nitride nanostructures by nitridation of electrochemically deposited gallium oxide on silicon substrate

    PubMed Central

    2014-01-01

    Gallium nitride (GaN) nanostructures were successfully synthesized by the nitridation of the electrochemically deposited gallium oxide (Ga2O3) through the utilization of a so-called ammoniating process. Ga2O3 nanostructures were firstly deposited on Si substrate by a simple two-terminal electrochemical technique at a constant current density of 0.15 A/cm2 using a mixture of Ga2O3, HCl, NH4OH and H2O for 2 h. Then, the deposited Ga2O3 sample was ammoniated in a horizontal quartz tube single zone furnace at various ammoniating times and temperatures. The complete nitridation of Ga2O3 nanostructures at temperatures of 850°C and below was not observed even the ammoniating time was kept up to 45 min. After the ammoniating process at temperature of 900°C for 15 min, several prominent diffraction peaks correspond to hexagonal GaN (h-GaN) planes were detected, while no diffraction peak of Ga2O3 structure was detected, suggesting a complete transformation of Ga2O3 to GaN. Thus, temperature seems to be a key parameter in a nitridation process where the deoxidization rate of Ga2O3 to generate gaseous Ga2O increase with temperature. The growth mechanism for the transformation of Ga2O3 to GaN was proposed and discussed. It was found that a complete transformation can not be realized without a complete deoxidization of Ga2O3. A significant change of morphological structures takes place after a complete transformation of Ga2O3 to GaN where the original nanorod structures of Ga2O3 diminish, and a new nanowire-like GaN structures appear. These results show that the presented method seems to be promising in producing high-quality h-GaN nanostructures on Si. PMID:25593562

  13. Electrochemical components employing polysiloxane-derived binders

    DOEpatents

    Delnick, Frank M.

    2013-06-11

    A processed polysiloxane resin binder for use in electrochemical components and the method for fabricating components with the binder. The binder comprises processed polysiloxane resin that is partially oxidized and retains some of its methyl groups following partial oxidation. The binder is suitable for use in electrodes of various types, separators in electrochemical devices, primary lithium batteries, electrolytic capacitors, electrochemical capacitors, fuel cells and sensors.

  14. Highly Selective Oxidation of Carbohydrates in an Efficient Electrochemical Energy Converter: Cogenerating Organic Electrosynthesis.

    PubMed

    Holade, Yaovi; Servat, Karine; Napporn, Teko W; Morais, Cláudia; Berjeaud, Jean-Marc; Kokoh, Kouakou B

    2016-02-01

    The selective electrochemical conversion of highly functionalized organic molecules into electricity, heat, and added-value chemicals for fine chemistry requires the development of highly selective, durable, and low-cost catalysts. Here, we propose an approach to make catalysts that can convert carbohydrates into chemicals selectively and produce electrical power and recoverable heat. A 100% Faradaic yield was achieved for the selective oxidation of the anomeric carbon of glucose and its related carbohydrates (C1-position) without any function protection. Furthermore, the direct glucose fuel cell (DGFC) enables an open-circuit voltage of 1.1 V in 0.5 m NaOH to be reached, a record. The optimized DGFC delivers an outstanding output power Pmax =2 mW cm(-2) with the selective conversion of 0.3 m glucose, which is of great interest for cogeneration. The purified reaction product will serve as a raw material in various industries, which thereby reduces the cost of the whole sustainable process. PMID:26777210

  15. COD and color removal of reactive orange 16 dye solution by electrochemical oxidation and adsorption method

    NASA Astrophysics Data System (ADS)

    Zakaria, Zuhailie; Ahmad, Wan Yaacob Wan; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali

    2015-09-01

    Degradation of Reactive Orange 16 (RO16) dye was investigated using electrochemical oxidation and adsorption (batch method) using mixture of coconut trunk charcoal-graphite-tin-polyvinyl chloride(PVC). In batch studies for adsorbents pellet and powder form of the charcoal mixture were used. RO16 was chosen as the model dye because of its high resistance towards conventional treatment methods. NaCl and RO16 concentration, treatment duration, weight of electrode and adsorbent and volume of solution were kept constant for both methods. The effectiveness of the treatments were compared and evaluated by percentage of RO16 decolorization and chemical oxygen demand (COD) removal and results indicated that electrochemical oxidation method ables to decolorized RO16 dye up to 98.5% after 20 minutes electrolysis time while pellet and powder in batch method only removed 17.1 and 33.6% of RO16 color respectively. However, only 45.6% of COD can be removed using electrochemical oxidation method while pellet and powder in batch method removed 47.8 and 49.6% of COD respectively. The decolorization and COD removal of RO16 was determined using UV-Vis spectrophotometer (by the changes of absorption spectrum intensity of azo chromophore (-N=N-) at λ=388 and 492.50 nm and Hach spectrophotometer respectively. FTIR was used to determine functional groups present in the coconut trunk charcoal.

  16. Electrochemical oxidation of the carbide wastes of hard alloys using alternating current

    NASA Astrophysics Data System (ADS)

    Bryukvin, V. A.; Palant, A. A.; Levchuk, O. M.; Tsybin, O. I.

    2012-03-01

    The electrochemical oxidation of the carbide wastes of a W-Co alloy has been studied by gas, electron-probe microanalysis, and X-ray diffraction analyses. The experiments are carried out using halfwave sinusoidal alternating current. It is established that a CO2 + CO mixture forms under such conditions in a gaseous phase in volumetric ratio of 2: 1 and that a tungsten deposit forms in an anode sludge mainly in the form of hydrated tungsten oxide WO2(OH)2. Marketable products are obtained in the form of pure CO3O4 and WO3.

  17. The electrochemical oxidation of methanol on a Pt/TNTs/Ti electrode enhanced by illumination

    NASA Astrophysics Data System (ADS)

    Wang, Y. Q.; Wei, Z. D.; Gao, B.; Qi, X. Q.; Li, L.; Zhang, Q.; Xia, M. R.

    A Pt/TNTs/Ti electrode is prepared by electrochemically depositing Pt using the modulated pulse current method onto high density, well ordered and uniformly distributed TiO 2 nanotubes (TNTs) on a Ti substrate. The results show that the performance and anti-poison ability of the Pt/TNTs/Ti electrode for methanol electro-oxidation under illumination is remarkably enhanced and is even better than the best bi-metallic Pt-Ru catalysts. CO poisoning is no longer a problem during methanol electro-oxidation with the Pt/TNTs/Ti electrode under illumination.

  18. Experimental study on electrochemical hydrogen pump of SrZrO{sub 3}-based oxide

    SciTech Connect

    Tanaka, M.; Asakura, Y.; Uda, T.

    2008-07-15

    The electrochemical hydrogen pump properties of the SrZr{sub 0.8}In{sub 0.2}O{sub 3-{alpha}} proton conducting oxide were evaluated under various atmospheres, temperatures and the effect of oxygen gas in the cathode for the recovery of hydrogen isotopes. It was found that high temperature is not necessarily required and protonic conductivity of the proton conducting oxide rather than total conductivity should be observed to improve the performance of the hydrogen pump. Furthermore, the presence of oxygen in the cathode compartment plays an important role in the enhancement of the hydrogen pump performance. (authors)

  19. Method of making sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

    DOEpatents

    Isenberg, Arnold O.

    1989-01-01

    An electrochemical apparatus is made containing an exterior electorde bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

  20. Preparation of silver nanoparticles/graphene nanosheets as a catalyst for electrochemical oxidation of methanol

    SciTech Connect

    Han, Kun; Miao, Peng; Tang, Yuguo; Tong, Hui; Zhu, Xiaoli; Liu, Tao; Cheng, Wenbo

    2014-02-03

    In this report, silver nanoparticles (AgNPs) decorated graphene nanosheets have been prepared based on the reduction of Ag ions by hydroquinone, and their catalytic performance towards the electrochemical oxidation of methanol is investigated. The synthesis of the nano-composite is confirmed by transmission electron microscope measurements and UV-vis absorption spectra. Excellent electrocatalytic performance of the material is demonstrated by cyclic voltammograms. This material also contributes to the low peak potential of methanol oxidation compared with most of the other materials.

  1. In situ monitoring of discharge/charge processes in Li-O2 batteries by electrochemical impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Landa-Medrano, Imanol; Ruiz de Larramendi, Idoia; Ortiz-Vitoriano, Nagore; Pinedo, Ricardo; Ignacio Ruiz de Larramendi, José; Rojo, Teófilo

    2014-03-01

    Gaining insight into the reaction mechanisms underway during charge and discharge in Li-air batteries is essential to allow the target development of improved power and performance devices. This work reports the in situ monitoring of Li-air cells by electrochemical impedance spectroscopy and, for the first time, the development of an electrochemical model allowing the identification and attribution of the processes involved. The voltage at which each reaction product forms has been identified, including Li2O2 or Li2CO3 during discharge, together with the delithiation of the outer part of Li2O2 and oxidation reactions and electrolyte decomposition. The developed model can be used as a valuable tool for the optimisation of composition and structure of the air electrode through the investigation of the resistance associated with each process.

  2. Writable electrochemical energy source based on graphene oxide

    PubMed Central

    Wei, Di

    2015-01-01

    Graphene oxide (GO) was mainly used as raw material for various types of reduced graphene oxide (rGO) as a cost effective method to make graphene like materials. However, applications of its own unique properties such as extraordinary proton conductivity and super-permeability to water were overlooked. Here GO based battery-like planar energy source was demonstrated on arbitrary insulating substrate (e.g. polymer sheet/paper) by coating PEDOT, GO ink and rGO on Ag charge collectors. Energy from such GO battery depends on its length and one unit cell with length of 0.5 cm can generate energy capacity of 30 Ah/L with voltage up to 0.7 V when room temperature ionic liquid (RTIL) is added. With power density up to 0.4 W/cm3 and energy density of 4 Wh/L, GO battery was demonstrated to drive an electrochromic device. This work is the first attempt to generate decent energy using the fast transported water molecules inside GO. It provides very safe energy source that enables new applications otherwise traditional battery technology can not make including building a foldable energy source on paper and platform for futuristic wearable electronics. A disposable energy source made of GO was also written on a plastic glove to demonstrate wearability. PMID:26462557

  3. Electrochemically-Controlled Compositional Oscillations of Oxide Surfaces

    SciTech Connect

    Mutoro, Eva; Crumlin, Ethan; Pöpke, Hendrik; Luerssen, Bjoern; Amati, Matteo; Abyaneh, Majid; Biegalski, Michael D; Christen, Hans M; Gregoratti, Luca; Janek, Jürgen; Shao-Horn, Yang

    2012-01-01

    Perovskite oxides can exhibit a wide range of interesting characteristics such as being catalytically active and electronically and/or ionically conducting, and thus they have been used in a number of solid-state devices such as solid oxide fuel cells and sensors. As the surface compositions of perovskites can greatly influence the catalytic properties, knowing and controlling their surface chemistries is crucial to enhance device performance. In this study, we demonstrate that the surface strontium (Sr) and cobalt (Co) concentrations of perovskite-based thin films can be controlled reversibly at elevated temperatures by applying small electrical potential biases. The surface chemistry changes of La0.8Sr0.2CoO3 (LSC113), LaSrCoO4 (LSC214), and LSC214-decorated LSC113 films (LSC113/214) were investigated in situ by utilizing synchrotron-based X-ray photoelectron spectroscopy (XPS), where the largest changes of surface Sr was found for the LSC113/214 surface. These findings offer the potential of reversibly controlling the surface functionality of perovskites.

  4. Writable electrochemical energy source based on graphene oxide.

    PubMed

    Wei, Di

    2015-01-01

    Graphene oxide (GO) was mainly used as raw material for various types of reduced graphene oxide (rGO) as a cost effective method to make graphene like materials. However, applications of its own unique properties such as extraordinary proton conductivity and super-permeability to water were overlooked. Here GO based battery-like planar energy source was demonstrated on arbitrary insulating substrate (e.g. polymer sheet/paper) by coating PEDOT, GO ink and rGO on Ag charge collectors. Energy from such GO battery depends on its length and one unit cell with length of 0.5 cm can generate energy capacity of 30 Ah/L with voltage up to 0.7 V when room temperature ionic liquid (RTIL) is added. With power density up to 0.4 W/cm(3) and energy density of 4 Wh/L, GO battery was demonstrated to drive an electrochromic device. This work is the first attempt to generate decent energy using the fast transported water molecules inside GO. It provides very safe energy source that enables new applications otherwise traditional battery technology can not make including building a foldable energy source on paper and platform for futuristic wearable electronics. A disposable energy source made of GO was also written on a plastic glove to demonstrate wearability. PMID:26462557

  5. Writable electrochemical energy source based on graphene oxide

    NASA Astrophysics Data System (ADS)

    Wei, Di

    2015-10-01

    Graphene oxide (GO) was mainly used as raw material for various types of reduced graphene oxide (rGO) as a cost effective method to make graphene like materials. However, applications of its own unique properties such as extraordinary proton conductivity and super-permeability to water were overlooked. Here GO based battery-like planar energy source was demonstrated on arbitrary insulating substrate (e.g. polymer sheet/paper) by coating PEDOT, GO ink and rGO on Ag charge collectors. Energy from such GO battery depends on its length and one unit cell with length of 0.5 cm can generate energy capacity of 30 Ah/L with voltage up to 0.7 V when room temperature ionic liquid (RTIL) is added. With power density up to 0.4 W/cm3 and energy density of 4 Wh/L, GO battery was demonstrated to drive an electrochromic device. This work is the first attempt to generate decent energy using the fast transported water molecules inside GO. It provides very safe energy source that enables new applications otherwise traditional battery technology can not make including building a foldable energy source on paper and platform for futuristic wearable electronics. A disposable energy source made of GO was also written on a plastic glove to demonstrate wearability.

  6. Cobalt Oxide Nanoflowers for Electrochemical Determination of Glucose

    NASA Astrophysics Data System (ADS)

    Balouch, Quratulain; Ibupoto, Zafar Hussain; Khaskheli, Ghulam Qadir; Soomro, Razium Ali; Sirajuddin; Samoon, Muhammad Kashif; Deewani, Vinod Kumar

    2015-10-01

    This study reports a simple, economic, and efficient approach for synthesis of cobalt oxide (Co3O4) nanostructures by a low-temperature aqueous chemical growth method. The synthesized Co3O4 nanostructures were characterized by various techniques such as x-ray diffraction, x-ray photoelectron spectroscopy, and scanning electron microscopy. The synthesized nanostructures exhibited flower-shaped morphology with thickness of each pellet in the range of 200 to 300 nm. The synthesized Co3O4 nanostructures with excellent structural features exhibited high electrocatalytic activity towards the oxidation of glucose in alkaline solution. This enabled development of a highly sensitive (1618.71 µA mM-1 cm-2), stable and reproducible non-enzymatic glucose sensor. The developed sensor demonstrated high anti-interference capability against common interferents such as dopamine, ascorbic acid and uric acid. Furthermore, the applicability of the developed sensor for the determination of glucose from human blood serum provides an alternative approach for the routine glucose analysis.

  7. Treatment of synthetic urine by electrochemical oxidation using conductive-diamond anodes.

    PubMed

    Dbira, Sondos; Bensalah, Nasr; Bedoui, Ahmed; Cañizares, Pablo; Rodrigo, Manuel A

    2015-04-01

    In this work, the electrochemical oxidation of synthetic urine by anodic oxidation using boron-doped diamond as anode and stainless steel as cathode was investigated. Results show that complete depletion of chemical oxygen demand (COD) and total organic carbon (TOC) can be attained regardless of the current density applied in the range 20-100 mA cm(-2). Oxalic and oxamic acids, and, in lower concentrations, creatol and guanidine were identified as the main intermediates. Chloride ions play a very important role as mediators and contribute not only to obtain a high efficiency in the removal of the organics but also to obtain an efficient removal of nitrogen by the transformation of the various raw nitrogen species into gaseous nitrogen through chloramine formation. The main drawback of the technology is the formation of chlorates and perchlorates as final chlorine products. The increase of current density from 20 to 60 mA cm(-2) led to an increase in the rate of COD and TOC removals although the process becomes less efficient in terms of energy consumption (removals of COD and TOC after applying 18 Ah dm(-3) were 93.94 and 94.94 %, respectively, at 20 mA cm(-2) and 89.17 and 86.72 %, respectively, at 60 mA cm(-2)). The most efficient conditions are low current densities and high temperature reaching total mineralization at an applied charge as low as 20 kAh m(-3). This result confirmed that the electrolysis using diamond anodes is a very interesting technology for the treatment of urine. PMID:25399531

  8. Electrochemical Oxidative Amination of Sodium Sulfinates: Synthesis of Sulfonamides Mediated by NH4I as a Redox Catalyst.

    PubMed

    Jiang, Yang-Ye; Wang, Qing-Qing; Liang, Sen; Hu, Li-Ming; Little, R Daniel; Zeng, Cheng-Chu

    2016-06-01

    An efficient protocol for the synthesis of sulfonamides via the electrochemical oxidative amination of sodium sulfinates has been developed. The chemistry proceeds in a simple undivided cell employing a substoichiometric amount of NH4I that serves both as a redox catalyst and a supporting electrolyte; in this manner additional conducting salt is not required. A wide range of substrates, including aliphatic or aromatic secondary and primary amines, as well as aqueous ammonia, proved to be compatible with the protocol. Scale-up was possible, thereby demonstrating the practicality of the approach. The electrolytic process avoids the utilization of external oxidants or corrosive molecular iodine and therefore represents an environmentally benign means by which to achieve the transformation. PMID:27137813

  9. Effect of the iridium oxide thin film on the electrochemical activity of platinum nanoparticles.

    PubMed

    Chen, Aicheng; La Russa, Daniel J; Miller, Brad

    2004-10-26

    The influence of the iridium oxide thin film on the electrocatalytic properties of platinum nanoparticles was investigated using the electro-oxidation of methanol and CO as a probe. The presence of the IrO(2) thin film leads to the homogeneous dispersion of Pt nanoparticles. For comparison, polycrystalline platinum and Pt nanoparticles dispersed on a Ti substrate in the absence of an IrO(2) layer (Ti/Pt) were also investigated in this study. Inverted and enhanced CO bipolar peaks were observed using an in situ electrochemical Fourier transform infrared technique during the methanol oxidation on the Pt nanoparticles dispersed on a Ti substrate. Electrochemical impedance studies showed that the charge transfer resistance was significantly lower for the Ti/IrO(2)/Pt electrode compared with that of the massive Pt and Ti/Pt nanoparticles. The presence of the IrO(2) thin film not only greatly increases the active surface area but also promotes CO oxidation at a much lower electrode potential, thus, significantly enhancing the electrocatalytic activity of Pt nanoparticles toward methanol electro-oxidation. PMID:15491204

  10. High-temperature "spectrochronopotentiometry": correlating electrochemical performance with in situ Raman spectroscopy in solid oxide fuel cells.

    PubMed

    Kirtley, John D; Halat, David M; McIntyre, Melissa D; Eigenbrodt, Bryan C; Walker, Robert A

    2012-11-20

    Carbon formation or "coking" on solid oxide fuel cell (SOFC) anodes adversely affects performance by blocking catalytic sites and reducing electrochemical activity. Quantifying these effects, however, often requires correlating changes in SOFC electrochemical efficiency measured during operation with results from ex situ measurements performed after the SOFC has been cooled and disassembled. Experiments presented in this work couple vibrational Raman spectroscopy with chronopotentiometry to observe directly the relationship between graphite deposited on nickel cermet anodes and the electrochemical performance of SOFCs operating at 725 °C. Raman spectra from Ni cermet anodes at open circuit voltage exposed to methane show a strong vibrational band at 1556 cm(-1) assigned to the "G" mode of highly ordered graphite. When polarized in the absence of a gas-phase fuel, these carbon-loaded anodes operate stably, oxidizing graphite to form CO and CO(2). Disappearance of graphite intensity measured in the Raman spectra is accompanied by a steep ∼0.8 V rise in the cell potential needed to keep the SOFC operating under constant current conditions. Continued operation leads to spectroscopically observable Ni oxidation and another steep rise in cell potential. Time-dependent spectroscopic and electrochemical measurements pass through correlated equivalence points providing unequivocal, in situ evidence that identifies how SOFC performance depends on the chemical condition of its anode. Chronopotentiometric data are used to quantify the oxide flux necessary to eliminate the carbon initially present on the SOFC anode, and data show that the oxidation mechanisms responsible for graphite removal correlate directly with the electrochemical condition of the anode as evidenced by voltammetry and impedance measurements. Electrochemically oxidizing the Ni anode damages the SOFC significantly and irreversibly. Anodes that have been reconstituted following electrochemical oxidation of

  11. Nanoparticle shape evolution and proximity effects during tip-induced electrochemical processes

    DOE PAGESBeta

    Yang, Sangmo; Paranthaman, Mariappan Parans; Noh, Tae Won; Kalinin, Sergei V.; Strelcov, Evgheni

    2016-01-08

    The voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When themore » grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag+/Ag redox reaction to Ag+-ion diffusion with the increase in the applied voltage and pulse duration. Our study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities.« less

  12. Nanoparticle Shape Evolution and Proximity Effects During Tip-Induced Electrochemical Processes.

    PubMed

    Yang, Sang Mo; Paranthaman, Mariappan Parans; Noh, Tae Won; Kalinin, Sergei V; Strelcov, Evgheni

    2016-01-26

    Voltage spectroscopies in scanning probe microscopy (SPM) techniques are widely used to investigate the electrochemical processes in nanoscale volumes, which are important for current key applications, such as batteries, fuel cells, catalysts, and memristors. The spectroscopic measurements are commonly performed on a grid of multiple points to yield spatially resolved maps of reversible and irreversible electrochemical functionalities. Hence, the spacing between measurement points is an important parameter to be considered, especially for irreversible electrochemical processes. Here, we report nonlocal electrochemical dynamics in chains of Ag particles fabricated by the SPM tip on a silver ion solid electrolyte. When the grid spacing is small compared with the size of the formed Ag particles, anomalous chains of unequally sized particles with double periodicity evolve. This behavior is ascribed to a proximity effect during the tip-induced electrochemical process, specifically, size-dependent silver particle growth following the contact between the particles. In addition, fractal shape evolution of the formed Ag structures indicates that the growth-limiting process changes from Ag(+)/Ag redox reaction to Ag(+)-ion diffusion with the increase in the applied voltage and pulse duration. This study shows that characteristic shapes of the electrochemical products are good indicators for determining the underlying growth-limiting process, and emergence of complex phenomena during spectroscopic mapping of electrochemical functionalities. PMID:26743324

  13. Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

    NASA Astrophysics Data System (ADS)

    Gupta, Sanju; Price, Carson

    2015-10-01

    Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO)1, (PPy/ErGO)1, (PAni/GO)1 and (PPy/GO)1. The rationale design is to create thin films that possess interconnected graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, Cs, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent Cs of ≥350 F g-1 as compared with constituents (˜70 F g-1) at discharge current density of 0.3 A g-1 that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine electrochemical (re)activity of surface ion adsorption sites

  14. Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

    SciTech Connect

    Gupta, Sanju Price, Carson

    2015-10-15

    Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO){sub 1}, (PPy/ErGO){sub 1}, (PAni/GO){sub 1} and (PPy/GO){sub 1}. The rationale design is to create thin films that possess interconnected graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, C{sub s}, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent C{sub s} of ≥350 F g{sup −1} as compared with constituents (∼70 F g{sup −1}) at discharge current density of 0.3 A g{sup −1} that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine

  15. Electrochemical oxidation of 243Am(III) in nitric acid by a terpyridyl-derivatized electrode

    SciTech Connect

    Dares, C. J.; Lapides, A. M.; Mincher, B. J.; Meyer, T. J.

    2015-11-05

    A high surface area, tin-doped indium oxide electrode surface-derivatized with a terpyridine ligand has been applied to the oxidation of trivalent americium to Am(V) and Am(VI) in nitric acid. Potentials as low as 1.8 V vs. the saturated calomel electrode are used, 0.7 V lower than the 2.6 V potential for one-electron oxidation of Am(III) to Am(IV) in 1 M acid. This simple electrochemical procedure provides, for the first time, a method for accessing the higher oxidation states of Am in non-complexing media for developing the coordination chemistries of Am(V) and Am(VI) and, more importantly, for separation of americium from nuclear waste streams.

  16. Solar-powered electrochemical oxidation of organic compounds coupled with the cathodic production of molecular hydrogen.

    PubMed

    Park, Hyunwoong; Vecitis, Chad D; Hoffmann, Michael R

    2008-08-21

    A Bi-doped TiO2 anode, which is prepared from a mixed metal oxide coating deposited on Ti metal, is shown to be efficient for conventional water splitting. In this hybrid photovoltaic-electrochemical system, a photovoltaic (PV) cell is used to convert solar light to electricity, which is then used to oxidize a series of phenolic compounds at the semiconductor anode to carbon dioxide with the simultaneous production of molecular hydrogen from water/proton reduction at the stainless steel cathode. Degradation of phenol in the presence of a background NaCl electrolyte produces chlorinated phenols as reaction intermediates, which are subsequently oxidized completely to carbon dioxide and low-molecular weight carboxylic acids. The anodic current efficiency for the complete oxidation of phenolic compounds ranges from 3% to 17%, while the cathodic current efficiency and the energy efficiency for hydrogen gas generation range from 68% to 95% and 30% to 70%, respectively. PMID:18656909

  17. Electrochemical properties of highly degenerate and low cost cadmium oxide thin films

    NASA Astrophysics Data System (ADS)

    Mundinamani, S. P.; Rabinal, M. K.

    2015-11-01

    In the present work, we describe a simple and easy method for the deposition of nanostructured cadmium oxide films on glass by spray pyrolysis. The electrochemical capacitive properties of these films have been studied for different electrolyte species under the different scan rates. The present results show a high value of specific capacitance of 18 F g-1 in 1 M NaOH electrolyte for the scan rate of 10 mV s-1. This value of specific capacitance is the highest ever reported value for cadmium oxide thin films. These results emphasize that the ion diffusion between the electrode and the electrolyte is significantly high due to the highly porous nanostructure of cadmium oxide and these results confirms the cadmium oxide as a capacitive material. The constructed devices were stable even after the 1000 cycle.

  18. Electrochemical oxidation of hydrazine and its derivatives on the surface of metal electrodes in alkaline media

    NASA Astrophysics Data System (ADS)

    Asazawa, Koichiro; Yamada, Koji; Tanaka, Hirohisa; Taniguchi, Masatoshi; Oguro, Keisuke

    Electrochemical oxidation of hydrazine and its derivatives on the surface of various metal electrodes in alkaline media was investigated. A comparison of various polycrystalline metal electrodes (Ni, Co, Fe, Cu, Ag, Au, and Pt) showed that Co and Ni electrodes have a lower onset potential for hydrazine oxidation than the Pt electrode. The onset oxidation potential of APA (aminopolyacrylamide), a hydrazine derivative (-0.127 V vs. reversible hydrogen electrode, RHE), was similar to that of hydrazine hydrate (-0.178 V vs. RHE) in the case of the Co electrode. APA oxidation was possible because of hydrazine desorption that was caused by APA hydrolysis. The hydrolysis reaction was brought about by a heat treatment. This result suggests that the hydrazine hydrolysis reaction of hydrazine derivatives makes it possible to store hydrazine hydrate safely.

  19. Surface Stress during Electro-Oxidation of Carbon Monoxide and Bulk Stress Evolution during Electrochemical Intercalation of Lithium

    NASA Astrophysics Data System (ADS)

    Mickelson, Lawrence

    2011-12-01

    This work investigates in-situ stress evolution of interfacial and bulk processes in electrochemical systems, and is divided into two projects. The first project examines the electrocapillarity of clean and CO-covered electrodes. It also investigates surface stress evolution during electro-oxidation of CO at Pt{111}, Ru/Pt{111} and Ru{0001} electrodes. The second project explores the evolution of bulk stress that occurs during intercalation (extraction) of lithium (Li) and formation of a solid electrolyte interphase during electrochemical reduction (oxidation) of Li at graphitic electrodes. Electrocapillarity measurements have shown that hydrogen and hydroxide adsorption are compressive on Pt{111}, Ru/Pt{111}, and Ru{0001}. The adsorption-induced surface stresses correlate strongly with adsorption charge. Electrocatalytic oxidation of CO on Pt{111} and Ru/Pt{111} gives a tensile surface stress. A numerical method was developed to separate both current and stress into background and active components. Applying this model to the CO oxidation signal on Ru{0001} gives a tensile surface stress and elucidates the rate limiting steps on all three electrodes. The enhanced catalysis of Ru/Pt{111} is confirmed to be bi-functional in nature: Ru provides adsorbed hydroxide to Pt allowing for rapid CO oxidation. The majority of Li-ion batteries have anodes consisting of graphite particles with polyvinylidene fluoride (PVDF) as binder. Intercalation of Li into graphite occurs in stages and produces anisotropic strains. As batteries have a fixed size and shape these strains are converted into mechanical stresses. Conventionally staging phenomena has been observed with X-ray diffraction and collaborated electrochemically with the potential. Work herein shows that staging is also clearly observed in stress. The Li staging potentials as measured by differential chronopotentiometry and stress are nearly identical. Relative peak heights of Li staging, as measured by these two

  20. Preparation and electrochemical performances of nanoporous/cracked cobalt oxide layer for supercapacitors

    NASA Astrophysics Data System (ADS)

    Gobal, Fereydoon; Faraji, Masoud

    2014-12-01

    Nanoporous/cracked structures of cobalt oxide (Co3O4) electrodes were successfully fabricated by electroplating of zinc-cobalt onto previously formed TiO2 nanotubes by anodizing of titanium, leaching of zinc in a concentrated alkaline solution and followed by drying and annealing at 400 °C. The structure and morphology of the obtained Co3O4 electrodes were characterized by X-ray diffraction, EDX analysis and scanning electron microscopy. The results showed that the obtained Co3O4 electrodes were composed of the nanoporous/cracked structures with an average pore size of about 100 nm. The electrochemical capacitive behaviors of the nanoporous Co3O4 electrodes were investigated by cyclic voltammetry, galvanostatic charge-discharge studies and electrochemical impedance spectroscopy in 1 M NaOH solution. The electrochemical data demonstrated that the electrodes display good capacitive behavior with a specific capacitance of 430 F g-1 at a current density of 1.0 A g-1 and specific capacitance retention of ca. 80 % after 10 days of being used in electrochemical experiments, indicating to be promising electroactive materials for supercapacitors. Furthermore, in comparison with electrodes prepared by simple cathodic deposition of cobalt onto TiO2 nanotubes(without dealloying procedure), the impedance studies showed improved performances likely due to nanoporous/cracked structures of electrodes fabricated by dealloying of zinc, which provide fast ion and electron transfer routes and large reaction surface area with the ensued fast reaction kinetics.

  1. Voltammetric Scanning Electrochemical Cell Microscopy: Dynamic Imaging of Hydrazine Electro-oxidation on Platinum Electrodes.

    PubMed

    Chen, Chang-Hui; Jacobse, Leon; McKelvey, Kim; Lai, Stanley C S; Koper, Marc T M; Unwin, Patrick R

    2015-06-01

    Voltammetric scanning electrochemical cell microscopy (SECCM) incorporates cyclic voltammetry measurements in the SECCM imaging protocol, by recording electrochemical currents in a wide potential window at each pixel in a map. This provides much more information compared to traditional fixed potential imaging. Data can be represented as movies (hundreds of frames) of current (over a surface region) at a series of potentials and are highly revealing of subtle variations in electrode activity. Furthermore, by combining SECCM data with other forms of microscopy, e.g. scanning electron microscopy and electron backscatter diffraction data, it is possible to directly relate the current-voltage characteristics to spatial position and surface structure. In this work we use a "hopping mode", where the SECCM pipet probe is translated toward the surface at a series of positions until meniscus contact. Small amounts of residue left on the surface, upon probe retraction, demark the precise area of each measurement. We use these techniques to study hydrazine oxidation on a polycrystalline platinum substrate both in air and in a deaerated environment. In both cases, the detected faradaic current shows a structural dependence on the surface crystallographic orientation. Significantly, in the presence of oxygen (aerated solution) the electrochemical current decreases strongly for almost all grains (crystallographic orientations). The results highlight the flexibility of voltammetric SECCM for electrochemical imaging and present important implications for hydrazine electroanalysis. PMID:25942527

  2. Electrochemical processes at solid electrode-electrolyte-gas interfaces

    SciTech Connect

    Youngblood, G.E.; Weber, W.J; Bates, J.L.

    1991-05-01

    Electrochemical reactions at solid electrolyte-electrode-gas interfaces are being investigated with ac impedance and dc polarization techniques using an unbonded interface cell (UIC). The UIC approach eliminates influence of sample size and interface morphology resulting from electrode-electrolyte fabrication. The electrochemical reactions of oxygen with solid electrode (La{sub 1-x}Sr{sub x}MnO{sub 3} or Pt) and solid electrolyte (0.08Y{sub 2}O{sub 3} - 0.92ZrO{sub 2}) interfaces are described. 6 refs., 4 figs., 2 tabs.

  3. Electrochemical photovoltaic cells and electrodes

    DOEpatents

    Skotheim, Terje A.

    1984-01-01

    Improved electrochemical photovoltaic cells and electrodes for use therein, particularly electrodes employing amorphous silicon or polyacetylene coating are produced by a process which includes filling pinholes or porous openings in the coatings by electrochemical oxidation of selected monomers to deposit insulating polymer in the openings.

  4. Electrochemical characterisation of solid oxide cell electrodes for hydrogen production

    NASA Astrophysics Data System (ADS)

    Bernuy-Lopez, Carlos; Knibbe, Ruth; He, Zeming; Mao, Xiaojian; Hauch, Anne; Nielsen, Karsten A.

    Oxygen electrodes and steam electrodes are designed and tested to develop improved solid oxide electrolysis cells for H 2 production with the cell support on the oxygen electrode. The electrode performance is evaluated by impedance spectroscopy testing of symmetric cells at open circuit voltage (OCV) in a one-atmosphere set-up. For the oxygen electrode, nano-structured La 0.75Sr 0.25MnO 3 (LSM25) is impregnated into a LSM25/yttria stabilised zirconia (YSZ) composite, whereas for the steam electrode, nano-structured Ni and Ce 0.8Gd 0.2O 2- δ (CGO) is impregnated into a Sr 0.94Ti 0.9Nb 0.10O 3- δ (STN) backbone. In the present study, the best performing oxygen electrode is a LSM25-YSZ composite with 20% porosity and impregnated with a LSM25 solution measuring a polarisation resistance (R p) of 0.12 Ω cm 2 at 850 °C in oxygen. For the steam electrode, the best performance is obtained for a STN backbone, sintered at 1200 °C and impregnated with CGO/Ni, with an R p of 0.08 Ω cm 2 at 850 °C in 3% H 2O/H 2.

  5. Non-covalent functionalization of graphene oxide by polyindole and subsequent incorporation of Ag nanoparticles for electrochemical applications

    NASA Astrophysics Data System (ADS)

    Dubey, Prashant; Kumar, Ashish; Prakash, Rajiv

    2015-11-01

    Reduced graphene oxide (r-GO) sheets have been modified by polyindole (PIn) via in situ chemical oxidation method to obtain stable dispersion in water and furthermore incorporation of Ag nanoparticles (Ag NPs); the resulting Ag NPs/PIn-r-GO nanocomposite is demonstrated for electrochemical applications. Ag NPs/r-GO and PIn/GO nanocomposites have also been prepared for its comparative study with Ag NPs/PIn-r-GO. Non-covalent functionalization of GO by PIn polymer leads to PIn-GO dispersion, which is stable for several months without any precipitation. This dispersed solution is used for formation of Ag NPs/PIn-r-GO nanocomposite. Various experimental tools like UV-vis, FTIR and TEM have been used to characterize as-synthesized materials. Thereafter electrochemical performance of as-synthesized nanocomposites have been compared for their charge capacitive behaviour (without its poisoning compared to Ag NPs/r-GO) which leads to be an excellent candidate for the possible applications such as electrocatalysis, charge storage devices, etc. We observed that Ag NPs/PIn-r-GO nanocomposite exhibits better processability and electroactivity as electrode material in comparison to Ag NPs/r-GO and PIn/GO nanocomposites due to synergistic effect of individual components.

  6. Assessment of Electrodes Prepared from Wafers of Boron-doped Diamond for the Electrochemical Oxidation of Waste Lubricants

    SciTech Connect

    Taylor, G.T.; Sullivan, I.A.; Newey, A.W.E.

    2006-07-01

    Electrochemical oxidation using boron-doped diamond electrodes is being investigated as a treatment process for radioactively contaminated oily wastes. Previously, it was shown that electrodes coated with a thin film of diamond were able to oxidise a cutting oil but not a mineral oil. These tests were inconclusive, because the electrodes lost their diamond coating during operation. Accordingly, an electrode prepared from a 'solid' wafer of boron-doped diamond is being investigated to determine whether it will oxidise mineral oils. The electrode has been tested with sucrose, a cutting oil and an emulsified mineral oil. Before and after each test, the state of the electrode was assessed by cyclic voltammetry with the ferro/ferricyanide redox couple. Analysis of the cyclic voltammogram suggested that material accumulated on the surface of the electrode during the tests. The magnitude of the effect was in the order: - emulsified mineral oil > cutting oil > sucrose. Despite this, the results indicated that the electrode was capable of oxidising the emulsified mineral oil. Confirmatory tests were undertaken in the presence of alkali to trap the carbon dioxide, but they had to be abandoned when the adhesive holding the diamond in the electrode was attacked by the alkali. Etching of the diamond wafer was also observed at the end of the tests. Surface corrosion is now regarded as an intrinsic part of the electrochemical oxidation on diamond, and it is expected that the rate of attack will determine the service life of the electrodes. (authors)

  7. Bio-functionalized graphene–graphene oxide nanocomposite based electrochemical immunosensing

    PubMed Central

    Sharma, Priyanka; Tuteja, Satish K.; Bhalla, Vijayender; Shekhawat, G.; Dravid, Vinayak P.; Suri, C.Raman

    2014-01-01

    We report a novel in-situ electrochemical synthesis approach for the formation of functionalized graphene–graphene oxide (fG–GO) nanocomposite on screen-printed electrodes (SPE). Electrochemically controlled nanocomposite film formation was studied by transmission electron microscopy (TEM) and Raman spectroscopy. Further insight into the nanocomposite has been accomplished by the Fourier transformed infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA) and X-ray diffraction (XRD) spectroscopy. Configured as a highly responsive screen-printed immunosensor, the fG–GO nanocomposite on SPE exhibits electrical and chemical synergies of the nano-hybrid functional construct by combining good electronic properties of functionalized graphene (fG) and the facile chemical functionality of graphene oxide (GO) for compatible bio-interface development using specific anti-diuron antibody. The enhanced electrical properties of nanocomposite biofilm demonstrated a significant increase in electrochemical signal response in a competitive inhibition immunoassay format for diuron detection, promising its potential applicability for ultra-sensitive detection of range of target analytes. PMID:22884654

  8. Bio-functionalized graphene-graphene oxide nanocomposite based electrochemical immunosensing.

    PubMed

    Sharma, Priyanka; Tuteja, Satish K; Bhalla, Vijayender; Shekhawat, G; Dravid, Vinayak P; Suri, C Raman

    2013-01-15

    We report a novel in-situ electrochemical synthesis approach for the formation of functionalized graphene-graphene oxide (fG-GO) nanocomposite on screen-printed electrodes (SPE). Electrochemically controlled nanocomposite film formation was studied by transmission electron microscopy (TEM) and Raman spectroscopy. Further insight into the nanocomposite has been accomplished by the Fourier transformed infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA) and X-ray diffraction (XRD) spectroscopy. Configured as a highly responsive screen-printed immunosensor, the fG-GO nanocomposite on SPE exhibits electrical and chemical synergies of the nano-hybrid functional construct by combining good electronic properties of functionalized graphene (fG) and the facile chemical functionality of graphene oxide (GO) for compatible bio-interface development using specific anti-diuron antibody. The enhanced electrical properties of nanocomposite biofilm demonstrated a significant increase in electrochemical signal response in a competitive inhibition immunoassay format for diuron detection, promising its potential applicability for ultra-sensitive detection of range of target analytes. PMID:22884654

  9. Layered method of electrode for solid oxide electrochemical cells

    DOEpatents

    Jensen, Russell R.

    1991-07-30

    A process for fabricating a fuel electrode comprising: slurry dipping to form layers which are structurally graded from all or mostly all stabilized zirconia at a first layer, to an outer most layer of substantially all metal powder, such an nickel. Higher performaance fuel electrodes may be achieved if sinter active stabilized zirconia doped for electronic conductivity is used.

  10. Electrochemically Driven Deactivation and Recovery in PrBaCo2 O5+δ Oxygen Electrodes for Reversible Solid Oxide Fuel Cells.

    PubMed

    Zhu, Lin; Wei, Bo; Wang, Zhihong; Chen, Kongfa; Zhang, Haiwu; Zhang, Yaohui; Huang, Xiqiang; Lü, Zhe

    2016-09-01

    The understanding of surface chemistry changes on oxygen electrodes is critical for the development of reversible solid oxide fuel cell (RSOFC). Here, we report for the first time that the electrochemical potentials can drastically affect the surface composition and hence the electrochemical activity and stability of PrBaCo2 O5+δ (PBCO) electrodes. Anodic polarization degrades the activity of the PBCO electrode, whereas the cathodic bias could recover its performance. Alternating anodic/cathodic polarization for 180 h confirms this behavior. Microstructure and chemical analysis clearly show that anodic bias leads to the accumulation and segregation of insulating nanosized BaO on the electrode surface, whereas cathodic polarization depletes the surface species. Therefore, a mechanism based on the segregation and incorporation of BaO species under electrochemical potentials is considered to be responsible for the observed deactivation and recovery process, respectively. PMID:27515117

  11. Nanoporous gold supported cobalt oxide microelectrodes as high-performance electrochemical biosensors.

    PubMed

    Lang, Xing-You; Fu, Hong-Ying; Hou, Chao; Han, Gao-Feng; Yang, Ping; Liu, Yong-Bing; Jiang, Qing

    2013-01-01

    Tremendous demands for electrochemical biosensors with high sensitivity and reliability, fast response and excellent selectivity have stimulated intensive research on developing versatile materials with ultrahigh electrocatalytic activity. Here we report flexible and self-supported microelectrodes with a seamless solid/nanoporous gold/cobalt oxide hybrid structure for electrochemical nonenzymatic glucose biosensors. As a result of synergistic electrocatalytic activity of the gold skeleton and cobalt oxide nanoparticles towards glucose oxidation, amperometric glucose biosensors based on the hybrid microelectrodes exhibit multi-linear detection ranges with ultrahigh sensitivities at a low potential of 0.26 V (versus Ag/AgCl). The sensitivity up to 12.5 mA mM⁻¹ cm⁻² with a short response time of less than 1 s gives rise to ultralow detection limit of 5 nM. The outstanding performance originates from a novel nanoarchitecture in which the cobalt oxide nanoparticles are incorporated into pore channels of the seamless solid/nanoporous Au microwires, providing excellent electronic/ionic conductivity and mass transport for the enhanced electrocatalysis. PMID:23851924

  12. Technology advancement of the electrochemical CO2 concentrating process

    NASA Technical Reports Server (NTRS)

    Schubert, F. H.; Heppner, D. B.; Hallick, T. M.; Woods, R. R.

    1979-01-01

    Two multicell, liquid-cooled, advanced electrochemical depolarized carbon dioxide concentrator modules were fabricated. The cells utilized advanced, lightweight, plated anode current collectors, internal liquid cooling and lightweight cell frames. Both were designed to meet the carbon dioxide removal requirements of one-person, i.e., 1.0 kg/d (2.2 lb/d).

  13. Electrochemically reduced graphene oxide on silicon nanowire arrays for enhanced photoelectrochemical hydrogen evolution.

    PubMed

    Meng, Huan; Fan, Ke; Low, Jingxiang; Yu, Jiaguo

    2016-09-21

    Photoelectrochemical (PEC) water splitting into hydrogen and oxygen by sunlight is a promising approach to solve energy and environmental problems. In this work, silicon nanowire arrays (SiNWs) photocathodes decorated with reduced graphene oxide (rGO) for PEC water splitting were successfully prepared by a flexible and scalable electrochemical reduction method. The SiNWs photocathode with the optimized rGO decoration (SiNWs/rGO20) shows an enhanced activity with a much higher photocurrent density and significantly positive shift of onset potential compared to the bare SiNWs arrays for the hydrogen evolution reaction (HER). The enhanced PEC activity is ascribed to the high electrical conductivity of rGO and improved separation of the photogenerated charge carriers. This work not only demonstrates a facile, rapid and tunable electrochemical reduction method to produce rGO, but also exhibits an efficient protocol to enhance the PEC water splitting of silicon-based materials. PMID:27461187

  14. Reduced graphene oxide-yttria nanocomposite modified electrode for enhancing the sensitivity of electrochemical genosensor.

    PubMed

    Rasheed, P Abdul; Radhakrishnan, Thulasi; Shihabudeen, P K; Sandhyarani, N

    2016-09-15

    Reduced graphene oxide-yttria nanocomposite (rGO:Y) is applied as electrochemical genosensor platform for ultrahigh sensitive detection of breast cancer 1 (BRCA1) gene for the first time. The sensor is based on the sandwich assay in which gold nanoparticle cluster labeled reporter DNA hybridize to the target DNA. Glassy carbon electrode modified with rGO-yttria serves as the immobilization platform for capture probe DNA. The sensor exhibited a fine capability of sensing BRCA1 gene with linear range of 10attomolar (aM) to 1nanomolar (nM) and a detection limit of 5.95attomolar. The minimum distinguishable response concentration is down to the attomolar level with a high sensitivity and selectivity. We demonstrated that the use of rGO:Y modified electrode along with gold nanoparticle cluster (AuNPC) label leads to the highly sensitive electrochemical detection of BRCA1 gene. PMID:27153526

  15. Synergetic antibacterial activity of reduced graphene oxide and boron doped diamond anode in three dimensional electrochemical oxidation system

    PubMed Central

    Qi, Xiujuan; Wang, Ting; Long, Yujiao; Ni, Jinren

    2015-01-01

    A 100% increment of antibacterial ability has been achieved due to significant synergic effects of boron-doped diamond (BDD) anode and reduced graphene oxide (rGO) coupled in a three dimensional electrochemical oxidation system. The rGO, greatly enhanced by BDD driven electric field, demonstrated strong antibacterial ability and even sustained its excellent performance during a reasonable period after complete power cut in the BDD-rGO system. Cell damage experiments and TEM observation confirmed much stronger membrane stress in the BDD-rGO system, due to the faster bacterial migration and charge transfer by the expanded electro field and current-carrying efficiency by quantum tunnel. Reciprocally the hydroxyl-radical production was eminently promoted with expanded area of electrodes and delayed recombination of the electron–hole pairs in presence of the rGO in the system. This implied a huge potential for practical disinfection with integration of the promising rGO and the advanced electrochemical oxidation systems. PMID:25994309

  16. Synergetic antibacterial activity of reduced graphene oxide and boron doped diamond anode in three dimensional electrochemical oxidation system

    NASA Astrophysics Data System (ADS)

    Qi, Xiujuan; Wang, Ting; Long, Yujiao; Ni, Jinren

    2015-05-01

    A 100% increment of antibacterial ability has been achieved due to significant synergic effects of boron-doped diamond (BDD) anode and reduced graphene oxide (rGO) coupled in a three dimensional electrochemical oxidation system. The rGO, greatly enhanced by BDD driven electric field, demonstrated strong antibacterial ability and even sustained its excellent performance during a reasonable period after complete power cut in the BDD-rGO system. Cell damage experiments and TEM observation confirmed much stronger membrane stress in the BDD-rGO system, due to the faster bacterial migration and charge transfer by the expanded electro field and current-carrying efficiency by quantum tunnel. Reciprocally the hydroxyl-radical production was eminently promoted with expanded area of electrodes and delayed recombination of the electron-hole pairs in presence of the rGO in the system. This implied a huge potential for practical disinfection with integration of the promising rGO and the advanced electrochemical oxidation systems.

  17. Amplified electrochemical determination of maltol in food based on graphene oxide-wrapped tin oxide@carbon nanospheres.

    PubMed

    Gan, Tian; Sun, Junyong; Yu, Miaomiao; Wang, Kaili; Lv, Zhen; Liu, Yanming

    2017-01-01

    The study presents a new approach for rapid and ultrasensitive detection of maltol using a glassy carbon electrode (GCE) modified with graphene oxide-wrapped tin oxide@carbon nanospheres (SnO2@C@GO). The morphological and components properties of SnO2@C@GO nanocomposites were investigated by means of X-ray diffraction spectroscopy, Raman spectroscopy, field emission scanning electron microscopy, high resolution transmission electron microscopy, and electrochemical impedance spectroscopy. SnO2@C@GO nanocomposite on a GCE had a synergetic effect on the electrochemical oxidation of maltol by means of square wave voltammetry. Under the optimum conditions, anodic peak current response of maltol was linear with its concentration in the range of 80nM-10μM, and a detection limit of 12nM was achieved for maltol. The experiment results presented that the method showed good selectivity, sensitivity, reproducibility, and long-term stability, as well as excellent potential for use as an ideal inexpensive voltammetric method applicable for complex food matrices. PMID:27507451

  18. Morphology, structural and optical properties of iron oxide thin film photoanodes in photoelectrochemical cell: Effect of electrochemical oxidation

    NASA Astrophysics Data System (ADS)

    Maabong, Kelebogile; Machatine, Augusto G.; Hu, Yelin; Braun, Artur; Nambala, Fred J.; Diale, Mmantsae

    2016-01-01

    Hematite (α-Fe2O3) is a promising semiconductor as photoanode in solar hydrogen production from photoelectrolysis of water due to its appropriate band gap, low cost and high electrochemical stability in aqueous caustic electrolytes. Operation of such photoanode in a biased photoelectrochemical cell constitutes an anodization with consequent redox reactions at the electrode surface. α-Fe2O3 thin film photoanodes were prepared by simple and inexpensive dip coating method on fluorine doped tin oxide (FTO) glass substrate, annealed in air at 500 °C for 2 h, then electrochemically oxidized (anodized) in 1 M KOH at 500 mV for 1 min in dark and light conditions. Changes in structural properties and morphology of α-Fe2O3 nanoparticles films were investigated by XRD, Raman spectroscopy and a high resolution FE-SEM. The average grain size was observed to increase from ~57 nm for pristine samples to 73 and 77 nm for anodized samples in dark and light respectively. Broadening and red shift in Raman spectra in anodized samples may be attributed to lattice expansion upon oxidation. The UV-visible measurements revealed enhanced absorption in the photoanodes after the treatment. The findings suggest that the anodization of the photoelectrode in a biased cell causes not only changes of the molecular structure at the surface, but also changes in the crystallographic structure which can be detected with x-ray diffractometry.

  19. Facile and novel electrochemical preparation of a graphene-transition metal oxide nanocomposite for ultrasensitive electrochemical sensing of acetaminophen and phenacetin

    NASA Astrophysics Data System (ADS)

    Jiang, Lin; Gu, Shuqing; Ding, Yaping; Jiang, Feng; Zhang, Zhen

    2013-12-01

    A facile and novel preparation strategy based on electrochemical techniques for the fabrication of electrodeposited graphene (EGR) and zinc oxide (ZnO) nanocomposite was developed. The morphology and structure of the EGR-based nanocomposite were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (XPS) and Raman spectroscopy. Meanwhile, the electrochemical performance of the nanocomposite was demonstrated with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Due to the synergistic effect of EGR and ZnO nanoparticles, an ultrasensitive electrochemical sensor for acetaminophen (AC) and phenacetin (PCT) was successfully fabricated. The linearity ranged from 0.02 to 10 μM for AC and 0.06 to 10 μM for PCT with high sensitivities of 54 295.82 μA mM-1 cm2 for AC and 21 344.66 μA mM-1 cm2 for PCT, respectively. Moreover, the practical applicability was validated to be reliable and desirable in pharmaceutical detections. The excellent results showed the promise of the proposed preparation strategy of EGR-transition metal oxide nanocomposite in the field of electroanalytical chemistry.A facile and novel preparation strategy based on electrochemical techniques for the fabrication of electrodeposited graphene (EGR) and zinc oxide (ZnO) nanocomposite was developed. The morphology and structure of the EGR-based nanocomposite were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (XPS) and Raman spectroscopy. Meanwhile, the electrochemical performance of the nanocomposite was demonstrated with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Due to the synergistic effect of EGR and ZnO nanoparticles, an ultrasensitive electrochemical sensor for acetaminophen (AC) and phenacetin (PCT) was successfully fabricated. The linearity ranged from 0.02 to 10 μM for AC and 0.06 to 10

  20. The kinetics of the oxidation of pyrite by ferric ions and dissolved oxygen: An electrochemical study

    SciTech Connect

    Holmes, P.R.; Crundwell, F.K.

    2000-01-01

    The dissolution of pyrite is important in the geochemical cycling of iron and sulphur, in the formation of acid mine drainage, and in the extraction of metals by bacterial leaching. Many researchers have studied the kinetics of dissolution, and the rate of dissolution has often been found to be half-order in ferric ions or oxygen. Previous work has not adequately explained the kinetics of dissolution of pyrite. The dissolution of pyrite is an oxidation-reduction reaction. The kinetics of the oxidation and reduction half-reactions was studied independently using electrochemical techniques of voltammetry. The kinetics of the overall reaction was studied by the electrochemical technique of potentiometry, which consisted of measuring the mixed potential of a sample of corroding pyrite in solutions of different compositions. The kinetics of the half reactions are related to the kinetics of the overall dissolution reaction by the condition that there is no accumulation of charge. This principle is used to derive expressions for the mixed potential and the rate of dissolution, which successfully describe the mixed potential measurements and the kinetics of dissolution reported in the literature. It is shown that the observations of half-order kinetics and that the oxygen in the sulphate product arises from water are both a direct consequence of the electrochemical mechanism. Thus it is concluded that the electrochemical reaction steps occurring at the mineral-solution interface control the rate of dissolution. Raman spectroscopy was used to analyze reaction products formed on the pyrite surface. The results indicated that small amounts of polysulphides form on the surface of the pyrite. However, it was also found that the mixed (corrosion) potential does not change over a 14-day leaching period. This indicates that even though polysulphide material is present on the surface, it does not influence the rate of the reactions occurring at the surface. Measurement of the

  1. Treatment of trichlorophenol by catalytic oxidation process.

    PubMed

    Chu, W; Law, C K

    2003-05-01

    The oxidation of 2,4,6-trichlorophenol (TCP) by ferrous-catalyzed hydrogen peroxide was quantified and modeled in the study. TCP was effectively degraded by hydroxyl radicals that were generated by Fe(II)/H(2)O(2) in the oxidation process. The oxidation capacity (OC) of the process depends on the concentrations of oxidant (hydrogen peroxide) and oxidative catalyst (ferrous ion). Up to 99.6% of TCP removal can be achieved in the process, provided the doses of Fe(II) and H(2)O(2) are selected correctly. The OC of the process was successfully predicted through a kinetic approach in a two-stage model with some simple and measurable parameters, which makes the model useful for predicting, controlling and optimizing the catalyzed oxidation process in the degradation of TCP. PMID:12727243

  2. Carbon activation process for increased surface accessibility in electrochemical capacitors

    DOEpatents

    Doughty, Daniel H.; Eisenmann, Erhard T.

    2001-01-01

    A process for making carbon film or powder suitable for double capacitor electrodes having a capacitance of up to about 300 F/cm.sup.3 is disclosed. This is accomplished by treating in aqueous nitric acid for a period of about 5 to 15 minutes thin carbon films obtained by carbonizing carbon-containing polymeric material having a high degree of molecular directionality, such as polyimide film, then heating the treated carbon film in a non-oxidizing atmosphere at a non-graphitizing temperature of at least 350.degree. C. for about 20 minutes, and repeating alternately the nitric acid step and the heating step from 7 to 10 times. Capacitors made with this carbon may find uses ranging from electronic devices to electric vehicle applications.

  3. Development of a tritium monitor combined with an electrochemical tritium pump using a proton conducting oxide

    SciTech Connect

    Tanaka, M.; Sugiyama, T.

    2015-03-15

    The detection of low level tritium is one of the key issues for tritium management in tritium handling facilities. Such a detection can be performed by tritium monitors based on proton conducting oxide technique. We tested a tritium monitoring system composed of a commercial proportional counter combined with an electrochemical hydrogen pump equipped with CaZr{sub 0.9}In{sub 0.1}O{sub 3-α} as proton conducting oxide. The hydrogen pump operated at 973 K under electrolysis conditions using tritiated water vapor (HTO). The proton conducting oxide extracts tritium molecules (HT) from HTO and tritium concentration is measured by the proportional counter. The advantage of the proposed tritium monitoring system is that it is able to convert HTO into molecular hydrogen.

  4. Cobalt (hydro)oxide electrodes under electrochemical conditions: a first principle study

    NASA Astrophysics Data System (ADS)

    Chen, Jia; Selloni, Annabella

    2013-03-01

    There is currently much interest in photoelectrochemical water splitting as a promising pathway towards sustainable energy production. A major issue of such photoelectrochemical devices is the limited efficiency of the anode, where the oxygen evolution reaction (OER) takes place. Cobalt (hydro)oxides, particularly Co3O4 and Co(OH)2, have emerged as promising candidates for use as OER anode materials. Interestingly, recent in-situ Raman spectroscopy studies have shown that Co3O4 electrodes undergo progressive oxidation and transform into oxyhydroxide, CoO(OH), under electrochemical working conditions. (Journal of the American Chemical Society 133, 5587 (2011))Using first principle electronic structure calculations, we provide insight into these findings by presenting results on the structural, thermodynamic, and electronic properties of cobalt oxide, hydroxide and oxydroxide CoO(OH), and on their relative stabilities when in contact with water under external voltage.

  5. Alternating voltage induced electrochemical synthesis of three-dimensionalization copper oxide for lithium-ion battery application

    NASA Astrophysics Data System (ADS)

    Jing, Mingjun; Ding, Zhiying; Hou, Hongshuai; Zhang, Yan; Zou, Guoqiang; Li, Simin; Ji, Xiaobo

    2016-06-01

    Three-dimensional copper oxide structures composed of single crystal nanosheets have been successfully prepared by a green electrochemical alternating voltage approach. This special structure of copper oxide grown along the [0 1 0] direction can be effective to accommodate the volume expansion during charge-discharge cycles. The obtained product as anode materials in lithium-ion batteries displays outstanding electrochemical performances with a high reversible capacity of 635.2 mA h g-1 after 50 cycles at 100 mA g-1 close to the theoretical capacity of copper oxide (674 mA h g-1).

  6. Photochemical, electrochemical, and photoelectrochemical water oxidation catalyzed by water-soluble mononuclear ruthenium complexes.

    PubMed

    Li, Ting-Ting; Zhao, Wei-Liang; Chen, Yong; Li, Fu-Min; Wang, Chuan-Jun; Tian, Yong-Hua; Fu, Wen-Fu

    2014-10-20

    Two mononuclear ruthenium complexes [Ru(H2tcbp)(isoq)2] (1) and [Ru(H2tcbp)(pic)2] (2) (H4tcbp=4,4',6,6'-tetracarboxy-2,2'-bipyridine, isoq=isoquinoline, pic=4-picoline) are synthesized and fully characterized. Two spare carboxyl groups on the 4,4'-positions are introduced to enhance the solubility of 1 and 2 in water and to simultaneously allow them to tether to the electrode surface by an ester linkage. The photochemical, electrochemical, and photoelectrochemical water oxidation performance of 1 in neutral aqueous solution is investigated. Under electrochemical conditions, water oxidation is conducted on the deposited indium-tin-oxide anode, and a turnover number higher than 15,000 per water oxidation catalyst (WOC) 1 is obtained during 10 h of electrolysis under 1.42 V vs. NHE, corresponding to a turnover frequency of 0.41 s(-1). The low overpotential (0.17 V) of electrochemical water oxidation for 1 in the homogeneous solution enables water oxidation under visible light by using [Ru(bpy)3](2+) (P1) (bpy=2,2'-bipyridine) or [Ru(bpy)2(4,4'-(COOEt)2-bpy)](2+) (P2) as a photosensitizer. In a three-component system containing 1 or 2 as a light-driven WOC, P1 or P2 as a photosensitizer, and Na2S2O8 or [CoCl(NH3)5]Cl2 as a sacrificial electron acceptor, a high turnover frequency of 0.81 s(-1) and a turnover number of up to 600 for 1 under different catalytic conditions are achieved. In a photoelectrochemical system, the WOC 1 and photosensitizer are immobilized together on the photoanode. The electrons efficiently transfer from the WOC to the photogenerated oxidizing photosensitizer, and a high photocurrent density of 85 μA cm(-2) is obtained by applying 0.3 V bias vs. NHE. PMID:25205065

  7. Activated carbon electrodes: electrochemical oxidation coupled with desalination for wastewater treatment.

    PubMed

    Duan, Feng; Li, Yuping; Cao, Hongbin; Wang, Yi; Crittenden, John C; Zhang, Yi

    2015-04-01

    The wastewater usually contains low-concentration organic pollutants and some inorganic salts after biological treatment. In the present work, the possibility of simultaneous removal of them by combining electrochemical oxidation and electrosorption was investigated. Phenol and sodium chloride were chosen as representative of organic pollutants and inorganic salts and a pair of activated carbon plate electrodes were used as anode and cathode. Some important working conditions such as oxygen concentration, applied potential and temperature were evaluated to reach both efficient phenol removal and desalination. Under optimized 2.0 V of applied potential, 38°C of temperature, and 500 mL min(-1) of oxygen flow, over 90% of phenol, 60% of TOC and 20% of salinity were removed during 300 min of electrolysis time. Phenol was removed by both adsorption and electrochemical oxidation, which may proceed directly or indirectly by chlorine and hypochlorite oxidation. Chlorophenols were detected as degradation intermediates, but they were finally transformed to carboxylic acids. Desalination was possibly attributed to electrosorption of ions in the pores of activated carbon electrodes. The charging/regeneration cycling experiment showed good stability of the electrodes. This provides a new strategy for wastewater treatment and recycling. PMID:25585871

  8. Electrochemical sulfide oxidation from domestic wastewater using mixed metal-coated titanium electrodes.

    PubMed

    Pikaar, Ilje; Rozendal, René A; Yuan, Zhiguo; Keller, Jürg; Rabaey, Korneel

    2011-11-01

    Hydrogen sulfide generation is a major issue in sewer management. A novel method based on electrochemical sulfide oxidation was recently shown to be highly effective for sulfide removal from synthetic and real sewage. Here, we compare the performance of five different mixed metal oxide (MMO) coated titanium electrode materials for the electrochemical removal of sulfide from domestic wastewater. All electrode materials performed similarly in terms of sulfide removal, removing 78±5%, 77±1%, 85±4%, 84±1%, and 83±2% at a current density of 10 mA/cm(2) using Ta/Ir, Ru/Ir, Pt/Ir, SnO(2) and PbO(2), respectively. Elevated chloride concentrations, often observed in coastal areas, did not entail any significant difference in performance. Independent of the electrode material used, sulfide oxidation by in situ generated oxygen was the predominant reaction mechanism. Passivation of the electrode surface by deposition of elemental sulfur did not occur. However, scaling was observed in the cathode compartment. This study shows that all the MMO coated titanium electrode materials studied are suitable anodic materials for sulfide removal from wastewater. Ta/Ir and Pt/Ir coated titanium electrodes seem the most suitable electrodes since they possess the lowest overpotential for oxygen evolution, are stable at low chloride concentration and are already used in full scale applications. PMID:21885081

  9. Study and optimisation of manganese oxide-based electrodes for electrochemical supercapacitors

    NASA Astrophysics Data System (ADS)

    Staiti, P.; Lufrano, F.

    A manganese oxide material was synthesised by an easy precipitation method based on reduction of potassium permanganate(VII) with a manganese(II) salt. The material was treated at different temperatures to study the effect of thermal treatment on capacitive property. The best capacitive performance was obtained with the material treated at 200 °C. This material was used to prepare electrodes with different amounts of polymer binder, carbon black and graphite fibres to individuate the optimal composition that gave the best electrochemical performances. It was found that graphite fibres improve the electrochemical performance of electrodes. The highest specific capacitance (267 F g -1 MnO x) was obtained with an electrode containing 70% of MnO x, 15% of carbon black, 10% of graphite fibres and 5% of PVDF. This electrode, with CB/GF ratio of 1.5, showed a higher utilization of manganese oxide. The results reported in the present paper further confirmed that manganese oxide is a very interesting material for supercapacitor application.

  10. Technology advancement of the electrochemical CO2 concentrating process

    NASA Technical Reports Server (NTRS)

    Schubert, F. H.; Woods, R. R.; Hallick, T. M.; Heppner, D. B.

    1977-01-01

    A five-cell, liquid-cooled advanced electrochemical depolarized carbon dioxide concentrator module was fabricated. The cells utilized the advanced, lightweight, plated anode current collector concept and internal liquid-cooling. The five cell module was designed to meet the carbon dioxide removal requirements of one man and was assembled using plexiglass endplates. This one-man module was tested as part of an integrated oxygen generation and recovery subsystem.

  11. Tunable Mixed Ionic/Electronic Conductivity and Permittivity of Graphene Oxide Paper for Electrochemical Energy Conversion.

    PubMed

    Bayer, Thomas; Bishop, Sean R; Perry, Nicola H; Sasaki, Kazunari; Lyth, Stephen M

    2016-05-11

    Graphene oxide (GO) is a two-dimensional graphitic carbon material functionalized with oxygen-containing surface functional groups. The material is of interest in energy conversion, sensing, chemical processing, gas barrier, and electronics applications. Multilayer GO paper has recently been applied as a new proton conducting membrane in low temperature fuel cells. However, a detailed understanding of the electrical/dielectric properties, including separation of the ionic vs electronic contributions under relevant operating conditions, has so far been lacking. Here, the electrical conductivity and dielectric permittivity of GO paper are investigated in situ from 30 to 120 °C, and from 0 to 100% relative humidity (RH) using impedance spectroscopy. These are related to the water content, measured by thermogravimetric analysis. With the aid of electron blocking measurements, GO is demonstrated to be a mixed electronic-protonic conductor, and the ion transference number is derived for the first time. For RH > 40%, conductivity is dominated by proton transport (with a maximum of 0.5 mS/cm at 90 °C and 100% RH). For RH < 40%, electronic conductivity dominates (with a maximum of 7.4 mS/cm at ∼80 °C and 0% RH). The relative permittivity of GO paper increases with decreasing humidity, from ∼10 at 100% RH to several 1000 at 10% RH. These results underline the potential of GO for application not only as a proton conducting electrolyte but also as a mixed conducting electrode material under appropriate conditions. Such materials are highly applicable in electrochemical energy conversion and storage devices such as fuel cells and electrolyzers. PMID:27088238

  12. Electrochemical degradation of polycyclic aromatic hydrocarbons in creosote solution using ruthenium oxide on titanium expanded mesh anode.

    PubMed

    Tran, Lan-Huong; Drogui, Patrick; Mercier, Guy; Blais, Jean-François

    2009-05-30

    In this study, expanded titanium (Ti) covered with ruthenium oxide (RuO(2)) electrode was used to anodically oxidize polycyclic aromatic hydrocarbons (PAH) in creosote solution. Synthetic creosote-oily solution (COS) was prepared with distilled water and a commercial creosote solution in the presence of an amphoteric surfactant; Cocamidopropylhydroxysultaine (CAS). Electrolysis was carried out using a parallelepipedic electrolytic 1.5-L cell containing five anodes (Ti/RuO(2)) and five cathodes (stainless steel, 316 L) alternated in the electrode pack. The effects of initial pH, temperature, retention time, supporting electrolyte, current density and initial PAH concentration on the process performance were examined. Experimental results revealed that a current density of 9.23 mA cm(-2) was beneficial for PAH oxidation. The sum of PAH concentrations for 16 PAHs could be optimally diminished up to 80-82% while imposing a residence time in the electrolysis cell of 90 min. There was not a significant effect of the electrolyte (Na(2)SO(4)) concentration on oxidation efficiency in the investigated range of 500-4000 mg/L. However, an addition of 500 mg Na(2)SO(4)L(-1) was required to reduce the energy consumption and the treatment cost. Besides, there was no effect of initial PAH concentration on oxidation efficiency in the investigated range of 270-540 mg PAHL(-1). Alkaline media was not favourable for PAH oxidation, whereas high performance of PAH degradation could be recorded without initial pH adjustment (original pH around 6.0). Likewise, under optimal conditions, 84% of petroleum hydrocarbon (C(10)-C(50)) was removed, whereas removal yields of 69% and 62% have been measured for O&G and COD, respectively. Microtox and Daphnia biotests showed that electrochemical oxidation using Ti/RuO(2) could be efficiently used to reduce more than 90% of the COS toxicity. PMID:18926633

  13. PROCESSES OF CHLORINATION OF URANIUM OXIDES

    DOEpatents

    Rosenfeld, S.

    1958-09-16

    An improvement is described in the process fur making UCl/sub 4/ from uranium oxide and carbon tetrachloride. In that process, oxides of uranium are contacted with carbon tetrachloride vapor at an elevated temperature. It has been fuund that the reaction product and yield are improved if the uranlum oxide charge is disposed in flat trays in the reaction zone, to a depth of not more than 1/2 centimeter.

  14. Electrochemical oxidation of recalcitrant organic compounds in biologically treated municipal solid waste leachate in a flow reactor.

    PubMed

    Quan, Xuejun; Cheng, Zhiliang; Chen, Bo; Zhu, Xincai

    2013-10-01

    Biologically-treated municipal solid waste (MSW) leachate still contains many kinds of bio-recalcitrant organic matter. A new plate and frame electrochemical reactor was designed to treat these materials under flow conditions. In the electrochemical oxidation process, NH3 and color could be easily removed by means of electro-generated chlorine/hypochlorite within 20 min. The effects of major process parameters on the removal of organic pollutants were investigated systematically. Under experimental conditions, the optimum operation parameters were current density of 65 mA/cm2, flow velocity of 2.6 cm/sec in electrode gap, and initial chloride ion concentration of 5000 mg/L. The COD in the leachate could be reduced below 100 mg/L after 1 hr of treatment. The kinetics and mechanism of COD removal were investigated by simultaneously monitoring the COD change and chlorine/hypochlorite production. The kinetics of COD removal exhibited a two-stage kinetic model, and the decrease of electro-generated chlorine/hypochlorite production was the major mechanism for the slowing down of the COD removal rate in the second stage. The narrowing of the electrode gap is beneficial for COD removal and energy consumption. PMID:24494488

  15. Accelerated oxidation processes is biodiesel

    SciTech Connect

    Canakci, M.; Monyem, A.; Van Gerpen, J.

    1999-12-01

    Biodiesel is an alternative fuel for diesel engines that can be produced from renewable feedstocks such as vegetable oil and animal fats. These feedstocks are reacted with an alcohol to produce alkyl monoesters that can be used in conventional diesel engines with little or no modification. Biodiesel, especially if produced from highly unsaturated oils, oxidizes more rapidly than diesel fuel. This article reports the results of experiments to track the chemical and physical changes that occur in biodiesel as it oxidizes. These results show the impact of time, oxygen flow rate, temperature, metals, and feedstock type on the rate of oxidation. Blending with diesel fuel and the addition of antioxidants are explored also. The data indicate that without antioxidants, biodiesel will oxidize very quickly at temperatures typical of diesel engines. This oxidation results in increases in peroxide value, acid value, and viscosity. While the peroxide value generally reaches a plateau of about 350 meq/kg ester, the acid value and viscosity increase monotonically as oxidation proceeds.

  16. Characterization of electro-oxidation catalysts using scanning electrochemical and mass spectral methods

    NASA Astrophysics Data System (ADS)

    Jambunathan, Krishnakumar

    Low temperature fuel cells have many potential benefits, including high efficiency, high energy density and environmental friendliness. However, logistically appealing fuels for this system, such as reformed hydrocarbons or alcohols, exhibit poor performance because of catalyst poisoning that occurs during oxidation at the anode. This research focuses on the analysis of several model fuels and catalyst materials to understand the impact of catalyst poisoning on reactivity. Two novel experimental tools were developed based upon the local measurement of catalyst performance using scanning, reactivity mapping probes. The Scanning Electrochemical Microscope (SECM) was used to directly measure the rate constant for hydrogen oxidation in the presence and absence of dissolved CO. The Scanning Differential Electrochemical Mass Spectrometer (SDEMS) was exploited to measure the partial and complete oxidation products of methanol and ethanol oxidation. The reactivity of Pt and Pt/Ru catalysts towards the hydrogen oxidation reaction in the absence and presence of adsorbed CO was elucidated using the SECM. Steady state rate constant measurements in the absence of CO showed that the rate of hydrogen oxidation reaction exceeded 1 cms-1 . Steady state rate constant measurements in the presence of CO indicated that the platinum surface is completely inactive due to adsorbed CO. Addition of as little as 6% Ru to the Pt electrode was found to significantly improve the activity of the electrode towards CO removal. SDEMS was used to study the electro-oxidation of methanol on Pt xRuy electrodes at different electrode potentials and temperatures. Screening measurements performed with the SDEMS showed that PtxRu y electrodes containing 6--40% Ru had the highest activity for methanol oxidation. Current efficiencies for CO2 were also calculated under different conditions. SDEMS was also used to study the electro-oxidation of ethanol on Pt xRuy electrodes. The reaction was found to occur

  17. Semiconductor and noble metal surface process characterization using electrochemical and optical methods

    NASA Astrophysics Data System (ADS)

    Srinivasan, Ramanathan

    Surface electrochemical processes are of importance in semiconductor manufacturing and electrochemical deposition. In this work, surface processes of noble metals are investigated by electrochemical and optical methods and the interpretations of the results are discussed. The specific adsorption of thiosulfate ions on polycrystalline silver electrode was studied by differential capacitance measurements using impedance analysis and the adsorption isotherm was found to be best explained by image dipole formation. The apparant dipole strength was determined to be 0.72 D. The determination of kinetics of galvanic deposition of gold on to silicon (111) was studied mainly by surface second harmonic generation (SHG). The results of SHG experiments along with atomic force microscopy (AFM) images indicate formation of clusters on the surface of silicon. The surface plasmon resonance of gold clusters causes strong enhancement of SHG and later, the growth of the clusters cause the drop in signal. By adding KF and HCl, the equilibria of HF dissociation were suitably altered and it was found that HF and not HF2- is the kinetically active species. Rutherford backscattering (RBS) measurements indicate that Au deposition is rate-limited by diffusion, while the SHG measurements indicate that Au cluster growth is rate-limited by either a surface reaction involving a fluoride-containing species or electron transfer. The reaction order for Au cluster growth with respect to HF is approximately ½, and the reaction order for Au cluster growth with respect to Au(CN)2- is near zero in the concentration range 10-4--10-5 M. The development and characteristics of a stable, high plating rate bath for electroless deposition of silver from silver cyanide and alkaline formaldehyde is described in the third chapter. Cyclic voltammograms indicate that the silver is passivated by cyanide ions which decrease the rate of silver reduction and hence the plating rate. Stirring the solution decreases the

  18. Plutonium Oxide Process Capability Work Plan

    SciTech Connect

    Meier, David E.; Tingey, Joel M.

    2014-02-28

    Pacific Northwest National Laboratory (PNNL) has been tasked to develop a Pilot-scale Plutonium-oxide Processing Unit (P3U) providing a flexible capability to produce 200g (Pu basis) samples of plutonium oxide using different chemical processes for use in identifying and validating nuclear forensics signatures associated with plutonium production. Materials produced can also be used as exercise and reference materials.

  19. Electrocatalytic Oxidation Properties of Ascorbic Acid at Poly(3, 4-ethylenedioxythiophene) Films Studied by Electrochemical-Surface Plasmon Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Baba, Akira; Sano, Yohsuke; Ohdaira, Yasuo; Shinbo, Kazunari; Kato, Keizo; Kaneko, Futao

    In this report, we demonstrate electrocatalytic oxidation properties of ascorbic acid at poly(3, 4-ethylenedioxythiophene) (PEDOT) thin films in view of their potential application for bio-sensing devices. PEDOT thin films were deposited on gold thin films by electropolymerization of EDOT monomer in acetonitrile solvent. In-situ electrochemical-surface plasmon resonance spectroscopy (EC-SPR) was used to detect both electrochemical and optical signals upon an injection of ascorbic acid.

  20. Glass composition and process for sealing void spaces in electrochemical devices

    DOEpatents

    Meinhardt, Kerry D.; Kirby, Brent W.

    2012-05-01

    A glass foaming material and method are disclosed for filling void spaces in electrochemical devices. The glass material includes a reagent that foams at a temperature above the softening point of the glass. Expansion of the glass fills void spaces including by-pass and tolerance channels of electrochemical devices. In addition, cassette to cassette seals can also be formed while channels and other void spaces are filled, reducing the number of processing steps needed.

  1. Comparative electrochemical studies of a nanostructured vanadium oxide electrode material in aqueous electrolyte

    NASA Astrophysics Data System (ADS)

    Soghomonian, Victoria; Yuan, Qifan; Ren, Shaola; Zukowski, Julia

    Electrochemical energy storage plays an increasing role in energy solutions. We report on a new hydrothermally synthesized vanadium oxide nanostructured material and study its performance as electrode material for insertion of various ions from aqueous solutions. The as-synthesized product is in the form of nanosheets forming quasi-spherical 3-dimensional objects. Variable temperature resistivity measurements indicate a thermally activated behavior. Electrodes are constructed, and comparative electrochemical insertion reactions of Li, Na, K and NH4 cations, over different cycle numbers, investigated. Concomitantly, morphological and microstructural changes are characterized by scanning electron microscopy, providing physical input to the observed electrochemical behavior. Specific charge is calculated. For Li and K, the specific charge decreases as the cycle number increases, while the reverse is observed for Na and NH4 cations. The trends are correlated to the morphological changes observed. The specific charge in the case of ammonium reaches 180 mAh/g after 20 cycles and continues increasing, indicating that ammonium cations may be considered as viable charge carriers for electrical energy storage system, and moreover in an aqueous electrolyte. We acknowledge support from the National Science Foundation, Grant No. DMR-1206338.

  2. Fabrication of highly catalytic silver nanoclusters/graphene oxide nanocomposite as nanotag for sensitive electrochemical immunoassay.

    PubMed

    Wang, Jiamian; Wang, Xiuyun; Wu, Shuo; Song, Jie; Zhao, Yanqiu; Ge, Yanqiu; Meng, Changgong

    2016-02-01

    Silver nanoclusters and graphene oxide nanocomposite (AgNCs/GRO) is synthesized and functionalized with detection antibody for highly sensitive electrochemical sensing of carcinoembryonic antigen (CEA), a model tumor marker involved in many cancers. AgNCs with large surface area and abundant amount of low-coordinated sites are synthesized with DNA as template and exhibit high catalytic activity towards the electrochemical reduction of H2O2. GRO is employed to assemble with AgNCs because it has large specific surface area, super electronic conductivity and strong π-π stacking interaction with the hydrophobic bases of DNA, which can further improve the catalytic ability of the AgNCs. Using AgNCs/GRO as signal amplification tag, an enzyme-free electrochemical immunosensing protocol is designed for the highly sensitive detection of CEA on the capture antibody functionalized immunosensing interface. Under optimal conditions, the designed immunosensor exhibits a wide linear range from 0.1 pg mL(-1) to 100 ng mL(-1) and a low limit of detection of 0.037 pg mL(-1). Practical sample analysis reveals the sensor has good accuracy and reproducibility, indicating the great application prospective of the AgNCs/GRO in fabricating highly sensitive immunosensors, which can be extended to the detection of various kinds of low abundance disease related proteins. PMID:26772127

  3. Rapid Online Non-Enzymatic Protein Digestion Combining Microwave Heating Acid Hydrolysis and Electrochemical Oxidation

    PubMed Central

    Basile, Franco; Hauser, Nicolas

    2010-01-01

    We report an online non-enzymatic method for site-specific digestion of proteins to yield peptides that are well suited for collision induced dissociation (CID) tandem mass spectrometry (MS/MS). The method combines online microwave heating acid hydrolysis at aspartic acid and online electrochemical oxidation at tryptophan and tyrosine. The combined microwave/electrochemical (microwave/echem) digestion is reproducible and produces peptides with an average sequence length of 10 amino acids. This peptide length is similar to the average peptide length of 9 amino acids obtained by digestion of proteins with the enzyme trypsin. As a result, the peptides produced by this novel non-enzymatic digestion method, when analyzed by ESI-MS, produce protonated molecules with mostly +1 and +2 charge states. The combination of these two non-enzymatic methods overcomes shortcomings with each individual method in that: i) peptides generated by the microwave-hydrolysis method have an average amino acid length of 16 amino acids, and ii) the inability of the electrochemical-cleavage method to reproducibly digest proteins with molecular masses above 4 kDa. Preliminary results are presented on the application and utility of this rapid online digestion (total of 6 min digestion time) on a series of standard peptides and proteins as well as an E. coli protein extract. PMID:21138252

  4. Branched zinc oxide nanorods arrays modified paper electrode for electrochemical immunosensing by combining biocatalytic precipitation reaction and competitive immunoassay mode.

    PubMed

    Sun, Guoqiang; Yang, Hongmei; Zhang, Yan; Yu, Jinghua; Ge, Shenguang; Yan, Mei; Song, Xianrang

    2015-12-15

    Branched zinc oxide nanorods (BZR) arrays, an array with high charge carries collection efficiency and specific surface area, are grown on the reduced graphene oxide-paper working electrode for the first time to construct a paper-based electrochemical (EC) immunosensor. Typically, the BZR are fabricated via a simple hydrothermal process, which can provide abundant sites for antibodies loading. By combining the large surface area of porous zinc oxide (PZS) and good biocompatibility of gold nanoparticles (AuNPs), PZS-AuNPs (PZS@Au) nanocomposites are designed to label horseradish peroxide (HRP) and antigens. After a competitive reaction between antigens and PZS@Au nanocomposites labeled antigens, the signal labels are introduced into the immunosensor, in which, HRP participate in biocatalytic precipitation process. The produced precipitate reduces the electrode surface area and hinders the electron transfer. With the increase of concentration of antigens, the signal labels introduced into the sensor decrease, thus, a signal-on immunoassay for α-fetoprotein detection is constructed. The proposed paper-based EC immunosensor combines enzymatic biocatalytic precipitation reaction and competitive immunoassay mode for the first time, and possesses a wide linear range from 0.2 pg mL(-1) to 500 ng mL(-1) with a detection limit of 0.08 pg mL(-1). In addition, the proposed method is simple, sensitive and specific and can be a promising platform for other protein detection. PMID:26232677

  5. Development of an optimized electrochemical process for subsequent coating of 316 stainless steel for stent applications.

    PubMed

    Haïdopoulos, M; Turgeon, S; Sarra-Bournet, C; Laroche, G; Mantovani, D

    2006-07-01

    Metallic endovascular stents are used as medical devices to scaffold biological lumen, most often diseased arteries, after balloon angioplasty. They are commonly made of 316L stainless steel or Nitinol, two alloys containing nickel, an element classified as potentially toxic and carcinogenic by the International Agency for Research on Cancer. Although they are largely implanted, the long-term safety of such metallic elements is still controversial, since the corrosion processes may lead to the release of several metallic ions, including nickel ions in diverse oxidation states. To avoid metallic ion release in the body, the strategy behind this work was to develop a process aiming the complete isolation of the stainless steel device from the body fluids by a thin, cohesive and strongly adherent coating of RF-plasma-polymerized fluoropolymer. Nevertheless, prior to the polymer film deposition, an essential aspect was the development of a pre-treatment for the metallic substrate, based on the electrochemical polishing process, aiming the removal of any fragile interlayer, including the native oxide layer and the carbon contaminated layer, in order to obtain a smooth, defect-free surface to optimize the adhesion of the plasma-deposited thin film. In this work, the optimized parameters for electropolishing, such as the duration and the temperature of the electrolysis, and the complementary acid dipping were presented and accurately discussed. Their effects on roughness as well as on the evolution of surface topography were investigated by Atomic Force Microscopy, stylus profilometry and Scanning Electron Microscopy. The modifications induced on the surface atomic concentrations were studied by X-ray Photoelectron Spectroscopy. The improvements in terms of the surface morphology after the pre-treatment were also emphasized, as well as the influence of the original stainless steel surface finish. PMID:16770550

  6. Electrochemical and electrochromic properties of niobium oxide thin films fabricated by pulsed laser deposition

    SciTech Connect

    Fu, Z.W.; Kong, J.J.; Qin, Q.Z.

    1999-10-01

    Niobium oxide thin films have been successfully fabricated on the indium-tin oxide coated glasses by pulsed laser deposition in an O{sub 3}/O{sub 2} gas mixture. Films are characterized by X-ray diffraction and Raman spectrometry. Electrochemical and electrochromic properties of Nb{sub 2}O{sub 5} films are examined by cyclic voltammogram and potential step coupled with an in situ charge-coupled device spectrophotometer. The unique characteristics of absorption spectra of Nb{sub 2}O{sub 5} films are observed for the first time, and the optical absorption from the trapped electrons in the surface states plays an important role in the electrochromic phenomenon.

  7. Electrochemical investigation of polyhalide ion oxidation-reduction on carbon nanotube electrodes for redox flow batteries

    SciTech Connect

    Shao, Yuyan; Engelhard, Mark H.; Lin, Yuehe

    2009-10-01

    Polyhalide ions (Br-/BrCl2-) are an important redox couple for redox flow batteries. The oxidation-reduction behavior of polyhalide ions on a carbon nanotube (CNT) electrode has been investigated with cyclic voltammetry and electrochemical impedance spectroscopy. The onset oxidation potential of Br-/BrCl2- is negatively shifted by >100 mV, and the redox current peaks are greatly enhanced on a CNT electrode compared with that on the most widely-used graphite electrode. The reaction resistance of the redox couple (Br-/BrCl2-) is decreased on a CNT electrode. The redox reversibility is increased on a CNT electrode even though it still needs further improvement. CNT is a promising electrode material for redox flow batteries.

  8. Influence of hydrogen-oxidizing bacteria on the corrosion of low carbon steel: Local electrochemical investigations.

    PubMed

    Moreira, Rebeca; Schütz, Marta K; Libert, Marie; Tribollet, Bernard; Vivier, Vincent

    2014-06-01

    Low carbon steel has been considered a suitable material for component of the multi-barrier system employed on the geological disposal of high-level radioactive waste (HLW). A non negligible amount of dihydrogen (H2) is expected to be produced over the years within the geological repository due to the anoxic corrosion of metallic materials and also to the water radiolysis. The influence of the activity of hydrogen-oxidizing bacteria (HOB) and iron-reducing bacteria (IRB) on carbon steel corrosion is considered in this study because of the high availability of energetic nutriments (H2, iron oxides and hydroxides) produced in anoxic disposal conditions. Local electrochemical techniques were used for investigating the activity of IRB as a promoter of local corrosion in the presence of H2 as electron donor. A local consumption of H2 by the bacteria has been evidenced and impedance measurements indicate the formation of a thick layer of corrosion products. PMID:24177135

  9. Cuprous Sulfide/Reduced Graphene Oxide Hybrid Nanomaterials: Solvothermal Synthesis and Enhanced Electrochemical Performance

    NASA Astrophysics Data System (ADS)

    He, Zhanjun; Zhu, Yabo; Xing, Zheng; Wang, Zhengyuan

    2016-01-01

    The cuprous sulfide nanoparticles (CuS NPs)-decorated reduced graphene oxide (rGO) nanocomposites have been successfully prepared via a facile and efficient solvothermal synthesis method. Scanning electron microscopy and transmission electron microscopy images demonstrated that CuS micronspheres composed of nanosheets and distributed on the rGO layer in well-monodispersed form. Fourier-transform infrared spectroscopy analyses and x-ray photoelectron spectroscopy showed that graphene oxide (GO) had been reduced to rGO. The electrochemical performances of CuS/rGO nanocomposites were investigated by cyclic voltammetry and charge/discharge techniques, which showed that the specific capacitance of CuS/rGO nanocomposites was enhanced because of the introduction of rGO.

  10. Hydrothermal synthesis of layered sodium manganese oxide nanowires and their electrochemical performance.

    PubMed

    Liu, Xian-Ming; Huang, Zhen-Dong; Oh, Sei-Woon; Ma, Peng-Cheng; Ma, Jun; Li, Bao-Hua; Kim, Jang-Kyo

    2010-11-01

    A new method for preparing black birnessite nanowires is introduced. Layer-structured manganese oxide nanowires were synthesized by a facile hydrothermal method, and using both NaMnO4 and CH3CH2OH as the precursors in a concentrated NaOH solution. The structure, composition, appearance and electrochemical performance of the product were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy diffraction (ED), high-resolution transmission electron microscopy (HRTEM), thermogravimetric analysis (TGA) and constant current charge/discharge. The XRD patterns showed a single phase corresponding to a crystalline birnessite-based manganese oxide. TEM studies suggested their wire-like structures. The TGA measurement demonstrated that they possessed an excellent thermal stability up to 400 degrees C. In the potential window of 2.0-4.3 V, the product exhibited excellent cyclic stability and rapid charge-discharge performance. PMID:21137939

  11. Microwave synthesis and electrochemical characterization of Mn/Ni mixed oxide for supercapacitor application

    SciTech Connect

    Prasankumar, T.; Jose, Sujin P.; Ilangovan, R.; Venkatesh, K. S.

    2015-06-24

    Nanostructured Mn/Ni mixed metal oxide was synthesized at ambient temperature by facile microwave irradiation technique. The crystal structure and surface morphology were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. X-ray diffraction analysis confirmed the formation of Mn/Ni mixed oxide in rhombohedral phase and the grain size calculated was found to be 87 nm. The irregular spherical morphology of the prepared sample was exhibited by the SEM images. The characteristic peaks of FTIR at about 630 cm{sup −1} and 749 cm{sup −1} were attributed to the Mn-O and Ni-O stretching vibrations respectively. The presence of both Mn and Ni in the prepared sample was validated by the EDS spectra which in turn confirmed the formation of mixed oxide. Cyclic voltammetry and galvanostatic chargedischarge measurements were employed to investigate the electrochemical performance of the mixed oxide. The cyclic voltammetry curves demonstrated good capacitive performance of the sample in the potential window −0.2V to 0.9V. The charge discharge study revealed the suitability of the prepared mixed oxide for the fabrication of supercapacitor electrode.

  12. Evidence for decoupled electron and proton transfer in the electrochemical oxidation of ammonia on Pt(100)

    DOE PAGESBeta

    Katsounaros, Ioannis; Chen, Ting; Gewirth, Andrew A.; Markovic, Nenad M.; Koper, Marc T. M.

    2016-01-12

    The two traditional mechanisms of the electrochemical ammonia oxidation consider only concerted proton-electron transfer elementary steps and thus they predict that the rate–potential relationship is independent of the pH on the pH-corrected RHE potential scale. In this letter we show that this is not the case: the increase of the solution pH shifts the onset of the NH3-to-N2 oxidation on Pt(100) to lower potentials and also leads to higher surface concentration of formed NOad before the latter is oxidized to nitrite. Therefore, we present a new mechanism for the ammonia oxidation which incorporates a deprotonation step occurring prior to themore » electron transfer. The deprotonation step yields a negatively charged surface-adsorbed species which is discharged in a subsequent electron transfer step before the N–N bond formation. The negatively charged species is thus a precursor for the formation of N2 and NO. The new mechanism should be a future guide for computational studies aiming at the identification of intermediates and corresponding activation barriers for the elementary steps. As a result, ammonia oxidation is a new example of a bond-forming reaction on (100) terraces which involves decoupled proton-electron transfer.« less

  13. LABORATORY EVALUATION OF A MICROFLUIDIC ELECTROCHEMICAL SENSOR FOR AEROSOL OXIDATIVE LOAD

    PubMed Central

    Koehler, Kirsten; Shapiro, Jeffrey; Sameenoi, Yupaporn; Henry, Charles; Volckens, John

    2014-01-01

    Human exposure to particulate matter (PM) air pollution is associated with human morbidity and mortality. The mechanisms by which PM impacts human health are unresolved, but evidence suggests that PM intake leads to cellular oxidative stress through the generation of reactive oxygen species (ROS). Therefore, reliable tools are needed for estimating the oxidant generating capacity, or oxidative load, of PM at high temporal resolution (minutes to hours). One of the most widely reported methods for assessing PM oxidative load is the dithiothreitol (DTT) assay. The traditional DTT assay utilizes filter-based PM collection in conjunction with chemical analysis to determine the oxidation rate of reduced DTT in solution with PM. However, the traditional DTT assay suffers from poor time resolution, loss of reactive species during sampling, and high limit of detection. Recently, a new DTT assay was developed that couples a Particle-Into-Liquid-Sampler with microfluidic-electrochemical detection. This ‘on-line’ system allows high temporal resolution monitoring of PM reactivity with improved detection limits. This study reports on a laboratory comparison of the traditional and on-line DTT approaches. An urban dust sample was aerosolized in a laboratory test chamber at three atmospherically-relevant concentrations. The on-line system gave a stronger correlation between DTT consumption rate and PM mass (R2 = 0.69) than the traditional method (R2 = 0.40) and increased precision at high temporal resolution, compared to the traditional method. PMID:24711675

  14. Facile preparation of polypyrrole/graphene oxide nanocomposites with large areal capacitance using electrochemical codeposition for supercapacitors

    NASA Astrophysics Data System (ADS)

    Zhou, Haihan; Han, Gaoyi; Xiao, Yaoming; Chang, Yunzhen; Zhai, Hua-Jin

    2014-10-01

    A simple and low-cost electrochemical codeposition method has been introduced to fabricate polypyrrole/graphene oxide (PPy/GO) nanocomposites and the areal capacitance of conducting polymer/GO composites is reported for the first time. Fourier transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) are implemented to determine the PPy/GO nanocomposites are successfully prepared and the interaction between PPy and GO. The as-prepared PPy/GO nanocomposites show the curly sheet-like morphology, superior capacitive behaviors and cyclic stability. Furthermore, the varying deposition time is implemented to investigate the impact of the loading amount on electrochemical behavior of the composites, and a high areal capacitance of 152 mF cm-2 is achieved at 10 mV s-1 CV scan. However, the thicker films caused by the long deposition time would result in larger diffusion resistance of electrolyte ions, consequently exhibit the relatively lower capacitance value at the high current density. The GCD tests indicate moderate deposition time is more suitable for the fast charge/discharge. Considering the very simple and effective synthetic process, the PPy/GO nanocomposites with relatively high areal capacitance are competitive candidate for supercapacitor application, and its capacitive performances can be easily tuned by varying the deposition time.

  15. Hydrothermal-reduction synthesis of manganese oxide nanomaterials for electrochemical supercapacitors.

    PubMed

    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). PMID:21138016

  16. Ionic and electrochemical phenomena induced by structural and chemical defects in oxide thin films

    NASA Astrophysics Data System (ADS)

    Aruta, Carmela

    Interactions at the surfaces/interfaces between complex oxides and gaseous environment are fundamental for the efficiency of many environmental friendly systems and applications. Such interactions can be modified by the intricate interrelationship between microstructure and chemical substitution defects, being their role on functional properties, such as ionic conductivity and surface reaction rates, as particularly relevant as difficult to discriminate. New possibilities in thin film fabrication allow growth of oxide thin films with a more precise control of the structure and chemical stoichiometry, thus unveiling new perspectives in the study of electrochemical effects for physical functionalities, through nanoscale characterizations by complementary state-of-art techniques. As an example of interfacial structural defect effects, we will discuss the case of yttrium doped barium zirconate thin films, where the cation substitutions represent a viable mechanism, alternative to the formation of dislocations near the interface, to relieve the strain building up in the film growing on a highly mismatched substrate, thus providing fast transport pathways together with enhanced interface electrochemical reactivity. The effect of the chemical defects will be further presented in the case of samarium-doped ceria films with different doping concentration. We will explain the role of the trivalent doping on the conduction mechanism, i.e. proton or oxygen ion, which in turns may greatly influence the surface reactivity.

  17. Selective oxidation of ethane using the Au|YSZ|Ag electrochemical membrane system

    SciTech Connect

    Hamakawa, Satoshi; Sato, Koichi; Hayakawa, Takashi; York, A.P.E.; Tsunoda, Tatsuo; Suzuki, Kunio; Shimizu, Masao; Takehira, Katsuomi

    1997-01-01

    The catalytic conversion of ethane to acetaldehyde on an inert gold electrode has been studied using the electrochemical membrane reactor with yttria-stabilized zirconia (YSZ) solid electrolyte at 475 C. On applying a direct current to the reaction cell, 5% ethane in N{sub 2}, Au|YSZ|Ag, 100% O{sub 2}, acetaldehyde was formed and the formation rate increased linearly with increasing current. Selectivities to acetaldehyde and carbon dioxide were 45 and 55%, respectively. The addition of oxygen to the ethane-mixed gas in the anode space did not affect the acetaldehyde formation. The use of YSZ powder as a fixed bed catalyst under the mixed gas flow of ethane and oxygen at 450 to 600 C resulted in the formation of carbon monoxide, carbon dioxide, and ethene. Even the use of N{sub 2}O instead of oxygen resulted in no formation of acetaldehyde. Hence, it is likely that partial oxidation of ethane to acetaldehyde was carried out by the oxygen species transferred electrochemically through the YSZ which appeared at the gold-YSZ-gas triple-phase boundary. From the results of ethanol oxidation over the Au|YSZ|Ag system, the following mechanism was proposed: ethane is dehydrogenated to an ethyl radical, then converted to ethoxide, and finally to acetaldehyde by the oxygen species transferred through the YSZ.

  18. Inhibited Ru(bpy)3 2+ electrochemiluminescence related to electrochemical oxidation activity of inhibitors.

    PubMed

    Chi, Yuwu; Dong, Yongqiang; Chen, Guonan

    2007-06-15

    Electrochemiluminescence (ECL) has been accepted by the analytical chemist as a powerful tool for detection of many inorganic and organic compounds. Ru(bpy)3 2+ has been the most popular ECL system, and many investigations have been focused on the application based on the enhancement or inhibition of Ru(bpy)3 2+ ECL system. However, not much attention has been paid to the theoretical investigation of this ECL system, especially to the inhibiting mechanism for the Ru(bpy)3 2+ ECL system. In the present study, many of the inorganic and organic compounds with electrochemical oxidation activity were found to strongly inhibit Ru(bpy)3 2+ ECL. To explain these inhibited ECL phenomena, a new "electrochemical oxidation inhibiting" mechanism has been proposed via the establishment of a corresponding model. The effects of applied potential, uncompensated resistance, and concentration of inhibitor on the inhibited ECL derived from the model have been verified by experiments. The new ECL inhibition mechanism can be commonly used to explain many kinds of inhibited ECL presently observed, and it is envisioned to result in finding of more inhibitors of this type and establishment of new sensitive ECL detection methods for them. PMID:17489558

  19. Fabrication of MnO 2-pillared layered manganese oxide through an exfoliation/reassembling and oxidation process

    NASA Astrophysics Data System (ADS)

    Yuan, Jiaqi; Liu, Zong-Huai; Qiao, Shanfeng; Ma, Xiangrong; Xu, Naicai

    MnO 2-pillared layered manganese oxide has been first fabricated by a delamination/reassembling process followed by oxidation reaction and then by heat treatment. The structural evolution of MnO 2-pillared layered manganese oxide has been characterized by XRD, SEM, DSC-GTA, IR and N 2 adsorption-desorption. MnO 2-pillared layered manganese oxide shows a relative high thermal stability and mesoporous characteristic. The layered structure with a basal spacing of 0.66 nm could be maintained up to 400 °C. The electrochemical properties of the synthesized MnO 2-pillared layered manganese oxide have been studied using cyclic voltammetry in a mild aqueous electrolyte. Sample MnO 2-BirMO (300 °C) shows good capacitive behavior and cycling stability, and the specific capacitance value is 206 F g -1.

  20. Spray absorption and electrochemical reduction of nitrogen oxides from flue gas.

    PubMed

    Guo, Qingbin; Sun, Tonghua; Wang, Yalin; He, Yi; Jia, Jinping

    2013-08-20

    This work developed an electrochemical reduction system which can effectively scrub NO× from flue gas by using aqueous solution of Fe(II)(EDTA) (ethylenediaminetetraacetate) as absorbent and electrolyte. This new system features (a) complete decomposition of NOX to harmless N2; and (b) fast regeneration of Fe(II)(EDTA) through electrochemical reaction. The Fe(II)(EDTA) solution was recycled and reused continuously during entire process, and no harmful waste was generated. The reaction mechanism was thoroughly investigated by using voltammetric, chromatographic and spectroscopic approaches. The operating conditions of the system were optimized based on NOX removal efficiency. Approximately 98% NO removal was obtained at the optimal condition. The interference of SO2 in flue gas and the system operating stability was also evaluated. PMID:23875953

  1. Electrochemical Potential Gradient as a Quantitative in Vitro Test Platform for Cellular Oxidative Stress.

    PubMed

    Bryant, Carson; Atha, Donald; Reipa, Vytas

    2016-01-01

    Oxidative stress in a biological system is often defined as a redox imbalance within cells or groups of cells within an organism. Reductive-oxidative (redox) imbalances in cellular systems have been implicated in several diseases, such as cancer. To better understand the redox environment within cellular systems, it is important to be able to characterize the relationship between the intensity of the oxidative environment, characterized by redox potential, and the biomolecular consequences of oxidative damage. In this study, we show that an in situ electrochemical potential gradient can serve as a tool to simulate exogenous oxidative stress in surface-attached mammalian cells. A culture plate design, which permits direct imaging and analysis of the cell viability, following exposure to a range of solution redox potentials, was developed. The in vitro oxidative stress test vessel consists of a cell growth flask fitted with two platinum electrodes that support a direct current along the flask bottom. The applied potential span and gradient slope can be controlled by adjusting the constant current magnitude across the vessel with spatially localized media potentials measured with a sliding reference electrode. For example, the viability of Chinese Hamster Ovary cells under a gradient of redox potentials indicated that cell death was initiated at approximately 0.4 V vs. standard hydrogen electrode (SHE) media potential and this potential could be modified with antioxidants. This experimental platform may facilitate studies of oxidative stress characteristics on different types of cells by enabling imaging live cell cultures that have been exposed to a gradient of exogenous redox potentials. PMID:27409641

  2. Electrochemical metallization switching with a platinum group metal in different oxides

    NASA Astrophysics Data System (ADS)

    Wang, Zhongrui; Jiang, Hao; Hyung Jang, Moon; Lin, Peng; Ribbe, Alexander; Xia, Qiangfei; Yang, J. Joshua

    2016-07-01

    In a normal electrochemical metallization (ECM) switch, electrochemically active metals, such as Ag and Cu are used to provide mobile ions for the conducting filament. In both ECM and valence change memory (VCM) devices, platinum group metals, such as Pt and Pd, are typically used as the counter electrode and assumed to be chemically and physically inert. In this study, we explore whether the so-called inert metal itself can form a conducting filament and result in repeatable resistance switching. Pd and different oxide host matrices are used for this purpose. We have observed that the transport of oxygen anions dominates over Pd metal cations in ALD deposited AlOx and HfOx. However, in sputtered SiOx, Pd cation transport was revealed, accompanied by the formation of nano-crystalline Pd filament(s) in the junctions. Based on these observations, memristors with reversible and repeatable switching were obtained by using Pd doped SiOx as the switching material.In a normal electrochemical metallization (ECM) switch, electrochemically active metals, such as Ag and Cu are used to provide mobile ions for the conducting filament. In both ECM and valence change memory (VCM) devices, platinum group metals, such as Pt and Pd, are typically used as the counter electrode and assumed to be chemically and physically inert. In this study, we explore whether the so-called inert metal itself can form a conducting filament and result in repeatable resistance switching. Pd and different oxide host matrices are used for this purpose. We have observed that the transport of oxygen anions dominates over Pd metal cations in ALD deposited AlOx and HfOx. However, in sputtered SiOx, Pd cation transport was revealed, accompanied by the formation of nano-crystalline Pd filament(s) in the junctions. Based on these observations, memristors with reversible and repeatable switching were obtained by using Pd doped SiOx as the switching material. Electronic supplementary information (ESI) available

  3. Basic paths in the development of electrochemical processes using ion exchange membranes. [118 references

    SciTech Connect

    Nikolaev, N.I.; Kirganova, E.V.; Churileva, G.G.

    1980-04-01

    A summary is given of Soviet and foreign literature on the use of cation exchange, anion exchange and bipolar membranes in processes of the desalination of water, demineralization of solutions and the electrochemical synthesis of various inorganic and organic compounds. The specific feature of the electrodialysis process and basic trends of its future development are discussed. 118 references, 2 figures.

  4. Surface Composition, Work Function, and Electrochemical Characteristics of Gallium-Doped Zinc Oxide

    SciTech Connect

    Ratcliff, E. L.; Sigdel, A. K.; Macech, M. R.; Nebesny, K.; Lee, P. A.; Ginley, D. S.; Armstrong, N. R.; Berry, J. J.

    2012-06-30

    Gallium-doped zinc oxide (GZO) possesses the electric conductivity, thermal stability, and earth abundance to be a promising transparent conductive oxide replacement for indium tin oxide electrodes in a number of molecular electronic devices, including organic solar cells and organic light emitting diodes. The surface chemistry of GZO is complex and dominated by the hydrolysis chemistry of ZnO, which influences the work function via charge transfer and band bending caused by adsorbates. A comprehensive characterization of the surface chemical composition and electrochemical properties of GZO electrodes is presented, using both solution and surface adsorbed redox probe molecules. The GZO surface is characterized using monochromatic X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy after the following pretreatments: (i) hydriodic acid etch, (ii) potassium hydroxide etch, (iii) RF oxygen plasma etching, and (iv) high-vacuum argon-ion sputtering. The O 1s spectra for the GZO electrodes have contributions from the stoichiometric oxide lattice, defects within the lattice, hydroxylated species, and carbonaceous impurities, with relative near-surface compositions varying with pretreatment. Solution etching procedures result in an increase of the work function and ionization potential of the GZO electrode, but yield different near surface Zn:Ga atomic ratios, which significantly influence charge transfer rates for a chemisorbed probe molecule. The near surface chemical composition is shown to be the dominant factor in controlling surface work function and significantly influences the rate of electron transfer to both solution and tethered probe molecules.

  5. Legitimate intermediates of oxygen evolution on iridium oxide revealed by in situ electrochemical evanescent wave spectroscopy.

    PubMed

    Ooka, Hideshi; Wang, Yuanqing; Yamaguchi, Akira; Hatakeyama, Makoto; Nakamura, Shinichiro; Hashimoto, Kazuhito; Nakamura, Ryuhei

    2016-06-01

    Understanding how the four-electron oxidation of water to dioxygen proceeds in different materials is critical to the rational design of efficient catalysts towards artificial photosynthetic systems. Here, using in situ electrochemical evanescent wave spectroscopy under oxygen-evolving conditions, we report two intermediates of iridium oxide (IrOx), which is the most active and stable catalyst characterized to date in acidic medium. The observed potential dependence of the two intermediates indicated that they were associated with different surface sites, and intermediate scavenging experiments using H2O2 provided insight into their role during catalysis. Notably, an Ir(V) species with an absorption maximum at 450 nm was found to mediate the initial two-electron oxidation of water. Inhibition of the Ir(V) species by H2O2, combined with computational modeling, indicates that the accumulation and concurrent spin-state change of the Ir(V) species is a prerequisite for efficient water oxidation by IrOx electrodes. PMID:27197557

  6. Influences of graphene oxide support on the electrochemical performances of graphene oxide-MnO2 nanocomposites

    PubMed Central

    2011-01-01

    MnO2 supported on graphene oxide (GO) made from different graphite materials has been synthesized and further investigated as electrode materials for supercapacitors. The structure and morphology of MnO2-GO nanocomposites are characterized by X-ray diffraction, X-ray photoemission spectroscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and Nitrogen adsorption-desorption. As demonstrated, the GO fabricated from commercial expanded graphite (denoted as GO(1)) possesses more functional groups and larger interplane gap compared to the GO from commercial graphite powder (denoted as GO(2)). The surface area and functionalities of GO have significant effects on the morphology and electrochemical activity of MnO2, which lead to the fact that the loading amount of MnO2 on GO(1) is much higher than that on GO(2). Elemental analysis performed via inductively coupled plasma optical emission spectroscopy confirmed higher amounts of MnO2 loading on GO(1). As the electrode of supercapacitor, MnO2-GO(1) nanocomposites show larger capacitance (307.7 F g-1) and better electrochemical activity than MnO2-GO(2) possibly due to the high loading, good uniformity, and homogeneous distribution of MnO2 on GO(1) support. PMID:21951643

  7. A green method to prepare Pd-Ag nanoparticles supported on reduced graphene oxide and their electrochemical catalysis of methanol and ethanol oxidation

    NASA Astrophysics Data System (ADS)

    Li, Lingzhi; Chen, Mingxi; Huang, Guanbo; Yang, Nian; Zhang, Li; Wang, Huan; Liu, Yu; Wang, Wei; Gao, Jianping

    2014-10-01

    Bimetallic palladium-silver nanoparticles (NPs) supported on reduced oxide graphene (RGO) with different Pd/Ag ratios (Pd-Ag/RGO) were prepared by an easy green method which did not use any additional reducing agents or a dispersing agent. During the process, simultaneous redox reactions between AgNO3, K2PdCl4 and graphene oxide (GO) led to bimetallic Pd-Ag NPs. The morphology and composition of the Pd-Ag/RGO were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis and Raman spectroscopy. Cyclic voltammetry and chronoamperometry were used to investigate the electrochemical activities and stabilities of these Pd-Ag/RGO catalysts for the electro-oxidation of methanol and ethanol in alkaline media. Among the different Pd/Ag ratios, the Pd-Ag (1:1)/RGO had the best catalytic activities and stability. So it is a promising catalyst for direct alcohol fuel cell applications.

  8. Process for catalytically oxidizing cycloolefins, particularly cyclohexene

    DOEpatents

    Mizuno, Noritaka; Lyon, David K.; Finke, Richard G.

    1993-01-01

    This invention is a process for catalytically oxidizing cycloolefins, particularly cyclohexenes, to form a variety of oxygenates. The catalyst used in the process is a covalently bonded iridium-heteropolyanion species. The process uses the catalyst in conjunction with a gaseous oxygen containing gas to form 2-cyclohexen-1-ol and also 2-cyclohexen-1-one.

  9. Size Dependence of [n]Cycloparaphenylenes (n=5-12) in Electrochemical Oxidation.

    PubMed

    Kayahara, Eiichi; Fukayama, Kei; Nishinaga, Tohru; Yamago, Shigeru

    2016-06-21

    The oxidation processes of [n]cycloparaphenylenes ([n]CPPs) (n=5-12) were systematically investigated by cyclic and rotating disk electrode voltammetry. All CPPs underwent pseudo-reversible two-electron oxidation irrespective of ring size, forming the corresponding radical cations and then dications. The results were in sharp contrast to those observed for linear oligoparaphenylenes, which only undergo one-electron oxidation. The difference in the first and second oxidation potentials in the CPP oxidation was affected by the ring size and became more significant as the decrease of CPP size. In other words, while the first oxidation from neutral CPP to the radical cation occurred faster as the size of CPP becomes smaller, the second oxidation from the radical cation to dication exhibited opposite size dependence. PMID:27137132

  10. Microwave processing of ceramic oxide filaments

    SciTech Connect

    Vogt, G.J.; Katz, J.D.

    1995-05-01

    The objective of the microwave filament processing project is to develop microwave techniques at 2.45 GHZ to manufacture continuous ceramic oxide filaments. Microwave processing uses the volumetric absorption of microwave power in oxide filament tows to drive off process solvents, to burn out organic binders, and to sinter the dried fibers to produce flexible, high-strength ceramic filaments. The technical goal is to advance filament processing technology by microwave heating more rapidly with less energy and at a lower cost than conventional processing, but with the same quality as conventional processing. The manufacturing goal is to collaborate with the 3M Company, a US manufacturer of ceramic oxide filaments, to evaluate the technology using a prototype filament system and to transfer the microwave technology to the 3M Company.

  11. Alleviation of membrane fouling in a submerged membrane bioreactor with electrochemical oxidation mediated by in-situ free chlorine generation.

    PubMed

    Chung, Chong Min; Tobino, Tomohiro; Cho, Kangwoo; Yamamoto, Kazuo

    2016-06-01

    The control of membrane fouling is still the biggest challenge that membrane bioreactor (MBR) for wastewater treatment faces with. In this report, we evince that an in-situ electrochemical free chlorine generation is effective for membrane fouling mitigation. An electrochemical oxidation (EO) apparatus with perforated Ti/IrO2 anodes and Ti/Pt cathodes was integrated into a conventional MBR with microfiltration module (EO-MBR). The membrane fouling characteristics of EO-MBR fed with synthetic wastewater were monitored for about 2 months in comparison to control MBRs. In the EO-MBR at a direct current density of 0.4 mA/cm(2), the frequency of membrane fouling when the trans-membrane pressure (TMP) reached 30 kPa was effectively reduced by 40% under a physical membrane cleaning regime. The evolution patterns of TMP together with hydraulic resistance analysis based on resistance-in-series model indicated that the electrochemically generated active chlorine alleviated the physically irremovable membrane fouling. Further analysis on extracellular polymeric substances (EPS) of sludge cake layer (SCL) revealed significant reductions of protein contents in soluble EPS and fluorescence emission intensities from humic acids and other fluorophores in bound EPS, which in-turn would decrease the hydrophobic accumulation of organic foulants on membrane pores. The chlorine dosage from the EO apparatus was estimated to be 4.7 mg Cl2/g MLVSS/day and the overall physicochemical properties (bio-solids concentration, floc diameter, zeta-potential) as well as the microbial activity in terms of specific oxygen utilization rate and removal efficiency of dissolved organic carbon (>97%) were not affected significantly. A T-RFLP (terminal restriction fragment length polymorphism) analysis suggested noticeable shifts in microbial community both in mixed liquor and sludge cake layer. Consequently, our electrochemical chlorination would be an efficient fouling control strategy in membrane

  12. Poly(zwitterionic liquids) functionalized polypyrrole/graphene oxide nanosheets for electrochemically detecting dopamine at low concentration.

    PubMed

    Mao, Hui; Liang, Jiachen; Ji, Chunguang; Zhang, Haifeng; Pei, Qi; Zhang, Yuyang; Zhang, Yu; Hisaeda, Yoshio; Song, Xi-Ming

    2016-08-01

    Poly(3-(1-vinylimidazolium-3-yl)propane-1-sulfonate) (PVIPS), a novel kind of poly(zwitterionic liquids) (PZILs) containing both imidazolium cation and sulfonate anion, was successfully modified on the surface of polypyrrole/graphene oxide nanosheets (PPy/GO) by covalent bonding. The obtained novel PZILs functionalized PPy/GO nanosheets (PVIPS/PPy/GO) modified glassy carbon electrode (GCE) presented the excellent electrochemical catalytic activity towards dopamine (DA) with high stability, sensitivity, selectivity and wide linear range (40-1220nM), especially having a lower detection limit (17.3nM). The excellent analytical performance is attributed to the strongly negative charges on the surface of modified GCE in aqueous solution, which is different from conventional poly(ionic liquids) modified GCE. DA cations could be quickly enriched on the electrode surface by electrostatic interaction in solution due to the existence of SO3(-) groups with negative charge at the end of pendant groups in zwitterionic PVIPS, resulting in a change of the electrons transmission mode in the oxidation of DA, that is, from a typical diffusion-controlled process at conventional poly(1-vinyl-3-ethylimidazole bromide) (PVEIB)/PPy/GO modified GCE to a typical surface-controlled process. PMID:27157737

  13. Electrochemical process for the preparation of nitrogen fertilizers

    SciTech Connect

    Jiang, Junhua; Aulich, Ted R; Ignatchenko, Alexey V

    2015-04-14

    Methods and apparatus for the preparation of nitrogen fertilizers including ammonium nitrate, urea, urea-ammonium nitrate, and/or ammonia are disclosed. Embodiments include (1) ammonium nitrate produced via the reduction of a nitrogen source at the cathode and the oxidation of a nitrogen source at the anode; (2) urea or its isomers produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source: (3) ammonia produced via the reduction of nitrogen source at the cathode and the oxidation of a hydrogen source or a hydrogen equivalent such as carbon monoxide or a mixture of carbon monoxide and hydrogen at the anode; and (4) urea-ammonium nitrate produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source.

  14. Electrochemical process for the preparation of nitrogen fertilizers

    DOEpatents

    Aulich, Ted R.; Olson, Edwin S.; Jiang, Junhua

    2013-03-19

    The present invention provides methods and apparatus for the preparation of nitrogen fertilizers including ammonium nitrate, urea, urea-ammonium nitrate, and/or ammonia utilizing a source of carbon, a source of nitrogen, and/or a source of hydrogen. Implementing an electrolyte serving as ionic charge carrier, (1) ammonium nitrate is produced via the reduction of a nitrogen source at the cathode and the oxidation of a nitrogen source at the anode; (2) urea or its isomers are produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source; (3) ammonia is produced via the reduction of nitrogen source at the cathode and the oxidation of a hydrogen source at the anode; and (4) urea-ammonium nitrate is produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source. The electrolyte can be solid.

  15. Study of degradation intermediates formed during electrochemical oxidation of pesticide residue 2,6-dichlorobenzamide (BAM) at boron doped diamond (BDD) and platinum-iridium anodes.

    PubMed

    Madsen, Henrik Tækker; Søgaard, Erik Gydesen; Muff, Jens

    2014-08-01

    Electrochemical oxidation is a promising technique for degradation of otherwise recalcitrant organic micropollutants in waters. In this study, the applicability of electrochemical oxidation was investigated concerning the degradation of the groundwater pollutant 2,6-dichlorobenzamide (BAM) through the electrochemical oxygen transfer process with two anode materials: Ti/Pt90-Ir10 and boron doped diamond (Si/BDD). Besides the efficiency of the degradation of the main pollutant, it is also of outmost importance to control the formation and fate of stable degradation intermediates. These were investigated quantitatively with HPLC-MS and TOC measurements and qualitatively with a combined HPLC-UV and HPLC-MS protocol. 2,6-Dichlorobenzamide was found to be degraded most efficiently by the BDD cell, which also resulted in significantly lower amounts of intermediates formed during the process. The anodic degradation pathway was found to occur via substitution of hydroxyl groups until ring cleavage leading to carboxylic acids. For the BDD cell, there was a parallel cathodic degradation pathway that occurred via dechlorination. The combination of TOC with the combined HPLC-UV/MS was found to be a powerful method for determining the amount and nature of degradation intermediates. PMID:24873711

  16. Insight of an easy topochemical oxidative reaction in obtaining high performance electrochemical capacitor based on CoIICoIII monometallic cobalt Layered Double Hydroxide

    NASA Astrophysics Data System (ADS)

    Vialat, Pierre; Rabu, Pierre; Mousty, Christine; Leroux, Fabrice

    2015-10-01

    A series of monometallic Layered Double Hydroxides (LDH) using electroactive cation, i.e. divalent or trivalent cobalt, was prepared by Topochemical Oxidation Reaction (TOR) under O2 atmosphere at 40 °C from pristine β-Co(OH)2 platelets. The oxidation state of the ill-defined layered materials was evaluated by coupling thermal measurements and chemical titration (iodometry). Their characterization by ancillary techniques was completed by the study of their magnetic behavior. The obtained magnetic moments suggest the presence of structural local deformation around the CoII ions, unhomogeneous charge distribution yielding to clustering effects cannot be discarded. Their pseudo-faradic properties as supercapacitor in KOH solution was thoroughly investigated by using Cyclic Voltammetry (CV), Galvanostatic Cycling with Potential Limitation (GCPL) and Electrochemical Impedance Spectroscopy (EIS) techniques. As a function of the oxygen treatment, the relative amount of CoII/CoIII was found to range into 5.3 and 13.3, which is unusually high when compared to classical LDH charge distribution. Pseudocapacitance as high as 1540 F g-1 was obtained underlining a high percentage of CoII, ≈40%, involved in electrochemical process. This high percentage is tentatively explained by an extended outer-active electrochemical surface which demonstrates that TOR is a quick and easy process to get a high pseudocapacitive performance.

  17. A label-free electrochemical aptasensor based on graphene oxide/double-stranded DNA nanocomposite.

    PubMed

    Li, Yu; Wang, Qi; Zhang, Yuting; Deng, Dongmei; He, Haibo; Luo, Liqiang; Wang, Zhenxin

    2016-09-01

    A novel label-free electrochemical impedance aptasensor based on a gold nanoparticles/double-stranded DNA-graphene (AuNPs/dsDNA-GO) nanocomposite modified glassy carbon electrode was presented for quantitative determination of thrombin. GO was covalently functionalized with dsDNA via a facile amidation process, and then AuNPs were electrodeposited onto the surface of dsDNA-GO. The morphology, conductivity and interaction of the as-prepared nanocomposites were characterized by scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy (EIS), Raman and Fourier transform infrared spectroscopy. The thrombin-binding aptamer (TBA) was conjugated to AuNPs via gold-thiol chemistry to construct electrochemical aptasensing platform, and the specific recognition between TBA and thrombin was monitored by EIS. Under optimum conditions, thrombin could be quantified in a wide range of 0.1-100nM (R(2)=0.9960) with low detection limit of 0.06nM (S/N=3). PMID:27182650

  18. Three-dimensionally grown thorn-like Cu nanowire arrays by fully electrochemical nanoengineering for highly enhanced hydrazine oxidation.

    PubMed

    Huang, Jianfei; Zhao, Shunan; Chen, Wei; Zhou, Ying; Yang, Xiaoling; Zhu, Yihua; Li, Chunzhong

    2016-03-21

    This communication reports fully electrochemical nanoengineering toward three-dimensionally grown thorn-like Cu nanowire arrays (CNWAs) as a highly efficient and durable electrocatalyst for hydrazine oxidation. Characterized by substantial negative shifting of the onset potential and an enlarged catalytic current density, the CNWAs afforded greatly enhanced hydrazine oxidation activity, even transcending that of the Pt/C catalyst at a higher reaction rate. The parameters of the electrochemical engineering and metallization methods were found to be essentially influential on the microstructure, and thus the electrocatalytic activity of the CNWAs. The present work typifies a flexible and expandible route toward integrated electrodes of metallic 1D nanostructures which are of interest in advancing the performance of cutting-edge electrochemical applications. PMID:26580842

  19. Observation and Quantification of Nanoscale Processes in Lithium Batteries by Operando Electrochemical (S)TEM

    SciTech Connect

    Mehdi, Beata L.; Qian, Jiangfeng; Nasybulin, Eduard; Park, Chiwoo; Welch, David A.; Faller, Roland; Mehta, Hardeep S.; Henderson, Wesley A.; Xu, Wu; Wang, Chong M.; Evans, James E.; Liu, Jun; Zhang, Jiguang; Mueller, Karl T.; Browning, Nigel D.

    2015-03-11

    An operando electrochemical stage for the transmission electron microscope has been configured to form a “Li battery” that is used to quantify the electrochemical processes that occur at the anode during charge/discharge cycling. Of particular importance for these observations is the identification of an image contrast reversal that originates from solid Li being less dense than the surrounding liquid electrolyte and electrode surface. This contrast allows Li to be identified from Li containing compounds that make up the solid-electrolyte interphase (SEI) layer. By correlating images showing the sequence of Li electrodeposition and the evolution of the SEI layer with simultaneously acquired and calibrated cyclic voltammograms (CV), electrodeposition and electrolyte breakdown processes can be quantified directly on the nanoscale. This approach opens up intriguing new possibilities to rapidly visualize and test the electrochemical performance of a wide range of electrode/electrolyte combinations for next generation battery systems.

  20. Observation and quantification of nanoscale processes in lithium batteries by operando electrochemical (S)TEM.

    PubMed

    Mehdi, B L; Qian, J; Nasybulin, E; Park, C; Welch, D A; Faller, R; Mehta, H; Henderson, W A; Xu, W; Wang, C M; Evans, J E; Liu, J; Zhang, J-G; Mueller, K T; Browning, N D

    2015-03-11

    An operando electrochemical stage for the transmission electron microscope has been configured to form a "Li battery" that is used to quantify the electrochemical processes that occur at the anode during charge/discharge cycling. Of particular importance for these observations is the identification of an image contrast reversal that originates from solid Li being less dense than the surrounding liquid electrolyte and electrode surface. This contrast allows Li to be identified from Li-containing compounds that make up the solid-electrolyte interphase (SEI) layer. By correlating images showing the sequence of Li electrodeposition and the evolution of the SEI layer with simultaneously acquired and calibrated cyclic voltammograms, electrodeposition, and electrolyte breakdown processes can be quantified directly on the nanoscale. This approach opens up intriguing new possibilities to rapidly visualize and test the electrochemical performance of a wide range of electrode/electrolyte combinations for next generation battery systems. PMID:25705928

  1. Electrochemical Processes for In-Situ Treatment of Contaminated Soils - Final Report - 09/15/1996 - 01/31/2001

    SciTech Connect

    Huang, Chin-Pao

    2001-05-31

    This project will study electrochemical processes for the in situ treatment of soils contaminated by mixed wastes, i.e., organic and inorganic. Soil samples collected form selected DOE waste sites will be characterized for specific organic and metal contaminants and hydraulic permeability. The soil samples are then subject to desorption experiments under various physical-chemical conditions such as pH and the presence of surfactants. Batch electro-osmosis experiments will be conducted to study the transport of contaminants in the soil-water systems. Organic contaminants that are released from the soil substrate will be treated by an advanced oxidation process, i.e., electron-Fantan. Finally, laboratory reactor integrating the elector-osmosis and elector-Fantan processes will be used to study the treatment of contaminated soil in situ.

  2. Three-dimensionally grown thorn-like Cu nanowire arrays by fully electrochemical nanoengineering for highly enhanced hydrazine oxidation

    NASA Astrophysics Data System (ADS)

    Huang, Jianfei; Zhao, Shunan; Chen, Wei; Zhou, Ying; Yang, Xiaoling; Zhu, Yihua; Li, Chunzhong

    2016-03-01

    This communication reports fully electrochemical nanoengineering toward three-dimensionally grown thorn-like Cu nanowire arrays (CNWAs) as a highly efficient and durable electrocatalyst for hydrazine oxidation. Characterized by substantial negative shifting of the onset potential and an enlarged catalytic current density, the CNWAs afforded greatly enhanced hydrazine oxidation activity, even transcending that of the Pt/C catalyst at a higher reaction rate. The parameters of the electrochemical engineering and metallization methods were found to be essentially influential on the microstructure, and thus the electrocatalytic activity of the CNWAs. The present work typifies a flexible and expandible route toward integrated electrodes of metallic 1D nanostructures which are of interest in advancing the performance of cutting-edge electrochemical applications.This communication reports fully electrochemical nanoengineering toward three-dimensionally grown thorn-like Cu nanowire arrays (CNWAs) as a highly efficient and durable electrocatalyst for hydrazine oxidation. Characterized by substantial negative shifting of the onset potential and an enlarged catalytic current density, the CNWAs afforded greatly enhanced hydrazine oxidation activity, even transcending that of the Pt/C catalyst at a higher reaction rate. The parameters of the electrochemical engineering and metallization methods were found to be essentially influential on the microstructure, and thus the electrocatalytic activity of the CNWAs. The present work typifies a flexible and expandible route toward integrated electrodes of metallic 1D nanostructures which are of interest in advancing the performance of cutting-edge electrochemical applications. Electronic supplementary information (ESI) available: Experimental details, additional figures and table. See DOI: 10.1039/c5nr06512g

  3. Electrochemically reduced graphene oxide/carbon nanotubes composites as binder-free supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Yang, Qin; Pang, Siu-Kwong; Yung, Kam-Chuen

    2016-04-01

    Binder-free composites of electrochemically reduced graphene oxide (ecrGO) and multiwalled carbon nanotubes (MWCNTs) were fabricated as supercapacitors electrodes operating in aqueous systems. GO was found to be electrochemically reduced according to the XRD and Raman data. Therefore, this facile and controllable method was applied to reduce GO in the GO/MWCNTs composites, generating ecrGO/MWCNTs composites. The ecrGO/MWCNTs composites exhibit higher specific capacitance (Csp) than ecrGO because the intercalation of MWCNTs into ecrGO sheets increases the surface areas, according to the TEM, XRD and N2 adsorption-desorption results. The composites with different mass ratios of GO to MWCNTs (10:1, 5:1, 1:1, 1:5, 1:10) were investigated. The ecrGO/MWCNTs composite (GO: MWCNTs = 5:1) showed the highest Csp from the cyclic voltammetry results at a scan rate of 10 mV s-1, and it expressed Csp of 165 F g-1 at a current density of 1 A g-1 and 93% retention after 4000 cycles of charge/discharge. When the mass ratio of GO to MWCNTs further decreases to 1:10, the Csp of the composites declines, and the ecrGO/MWCNTs composite (GO: MWCNTs = 1:10) performs a nearly pure double-layer capacitor. However, the composites containing more MWCNTs can maintain better capacitive behavior at higher rates of charge/discharge.

  4. Direct and environmentally benign synthesis of manganese oxide/graphene composites from graphite for electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Lee, Hae-Min; Jeong, Gyoung Hwa; Kang, Doo Won; Kim, Sang-Wook; Kim, Chang-Koo

    2015-05-01

    We develop a direct and environmentally benign method to prepare manganese oxide (Mn3O4)/graphene composites via one-step hydrothermal synthesis from graphite without using strong acids and toxic reducing agents. Structural and morphological analyses reveals that the irregularly shaped Mn3O4 nanoparticles are well-dispersed on the graphene flakes. Cyclic voltammetry and galvanostatic charge-discharge tests indicate that the charge-storing mechanism of the Mn3O4/graphene composites is pseudocapacitive. The Mn3O4/graphene composite exhibits a specific capacitance of 367 F/g at a current density of 5 A/g. After 3000 charge-discharge cycles, the Mn3O4/graphene electrode retains 91.8% of its initial specific capacitance. From electrochemical impedance spectra, it is evident that the changes in both the equivalent series resistance and charge-transfer resistance of the Mn3O4/graphene electrode before and after 3000 charge-discharge cycles are small, indicating good cycling and electrochemical stability of the Mn3O4/graphene electrode.

  5. Multi-resistive Reduced Graphene Oxide Diode with Reversible Surface Electrochemical Reaction induced Carrier Control

    PubMed Central

    Seo, Hyungtak; Ahn, Seungbae; Kim, Jinseo; Lee, Young-Ahn; Chung, Koo-Hyun; Jeon, Ki-Joon

    2014-01-01

    The extended application of graphene-based electronic devices requires a bandgap opening in order to realize the targeted device functionality. Since the bandgap tuning of pristine graphene is limited to 360 meV, the chemical modification of graphene is considered essential to achieve a large bandgap opening at the expense of electrical properties degradation. Reduced graphene oxide (RGO) has attracted significant interest for fabricating graphene-based semiconductors since it has several advantages over other forms of chemically modified graphene; such as tunable bandgap opening, decent electrical properties, and easy synthesis. Because of the reduced bonding nature of RGO, the role of metastable oxygen in the RGO matrix is recently highlighted and it may offer emerging ionic devices. In this study, we show that multi-resistivity RGO/n-Si diodes can be obtained by controlling the RGO thickness at a nanometer scale. This is made possible by (1) a metastable lattice-oxygen drift within bulk RGO and (2) electrochemical ambient hydroxyl (OH) formation at the RGO surface. The effect demonstrated in a p-RGO/n-Si heterojunction diode is equivalent to electrochemically driven reversible electronic manipulation and therefore provides an important basis for the application of O bistability in RGO for chemical sensors and electrocatalysis. PMID:25007942

  6. Defect physics vis-à-vis electrochemical performance in layered mixed-metal oxide cathode materials

    NASA Astrophysics Data System (ADS)

    Hoang, Khang; Johannes, Michelle

    Layered mixed-metal oxides with different compositions of (Ni,Co,Mn) [NCM] or (Ni,Co,Al) [NCA] have been used in commercial lithium-ion batteries. Yet their defect physics and chemistry is still not well understood, despite having important implications for the electrochemical performance. In this presentation, we report a hybrid density functional study of intrinsic point defects in the compositions LiNi1/3Co1/3Mn1/3O2 (NCM1/3) and LiNi1/3Co1/3Al1/3O2 (NCA1/3) which can also be regarded as model compounds for NCM and NCA. We will discuss defect landscapes in NCM1/3 and NCA1/3 under relevant synthesis conditions with a focus on the formation of metal antisite defects and its implications on the electrochemical properties and ultimately the design of NCM and NCA cathode materials.

  7. Electrochemical effect of lithium tungsten oxide modification on LiCoO2 thin film electrode

    NASA Astrophysics Data System (ADS)

    Hayashi, Tetsutaro; Okada, Jiro; Toda, Eiji; Kuzuo, Ryuichi; Matsuda, Yasutaka; Kuwata, Naoaki; Kawamura, Junichi

    2015-07-01

    We fabricated a lithium tungsten oxide (LWO)-modified LiCoO2 (LCO) thin film electrode by pulsed laser deposition and investigated the reason for its lower resistance as compared with a bare LCO electrode. X-ray diffraction revealed that the LWO layer has a randomly oriented Li2WO4 structure with tetragonal symmetry. Scanning electron microscopy and energy-dispersive X-ray spectroscopy (EDX) indicated that the LWO modification changes the LCO particle surface, and the electrochemical impedance spectroscopy demonstrated that the LWO modification on LCO decreases the lithium ion transfer resistance at the interface between the positive electrode and the liquid electrolyte and increases the frequency factor at the interface. X-ray photoemission spectroscopy, EDX, and electron energy loss spectroscopy (EELS) indicated the presence of phosphate on the surface of the unmodified LCO electrode after electrochemical tests, but EDX and EELS did not indicate the presence of phosphate in the LWO-modified LCO electrode. The absence of phosphates apparently alleviates the hindrance of Li+ ion diffusion and increases the frequency factor in LCO, resulting in lowered Li+ ion transfer resistance at the interface.

  8. Exhaled nitric oxide monitoring by quantum cascade laser: comparison with chemiluminescent and electrochemical sensors

    NASA Astrophysics Data System (ADS)

    Mandon, Julien; Högman, Marieann; Merkus, Peter J. F. M.; van Amsterdam, Jan; Harren, Frans J. M.; Cristescu, Simona M.

    2012-01-01

    Fractional exhaled nitric oxide (FENO) is considered an indicator in the diagnostics and management of asthma. In this study we present a laser-based sensor for measuring FENO. It consists of a quantum cascade laser (QCL) combined with a multi-pass cell and wavelength modulation spectroscopy for the detection of NO at the sub-part-per-billion by volume (ppbv, 1∶10-9) level. The characteristics and diagnostic performance of the sensor were assessed. A detection limit of 0.5 ppbv was demonstrated with a relatively simple design. The QCL-based sensor was compared with two market sensors, a chemiluminescent analyzer (NOA 280, Sievers) and a portable hand-held electrochemical analyzer (MINO®, Aerocrine AB, Sweden). FENO from 20 children diagnosed with asthma and treated with inhaled corticosteroids were measured. Data were found to be clinically acceptable within 1.1 ppbv between the QCL-based sensor and chemiluminescent sensor and within 1.7 ppbv when compared to the electrochemical sensor. The QCL-based sensor was tested on healthy subjects at various expiratory flow rates for both online and offline sampling procedures. The extended NO parameters, i.e. the alveolar region, airway wall, diffusing capacity, and flux were calculated and showed a good agreement with the previously reported values.

  9. Synthesis of Electrochemically Reduced Graphene Oxide Bonded to Thiodiazole-Pd and Applications to Biosensor.

    PubMed

    You, Jung-Min; Han, Hyoung Soon; Jeon, Seungwon

    2015-08-01

    A novel biosensor for the determination of hydrogen peroxide and glucose was developed based on EGN-TDZ-Pd, as an electrocatalyst. The preparation of graphene oxide (GO) nanosheets was functionalized by combining it with 5-amino-1,3,4-thiadiazole-2-thiol (TDZ) and by covalently bonding it to palladium (Pd) nanoparticles (GO-TDZ-Pd). In the electrochemical investigation, EGN-TDZ-Pd was characterized via scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS). Cyclic voltammetry (CV) and chronoamperometry (CA) were used to characterize the performance of EGN-TDZ-Pd. The proposed H2O2 biosensor exhibited a wide linear range from 10 µM to 6.5 mM. Also, a glucose biosensor was prepared using glucose oxidase and EGN-TDZ-Pd placed onto a glassy carbon electrode (GCE). The GOx/EGN-TDZ-Pd/GCE was easily prepared using a rapid and simple procedure, and it was utilized for highly sensitive glucose determination. PMID:26369140

  10. Electrochemical deposition of silver on manganese dioxide coated reduced graphene oxide for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Lee, Kyungmi; Ahmed, Mohammad Shamsuddin; Jeon, Seungwon

    2015-08-01

    We have prepared a reduced graphene oxide (rGO)-supported silver (Ag) and manganese dioxide (MnO2) deposited porous-like catalyst (denoted as rGO/MnO2/Ag) through a facile electrochemical deposition route and have been used as a cathode catalyst for oxygen reduction reaction (ORR) in alkaline fuel cells. The physical properties of rGO/MnO2/Ag have been investigated via several instrumental methods. This material exhibits a polycrystalline structure characterized by Ag/MnO2 microsphere formation as a result of Ostwald ripening. The X-ray diffraction and X-ray photoelectron spectroscopy data reveal that the MnO2 and Ag have been slightly alloyed and Mn presents with the dioxide form on rGO. The electrochemical properties of the electrocatalyst have been studied via several voltammetric methods. The results demonstrated that the rGO/MnO2/Ag has an excellent catalytic activity for ORR in alkaline media compared to the other tested electrodes. Particularly, it shows 1.2 times higher current density and better electron transfer rate at 0.3 V per O2 than that of 20 wt% Pt/C. The other kinetic analysis reveals that the O2 has reduced directly to H2O through a nearly four-electron pathway with better anodic fuel tolerance and duration performance than that of 20% Pt/C.

  11. Electrochemical metallization switching with a platinum group metal in different oxides.

    PubMed

    Wang, Zhongrui; Jiang, Hao; Hyung Jang, Moon; Lin, Peng; Ribbe, Alexander; Xia, Qiangfei; Yang, J Joshua

    2016-08-01

    In a normal electrochemical metallization (ECM) switch, electrochemically active metals, such as Ag and Cu are used to provide mobile ions for the conducting filament. In both ECM and valence change memory (VCM) devices, platinum group metals, such as Pt and Pd, are typically used as the counter electrode and assumed to be chemically and physically inert. In this study, we explore whether the so-called inert metal itself can form a conducting filament and result in repeatable resistance switching. Pd and different oxide host matrices are used for this purpose. We have observed that the transport of oxygen anions dominates over Pd metal cations in ALD deposited AlOx and HfOx. However, in sputtered SiOx, Pd cation transport was revealed, accompanied by the formation of nano-crystalline Pd filament(s) in the junctions. Based on these observations, memristors with reversible and repeatable switching were obtained by using Pd doped SiOx as the switching material. PMID:27166623

  12. Electrochemically reduced graphene oxide-modified screen-printed carbon electrodes for a simple and highly sensitive electrochemical detection of synthetic colorants in beverages.

    PubMed

    Jampasa, Sakda; Siangproh, Weena; Duangmal, Kiattisak; Chailapakul, Orawon

    2016-11-01

    A simple and highly sensitive electrochemical sensor based on an electrochemically reduced graphene oxide-modified screen-printed carbon electrode (ERGO-SPCE) for the simultaneous determination of sunset yellow (SY) and tartrazine (TZ) was proposed. An ERGO film was coated onto the electrode surface using a cyclic voltammetric method and then characterized by scanning electron microscopy (SEM). In 0.1M phosphate buffer at a pH of 6, the two oxidation peaks of SY and TZ appeared separately at 0.41 and 0.70V, respectively. Surprisingly, the electrochemical response remarkably increased approximately 90- and 20-fold for SY and TZ, respectively, using the modified electrode in comparison to the unmodified electrode. The calibration curves exhibited linear ranges from 0.01 to 20.0µM for SY and from 0.02 to 20.0µM for TZ. The limits of detection were found to be 0.50 and 4.50nM (at S/N=3) for SY and TZ, respectively. Furthermore, this detection platform provided very high selectivity for the measurement of both colorants. This electrochemical sensor was successfully applied to determine the amount of SY and TZ in commercial beverages. Comparison of the results obtained from this proposed method to those obtained by an in-house standard technique proved that this developed method has good agreement in terms of accuracy for practical applications. This sensor offers an inexpensive, rapid and sensitive determination. The proposed system is therefore suitable for routine analysis and should be an alternative method for the analysis of food colorants. PMID:27591594

  13. Removal of perfluorinated compounds in wastewater treatment plant effluents by electrochemical oxidation.

    PubMed

    Zhang, Chunhui; Wang, Liangliang; Li, Juan; Su, Peidong; Peng, Chen

    2015-01-01

    The presence of perfluorinated compounds (PFCs) in the effluents of a wastewater treatment plant (WWTP) in Beijing was investigated in the current study. Perfluorooctanoate acid and perfluorooctane sulfonate were the predominant PFCs in wastewater, accounting for 19-27% and 18-31%, respectively. The concentrations of PFCs with long chains were much lower than those PFCs with short chains (≤C8). An electrochemical oxidation reactor was employed for advanced treatment of PFCs in WWTP effluents using stainless steel plates as anode and cathode electrodes. It was concluded that the removal efficiency of PFCs was improved accordingly with the increasing applied current density. The removal efficiencies of target PFCs ranged from 23.53 to 51.79% with a reaction time of 30 minutes, current density of 20 mA/cm(2), electrode plate distance of 1.0 cm and electrode plate amounts of five pairs. PMID:26067497

  14. Solid flexible electrochemical supercapacitor using Tobacco mosaic virus nanostructures and ALD ruthenium oxide

    NASA Astrophysics Data System (ADS)

    Gnerlich, M.; Pomerantseva, E.; Gregorczyk, K.; Ketchum, D.; Rubloff, G.; Ghodssi, R.

    2013-11-01

    An all-solid electrochemical supercapacitor has been developed using a nanostructured nickel and titanium nitride template that is coated with ruthenium oxide by atomic layer deposition (ALD). The electrode morphology was based on a high surface area biotemplate of genetically modified Tobacco mosaic virus. The biotemplate automatically self-assembles at room temperature in aqueous solution. Nafion® perfluorosulfonate ionomer dispersion was cast on the electrodes and used as a solid proton-conducting electrolyte. A 5.8 F g-1 gravimetric capacity (578 µF cm-2 based on footprint) was achieved in Nafion electrolyte, and the device retained 80% of its capacity after 25 000 cycles. The technology presented here will enable thin, solid, flexible supercapacitors that are compatible with standard microfabrication techniques.

  15. A Novel Electrochemical Detector using Prussian Blue Modified Indium Tin Oxide Electrode

    NASA Astrophysics Data System (ADS)

    Yi, In-Je; Kim, Ju-Ho; Kang, C. J.; Choi, Y. J.; Lee, Kisay; Kim, Yong-Sang

    2006-01-01

    We propose a novel electrochemical detector (ECD) to catalyze redox efficiently by electrodepositing Prussian blue (PB, ferric hexacyanoferrate) on the indium tin oxide (ITO) electrode. Capillary electrophoresis (CE) and amperometric methods were used. We investigated the PB surface properties by topography from atomic force microscopy (AFM). The PB film on dense and smooth surfaces could catalyze redox reaction efficiently. Compared with CE-ECD microchips using a bare-ITO electrode, the proposed CE-ECD microchip using a PB modified electrode has shown better sensitivity of the electropherograms. It has been verified that wide-ranging detection can be performed under the limits of 0.01 mM of dopamine and catechol respectively when we use a PB modified electrode.

  16. Electrochemical Deposition of Nanostructured Manganese Oxide on Carbon Cloth for Flexible High-Performance Supercapacitor Electrodes.

    PubMed

    Huang, Zilong; Zhao, Xin; Ren, Jianli; Zhang, Junxian; Li, Yingzhi; Zhang, Qinghua

    2016-06-01

    Well-ordered manganese oxide (MnO2) arrays were directly grown on the treated carbon cloth (CC) though a simple electrochemical deposition method. The structures and the thickness of MnO2 film were controlled by tuning the deposition time. The morphologies and structures of MnO2 deposited on CC were examined by scanning electron microscopy, Raman and X-ray photoelectron spectroscopy. With appropriate reaction time, the MnO2/CC composite demonstrates a high specific capacitance of 291 mF/cm2 and a superior cycling stability at a current density of 0.2 mA/cm2. The specific capacitance shows a little improvement at the first 200 cycles and remains unchanged after continuous 2000 charge/discharge cycles. The MnO2 nanosheet arrays with high degree of ordering, combined with the flexible carbon cloth substrate can coffer great promise for supercapacitor applications. PMID:27427613

  17. Electrochemical regeneration of sodium hypochlorite in the absorption-oxidation method of desorbing waste gases

    SciTech Connect

    Znamenskii, Yu.D.; Perchugov, G.Ya.

    1988-07-10

    The electrochemical synthesis of sodium hypochlorite from a solution with a reduced concentration of sodium chloride is efficiently carried out with the use of ruthenium oxide-titanium anodes (ROTA). In this context they investigated the electrolysis of a solution of sodium chloride with concentrations equal to 20 and 50 kg/m/sup 3/ in a single cell flow-type electrolyzer with an ROTA and, for comparison, with a graphite anode under laboratory conditions. A flow-type electrolyzer was selected in view of the fact that it most closely satisfies the purposes of gas purification. The current efficiency with respect to sodium hypochlorite was almost two times higher, and the specific consumption of electrical energy was 1.6-1.8 times lower in the case of the ROTA than in the case of the graphite electrode. The yield of sodium chlorate remained on the same level in both cases.

  18. Electrochemically Reduced Graphene Oxide Multilayer Films as Efficient Counter Electrode for Dye-Sensitized Solar Cells

    PubMed Central

    Xu, Xiaobao; Huang, Dekang; Cao, Kun; Wang, Mingkui; Zakeeruddin, Shaik M.; Grätzel, Michael

    2013-01-01

    We report on a new counter electrode for dye-sensitized solar cells (DSCs), which is prepared using layer-by-layer assembly of negatively charged graphene oxide and positively charged poly (diallyldimethylammonium chloride) followed by an electrochemical reduction procedure. The DSC devises using the heteroleptic Ru complex C106TBA as sensitizer and this new counter electrode reach power conversion efficiencies of 9.5% and 7.6% in conjunction with low volatility and solvent free ionic liquid electrolytes, respectively. The new counter electrode exhibits good durability (60°C for 1000 h in a solar simulator, 100 mW cm−2) during the accelerated tests when used in combination with an ionic liquid electrolyte. This work identifies a new class of electro-catalysts with potential for low cost photovoltaic devices. PMID:23508212

  19. Graphene oxide as nanocarrier for sensitive electrochemical immunoassay of clenbuterol based on labeling amplification strategy.

    PubMed

    Lai, Yanjun; Bai, Jing; Shi, Xinhao; Zeng, Yanbo; Xian, Yuezhong; Hou, Jie; Jin, Litong

    2013-03-30

    A novel electrochemical immunosensor for sensitive detection of clenbuterol (CLB) is fabricated using glucose oxidase (GOD)-functionalized grahene oxide (GO) nanocomposites to label CLB. The immunosensor was constructed by layer-by-layer assembly colloidal prussian blue (PB), multiwalled carbon nanotubes (MWCNTs) and CLB antibodies (Abs) on a glassy carbon electrode (GCE). In this competitive immunoassay system, PB acts as the redox mediator to reduce H2O2 originated from the catalyst cycle of GOD. The high ratio of GOD to GO effectively amplified the signal for this competitive-type immunoassay. Under optimized conditions, the immunosensor shows a wide linear range from 0.5 to 1,000 ng/mL with a low detection limit of 0.25 ng/mL. The dual signal amplification of GOD-functionalized GO nanocomposites as a label is promising to be applied to design other sensitive immunosenseors. PMID:23598209

  20. Mössbauer study of electrochemically deposited amorphous iron-sulfide-oxide thin films

    NASA Astrophysics Data System (ADS)

    Ichimura, Masaya; Kajima, Takahiro; Kawai, Shoichi; Mibu, Ko

    2016-03-01

    Iron-sulfide-oxide thin films, which are promising candidates for solar cell materials, were deposited by electrochemical deposition. As-deposited and annealed films were characterized by Mössbauer spectroscopy, X-ray diffraction (XRD), and Raman scattering at room temperature. The as-deposited film is amorphous, and the oxygen content is about 1/4 of the sulfur content (S/Fe ≈ 1.5, O/Fe ≈ 0.4). The Mössbauer spectrum for the as-deposited film is a doublet with a broad line profile having hyperfine parameters similar to those of FeS2 pyrite or marcasite. This indicates that Fe atoms are in the Fe2+ low-spin state, as in FeS2.

  1. SOLID OXIDE FUEL CELL CATHODES: Polarization Mechanisms and Modeling of the Electrochemical Performance

    NASA Astrophysics Data System (ADS)

    Fleig, Jurgen

    2003-08-01

    Several recent experimental and numerical investigations have contributed to the improved understanding of the electrochemical mechanisms taking place at solid oxide fuel cell (SOFC) cathodes and yielded valuable information on the relationships between alterable parameters (geometry/material) and the cathodic polarization resistance. Efforts to reduce the polarization resistance in SOFCs can benefit from these results, and some important aspects of the corresponding studies are reviewed. Experimental results, particularly measurements using geometrically well-defined Sr-doped LaMnO3 (LSM) cathodes, are discussed. In regard to simulations, the different levels of sophistication used in SOFC electrode modeling studies are summarized and compared. Exemplary simulations of mixed conducting cathodes that show the capabilities and limits of different modeling levels are described.

  2. Copper recovery and gold enrichment from waste printed circuit boards by mediated electrochemical oxidation.

    PubMed

    Fogarasi, Szabolcs; Imre-Lucaci, Florica; Imre-Lucaci, Arpád; Ilea, Petru

    2014-05-30

    The present study aims to develop an eco-friendly chemical-electrochemical process for the simultaneous recovery of copper and separation of a gold rich residue from waste printed circuit boards (WPCBs). The process was carried out by employing two different types of reactors coupled in series: a leaching reactor with a perforated rotating drum, for the dissolution of base metals and a divided electrochemical reactor for the regeneration of the leaching solution with the parallel electrowinning of copper. The process performances were evaluated on the basis of the dissolution efficiency, current efficiency and specific energy consumptions. Finally a process scale up was realized taking into consideration the optimal values of the operating parameters. The laboratory scale leaching plant allowed the recovery of a high purity copper deposit (99.04wt.%) at a current efficiency of 63.84% and specific energy consumption of 1.75kWh/kg cooper. The gold concentration in the remained solid residue was 25 times higher than the gold concentration in the initial WPCB samples. PMID:24747374

  3. Electrochemical synthesis of new magnetic mixed oxides of Sr and Fe: Composition, magnetic properties, and microstructure

    SciTech Connect

    Amigo, R.; Asenjo, J.; Krotenko, E.; Torres, F.; Tejada, J.; Brillas, E.

    2000-02-01

    An electrochemical method for the preparation of magnetic nanoparticles of new Sr-Fe oxides is presented in this work. It consists of the electrolysis of nitrate or chloride solutions with Sr{sup 2+} and Fe{sup 3+} salts using commercial Fe electrodes. Magnetic materials are collected as precipitates from nitrate media in the pH range 1-3 and from chloride media within the pH range 1--12. The presence of 100--300 ppm aniline in acidic nitrate media yields a decrease in energy cost and particle size. Inductively coupled plasma analysis of materials and energy-dispersive X-ray spectrometry of single particles confirm that they are composed of mixed oxides of Sr and Fe. All synthesized materials crystallize as inverse cubic spinels, usually with intermediate structures between magnetite and maghemite. They are formed by nanoparticles with average sizes from 2 nm to {approximately} 50 nm, as observed by scanning electron microscopy. The electrogenerated mixed oxides have higher saturation magnetization, but lower remanent magnetization and coercive field, than commercial strontium hexaferrite with micrometric particle size.

  4. Electrochemical gas-electricity cogeneration through direct carbon solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Xie, Yongmin; Cai, Weizi; Xiao, Jie; Tang, Yubao; Liu, Jiang; Liu, Meilin

    2015-03-01

    Solid oxide fuel cells (SOFCs), with yttrium stabilized zirconia (YSZ) as electrolyte, composite of strontium-doped lanthanum manganate (LSM) and YSZ as cathode, and cermet of silver and gadolinium-doped ceria (GDC) as anode, are prepared and tested with 5wt% Fe-loaded activated carbon as fuel and ambient air as oxidant. It is found that electricity and CO gas can be cogenerated in the direct carbon SOFCs through the electrochemical oxidation of CO and the Boudouard reaction. The gas-electricity cogeneration performances are investigated by taking the operating time of the DC-SOFCs as a measure of rate decrease of the Boudouard reaction. Three single cells and a two-cell-stack are tested and characterized in terms of electrical power output, CO production rate, electrical conversion efficiency, and overall conversion efficiency. It turns out that a rapid rate of the Boudouard reaction is necessary for getting high electrical power and CO production. Taking the emitted CO as part of the power output, an overall efficiency of 76.5% for the single cell, and of 72.5% for the stack, is obtained.

  5. Synthesis and Electrochemical Analyses of Manganese Oxides for Super-Capacitors.

    PubMed

    Kim, Taewoo; Hwang, Hyein; Jang, Jaeyong; Park, Inyeong; Shim, Sang Eun; Baeck, Sung-Hyeon

    2015-11-01

    δ-Phase and α-phase manganese oxides were prepared using a hydrothermal method and their electrochemical properties were characterized. The influence of calcination temperature on the properties of manganese oxides was studied. Crystallinities were studied by X-ray diffraction, and scanning and transmission electron microscopy were utilized to examine morphologies. Average pore sizes and specific surface areas of samples were analyzed using the Barret-Joyner-Halenda and Brunauer-Emmett-Teller methods, respectively. After calcination in the range 300 degrees C to 600 degrees C, changes in morphology and crystallinity were observed. The flower-like shape of as synthesized samples became nanorod-like and the δ-phase changed to the α-phase. These changes may have been due to the removal of water during calcination. Furthermore, a transition stage in which the two phases coexisted was observed. Synthesized manganese oxides were mixed with carbon by sonification, to increase electric conductivity and to induce a synergistic effect between pseudo-capacitor and electric double layer capacitor (EDLC). Specific capacitances and rate durability of each composite were investigated by cyclic voltammetry in 1 M Na2SO4 electrolyte at different scan rates. MnO2 calcined at 400 degrees C exhibited the highest capacitance, probably due to its high surface area and more porous structure. PMID:26726613

  6. Reversible oxygen scavenging at room temperature using electrochemically reduced titanium oxide nanotubes

    NASA Astrophysics Data System (ADS)

    Close, Thomas; Tulsyan, Gaurav; Diaz, Carlos A.; Weinstein, Steven J.; Richter, Christiaan

    2015-05-01

    A material capable of rapid, reversible molecular oxygen uptake at room temperature is desirable for gas separation and sensing, for technologies that require oxygen storage and oxygen splitting such as fuel cells (solid-oxide fuel cells in particular) and for catalytic applications that require reduced oxygen species (such as removal of organic pollutants in water and oil-spill remediation). To date, however, the lowest reported temperature for a reversible oxygen uptake material is in the range of 200-300 °C, achieved in the transition metal oxides SrCoOx (ref. 1) and LuFe2O4+x (ref. 2) via thermal cycling. Here, we report rapid and reversible oxygen scavenging by TiO2-x nanotubes at room temperature. The uptake and release of oxygen is accomplished by an electrochemical rather than a standard thermal approach. We measure an oxygen uptake rate as high as 14 mmol O2 g-1 min-1, ˜2,400 times greater than commercial, irreversible oxygen scavengers. Such a fast oxygen uptake at a remarkably low temperature suggests a non-typical mechanistic pathway for the re-oxidation of TiO2-x. Modelling the diffusion of oxygen, we show that a likely pathway involves ‘exceptionally mobile’ interstitial oxygen produced by the oxygen adsorption and decomposition dynamics, recently observed on the surface of anatase.

  7. An electrochemical dopamine aptasensor incorporating silver nanoparticle, functionalized carbon nanotubes and graphene oxide for signal amplification.

    PubMed

    Bahrami, Shokoh; Abbasi, Amir Reza; Roushani, Mahmoud; Derikvand, Zohreh; Azadbakht, Azadeh

    2016-10-01

    In this work, immobilization of a dopamine (DA) aptamer was performed at the surface of an amino functionalized silver nanoparticle-carbon nanotube graphene oxide (AgNPs/CNTs/GO) nanocomposite. A 58-mer DA-aptamer was immobilized through the formation of phosphoramidate bonds between the amino group of chitosan and the phosphate group of the aptamer at the 5' end. An AgNPs/CNTs/GO nanocomposite was employed as a highly catalytic label for electrochemical detection of DA based on electrocatalytic activity of the nanocomposite toward hydrogen peroxide (H2O2). Interaction of DA with the aptamer caused conformational changes of the aptamer which, in turn, decreased H2O2 oxidation and reduction peak currents. On the other hand, the presumed folding of the DA-aptamer complexes on the sensing interface inhibited the electrocatalytic activity of AgNPs/CNTs/GO toward H2O2. Sensitive quantitative detection of DA was carried out by monitoring the decrease of differential pulse voltammetric (DPV) responses of AgNPs/CNTs/GO nanocomposite toward H2O2 oxidation. The DPV signal linearly decreased with increased concentration of DA from 3 to 110nmolL(-1) with a detection limit of 700±19.23pmolL(-1). Simple preparation, low operation cost, speed and validity are the decisive factors of this method motivating its application to biosensing investigation. PMID:27474313

  8. Electrochemical modification of indium tin oxide using di(4-nitrophenyl) iodonium tetrafluoroborate.

    PubMed

    Charlton, Matthew R; Suhr, Kristin J; Holliday, Bradley J; Stevenson, Keith J

    2015-01-20

    Optoelectronic applications often rely on indium tin oxide (ITO) as a transparent electrode material. Improvements in the performance of such devices as photovoltaics and light-emitting diodes often requires robust, controllable modification of the ITO surface to enhance interfacial charge transfer properties. In this work, modifier films were deposited onto ITO by the electrochemical reduction of di(4-nitrophenyl) iodonium tetrafluoroborate (DNP), allowing for control over surface functionalization. The surface coverage could be tuned from submonolayer to multilayer coverage by either varying the DNP concentration or the number of cyclic voltammetry (CV) grafting scans. Modification of ITO with 0.8 mM DNP resulted in near-monolayer surface coverage (4.95 × 10(14) molecules/cm(2)). X-ray photoelectron spectroscopy (XPS) analysis confirmed the presence of 4-nitrophenyl (NO2Ph) moieties on the ITO surface through the detection of a NO2 nitrogen signal at 405.6 eV after grafting. Further XPS evidence suggests that the NO2Ph radicals do not bond to the surface indium or tin sites, consistent with modification occurring either through bonding to surface hydroxyl groups or through strong physisorption on ITO. CV in the presence of an electroactive probe and electrochemical impedance spectroscopy (EIS) were used to investigate the electronic effects that modification via DNP has on ITO. Even at submonolayer coverage, the insulating organic films can reduce the current response to ferrocene oxidation and reduction by more than 25% and increase the charge transfer resistance by a factor of 10. PMID:25526354

  9. Boron-doped cadmium oxide composite structures and their electrochemical measurements

    SciTech Connect

    Lokhande, B.J.; Ambare, R.C.; Mane, R.S.; Bharadwaj, S.R.

    2013-08-01

    Graphical abstract: Conducting nano-fibrous 3% boron doped cadmium oxide thin films were prepared by SILAR and its super capacitive properties were studied. - Highlights: • Samples are of nanofibrous nature. • All samples shows pseudocapacitive behavior. • 3% B doped CdO shows good specific capacitance. • 3% B doped CdO shows maximum 74.93% efficiency at 14 mA/cm{sup 2}. • 3% B doped CdO shows 0.8 Ω internal resistance. - Abstract: Boron-doped and undoped cadmium oxide composite nanostructures in thin film form were prepared onto stainless steel substrates by a successive ionic layer adsorption and reaction method using aqueous solutions of cadmium nitrate, boric acid and 1% H{sub 2}O{sub 2}. As-deposited films were annealed at 623 K for 1 h. The X-ray diffraction study shows crystalline behavior for both doped and undoped films with a porous topography and nano-wires type architecture, as observed in SEM image. Wettability test confirms the hydrophilic surface with 58° contact angle value. Estimated band gap energy is around 1.9 eV. Electrochemical behavior of the deposited films is attempted in 1 M KOH electrolyte using cyclic voltammetry (CV), electrochemical impedance spectroscopy and galvanostatic charge–discharge tests. Maximum values of the specific capacitance, specific energy and specific power obtained for 3% B doped CdO film at 2 mV/s scan rate are 20.05 F/g, 1.22 Wh/kg and 3.25 kW/kg, respectively.

  10. Chiral conducting surfaces via electrochemical oxidation of L-leucine-oligothiophenes.

    PubMed

    McTiernan, Christopher D; Omri, Karim; Chahma, M'hamed

    2010-09-17

    Polythiophenes bearing a specific chiral center such as L-leucine have been prepared via the electrochemical oxidation of a series of L-leucine functionalized oligothiophenes (monothiophenes and terthiophenes). These oligothiophenes have been prepared through the condensation of L-leucine methyl ester and the corresponding thiophene monomers in the presence of hydroxybenzotriazole (HOBt) and N,N'-dicyclohexylcarbodiimide (DCC) followed by hydrolysis of the esters. The electroactive polymers are electrochemically stable and exhibit excellent adhesive properties on electrode surfaces (platinum, gold, and glassy carbon) as well as interesting optical properties in both doped and undoped states. Hydrogen bonds between a free amino acid (L-leucine, D-leucine, L-alanine, D-alanine, and D/L-alanine) and the L-leucine based polythiophenes (chiral conducting surface) were probed using cyclic voltammetry. Preliminary results show that the capacitive current of a modified L-leucine-polythiophene electrode decreases as a result of the formation of a hydrogen bond barrier on the surface of the chiral conducting surface accompanied with a shift of the oxidation potential. Cyclic voltammetry responses resulting from the interaction of the chiral conducting surface with L and Dfree amino acid isomers are similar. The formation of hydrogen bonds between the chiral conducting surfaces and the free amino acids was characterized by (1)H NMR. A chemical shift was observed for the N-H group in monomer 6 as a result of the hydrogen bond formation between the L-leucine methyl ester (D-leucine methyl ester, D/L-leucine methyl ester) and monomer 6. PMID:20718451

  11. Electrochemical process for the preparation of nitrogen fertilizers

    DOEpatents

    Aulich, Ted R.; Olson, Edwin S.; Jiang, Junhua

    2012-04-10

    The present invention provides methods and apparatus for the preparation of nitrogen fertilizers including ammonium nitrate, urea, urea-ammonium nitrate, and/or ammonia, at low temperature and pressure, preferably at ambient temperature and pressure, utilizing a source of carbon, a source of nitrogen, and/or a source of hydrogen or hydrogen equivalent. Implementing an electrolyte serving as ionic charge carrier, (1) ammonium nitrate is produced via the reduction of a nitrogen source at the cathode and the oxidation of a nitrogen source at the anode; (2) urea or its isomers are produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source; (3) ammonia is produced via the reduction of nitrogen source at the cathode and the oxidation of a hydrogen source or a hydrogen equivalent such as carbon monoxide or a mixture of carbon monoxide and hydrogen at the anode; and (4) urea-ammonium nitrate is produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source. The electrolyte can be aqueous, non-aqueous, or solid.

  12. DECHLORINATION OF TRICHLOROETHYLENE USING ELECTROCHEMICAL METHODS

    EPA Science Inventory

    Electrochemical degradation (ECD) is used to decontaminate organic and inorganic contaminants through oxidative or reductive processes. The ECD of Trichloroethylene (TCE) dechlorinates TCE through electric reduction. TCE dechlorination presented in the literature utilized electro...

  13. Processes regulating nitric oxide emissions from soils.

    PubMed

    Pilegaard, Kim

    2013-07-01

    Nitric oxide (NO) is a reactive gas that plays an important role in atmospheric chemistry by influencing the production and destruction of ozone and thereby the oxidizing capacity of the atmosphere. NO also contributes by its oxidation products to the formation of acid rain. The major sources of NO in the atmosphere are anthropogenic emissions (from combustion of fossil fuels) and biogenic emission from soils. NO is both produced and consumed in soils as a result of biotic and abiotic processes. The main processes involved are microbial nitrification and denitrification, and chemodenitrification. Thus, the net result is complex and dependent on several factors such as nitrogen availability, organic matter content, oxygen status, soil moisture, pH and temperature. This paper reviews recent knowledge on processes forming NO in soils and the factors controlling its emission to the atmosphere. Schemes for simulating these processes are described, and the results are discussed with the purpose of scaling up to global emission. PMID:23713124

  14. Electrochemical and mechanical processes at surfaces and interfaces of advanced materials for energy storage

    NASA Astrophysics Data System (ADS)

    Shi, Feifei

    Energy storage is a rapidly emerging field. In almost all energy storage applications, surfaces and interfaces are playing dominant roles. Examples are fuel cell electrodes, where electro-catalytic reactions occur, Li-ion battery (LIB) electrodes, where electrolyte decomposition and passivation commence simultaneously, and failure (fracture) of battery electrodes, where surface crack initiation greatly affects battery endurance. The most fundamental chemical, electrochemical, and mechanical problems in energy storage applications originate from surfaces and interfaces. This thesis investigates the electrochemical and mechanical processes at surfaces and interfaces of advanced materials for energy applications. The thesis includes the following five main research topics. (Abstract shortened by ProQuest.).

  15. The definition of the process of electrochemical impregnation of nickel electrodes

    NASA Technical Reports Server (NTRS)

    Antoine, P.

    1983-01-01

    Electrochemical impregnation was studied during a series of experiments designed to define the optimal conditions for the fabrication of dimensionally stable cell anodes of Ni-H2 and Ni-Cd systems. The influence of various parameters, such as current and duration of electrolysis, temperature and acidity of the chemical bath, the concentrations of Ni and Co as well as the use of ethanol was determined. Results show that the electrochemical impregnation process as defined is industrially feasible and it is suggested that Ni-H2 and Ni-Cd type electrodes be produced in sufficient quantity to further evaluate their performance characteristics.

  16. Single cells and intracellular processes studied by a plasmonic-based electrochemical impedance microscopy

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Foley, Kyle; Shan, Xiaonan; Wang, Shaopeng; Eaton, Seron; Nagaraj, Vinay J.; Wiktor, Peter; Patel, Urmez; Tao, Nongjian

    2011-03-01

    Electrochemical impedance spectroscopy is a crucial tool for the detection and study of various biological substances, from DNA and proteins to viruses and bacteria. It does not require any labelling species, and methods based on it have been developed to study cellular processes (such as cell spreading, adhesion, invasion, toxicology and mobility). However, data have so far lacked spatial information, which is essential for investigating heterogeneous processes and imaging high-throughput microarrays. Here, we report an electrochemical impedance microscope based on surface plasmon resonance that resolves local impedance with submicrometre spatial resolution. We have used an electrochemical impedance microscope to monitor the dynamics of cellular processes (apoptosis and electroporation of individual cells) with millisecond time resolution. The high spatial and temporal resolution makes it possible to study individual cells, but also resolve subcellular structures and processes without labels, and with excellent detection sensitivity (~2 pS). We also describe a model that simulates cellular and electrochemical impedance microscope images based on local dielectric constant and conductivity.

  17. Enhanced electrochemical performance of a crosslinked polyaniline-coated graphene oxide-sulfur composite for rechargeable lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Moon, San; Jung, Young Hwa; Kim, Do Kyung

    2015-10-01

    Due to the extraordinarily high theoretical capacity of sulfur (1675 mAh g-1), the lithium-sulfur (Li-S) battery has been considered a promising candidate for future high-energy battery applications. Li-S batteries, however, have suffered from limited cycle lives, mainly due to the formation of soluble polysulfides, which prevent the practical application of this attractive technology. The encapsulation of sulfur with various conductive materials has addressed this issue to some extent. Nevertheless, most approaches still present partial encapsulation of sulfur and moreover require a large quantity of conductive material (typically, >30 wt%), making the use of sulfur less desirable from the viewpoint of capacity. Here, we address these chronic issues of Li-S cells by developing a graphene oxide-sulfur composite with a thin crosslinked polyaniline (PANI) layer. Graphene oxide nanosheets with large surface area, high conductivity and a uniform conductive PANI layer, which are synthesized by a layer-by-layer method, have a synergetic interaction with a large portion of the sulfur in the active material. Furthermore, a simple crosslinking process efficiently prevents polysulfide dissolution, resulting in unprecedented electrochemical performance, even with a high sulfur content (∼75%): a high capacity retention of ∼80% is observed, in addition to 97.53% of the average Coulombic efficiency being retained after 500 cycles. The performance we demonstrate represents an advance in the field of lithium-sulfur batteries for applications such as power tools.

  18. Electrochemical oxidation of tramadol in low-salinity reverse osmosis concentrates using boron-doped diamond anodes.

    PubMed

    Lütke Eversloh, Christian; Schulz, Manoj; Wagner, Manfred; Ternes, Thomas A

    2015-04-01

    The electrochemical treatment of low-salinity reverse osmosis (RO) concentrates was investigated using tramadol (100 μM) as a model substance for persistent organic contaminants. Galvanostatic degradation experiments using boron-doped diamond electrodes at different applied currents were conducted in RO concentrates as well as in ultra-pure water containing either sodium chloride or sodium sulfate. Kinetic investigations revealed a significant influence of in-situ generated active chlorine besides direct anodic oxidation. Therefore, tramadol concentrations decreased more rapidly at elevated chloride content. Nevertheless, reduction of total organic carbon (TOC) was found to be comparatively low, demonstrating that transformation rather than mineralization was taking place. Early stage product formation could be attributed to both direct and indirect processes, including demethylation, hydroxylation, dehydration, oxidative aromatic ring cleavage and halogenation reactions. The latter led to various halogenated derivatives and resulted in AOX (adsorbable organic halogens) formation in the lower mg/L-range depending on the treatment conditions. Characterisation of transformation products (TPs) was achieved via MS(n) experiments and additional NMR measurements. Based on identification and quantification of the main TPs in different matrices and on additional potentiostatic electrolysis, a transformation pathway was proposed. PMID:25660808

  19. Solid-state voltammetry-based electrochemical immunosensor for Escherichia coli using graphene oxide-Ag nanoparticle composites as labels.

    PubMed

    Jiang, Xiaochun; Chen, Kun; Wang, Jing; Shao, Kang; Fu, Tao; Shao, Feng; Lu, Donglian; Liang, Jiangong; Foda, M Frahat; Han, Heyou

    2013-06-21

    A new electrochemical immunosensor based on solid-state voltammetry was fabricated for the detection of Escherichia coli (E. coli) by using graphene oxide-Ag nanoparticle composites (P-GO-Ag) as labels. To construct the platform, Au nanoparticles (AuNPs) were first self-assembled on an Au electrode surface through cysteamine and served as an effective matrix for antibody (Ab) attachment. Under a sandwich-type immunoassay format, the analyte and the probe (P-GO-Ag-Ab) were successively captured onto the immunosensor. Finally, the bonded AgNPs were detected through a solid-state redox process in 0.2 M of KCl solution. Combining the advantages of the high-loading capability of graphene oxide with promoted electron-transfer rate of AuNPs, this immunosensor produced a 26.92-fold signal enhancement compared with the unamplified protocol. Under the optimal conditions, the immunosensor exhibited a wide linear dependence on the logarithm of the concentration of E. coli ranging from 50 to 1.0 × 10(6) cfu mL(-1) with a detection limit of 10 cfu mL(-1). Moreover, as a practical application, the proposed immunosensor was used to monitor E. coli in lake water with satisfactory results. PMID:23662298

  20. Process for etching mixed metal oxides

    DOEpatents

    Ashby, C.I.H.; Ginley, D.S.

    1994-10-18

    An etching process is described using dicarboxylic and tricarboxylic acids as chelating etchants for mixed metal oxide films such as high temperature superconductors and ferroelectric materials. Undesirable differential etching rates between different metal oxides are avoided by selection of the proper acid or combination of acids. Feature sizes below one micron, excellent quality vertical edges, and film thicknesses in the 100 Angstrom range may be achieved by this method. 1 fig.

  1. Process for etching mixed metal oxides

    DOEpatents

    Ashby, Carol I. H.; Ginley, David S.

    1994-01-01

    An etching process using dicarboxylic and tricarboxylic acids as chelating etchants for mixed metal oxide films such as high temperature superconductors and ferroelectric materials. Undesirable differential etching rates between different metal oxides are avoided by selection of the proper acid or combination of acids. Feature sizes below one micron, excellent quality vertical edges, and film thicknesses in the 100 Angstom range may be achieved by this method.

  2. Reduction of metal oxides through mechanochemical processing

    DOEpatents

    Froes, Francis H.; Eranezhuth, Baburaj G.; Senkov, Oleg N.

    2000-01-01

    The low temperature reduction of a metal oxide using mechanochemical processing techniques. The reduction reactions are induced mechanically by milling the reactants. In one embodiment of the invention, titanium oxide TiO.sub.2 is milled with CaH.sub.2 to produce TiH.sub.2. Low temperature heat treating, in the range of 400.degree. C. to 700.degree. C., can be used to remove the hydrogen in the titanium hydride.

  3. Functionalized gold nanoparticles/reduced graphene oxide nanocomposites for ultrasensitive electrochemical sensing of mercury ions based on thymine-mercury-thymine structure.

    PubMed

    Wang, Nan; Lin, Meng; Dai, Hongxiu; Ma, Houyi

    2016-05-15

    A sensitive, selective and reusable electrochemical biosensor for the determination of mercury ions (Hg(2+)) has been developed based on thymine (T) modified gold nanoparticles/reduced graphene oxide (AuNPs/rGO) nanocomposites. Graphene oxide (GO) was electrochemically reduced on a glassy carbon substrate. Subsequently, AuNPs were deposited onto the surface of rGO by cyclic voltammetry. For functionalization of the electrode, the carboxylic group of the thymine-1-acetic acid was covalently coupled with the amine group of the cysteamine which self-assembled onto AuNPs. The structural features of the T bases functionalized AuNPs/rGO electrode were confirmed by attenuated total reflection infrared (ATR-IR) spectroscopy and scanning electron microscopy (SEM) spectroscopy. Each step of the modification process was characterized by cyclic voltammetry (CV) and electrochemical impedence spectroscopy (EIS). The T bases modified AuNPs/rGO electrode was applied to detect various trace metal ions by differential pulse voltammetry (DPV). The proposed biosensor was found to be highly sensitive to Hg(2+) in the range of 10ng/L-1.0µg/L. The biosensor afforded excellent selectivity for Hg(2+) against other heavy metal ions such as Zn(2+), Cd(2+), Pb(2+), Cu(2+), Ni(2+), and Co(2+). Furthermore, the developed sensor exhibited a high reusability through a simple washing. In addition, the prepared biosensor was successfully applied to assay Hg(2+) in real environmental samples. PMID:26720921

  4. Electrochemical degradation of nitrobenzene by anodic oxidation on the constructed TiO2-NTs/SnO2-Sb/PbO2 electrode.

    PubMed

    Chen, Yong; Li, Hongyi; Liu, Weijing; Tu, Yong; Zhang, Yaohui; Han, Weiqing; Wang, Lianjun

    2014-10-01

    The interlayer of Sb-doped SnO2 (SnO2-Sb) and TiO2 nanotubes (TiO2-NTs) on Ti has been introduced into the PbO2 electrode system with the aim to reveal the mechanism of enhanced electrochemical performance of TiO2-NTs/SnO2-Sb/PbO2 electrode. In contrast with the traditional Ti/SnO2-Sb/PbO2 electrode, the constructed PbO2 electrode has a more regular and compact morphology with better oriented crystals of lower size. The TiO2-NTs/SnO2-Sb interlayer prepared by electrodeposition process improves PbO2 coating structure effectively, and enhances the electrochemical performance of PbO2 electrode. Kinetic analyses indicated that the electrochemical oxidation of nitrobenzene on the PbO2 electrodes followed pseudo-first-order reaction, and mass transport was enhanced at the constructed electrode. The accumulation of nitrocompounds of degradation intermediates on constructed electrode was lower, and almost all of the nitro groups were eliminated from aromatic rings after 6h of electrolysis. Higher combustion efficiency was obtained on the constructed TiO2-NTs/SnO2-Sb/PbO2 electrode. The intermediates of nitrobenzene oxidation were confirmed by IC and GC/MS. PMID:25065789

  5. Degradation of the commercial surfactant nonylphenol ethoxylate by advanced oxidation processes.

    PubMed

    da Silva, Salatiel Wohlmuth; Klauck, Cláudia Regina; Siqueira, Marco Antônio; Bernardes, Andréa Moura

    2015-01-23

    Four different oxidation process, namely direct photolysis (DP) and three advanced oxidation processes (heterogeneous photocatalysis - HP, eletrochemical oxidation - EO and photo-assisted electrochemical oxidation - PEO) were applied in the treatment of wastewater containing nonylphenol ethoxylate (NPnEO). The objective of this work was to determine which treatment would be the best option in terms of degradation of NPnEO without the subsequent generation of toxic compounds. In order to investigate the degradation of the surfactant, the processes were compared in terms of UV/Vis spectrum, mineralization (total organic carbon), reaction kinetics, energy efficiency and phytotoxicity. A solution containing NPnEO was prepared as a surrogate of the degreasing wastewater, was used in the processes. The results showed that the photo-assisted processes degrade the surfactant, producing biodegradable intermediates in the reaction. On the other hand, the electrochemical process influences the mineralization of the surfactant. The process of PEO carried out with a 250W lamp and a current density of 10mA/cm(2) showed the best results in terms of degradation, mineralization, reaction kinetics and energy consumption, in addition to not presenting phytotoxicity. Based on this information, this process can be a viable alternative for treating wastewater containing NPnEO, avoiding the contamination of water resources. PMID:25262384

  6. In-situ generated H₂O₂ induced efficient visible light photo-electrochemical catalytic oxidation of PCP-Na with TiO₂.

    PubMed

    Liu, Wei; Liu, Huichao; Ai, Zhihui

    2015-05-15

    In this study, we developed a novel photo-electrochemical catalytic oxidation wastewater treatment system by interacting the cathodic in-situ generated H₂O₂ with TiO₂ suspension to form interfacial ≡ Ti(IV)OOH species, which endowed the PEC system with superior efficiency for degrading sodium pentachlorophenate (PCP-Na) under visible light irradiation at neutral pH. The apparent PCP-Na degradation rate constant of the PEC system was more than 10 times that of the electrochemical oxidation counterpart. In the PEC system, the interfacial ≡ Ti(IV)OOH species injected electrons to the conduction band of TiO₂ to initiate the activation of O₂ and the in-situ generated H₂O₂ adsorbed on the surface of TiO₂, lead to producing reactive oxygen species of superoxide anions and hydroxyl radicals, which were responsible for the dechlorination and mineralization of PCP-Na during the PEC process, respectively. The dosage of TiO₂ catalyst and the current intensity applied on PCP-Na degradation were optimized. This study develops a high efficient PEC oxidation system for wastewater treatment and provides new insight into the role of cathodic in-situ generated H₂O₂ on PEC oxidation of PCP-Na with TiO₂ under visible light irradiation. PMID:25698570

  7. Glucose sensor based on an electrochemical reduced graphene oxide-poly(L-lysine) composite film modified GC electrode.

    PubMed

    Hua, Liang; Wu, Xiaqin; Wang, Rong

    2012-12-21

    A convenient and environmentally friendly method of fabricating glucose biosensors is proposed. Glucose oxidase (GOD) was immobilized on electrochemically reduced graphene oxide (ERGO) which was adsorbed on the poly-L-lysine (PLL) modified glassy carbon electrode after being immersed in GO solution for 4 h. The electrochemical behaviors of GOD/ERGO/PLL/GC electrode have been investigated by cyclic voltammetry. Direct electron transfer between GOD immobilized with ERGO/PLL and GC electrode was observed. Moreover, the GOD/ERGO/PLL/GC electrode exhibited excellent electrocatalytic activity for the detection of glucose with a linear range from 0.25 to 5 mmol L(-1). PMID:23082313

  8. Flotation process for removal of precipitates from electrochemical chromate reduction unit

    DOEpatents

    DeMonbrun, James R.; Schmitt, Charles R.; Williams, Everett H.

    1976-01-01

    This invention is an improved form of a conventional electrochemical process for removing hexavalent chromium or other metal-ion contaminants from cooling-tower blowdown water. In the conventional process, the contaminant is reduced and precipitated at an iron anode, thus forming a mixed precipitate of iron and chromium hydroxides, while hydrogen being evolved copiously at a cathode is vented from the electrochemical cell. In the conventional process, subsequent separation of the fine precipitate has proved to be difficult and inefficient. In accordance with this invention, the electrochemical operation is conducted in a novel manner permitting a much more efficient and less expensive precipitate-recovery operation. That is, the electrochemical operation is conducted under an evolved-hydrogen partial pressure exceeding atmospheric pressure. As a result, most of the evolved hydrogen is entrained as bubbles in the blowdown in the cell. The resulting hydrogen-rich blowdown is introduced to a vented chamber, where the entrained hydrogen combines with the precipitate to form a froth which can be separated by conventional techniques. In addition to the hydrogen, two materials present in most blowdown act as flotation promoters for the precipitate. These are (1) air, with which the blowdown water becomes saturated in the course of normal cooling-tower operation, and (2) surfactants which commonly are added to cooling-tower recirculating-water systems to inhibit the growth of certain organisms or prevent the deposition of insoluble particulates.

  9. Decolorization of C. I. Reactive Orange 4 and Textile Effluents by Electrochemical Oxidation Technique using Silver-Carbon Composite Electrode.

    PubMed

    Nordin, Norazzizi; Fathrita Mohd Amir, Siti; Rahimi Yusop, Muhammad; Rozali Othman, Mohamed

    2015-01-01

    In this study, the electrochemical oxidation of C. I. Reactive Orange 4 (RO4) on a silver-carbon composite (AgC-PVC) electrode was studied using the cyclic voltammetry, potential liner V, and electrolysis methods. The AgC-PVC electrode was used as the working electrode in the electrochemical measurement of RO4 in the presence of NaCl as a supporting electrolyte. The UV-Vis spectra of RO4 after the electrochemical oxidation showed the complete decolorization of the solution. The electrolysis products were characterized using FTIR and GC-MS. The results showed that in the presence of OCl- as an active oxidant, RO4 molecules are broken down into several lower-molecular-weight molecules by the electrochemical technique. The electrode used was also able to reduce the COD, BOD(5) and surfactant contents in the textile effluents using a pilot scale reactor. This proved that the prepared AgC-PVC electrode was beneficial for removing both the color and other pollutants from textile effluents. PMID:26454599

  10. Electrochemical incineration of wastes

    NASA Technical Reports Server (NTRS)

    Kaba, L.; Hitchens, G. D.; Bockris, J. O'M.

    1989-01-01

    A low temperature electrolysis process has been developed for the treatment of solid waste material and urine. Experiments are described in which organic materials are oxidized directly at the surface of an electrode. Also, hypochlorite is generated electrochemically from chloride component of urine. Hypochlorite can act as a strong oxidizing agent in solution. The oxidation takes place at 30-60 C and the gaseous products from the anodic reaction are carbon dioxide, nitrogen, oxygen. Hydrogen is formed at the cathode. Carbon monoxide, and nitrogen oxides and methane were not detected in the off gases. Chlorine was evolved at the anode in relatively low amounts.

  11. A Straightforward Electrochemical Approach to Imine‐ and Amine‐bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State

    PubMed Central

    Chapman, Michael R.; Henkelis, Susan E.; Kapur, Nikil

    2016-01-01

    Abstract Synthetic methods to prepare organometallic and coordination compounds such as Schiff‐base complexes are diverse, with the route chosen being dependent upon many factors such as metal–ligand combination and metal oxidation state. In this work we have shown that electrochemical methodology can be employed to synthesize a variety of metal–salen/salan complexes which comprise diverse metal–ligand combinations and oxidation states. Broad application has been demonstrated through the preparation of 34 complexes under mild and ambient conditions. Unprecedented control over metal oxidation state (MII/III/IV where M=Fe, Mn) is presented by simple modification of reaction conditions. Along this route, a general protocol‐switch is described which allows access to analytically pure FeII/III–salen complexes. Tuning electrochemical potential, selective metalation of a Mn/Ni alloy is also presented which exclusively delivers MnII/IV–salen complexes in high yield. PMID:27547645

  12. A Straightforward Electrochemical Approach to Imine- and Amine-bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State.

    PubMed

    Chapman, Michael R; Henkelis, Susan E; Kapur, Nikil; Nguyen, Bao N; Willans, Charlotte E

    2016-08-01

    Synthetic methods to prepare organometallic and coordination compounds such as Schiff-base complexes are diverse, with the route chosen being dependent upon many factors such as metal-ligand combination and metal oxidation state. In this work we have shown that electrochemical methodology can be employed to synthesize a variety of metal-salen/salan complexes which comprise diverse metal-ligand combinations and oxidation states. Broad application has been demonstrated through the preparation of 34 complexes under mild and ambient conditions. Unprecedented control over metal oxidation state (M(II/III/IV) where M=Fe, Mn) is presented by simple modification of reaction conditions. Along this route, a general protocol-switch is described which allows access to analytically pure Fe(II/III)-salen complexes. Tuning electrochemical potential, selective metalation of a Mn/Ni alloy is also presented which exclusively delivers Mn(II/IV)-salen complexes in high yield. PMID:27547645

  13. FINAL REPORT. AQUEOUS ELECTROCHEMICAL MECHANISMS IN ACTINIDE RESIDUE PROCESSING

    EPA Science Inventory

    Plutonium and uranium residues (e.g., incinerator ash, combustibles, and sand/slag/crucibles) resulting from the purification and processing of nuclear materials constitute an enormous volume of lean processing waste and represent a significant fraction of the U. S. Department of...

  14. Facile synthesis of cobalt oxide/reduced graphene oxide composites for electrochemical capacitor and sensor applications

    NASA Astrophysics Data System (ADS)

    Nguyen, Thi Toan; Nguyen, Van Hoa; Deivasigamani, Ranjith Kumar; Kharismadewi, Dian; Iwai, Yoshio; Shim, Jae-Jin

    2016-03-01

    Reduced graphene oxide sheets decorated with cobalt oxide nanoparticles (Co3O4/rGO) were produced using a hydrothermal method without surfactants. Both the reduction of GO and the formation of Co3O4 nanoparticles occurred simultaneously under this condition. At the same current density of 0.5 A g-1, the Co3O4/rGO nanocomposites exhibited much a higher specific capacitance (545 F g-1) than that of bare Co3O4 (100 F g-1). On the other hand, for the detection of H2O2, the peak current of Co3O4/rGO was 4 times higher than that of Co3O4. Moreover, the resulting composite displayed a low detection limit of 0.62 μM and a high sensitivity of 28,500 μA mM-1cm-2 for the H2O2 sensor. These results suggest that the Co3O4/rGO nanocomposite is a promising material for both supercapacitor and non-enzymatic H2O2 sensor applications.

  15. Electrochemical processing of a new class of composite materials

    SciTech Connect

    Gabriel, J.C.; Bouteillon, J.; Poignet, J.C.; Roman, J.M.

    1995-06-01

    Ceramic layer coatings obtained by air plasma spraying processes contain pores and cracks. By filling the open pores of these layers with an element having physical and chemical properties complementary and compatible with those of the ceramics, the authors developed a simple process for producing a new class of materials. Two examples illustrating possible applications of this process for corrosion-protection and autolubrication purposes are presented in the second part of this paper. ZrO{sub 2}-Y{sub 2}O{sub 3} ceramic layer coatings present interesting properties which were improved or modified by adding specific materials to their open pores.

  16. Recent advances in metal oxide-based electrode architecture design for electrochemical energy storage.

    PubMed

    Jiang, Jian; Li, Yuanyuan; Liu, Jinping; Huang, Xintang; Yuan, Changzhou; Lou, Xiong Wen David

    2012-10-01

    Metal oxide nanostructures are promising electrode materials for lithium-ion batteries and supercapacitors because of their high specific capacity/capacitance, typically 2-3 times higher than that of the carbon/graphite-based materials. However, their cycling stability and rate performance still can not meet the requirements of practical applications. It is therefore urgent to improve their overall device performance, which depends on not only the development of advanced electrode materials but also in a large part "how to design superior electrode architectures". In the article, we will review recent advances in strategies for advanced metal oxide-based hybrid nanostructure design, with the focus on the binder-free film/array electrodes. These binder-free electrodes, with the integration of unique merits of each component, can provide larger electrochemically active surface area, faster electron transport and superior ion diffusion, thus leading to substantially improved cycling and rate performance. Several recently emerged concepts of using ordered nanostructure arrays, synergetic core-shell structures, nanostructured current collectors, and flexible paper/textile electrodes will be highlighted, pointing out advantages and challenges where appropriate. Some future electrode design trends and directions are also discussed. PMID:22912066

  17. Electrochemical oxidation of landfill leachate in a flow reactor: optimization using response surface methodology.

    PubMed

    Silveira, Jefferson E; Zazo, Juan A; Pliego, Gema; Bidóia, Edério D; Moraes, Peterson B

    2015-04-01

    Response surface methodology based on Box-Behnken (BBD) design was successfully applied to the optimization in the operating conditions of the electrochemical oxidation of sanitary landfill leachate aimed for making this method feasible for scale up. Landfill leachate was treated in continuous batch-recirculation system, where a dimensional stable anode (DSA(©)) coated with Ti/TiO2 and RuO2 film oxide were used. The effects of three variables, current density (milliampere per square centimeter), time of treatment (minutes), and supporting electrolyte dosage (moles per liter) upon the total organic carbon removal were evaluated. Optimized conditions were obtained for the highest desirability at 244.11 mA/cm(2), 41.78 min, and 0.07 mol/L of NaCl and 242.84 mA/cm(2), 37.07 min, and 0.07 mol/L of Na2SO4. Under the optimal conditions, 54.99% of chemical oxygen demand (COD) and 71.07 ammonia nitrogen (NH3-N) removal was achieved with NaCl and 45.50 of COD and 62.13 NH3-N with Na2SO4. A new kinetic model predicted obtained from the relation between BBD and the kinetic model was suggested. PMID:25339535

  18. THERMAL AND ELECTROCHEMICAL THREE DIMENSIONAL CFD MODEL OF A PLANAR SOLID OXIDE ELECTROLYSIS CELL

    SciTech Connect

    Grant Hawkes; Jim O'Brien; Carl Stoots; Steve Herring; Mehrdad Shahnam

    2005-07-01

    A three-dimensional computational fluid dynamics (CFD) model has been created to model high-temperature steam electrolysis in a planar solid oxide electrolysis cell (SOEC). The model represents a single cell, as it would exist in an electrolysis stack. Details of the model geometry are specific to a stack that was fabricated by Ceramatec , Inc. and tested at the Idaho National Laboratory. Mass, momentum, energy, and species conservation and transport are provided via the core features of the commercial CFD code FLUENT2. A solid-oxide fuel cell (SOFC) model adds the electrochemical reactions and loss mechanisms and computation of the electric field throughout the cell. The FLUENT SOFC user-defined subroutine was modified for this work to allow for operation in the SOEC mode. Model results provide detailed profiles of temperature, Nernst potential, operating potential, anode-side gas composition, cathode-side gas composition, current density and hydrogen production over a range of stack operating conditions. Mean model results are shown to compare favorably with experimental results obtained from an actual ten-cell stack tested at INL.

  19. Electrochemical enzyme-less urea sensor based on nano-tin oxide synthesized by hydrothermal technique.

    PubMed

    Ansari, S G; Fouad, H; Shin, Hyung-Shik; Ansari, Z A

    2015-12-01

    Nano-Tin oxide was synthesized using hydrothermal method at 150 °C for 6 h and then thin films were deposited by electrophoretic method at an optimized voltage of 100 V for 5 min on electropolished aluminum substrate. Spherical particles of about 30-50 nm diameters are observed with partial agglomeration when observed under electron microscope, which are tetragonal rutile structure. XPS results showed peaks related to Sn 4d, Sn 3d, O 1s & C 1s with spin-orbit splitting of 8.4 eV for Sn 3d. Feasibility studies of enzyme less urea sensing characteristics of nano-tin oxide thin films are exhibited herein. The deposited films have been used for enzyme less urea sensing from 1 to 20 mM concentration in buffer solution. The sensors were characterized electrochemically to obtain cyclic voltammogram as a function of urea concentration and scan rate. The sensitivity is estimated as 18.9 μA/mM below 5 mM and 2.31 μA/mM above 5 mM with a limit of detection of 0.6 mM. PMID:26381425

  20. Novel imazethapyr detoxification applying advanced oxidation processes.

    PubMed

    Stathis, Ioannis; Hela, Dimitra G; Scrano, Laura; Lelario, Filomena; Emanuele, Lucia; Bufo, Sabino A

    2011-01-01

    Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O₃), and hydrogen peroxide tied to UV-irradiation (H₂O₂/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed. Ozonation joined to UV-irradiation (O₃/UV), ozonation joined to titanium dioxide photo-catalysis (TiO₂/UV+O₃), sole photo-catalysis (TiO₂/UV), and photo-catalysis reinforced with hydrogen peroxide-oxidation (TiO₂/UV+H₂O₂) were characterized by a faster degradation and rapid formation of a lot of small molecules, which were quickly degraded to complete mineralization. The most effective oxidation methods were those using titanium dioxide photo-catalysis enhanced either by ozonation or hydrogen peroxide. Most of all, these last processes were useful to avoid the development of dangerous by-products. PMID:21726140

  1. Surface chemistry of RuO(2)/IrO(2)/TiO(2) mixed-oxide electrodes: secondary ion mass spectrometric study of the changes induced by electrochemical treatment.

    PubMed

    Barison, S; De Battisti, A; Fabrizio, M; Daolio, S; Piccirillo, C

    2000-01-01

    The IrO(2)/RuO(2)/TiO(2) ternary system is well known for its electrocatalytic activity towards oxygen- and chlorine-evolution reactions. Electrochemical processing induces noticeable chemical and morphological modifications on these electrodes, depending on the noble metal oxide content. In this work, cathodic/anodic polarization and the oxygen-evolution reaction were studied in order to evaluate the electrocatalytic activity at various noble metal oxide percentages. The best performing electrode (30 mol% noble metal oxides) was analyzed before and after electrochemical tests by means of secondary ion mass spectrometry (SIMS) in order to determine the chemical composition modification which occurred on the surface and in deeper regions of the mixed-oxide film. PMID:11114026

  2. Electrochemical performance of a solid oxide fuel cell with an anode based on Cu-Ni/CeO2 for methane direct oxidation

    NASA Astrophysics Data System (ADS)

    Hornés, Aitor; Escudero, María J.; Daza, Loreto; Martínez-Arias, Arturo

    2014-03-01

    A CuNi-CeO2/YSZ/LSF solid oxide fuel cell has been fabricated and tested with respect to its electrochemical activity for direct oxidation of dry methane. The electrodes have been prepared by impregnation of corresponding porous YSZ layers, using reverse microemulsions as impregnating medium for the anode (constituted by Cu-Ni at 1:1 atomic ratio in combination with CeO2). On the basis of I-V electrochemical testing complemented by impedance spectroscopy (IS) measurements it is shown the ability of the SOFC for direct oxidation of methane in a rather stable way. Differences in the behavior as a function of operating temperature (1023-1073 K) are also revealed and examined on the basis of analysis of IS spectra.

  3. Bipolar plating of metal contacts onto oxide interconnection for solid oxide electrochemical cell

    DOEpatents

    Isenberg, A.O.

    1987-03-10

    Disclosed is a method of forming an adherent metal deposit on a conducting layer of a tube sealed at one end. The tube is immersed with the sealed end down into an aqueous solution containing ions of the metal to be deposited. An ionically conducting aqueous fluid is placed inside the tube and a direct current is passed from a cathode inside the tube to an anode outside the tube. Also disclosed is a multi-layered solid oxide fuel cell tube which consists of an inner porous ceramic support tube, a porous air electrode covering the support tube, a non-porous electrolyte covering a portion of the air electrode, a non-porous conducting interconnection covering the remaining portion of the electrode, and a metal deposit on the interconnection. 1 fig.

  4. Bipolar plating of metal contacts onto oxide interconnection for solid oxide electrochemical cell

    DOEpatents

    Isenberg, Arnold O.

    1987-01-01

    Disclosed is a method of forming an adherent metal deposit on a conducting layer of a tube sealed at one end. The tube is immersed with the sealed end down into an aqueous solution containing ions of the metal to be deposited. An ionically conducting aqueous fluid is placed inside the tube and a direct current is passed from a cathode inside the tube to an anode outside the tube. Also disclosed is a multi-layered solid oxide fuel cell tube which consists of an inner porous ceramic support tube, a porous air electrode covering the support tube, a non-porous electrolyte covering a portion of the air electrode, a non-porous conducting interconnection covering the remaining portion of the electrode, and a metal deposit on the interconnection.

  5. Electrochemical fluorination for processing of used nuclear fuel

    DOEpatents

    Garcia-Diaz, Brenda L.; Martinez-Rodriguez, Michael J.; Gray, Joshua R.; Olson, Luke C.

    2016-07-05

    A galvanic cell and methods of using the galvanic cell is described for the recovery of uranium from used nuclear fuel according to an electrofluorination process. The galvanic cell requires no input energy and can utilize relatively benign gaseous fluorinating agents. Uranium can be recovered from used nuclear fuel in the form of gaseous uranium compound such as uranium hexafluoride, which can then be converted to metallic uranium or UO.sub.2 and processed according to known methodology to form a useful product, e.g., fuel pellets for use in a commercial energy production system.

  6. The effect of the addition of colloidal iridium oxide into sol-gel obtained titanium and ruthenium oxide coatings on titanium on their electrochemical properties.

    PubMed

    Panić, Vladimir V; Dekanski, Aleksandar B; Mitrić, Miodrag; Milonjić, Slobodan K; Misković-Stanković, Vesna B; Nikolić, Branislav Z

    2010-07-21

    Electrochemical properties of sol-gel processed Ti(0.6)Ir(0.4)O(2) and Ti(0.6)Ru(0.3)Ir(0.1)O(2) coatings on titanium substrate were investigated using cyclic voltammetry, polarization measurements and electrochemical impedance spectroscopy and compared to the properties of Ti(0.6)Ru(0.4)O(2) coating. The role of iridium oxide in the improvement of the electrocatalytic, capacitive and stability properties of titanium anodes activated by a RuO(2)-TiO(2) coating is discussed. The oxide sols were prepared by forced hydrolysis of the metal chlorides. The characterization by dynamic light scattering and X-ray diffraction showed that polydisperse oxide sols were obtained with the particles tending to form agglomerates. The presence of IrO(2) causes a suppression of the X-ray diffraction peaks of TiO(2) and RuO(2) in the sol-gel prepared Ti(0.6)Ir(0.4)O(2) and Ti(0.6)Ru(0.3)Ir(0.1)O(2) coatings. The IrO(2)-containing coatings had an enhanced charge storage ability and activity for the oxygen evolution reaction (OER) in comparison to Ti(0.6)Ru(0.4)O(2) coating. The voltammogram of the Ti(0.6)Ir(0.4)O(2)/Ti electrode showed well-resolved peaks related to Ir redox transitions, which are responsible for the enhanced charge storage ability of IrO(2)-containing coatings. Redox transitions of Ir were also registered in the high-frequency domain of the ac impedance spectra of the coatings as a semicircle with characteristics insensitive to the electrolyte composition and to the electrode potential prior to OER. However, the semicircle characteristics were different for the two IrO(2)-containing coatings, as well as at potentials outside the OER in comparison to those at which the OER occurs. PMID:20544088

  7. Vanadium Oxide Electrochemical Capacitors: An Investigation into Aqueous Capacitive Degradation, Alternate Electrolyte-Solvent Systems, Whole Cell Performance and Graphene Oxide Composite Electrodes

    NASA Astrophysics Data System (ADS)

    Engstrom, Allison Michelle

    Vanadium oxide has emerged as a potential electrochemical capacitor material due to its attractive pseudocapacitive performance; however, it is known to suffer from capacitive degradation upon sustained cycling. In this work, the electrochemical cycling behavior of anodically electrodeposited vanadium oxide films with various surface treatments in aqueous solutions is investigated at different pH. Quantitative compositional analysis and morphological studies provide additional insight into the mechanism responsible for capacitive degradation. Furthermore, the capacitance and impedance behavior of vanadium oxide electrochemical capacitor electrodes is compared for both aqueous and nonaqueous electrolyte-solvent systems. Alkali metal chloride and bromide electrolytes were studied in aqueous systems, and nonaqueous systems containing alkali metal bromides were studied in polar aprotic propylene carbonate (PC) or dimethyl sulfoxide (DMSO) solvents. The preferred aqueous and nonaqueous systems identified in the half-cell studies were utilized in symmetric vanadium oxide whole-cells. An aqueous system utilizing a 3.0 M NaCl electrolyte at pH 3.0 exhibited an excellent 96% capacitance retention over 3000 cycles at 10 mV s-1. An equivalent system tested at 500 mV s-1 displayed an increase in capacitance over the first several thousands of cycles, and eventually stabilized over 50,000 cycles. Electrodes cycled in nonaqueous 1.0 M LiBr in PC exhibited mostly non-capacitive charge-storage, and electrodes cycled in LiBr-DMSO exhibited a gradual capacitive decay over 10,000 cycles at 500 mV s-1. Morphological and compositional analyses, as well as electrochemical impedance modeling, provide additional insight into the cause of the cycing behavior. Lastly, reduced graphene oxide and vanadium oxide nanowire composites have been successfully synthesized using electrophoretic deposition for electrochemical capacitor electrodes. The composite material was found to perform with a

  8. Hydrothermal synthesis of mesoporous metal oxide arrays with enhanced properties for electrochemical energy storage

    SciTech Connect

    Xiao, Anguo Zhou, Shibiao; Zuo, Chenggang; Zhuan, Yongbing; Ding, Xiang

    2015-01-15

    Highlights: • NiO mesoporous nanowall arrays are prepared via hydrothermal method. • Mesoporous nanowall arrays are favorable for fast ion/electron transfer. • NiO mesoporous nanowall arrays show good supercapacitor performance. - Abstract: Mesoporous nanowall NiO arrays are prepared by a facile hydrothermal synthesis method with a following annealing process. The NiO nanowall shows continuous mesopores ranging from 5 to 10 nm and grows vertically on the substrate forming a porous net-like structure with macropores of 20–300 nm. A plausible mechanism is proposed for the growth of mesoporous nanowall NiO arrays. As cathode material of pseudocapacitors, the as-prepared mesoporous nanowall NiO arrays show good pseudocapacitive performances with a high capacitance of 600 F g{sup −1} at 2 A g{sup −1} and impressive high-rate capability with a specific capacitance of 338 F g{sup −1} at 40 A g{sup −1}. In addition, the mesoporous nanowall NiO arrays possess good cycling stability. After 6000 cycles at 2 A g{sup −1}, a high capacitance of 660 F g{sup −1} is attained, and no obvious degradation is observed. The good electrochemical performance is attributed to its highly porous morphology, which provides large reaction surface and short ion diffusion paths, leading to enhanced electrochemical properties.

  9. HANDBOOK ON ADVANCED NONPHOTOCHEMICAL OXIDATION PROCESSES

    EPA Science Inventory

    The purpose of this handbook is to summarize commercial-scale system performance and cost data for advanced nonphotochemical oxidation (ANPO) treatment of contaminated water, air, and soil. Similar information from pilot-and bench-scale evaluations of ANPO processes is also inclu...

  10. HANDBOOK ON ADVANCED PHOTOCHEMICAL OXIDATION PROCESSES

    EPA Science Inventory

    This handbook summarizes commercial-scale system performance and cost data for advanced photochemical oxidation (APO) treatment of contaminated water, air, and solids. Similar information from pilot- and bench-scale evaluations of APO processes is also included to supplement the...

  11. Processing of effluent salt from the direct oxide reduction process

    SciTech Connect

    Mishra, B.; Olson, D.L. . Kroll Inst. for Extractive Metallurgy); Averill, W.A. )

    1992-01-01

    The production of reactive metals by Direct Oxide Reduction (DOR) process using calcium in a molten calcium salt system generates significant amount of contaminated waste as calcium oxide saturated calcium chloride salt mix with calcium oxide content of up to 15 wt. pct. Fused salt electrolysis of a simulated salt mix has been carried out to electrowin calcium, which can be recycled to the DOR reactor along with the calcium chloride salt or may be used in-situ in a combined DOR and electrowinning process. Many reactive metal oxides could thus be reduced in a one-step process without generating a significant amount of waste. The process has been optimized in terms of the calcium solubility, cell temperature, current density and the cell design to maximize the current efficiency. Based on the information available regarding the solubility of calcium in calcium chloride salt in the presence of calcium oxide, and the back reactions occurring in-situ between the electrowon calcium and other components present in the cell, e.g. carbon, oxygen, carbon dioxide and calcium oxide, it is difficult to recover elemental calcium within the system. However, a liquid cathode or a rising cathode has been used in the past to recover calcium. The solubility has also been found to depend on the use of graphite as the anode material as evidenced by the presence of calcium carbonate in the final salt. The rate of recovery for metallic calcium has to be enhanced to levels that overcome the back reactions in a system where quick removal of anodic gases is achieved. Calcium has been detected by the hydrogen evolution technique and the amount of calcia has been determined by titration. A porous ceramic sheath has been used in the cell to prevent the chemical reaction of electrowon calcium to produce oxide or carbonate and to prevent the contamination of salt by the anodic carbon.

  12. Processing of effluent salt from the direct oxide reduction process

    SciTech Connect

    Mishra, B.; Olson, D.L.; Averill, W.A.

    1992-05-01

    The production of reactive metals by Direct Oxide Reduction (DOR) process using calcium in a molten calcium salt system generates significant amount of contaminated waste as calcium oxide saturated calcium chloride salt mix with calcium oxide content of up to 15 wt. pct. Fused salt electrolysis of a simulated salt mix has been carried out to electrowin calcium, which can be recycled to the DOR reactor along with the calcium chloride salt or may be used in-situ in a combined DOR and electrowinning process. Many reactive metal oxides could thus be reduced in a one-step process without generating a significant amount of waste. The process has been optimized in terms of the calcium solubility, cell temperature, current density and the cell design to maximize the current efficiency. Based on the information available regarding the solubility of calcium in calcium chloride salt in the presence of calcium oxide, and the back reactions occurring in-situ between the electrowon calcium and other components present in the cell, e.g. carbon, oxygen, carbon dioxide and calcium oxide, it is difficult to recover elemental calcium within the system. However, a liquid cathode or a rising cathode has been used in the past to recover calcium. The solubility has also been found to depend on the use of graphite as the anode material as evidenced by the presence of calcium carbonate in the final salt. The rate of recovery for metallic calcium has to be enhanced to levels that overcome the back reactions in a system where quick removal of anodic gases is achieved. Calcium has been detected by the hydrogen evolution technique and the amount of calcia has been determined by titration. A porous ceramic sheath has been used in the cell to prevent the chemical reaction of electrowon calcium to produce oxide or carbonate and to prevent the contamination of salt by the anodic carbon.

  13. Electrochemical Study of Ni20Cr Coatings Applied by HVOF Process in ZnCl2-KCl at High Temperatures.

    PubMed

    Porcayo-Calderón, J; Sotelo-Mazón, O; Casales-Diaz, M; Ascencio-Gutierrez, J A; Salinas-Bravo, V M; Martinez-Gomez, L

    2014-01-01

    Corrosion behavior of Ni20Cr coatings deposited by HVOF (high velocity oxygen-fuel) process was evaluated in ZnCl2-KCl (1 : 1 mole ratio) molten salts. Electrochemical techniques employed were potentiodynamic polarization curves, open circuit potential, and linear polarization resistance (LPR) measurements. Experimental conditions included static air and temperatures of 350, 400, and 450°C. 304-type SS was evaluated in the same conditions as the Ni20Cr coatings and it was used as a reference material to assess the coatings corrosion resistance. Coatings were evaluated as-deposited and with a grinded surface finished condition. Results showed that Ni20Cr coatings have a better corrosion performance than 304-type SS. Analysis showed that Ni content of the coatings improved its corrosion resistance, and the low corrosion resistance of 304 stainless steel was attributed to the low stability of Fe and Cr and their oxides in the corrosive media used. PMID:25210645

  14. Electrochemical Study of Ni20Cr Coatings Applied by HVOF Process in ZnCl2-KCl at High Temperatures

    PubMed Central

    Porcayo-Calderón, J.; Sotelo-Mazón, O.; Casales-Diaz, M.; Ascencio-Gutierrez, J. A.; Salinas-Bravo, V. M.; Martinez-Gomez, L.

    2014-01-01

    Corrosion behavior of Ni20Cr coatings deposited by HVOF (high velocity oxygen-fuel) process was evaluated in ZnCl2-KCl (1 : 1 mole ratio) molten salts. Electrochemical techniques employed were potentiodynamic polarization curves, open circuit potential, and linear polarization resistance (LPR) measurements. Experimental conditions included static air and temperatures of 350, 400, and 450°C. 304-type SS was evaluated in the same conditions as the Ni20Cr coatings and it was used as a reference material to assess the coatings corrosion resistance. Coatings were evaluated as-deposited and with a grinded surface finished condition. Results showed that Ni20Cr coatings have a better corrosion performance than 304-type SS. Analysis showed that Ni content of the coatings improved its corrosion resistance, and the low corrosion resistance of 304 stainless steel was attributed to the low stability of Fe and Cr and their oxides in the corrosive media used. PMID:25210645

  15. Sensitive electrochemical aptasensor for thrombin detection based on graphene served as platform and graphene oxide as enhancer.

    PubMed

    He, Chun; Xu, Zenghong; Sun, Tao; Wang, Li

    2014-01-01

    A sensitive electrochemical aptasensor was developed with conductive graphene served as platform and inert graphene oxide (GO) as enhancer. An electrodeposited nano-Au layer was firstly formed on conductive graphene modified glass carbon electrode surface for further immobilizing of electrochemical redox probe hexacyanoferrates nanoparticles (NiHCFNPs). Subsequently, another nano-Au layer was formed for immobilizing of thrombin aptamer (TBA). In the presence of thrombin, the TBA on the electrode surface could bind with thrombin, which made a barrier for electrons and inhibited the electro-transfer, resulting in the decreased electrochemical signals of NiHCFNPs. Owing to the non-conductivity property of graphene oxide, further decreased electrochemical signals of NiHCFNPs could be obtained via the sandwich reaction with GO-labeled TBA. According to the signal changes before the thrombin recognition and after sandwich reaction, trace detection of thrombin could be achieved. As a result, the proposed approach showed a high sensitivity and a wider linearity to thrombin in the range from 0.005 nM to 50 nM with a detection limit of 1 pM. PMID:24142359

  16. Electrochemical and Passive Behaviors of Pure Copper Fabricated by Accumulative Roll-Bonding (ARB) Process

    NASA Astrophysics Data System (ADS)

    Imantalab, O.; Fattah-alhosseini, A.

    2015-07-01

    In the present work, electrochemical and passive behaviors of pure copper fabricated by accumulative roll-bonding (ARB) process in 0.01 M borax solution (pH = 9.1) have been studied. Before any electrochemical measurements, evaluation of microstructure was obtained by Vickers microhardness, x-ray diffraction (XRD), and transmission electron microscopy. The results of microhardness tests revealed that microhardness values increased with the increasing number of ARB cycles. Also a sharp increase was seen in microhardness after the first ARB cycle, whereas mediocre additional increases were observed afterward up to the seven cycles. Moreover, XRD patterns showed that the mean crystallite size values decrease with the increasing number of ARB cycles. To investigate the electrochemical and passive behaviors of the samples, the potentiodynamic polarization, Mott-Schottky analysis and electrochemical impedance spectroscopy (EIS) were carried out. Polarization plots revealed that as a result of ARB, the corrosion behavior of the specimens improves compared with the annealed pure copper. Also, the Mott-Schottky analysis and EIS measurements showed that the increasing number of ARB cycles offer better conditions for forming the passive films with higher protection behavior, due to the growth of less-defective films.

  17. Removal of arsenite by simultaneous electro-oxidation and electro-coagulation process.

    PubMed

    Zhao, Xu; Zhang, Baofeng; Liu, Huijuan; Qu, Jiuhui

    2010-12-15

    An electrochemical reactor was built and used to remove arsenite from water. In this reactor, arsenite can be oxidized into arsenate, which was removed by electro-coagulation process simultaneously. The reactor mainly included dimension stable anode (DSA) and iron plate electrode. Oxidation of arsenite will occur at the DSA electrode in the electrochemical process. Meantime, the iron ions can be generated by the electro-induced process and iron oxides will form. Thus, the arsenic was removed by coagulation process. Influencing factors on the removal of arsenite were investigated. It is found that Ca(2+) and Mg(2+) ions promoted the removal of arsenite. However, Cl(-), CO(3)(2-), SiO(3)(2-), and PO(4)(3-) ions inhibited the arsenic removal. And, it is observed that the inhibition effect was the largest in the presence of PO(4)(3-). Furthermore, it is observed that the removal efficiency of arsenate is the largest in the pH value of 8. Increase or decrease of pH value did not benefit to the arsenite removal. Fourier transform infrared spectra were used to analyze the floc particles, it is suggested that the removal mechanism of As(III) in this system seems to be oxidative of As(III) to As(V) and to be removed by adsorption/complexation with metal hydroxides generated in the process. PMID:20863616

  18. Ionic liquid-assisted electrochemical determination of pyrimethanil using reduced graphene oxide conjugated to flower-like NiCo2O4.

    PubMed

    Yang, Lijun; Hu, Yandong; Wang, Qiong; Dong, Yuanyuan; Zhang, Lei

    2016-09-01

    The novel hierarchical flower-like superstructure NiCo2O4/reduced graphene oxide (rGO) hybrids have been successfully synthesized with a facile one-step hydrothermal process for the determination of fungicide pyrimethanil (PMT). For comparison, various structures of NiCo2O4/rGO including hexagonal nanoplates and nanorods were also synthesized. Among them, three-dimensional (3D) flower-like NiCo2O4/rGO exhibited the highest electrocatalytic activity for the oxidation of PMT. With the synergistic effect of [OMIM]PF6 ionic liquid (IL), the electrochemical sensor film (NiCo2O4/rGO/IL) further facilitated interfacial electron transfer and enhanced electrocatalytic activity for the oxidation of PMT. Under the optimum conditions, the electrochemical sensor exhibited two linear ranges of 0.1-10.0 μmol/L and 20.0-140 μmol/L for PMT with a low detection concentration of 11.0 nmol/L. Besides, the interference, repeatability, reproducibility and stability measurements were also evaluated. The proposed method was successfully applied to the detection of PMT in water, seawater, fruits and vegetables with good recovery ranging from 93% to 105%, and possessed potential applications in the analysis of real samples. PMID:27543019

  19. Process for preparing active oxide powders

    DOEpatents

    Berard, Michael F.; Hunter, Jr., Orville; Shiers, Loren E.; Dole, Stephen L.; Scheidecker, Ralph W.

    1979-02-20

    An improved process for preparing active oxide powders in which cation hydroxide gels, prepared in the conventional manner are chemically dried by alternately washing the gels with a liquid organic compound having polar characteristics and a liquid organic compound having nonpolar characteristics until the mechanical water is removed from the gel. The water-free cation hydroxide is then contacted with a final liquid organic wash to remove the previous organic wash and speed drying. The dried hydroxide treated in the conventional manner will form a highly sinterable active oxide powder.

  20. A novel electrochemical process for the recovery and recycling of ferric chloride from precipitation sludge.

    PubMed

    Mejia Likosova, E; Keller, J; Poussade, Y; Freguia, S

    2014-03-15

    During wastewater treatment and drinking water production, significant amounts of ferric sludge (comprising ferric oxy-hydroxides and FePO4) are generated that require disposal. This practice has a major impact on the overall treatment cost as a result of both chemical addition and the disposal of the generated chemical sludge. Iron sulfide (FeS) precipitation via sulfide addition to ferric phosphate (FePO4) sludge has been proven as an effective process for phosphate recovery. In turn, iron and sulfide could potentially be recovered from the FeS sludge, and recycled back to the process. In this work, a novel process was investigated at lab scale for the recovery of soluble iron and sulfide from FeS sludge. Soluble iron is regenerated electrochemically at a graphite anode, while sulfide is recovered at the cathode of the same electrochemical cell. Up to 60 ± 18% soluble Fe and 46 ± 11% sulfide were recovered on graphite granules for up-stream reuse. Peak current densities of 9.5 ± 4.2 A m(-2) and minimum power requirements of 2.4 ± 0.5 kWh kg Fe(-1) were reached with real full strength FeS suspensions. Multiple consecutive runs of the electrochemical process were performed, leading to the successful demonstration of an integrated process, comprising FeS formation/separation and ferric/sulfide electrochemical regeneration. PMID:24397913