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.

Creating an Electronic Reference and Information Database for Computer-aided ECM Design

NASA Astrophysics Data System (ADS)

Nekhoroshev, M. V.; Pronichev, N. D.; Smirnov, G. V.

2018-01-01

The paper presents a review on electrochemical shaping. An algorithm has been developed to implement a computer shaping model applicable to pulse electrochemical machining. For that purpose, the characteristics of pulse current occurring in electrochemical machining of aviation materials have been studied. Based on integrating the experimental results and comprehensive electrochemical machining process data modeling, a subsystem for computer-aided design of electrochemical machining for gas turbine engine blades has been developed; the subsystem was implemented in the Teamcenter PLM system.

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

NASA Astrophysics Data System (ADS)

Kumar, Amit; Arruda, Thomas M.; Tselev, Alexander; Ivanov, Ilia N.; Lawton, Jamie S.; Zawodzinski, Thomas A.; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V.

2013-04-01

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes.

PubMed

Kumar, Amit; Arruda, Thomas M; Tselev, Alexander; Ivanov, Ilia N; Lawton, Jamie S; Zawodzinski, Thomas A; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V

2013-01-01

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

PubMed Central

Kumar, Amit; Arruda, Thomas M.; Tselev, Alexander; Ivanov, Ilia N.; Lawton, Jamie S.; Zawodzinski, Thomas A.; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V.

2013-01-01

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes. PMID:23563856

An electrochemical sensing approach for scouting microbial chemolithotrophic metabolisms.

PubMed

Saavedra, Albert; Figueredo, Federico; Cortón, Eduardo; Abrevaya, Ximena C

2018-05-01

The present study was aimed to test an electrochemical sensing approach for the detection of an active chemolithotrophic metabolism (and therefore the presence of chemolithotrophic microorganisms) by using the corrosion of pyrite by Acidithiobacillus ferrooxidans as a model. Different electrochemical techniques were combined with adhesion studies and scanning electron microscopy (SEM). The experiments were performed in presence or absence of A. ferrooxidans and without or with ferrous iron in the culture medium (0 and 0.5 g L -1 , respectively). Electrochemical parameters were in agreement with voltammetric studies and SEM showing that it is possible to distinguish between an abiotically-induced corrosion process (AIC) and a microbiologically-induced corrosion process (MIC). The results show that our approach not only allows the detection of chemolithotrophic activity of A. ferrooxidans but also can characterize the corrosion process. This may have different kind of applications, from those related to biomining to life searching missions in other planetary bodies. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrolysis Performance Improvement Concept Study (EPICS) flight experiment phase C/D

NASA Technical Reports Server (NTRS)

Schubert, F. H.; Lee, M. G.

1995-01-01

The overall purpose of the Electrolysis Performance Improvement Concept Study flight experiment is to demonstrate and validate in a microgravity environment the Static Feed Electrolyzer concept as well as investigate the effect of microgravity on water electrolysis performance. The scope of the experiment includes variations in microstructural characteristics of electrodes and current densities in a static feed electrolysis cell configuration. The results of the flight experiment will be used to improve efficiency of the static feed electrolysis process and other electrochemical regenerative life support processes by reducing power and expanding the operational range. Specific technologies that will benefit include water electrolysis for propulsion, energy storage, life support, extravehicular activity, in-space manufacturing and in-space science in addition to other electrochemical regenerative life support technologies such as electrochemical carbon dioxide and oxygen separation, electrochemical oxygen compression and water vapor electrolysis. The Electrolysis Performance Improvement Concept Study flight experiment design incorporates two primary hardware assemblies: the Mechanical/Electrochemical Assembly and the Control/Monitor Instrumentation. The Mechanical/Electrochemical Assembly contains three separate integrated electrolysis cells along with supporting pressure and temperature control components. The Control/Monitor Instrumentation controls the operation of the experiment via the Mechanical/Electrochemical Assembly components and provides for monitoring and control of critical parameters and storage of experimental data.

Toward quantitative electrochemical measurements on the nanoscale by scanning probe microscopy: environmental and current spreading effects.

PubMed

Arruda, Thomas M; Kumar, Amit; Jesse, Stephen; Veith, Gabriel M; Tselev, Alexander; Baddorf, Arthur P; Balke, Nina; Kalinin, Sergei V

2013-09-24

The application of electric bias across tip-surface junctions in scanning probe microscopy can readily induce surface and bulk electrochemical processes that can be further detected though changes in surface topography, Faradaic or conductive currents, or electromechanical strain responses. However, the basic factors controlling tip-induced electrochemical processes, including the relationship between applied tip bias and the thermodynamics of local processes, remains largely unexplored. Using the model Li-ion reduction reaction on the surface in Li-ion conducting glass ceramic, we explore the factors controlling Li-metal formation and find surprisingly strong effects of atmosphere and back electrode composition on the process. We find that reaction processes are highly dependent on the nature of the counter electrode and environmental conditions. Using a nondepleting Li counter electrode, Li particles could grow significantly larger and faster than a depleting counter electrode. Significant Li ion depletion leads to the inability for further Li reduction. Time studies suggest that Li diffusion replenishes the vacant sites after ∼12 h. These studies suggest the feasibility of SPM-based quantitative electrochemical studies under proper environmental controls, extending the concepts of ultramicroelectrodes to the single-digit nanometer scale.

Integration of thermocouple microelectrode in the scanning electrochemical microscope at variable temperatures: simultaneous temperature and electrochemical imaging and its kinetic studies.

PubMed

Pan, He; Zhang, Hailing; Lai, Junhui; Gu, Xiaoxin; Sun, Jianjun; Tang, Jing; Jin, Tao

2017-03-24

We describe herein a method for the simultaneous measurement of temperature and electrochemical signal with a new type of thermocouple microelectrode. The thermocouple microelectrode can be used not only as a thermometer but also as a scanning electrochemical microscope (SECM) tip in the reaction between tip-generated bromine and a heated Cu sample. The influence of temperature on the SECM imaging process and the related kinetic parameters have been studied, such as kinetic constant and activation energy.

Integration of thermocouple microelectrode in the scanning electrochemical microscope at variable temperatures: simultaneous temperature and electrochemical imaging and its kinetic studies

PubMed Central

Pan, He; Zhang, Hailing; Lai, Junhui; Gu, Xiaoxin; Sun, Jianjun; Tang, Jing; Jin, Tao

2017-01-01

We describe herein a method for the simultaneous measurement of temperature and electrochemical signal with a new type of thermocouple microelectrode. The thermocouple microelectrode can be used not only as a thermometer but also as a scanning electrochemical microscope (SECM) tip in the reaction between tip-generated bromine and a heated Cu sample. The influence of temperature on the SECM imaging process and the related kinetic parameters have been studied, such as kinetic constant and activation energy. PMID:28338002

Reversible mechano-electrochemical writing of metallic nanostructures with the tip of an atomic force microscope.

PubMed

Obermair, Christian; Kress, Marina; Wagner, Andreas; Schimmel, Thomas

2012-01-01

We recently introduced a method that allows the controlled deposition of nanoscale metallic patterns at defined locations using the tip of an atomic force microscope (AFM) as a "mechano-electrochemical pen", locally activating a passivated substrate surface for site-selective electrochemical deposition. Here, we demonstrate the reversibility of this process and study the long-term stability of the resulting metallic structures. The remarkable stability for more than 1.5 years under ambient air without any observable changes can be attributed to self-passivation. After AFM-activated electrochemical deposition of copper nanostructures on a polycrystalline gold film and subsequent AFM imaging, the copper nanostructures could be dissolved by reversing the electrochemical potential. Subsequent AFM-tip-activated deposition of different copper nanostructures at the same location where the previous structures were deleted, shows that there is no observable memory effect, i.e., no effect of the previous writing process on the subsequent writing process. Thus, the four processes required for reversible information storage, "write", "read", "delete" and "re-write", were successfully demonstrated on the nanometer scale.

Reversible mechano-electrochemical writing of metallic nanostructures with the tip of an atomic force microscope

PubMed Central

Kress, Marina; Wagner, Andreas; Schimmel, Thomas

2012-01-01

Summary We recently introduced a method that allows the controlled deposition of nanoscale metallic patterns at defined locations using the tip of an atomic force microscope (AFM) as a “mechano-electrochemical pen”, locally activating a passivated substrate surface for site-selective electrochemical deposition. Here, we demonstrate the reversibility of this process and study the long-term stability of the resulting metallic structures. The remarkable stability for more than 1.5 years under ambient air without any observable changes can be attributed to self-passivation. After AFM-activated electrochemical deposition of copper nanostructures on a polycrystalline gold film and subsequent AFM imaging, the copper nanostructures could be dissolved by reversing the electrochemical potential. Subsequent AFM-tip-activated deposition of different copper nanostructures at the same location where the previous structures were deleted, shows that there is no observable memory effect, i.e., no effect of the previous writing process on the subsequent writing process. Thus, the four processes required for reversible information storage, “write”, “read”, “delete” and “re-write”, were successfully demonstrated on the nanometer scale. PMID:23365795

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.

Electrochemical monitoring of high-temperature molten-salt corrosion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, G.; Stott, F.H.; Dawson, J.L.

1990-02-01

Hot molten-salt corrosion can cause serious metal degradation in boiler plant, incinerators, and furnaces. In this research, electrochemical-impedance and electrochemical-noise techniques have been evaluated for the monitoring of hot-corrosion processes in such plants. Tests have been carried out on Ni-1% Co and Alloy 800, a commercial material of interest to operators of industrial plants. Electrochemical-impedance and electrochemical-noise data were compared with the results of metallographic examination of the test alloys and showed reasonable correlation between the electrochemical data and the actual degradation processes. This preliminary work indicated that the electrochemical techniques show considerable promise as instruments for the monitoring ofmore » high-temperature corrosion processes.« less

Cold pressure welding of aluminium-steel blanks: Manufacturing process and electrochemical surface preparation

NASA Astrophysics Data System (ADS)

Schmidt, Hans Christian; Homberg, Werner; Orive, Alejandro Gonzalez; Grundmeier, Guido; Hordych, Illia; Maier, Hans Jürgen

2018-05-01

In this study the manufacture of aluminium-steel blanks by cold pressure welding and their preparation for a welding process through electrochemical surface treatment are investigated and discussed. The cold pressure welding process was done with an incremental rolling tool that allows for the partial pressure welding of two blanks along a prepared path. The influence of the surface preparation by electrochemical deposition of bond promoting organosilane-based agents and roughening on a nano-scale is investigated and compared to conventional surface treatments. Coating the surfaces with a thin organosilane-based film incorporating specific functional groups should promote additional bonding between the mating oxide layers; its influence on the total weld strength is studied. Pressure welding requires suitable process strategies, and the current advances in the proposed incremental rolling process for the combination of mild steel and aluminium are presented.

Electrochemical carbon dioxide concentrator advanced technology tasks

NASA Technical Reports Server (NTRS)

Schneider, J. J.; Schubert, F. H.; Hallick, T. M.; Woods, R. R.

1975-01-01

Technology advancement studies are reported on the basic electrochemical CO2 removal process to provide a basis for the design of the next generation cell, module and subsystem hardware. An Advanced Electrochemical Depolarized Concentrator Module (AEDCM) is developed that has the characteristics of low weight, low volume, high CO2, removal, good electrical performance and low process air pressure drop. Component weight and noise reduction for the hardware of a six man capacity CO2 collection subsystem was developed for the air revitalization group of the Space Station Prototype (SSP).

Comparison of phthalic acid removal from aqueous solution by electrochemical methods: Optimization, kinetic and sludge study.

PubMed

Sandhwar, Vishal Kumar; Prasad, Basheshwar

2017-12-01

In this work, comparative study between electrochemical processes such as electrocoagulation (EC), peroxi-coagulation (PC) and peroxi-electrocoagulation (PEC) was performed for the removal of phthalic acid (PA) and chemical oxygen demand (COD) from aqueous medium. Initially, acid treatment was studied at various pH (1-3) and temperature (10-55 °C). Subsequently, the supernatant was re-treated by electrochemical processes such as EC, PC and PEC separately. Independent parameters viz. pH, current density (CD), electrolyte concentration (m), electrode gap (g), H 2 O 2 concentration and electrolysis time (t) were optimized by Central Composite Design (CCD) for these electrochemical processes. All three processes were compared based on removal, energy consumption, kinetic analysis, operating cost and sludge characteristics. In this study, PEC process was found more efficient among EC, PC and PEC processes in order to get maximum removal, minimum energy consumption and minimum operating cost. Maximum removal of PA- 68.21%, 74.36%, 82.25% & COD- 64.79%, 68.15%, 75.21% with energy consumption - 120.95, 97.51, 65.68 (kWh/kg COD removed) were attained through EC, PC and PEC processes respectively at their corresponding optimum conditions. Results indicated that PA and COD removals are in order of PEC > PC > EC under optimum conditions. First order kinetic model was found able to describe the degradation kinetics and provided best correlation for the removal rate within the acceptable error range. Copyright © 2017 Elsevier Ltd. All rights reserved.

A Comprehensive Pitting Study of High Velocity Oxygen Fuel Inconel 625 Coating by Using Electrochemical Testing Techniques

NASA Astrophysics Data System (ADS)

Niaz, Akbar; Khan, Sajid Ullah

2016-01-01

In the present work, Inconel 625 was coated on a mild steel substrate using a high velocity oxygen fuel coating process. The pitting propensity of the coating was tested by using open circuit potential versus time, potentiodynamic polarization, electrochemical potentiokinetic reactivation, and scanning electrochemical microscopy. The pitting propensity of the coating was compared with bulk Inconel 625 alloy. The results confirmed that there were regions of different electrochemical activities on the coating which have caused pitting corrosion.

Local probing of ionic diffusion by electrochemical strain microscopy: Spatial resolution and signal formation mechanisms

NASA Astrophysics Data System (ADS)

Morozovska, A. N.; Eliseev, E. A.; Balke, N.; Kalinin, S. V.

2010-09-01

Electrochemical insertion-deintercalation reactions are typically associated with significant change in molar volume of the host compound. This strong coupling between ionic currents and strains underpins image formation mechanisms in electrochemical strain microscopy (ESM), and allows exploring the tip-induced electrochemical processes locally. Here we analyze the signal formation mechanism in ESM, and develop the analytical description of operation in frequency and time domains. The ESM spectroscopic modes are compared to classical electrochemical methods including potentiostatic and galvanostatic intermittent titration, and electrochemical impedance spectroscopy. This analysis illustrates the feasibility of spatially resolved studies of Li-ion dynamics on the sub-10-nm level using electromechanical detection.

Simulation of electrochemical behavior in Lithium ion battery during discharge process.

PubMed

Chen, Yong; Huo, Weiwei; Lin, Muyi; Zhao, Li

2018-01-01

An electrochemical Lithium ion battery model was built taking into account the electrochemical reactions. The polarization was divided into parts which were related to the solid phase and the electrolyte mass transport of species, and the electrochemical reactions. The influence factors on battery polarization were studied, including the active material particle radius and the electrolyte salt concentration. The results showed that diffusion polarization exist in the positive and negative electrodes, and diffusion polarization increase with the conducting of the discharge process. The physicochemical parameters of the Lithium ion battery had the huge effect on cell voltage via polarization. The simulation data show that the polarization voltage has close relationship with active material particle size, discharging rate and ambient temperature.

Simulation of electrochemical behavior in Lithium ion battery during discharge process

PubMed Central

Chen, Yong; Lin, Muyi; Zhao, Li

2018-01-01

An electrochemical Lithium ion battery model was built taking into account the electrochemical reactions. The polarization was divided into parts which were related to the solid phase and the electrolyte mass transport of species, and the electrochemical reactions. The influence factors on battery polarization were studied, including the active material particle radius and the electrolyte salt concentration. The results showed that diffusion polarization exist in the positive and negative electrodes, and diffusion polarization increase with the conducting of the discharge process. The physicochemical parameters of the Lithium ion battery had the huge effect on cell voltage via polarization. The simulation data show that the polarization voltage has close relationship with active material particle size, discharging rate and ambient temperature. PMID:29293535

Reuse of Textile Dyeing Effluents Treated with Coupled Nanofiltration and Electrochemical Processes

PubMed Central

Buscio, Valentina; García-Jiménez, María; Vilaseca, Mercè; López-Grimau, Victor; Crespi, Martí; Gutiérrez-Bouzán, Carmen

2016-01-01

The reactive dye Cibacron Yellow S-3R was selected to evaluate the feasibility of combining nanofiltration membranes with electrochemical processes to treat textile wastewater. Synthetic dyeing effluents were treated by means of two nanofiltration membranes, Hydracore10 and Hydracore50. Up to 98% of dye removal was achieved. The influence of salt concentration and pH on membrane treatment was studied. The best dye removal yield was achieved at pH 3 in the presence of 60 g/L of NaCl. After the membrane filtration, the concentrate containing high dye concentration was treated by means of an electrochemical process at three different current densities: 33, 83, and 166 mA/cm2. Results showed a lineal relationship between treatment time and applied current density. Both permeates and electrochemically-decoloured effluents were reused in new dyeing processes (100% of permeate and 70% of decoloured concentrates). Dyed fabrics were evaluated with respect to original dyeing. Colour differences were found to be into the acceptance range. PMID:28773614

Production of Titanium Metal by an Electrochemical Molten Salt Process

NASA Astrophysics Data System (ADS)

Fatollahi-Fard, Farzin

Titanium production is a long and complicated process. What we often consider to be the standard method of primary titanium production (the Kroll process), involves many complex steps both before and after to make a useful product from titanium ore. Thus new methods of titanium production, especially electrochemical processes, which can utilize less-processed feedstocks have the potential to be both cheaper and less energy intensive than current titanium production processes. This project is investigating the use of lower-grade titanium ores with the electrochemical MER process for making titanium via a molten salt process. The experimental work carried out has investigated making the MER process feedstock (titanium oxycarbide) with natural titanium ores--such as rutile and ilmenite--and new ways of using the MER electrochemical reactor to "upgrade" titanium ores or the titanium oxycarbide feedstock. It is feasible to use the existing MER electrochemical reactor to both purify the titanium oxycarbide feedstock and produce titanium metal.

An insight into the adsorption and electrochemical processes occurring during the analysis of copper and lead in wines, using an electrochemical quartz crystal nanobalance.

PubMed

Yamasaki, Alzira; Oliveira, João A B P; Duarte, Armando C; Gomes, M Teresa S R

2012-08-30

Copper and lead in wine were quantified by anodic stripping voltammetry (ASV), performed onto the gold electrode of a piezoelectric quartz crystal. Both current or mass changes could be used as analytical signals, without a statistical difference in the results (α=0.05). However, the plot of mass vs. potential provided an in depth understanding of the electrochemical processes and allowed studying adsorption phenomena. Copper interaction with fructose is an example of a process which was not possible to ignore by observing the mass change on the gold electrode of the piezoelectric quartz crystal. Copyright © 2012 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Xiao-Ying; Liu, Bingwen; Yang, Li

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.

Insights into electrochemical reactions from ambient pressure photoelectron spectroscopy.

PubMed

Stoerzinger, Kelsey A; Hong, Wesley T; Crumlin, Ethan J; Bluhm, Hendrik; Shao-Horn, Yang

2015-11-17

The understanding of fundamental processes in the bulk and at the interfaces of electrochemical devices is a prerequisite for the development of new technologies with higher efficiency and improved performance. One energy storage scheme of great interest is splitting water to form hydrogen and oxygen gas and converting back to electrical energy by their subsequent recombination with only water as a byproduct. However, kinetic limitations to the rate of oxygen-based electrochemical reactions hamper the efficiency in technologies such as solar fuels, fuel cells, and electrolyzers. For these reactions, the use of metal oxides as electrocatalysts is prevalent due to their stability, low cost, and ability to store oxygen within the lattice. However, due to the inherently convoluted nature of electrochemical and chemical processes in electrochemical systems, it is difficult to isolate and study individual electrochemical processes in a complex system. Therefore, in situ characterization tools are required for observing related physical and chemical processes directly at the places where and while they occur and can help elucidate the mechanisms of charge separation and charge transfer at electrochemical interfaces. X-ray photoelectron spectroscopy (XPS), also known as ESCA (electron spectroscopy for chemical analysis), has been used as a quantitative spectroscopic technique that measures the elemental composition, as well as chemical and electronic state of a material. Building from extensive ex situ characterization of electrochemical systems, initial in situ studies were conducted at or near ultrahigh vacuum (UHV) conditions (≤10(-6) Torr) to probe solid-state electrochemical systems. However, through the integration of differential-pumping stages, XPS can now operate at pressures in the torr range, comprising a technique called ambient pressure XPS (AP-XPS). In this Account, we briefly review the working principles and current status of AP-XPS. We use several recent in situ studies on model electrochemical components as well as operando studies performed by our groups at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory to illustrate that AP-XPS is both a chemically and an electrically specific tool since photoelectrons carry information on both the local chemistry and electrical potentials. The applications of AP-XPS to oxygen electrocatalysis shown in this Account span well-defined studies of (1) the oxide/oxygen gas interface, (2) the oxide/water vapor interface, and (3) operando measurements of half and full electrochemical cells. Using specially designed model devices, we can expose and isolate the electrode or interface of interest to the incident X-ray beam and AP-XPS analyzer to relate the electrical potentials to the composition/chemical state of the key components and interfaces. We conclude with an outlook on new developments of AP-XPS end stations, which may provide significant improvement in the observation of dynamics over a wide range of time scales, higher spatial resolution, and improved characterization of boundary or interface layers (solid/solid and liquid/solid).

Dye-doped nanostructure polypyrrole film for electrochemically switching solid-phase microextraction of Ni(II) and ICP-OES analysis of waste water.

PubMed

Shamaeli, Ehsan; Alizadeh, Naader

2012-01-01

A nanostructure fiber based on conducting polypyrrole synthesized by an electrochemical method has been developed, and used for electrochemically switching solid-phase microextraction (ES-SPME). The ES-SPME was prepared by the doping of eriochrome blue in polypyrrole (PPy-ECB) and used for selectively extracting the Ni(II) cation in the presence of some transition and heavy metal ions. The cation-exchange behavior of electrochemically prepared polypyrrole on stainless-steel with and without eriochrome blue (ECB) dye was characterized using ICP-OES analysis. The effects of the scan rate for electrochemical synthesis, uptake and the release potential on the extraction behavior of the PPy-ECB conductive fiber were studied. Uptake and release time profiles show that the process of electrically switched cation exchange could be completed within 250 s. The results of the present study point concerning the possibility of developing a selective extraction process for Ni(II) from waste water was explored using such a nanostructured PPy-ECB film through an electrically switched cation exchange. 2012 © The Japan Society for Analytical Chemistry

The effect of strain hardening on resistance to electrochemical corrosion of wires for orthopaedics

NASA Astrophysics Data System (ADS)

Przondziono, J.; Walke, W.; Hadasik, E.; Szymszal, J.

2012-05-01

The purpose of this research is to evaluate electrochemical corrosion resistance of wire with modified surface, made of stainless steel of Cr-Ni-Mo type, widely used in implants for orthopaedics, depending on hardening created in the process of drawing. Tests have been carried out in the environment imitating human osseous tissue. Pitting corrosion was determined on the ground of registered anodic polarisation curves by means of potentiodynamic method with application of electrochemical testing system VoltaLab® PGP 201. Wire corrosion tests were carried out in Tyrode solution on samples that were electrochemically polished as well as electrochemically polished and finally chemically passivated. Initial material for tests was wire rod made of X2CrNiMo17-12-2 steel with diameter of 5.5 mm in supersaturated condition. Wire rod was drawn up to diameter of 1.35 mm. This work shows the course of flow curve of wire made of this grade of steel and mathematical form of yield stress function. The study also presents exemplary curves showing the dependence of polarisation resistance in strain function in the drawing process of electrochemically passivated and electrochemically polished and then chemically passivated wire.

Mass spectrometric methods for monitoring redox processes in electrochemical cells.

PubMed

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. © 2013 The Authors. Mass Spectrometry Reviews published by Wiley Periodicals, Inc.

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

In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

PubMed

Chen, Daqun; Hu, Weihua

2017-04-18

Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of the homogeneous polymerization and heterogeneous systems (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining the electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by the self-assembled monolayer of the ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information for eSI-ATRP and offers a powerful platform for in situ investigation of such complicated processes.

System and method for networking electrochemical devices

DOEpatents

Williams, Mark C.; Wimer, John G.; Archer, David H.

1995-01-01

An improved electrochemically active system and method including a plurality of electrochemical devices, such as fuel cells and fluid separation devices, in which the anode and cathode process-fluid flow chambers are connected in fluid-flow arrangements so that the operating parameters of each of said plurality of electrochemical devices which are dependent upon process-fluid parameters may be individually controlled to provide improved operating efficiency. The improvements in operation include improved power efficiency and improved fuel utilization in fuel cell power generating systems and reduced power consumption in fluid separation devices and the like through interstage process fluid parameter control for series networked electrochemical devices. The improved networking method includes recycling of various process flows to enhance the overall control scheme.

Electrochemical and/or microbiological treatment of pyrolysis wastewater.

PubMed

Silva, José R O; Santos, Dara S; Santos, Ubiratan R; Eguiluz, Katlin I B; Salazar-Banda, Giancarlo R; Schneider, Jaderson K; Krause, Laiza C; López, Jorge A; Hernández-Macedo, Maria L

2017-10-01

Electrochemical oxidation may be used as treatment to decompose partially or completely organic pollutants (wastewater) from industrial processes such as pyrolysis. Pyrolysis is a thermochemical process used to obtain bio-oil from biomasses, generating a liquid waste rich in organic compounds including aldehydes and phenols, which can be submitted to biological and electrochemical treatments in order to minimize its environmental impact. Thus, electrochemical systems employing dimensionally stable anodes (DSAs) have been proposed to enable biodegradation processes in subsurface environments. In order to investigate the organic compound degradation from residual coconut pyrolysis wastewater, ternary DSAs containing ruthenium, iridium and cerium synthetized by the 'ionic liquid method' at different calcination temperatures (500, 550, 600 and 700 °C) for the pretreatment of these compounds, were developed in order to allow posterior degradation by Pseudomonas sp., Bacillus sp. or Acinetobacter sp. bacteria. The electrode synthesized applying 500 °C displayed the highest voltammetric charge and was used in the pretreatment of pyrolysis effluent prior to microbial treatment. Regarding biological treatment, the Pseudomonas sp. exhibited high furfural degradation in wastewater samples electrochemically pretreated at 2.0 V. On the other hand, the use of Acinetobacter efficiently degraded phenolic compounds such as phenol, 4-methylphenol, 2,5-methylphenol, 4-ethylphenol and 3,5-methylphenol in both wastewater samples, with and without electrochemical pretreatment. Overall, the results indicate that the combination of both processes used in this study is relevant for the treatment of pyrolysis wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrochemical reduction of carbon dioxide. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

LaConti, A.B.; Molter, T.M.; Zagaja, J.A.

1986-05-01

Many researchers have studied the electrochemical reduction of carbon dioxide and related organic species to form concentrated liquid/gaseous products in laboratory-scale hardware. Hamilton Standard has developed a high pressure SPE electrolysis cell capable of reducing carbon dioxide streams to form pure, concentrated alcohols, carboxylic acids, and other hydrocarbons. The process is unique in that the byproducts of reaction include oxygen and, under some test conditions water. In addition, a relatively simple test system was designed and constructed permitting both batch and semibatch type electrochemical reduction studies. In this study, cathode materials were developed which 1) had a characteristic high hydrogenmore » overvoltage, and 2) possessed the intrinsic affinity for electrochemical reduction of the carbon dioxide species. In addition, suitable anode electrocatalyst materials were identified. Studies involving the electrochemical reduction of carbon dioxide required the ability to identify and quantify reaction products obtained during cell evaluation. Gas chromatographic techniques were developed along with the establishment of ion chromatographic methods permitting the analysis of organic reaction products. Hamilton Standard has evaluated electrochemical carbon dioxide reduction cells under a variety of test conditions.« less

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.

Conductive diamond sono-electrochemical disinfection (CDSED) for municipal wastewater reclamation.

PubMed

Llanos, Javier; Cotillas, Salvador; Cañizares, Pablo; Rodrigo, Manuel A

2015-01-01

In the present work, the disinfection of actual effluents from a municipal wastewater treatment plant (WWTP) by a conductive diamond sono-electrochemical process was assessed. First, efficiency of single electrodisinfection process with diamond anodes (without the contribution of ultrasounds) was studied, finding that the total disinfection can be attained at current charges applied below 0.02kAhm(-3). It was also found that the main disinfection mechanism is the attack of Escherichia coli (E. coli) by the disinfectants produced in the electrochemical cell and that the production of chlorates is avoided when working at current densities not higher than 1.27Am(-2). Next, a marked synergistic effect was found when coupling ultrasound (US) irradiation to the electrochemical system (sono-electrochemical disinfection). This increase in the disinfection rate was found to be related to the suppression of the agglomeration of E. coli cells and the enhancement in the production of disinfectant species. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrochemical characterization and electrode kinetics for antimony electrodeposition from its oxychloride solution in the presence of tartaric acid

NASA Astrophysics Data System (ADS)

Majidzade, Vusala Asim; Guliyev, Parvin Heydar; Aliyev, Akif Shikhan; Elrouby, Mahmoud; Tagiyev, Dilgam Babir

2017-05-01

This work is devoted to investigate the process of the electrochemical deposition of antimony from antimony oxychloride solution in the presence of tartaric acid in aqueous media. The kinetics and the mechanism of the electrodeposition process at the electrode surface are studied and proposed by the aid of cyclic, linear sweep voltammetric and chronoamperometric characterization methods. It is found that, the process is affected by the presence of tartaric acid and some factors during the electro-reduction process. The results also show that, the temperature, the potential sweep rate and the concentration of antimony have a great influence on the achievement of the electrodeposition process. Some important parameters are calculated such as, the activation energy of the electrochemical reaction, the diffusion coefficient and the number of saturated nucleation sites. The electrodeposited film is examined using X-ray diffraction, scanning electron microscopy and Energy Dispersive Spectroscopy.

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.

Cyclically optimized electrochemical processes

NASA Astrophysics Data System (ADS)

Ruedisueli, Robert Louis

It has been frequently observed in experiment and industry practice that electrochemical processes (deposition, dissolution, fuel cells) operated in an intermittent or cyclic (AC) mode show improvements in efficiency and/or quality and yield over their steady (DC) mode of operation. Whether rationally invoked by design or empirically tuned-in, the optimal operating frequency and duty cycle is dependent upon the dominant relaxation time constant for the process in question. The electrochemical relaxation time constant is a function of: double-layer and reaction intermediary pseudo-capacitances, ion (charge) transport via electrical migration (mobility), and diffusion across a concentration gradient to electrode surface reaction sites where charge transfer and species incorporation or elimination occurs. The rate determining step dominates the time constant for the reaction or process. Electrochemical impedance spectroscopy (EIS) and piezoelectric crystal electrode (PCE) response analysis have proven to be useful tools in the study and identification of reaction mechanisms. This work explains and demonstrates with the electro-deposition of copper the application of EIS and PCE measurement and analysis to the selection of an optimum cyclic operating schedule, an optimum driving frequency for efficient, sustained cyclic (pulsed) operation.

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.

Electrochemical studies of aluminium 7075 reinforced with Al2O3/SiCp hybrid composites in acid chloride medium

NASA Astrophysics Data System (ADS)

Ravikumar, M.; Reddappa, H. N.; Suresh, R.

2018-04-01

The study of corrosion rate and the inhibition efficiency of inhibitor for Al 7075 and Al 7075/Al2O3/SiCp corrosion in 1 M hydrochloride acid solution under Laboratory temperature by electrochemical measurements process. The efficiency increases by increasing of wt. % of reinforcement. The premier efficiency 99.1% is observed in the presence of reinforcement. The Electrochemical Impedance spectroscopic (EIS) method exhibit the capacitive loop representing the corrosion effect was controlled by the charge transfer method.

Electrochemical process for electrode material of spent lithium ion batteries.

PubMed

Prabaharan, G; Barik, S P; Kumar, N; Kumar, L

2017-10-01

Electrochemical method for recovering cobalt and manganese from electrode materials of spent lithium ion batteries was studied. Electrochemical leaching of cobalt and manganese from electrode material was optimized by varying different process parameters such as time, acid concentration and current density. Both cobalt and manganese could effectively be leached out at a current density of 400A/m 2 in 3h using 2M sulphuric acid. In the subsequent study, the metallic cobalt and electrolytic manganese dioxides was recovered from the leach liquor at 200A/m 2 , pH 2-2.5 and 90°C after removing aluminum. The commercial feasibility of the study was tested in pilot scale. Overall recovery of Co, Cu and Mn was above 96%, 97% and 99%, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrochemical oxidation of ciprofloxacin in two different processes: the electron transfer process on the anode surface and the indirect oxidation process in bulk solutions.

PubMed

Shen, Bo; Wen, Xianghua; Korshin, Gregory V

2018-05-14

Herein, the rotating disk electrode technique was used for the first time to investigate the effects of mass-transfer limitations and pH on the electrochemical oxidation of CPX, to determine the kinetics of CPX oxidation and to explore intrinsic mechanisms during the electron transfer process. Firstly, cyclic voltammetry revealed that an obvious irreversible CPX oxidation peak was observed within the potential window from 0.70 to 1.30 V at all pHs. Based on the Levich equation, the electrochemical oxidation of CPX in the electron transfer process was found to be controlled by both diffusion and kinetic processes when pH = 2, 5, 7 and 9; the diffusion coefficient of CPX at pH = 2 was calculated to be 1.5 × 10-7 cm2 s-1. Kinetic analysis indicated that the reaction on the electrode surface was adsorption-controlled compared to a diffusion process; the surface concentration of electroactive species was estimated to be 1.15 × 10-9 mol cm-2, the standard rate constant of the surface reaction was calculated to be 1.37 s-1, and CPX oxidation was validated to be a two-electron transfer process. Finally, a possible CPX oxidation pathway during the electron transfer process was proposed. The electrochemical degradation of CPX on a Ti-based anode was also conducted subsequently to investigate the electrochemical oxidation of CPX in the indirect oxidation process in bulk solutions. The effects of pH and current density were determined and compared to related literature results. The oxidation of CPX at different pHs is believed to be the result of a counterbalance between favorable and unfavorable factors, namely electromigration and side reactions of oxygen evolution, respectively. The effects of current density indicated a diffusion- and reaction-controlled process at low currents followed by a reaction-controlled process at high currents. The results presented in this study provide better understanding of the electrochemical oxidation of CPX and would enable the development of new treatment methods based on electrochemistry.

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.

Application of electrochemical processes to membrane bioreactors for improving nutrient removal and fouling control.

PubMed

Borea, Laura; Naddeo, Vincenzo; Belgiorno, Vincenzo

2017-01-01

Membrane bioreactor (MBR) technology is becoming increasingly popular as wastewater treatment due to the unique advantages it offers. However, membrane fouling is being given a great deal of attention so as to improve the performance of this type of technology. Recent studies have proven that the application of electrochemical processes to MBR represents a promising technological approach for membrane fouling control. In this work, two intermittent voltage gradients of 1 and 3 V/cm were applied between two cylindrical perforated electrodes, immersed around a membrane module, at laboratory scale with the aim of investigating the treatment performance and membrane fouling formation. For comparison purposes, the reactor also operated as a conventional MBR. Mechanisms of nutrient removal were studied and membrane fouling formation evaluated in terms of transmembrane pressure variation over time and sludge relative hydrophobicity. Furthermore, the impact of electrochemical processes on transparent exopolymeric particles (TEP), proposed as a new membrane fouling precursor, was investigated in addition to conventional fouling precursors such as bound extracellular polymeric substances (bEPS) and soluble microbial products (SMP). All the results indicate that the integration of electrochemical processes into a MBR has the advantage of improving the treatment performance especially in terms of nutrient removal, with an enhancement of orthophosphate (PO 4 -P) and ammonia nitrogen (NH 4 -N) removal efficiencies up to 96.06 and 69.34 %, respectively. A reduction of membrane fouling was also observed with an increase of floc hydrophobicity to 71.72 %, a decrease of membrane fouling precursor concentrations, and, thus, of membrane fouling rates up to 54.33 %. The relationship found between TEP concentration and membrane fouling rate after the application of electrochemical processes confirms the applicability of this parameter as a new membrane fouling indicator.

Flow Visualization of Low Prandtl Number Fluids using Electrochemical Measurements

NASA Technical Reports Server (NTRS)

Crunkleton, D.; Anderson, T.; Narayanan, R.; Labrosse, G.

2003-01-01

It is well established that residual flows exist in contained liquid metal processes. In 1-g processing, buoyancy forces often drive these flows and their magnitudes can be substantial. It is also known that residual flows can exist during microgravity processing, and although greatly reduced in magnitude, they can influence the properties of the processed materials. Unfortunately, there are very few techniques to visualize flows in opaque, high temperature liquid metals, and those available are not easily adapted to flight investigation. In this study, a novel technique is developed that uses liquid tin as the model fluid and solid-state electrochemical cells constructed from Yttria-Stabilized Zirconia (YSZ) to establish and measure dissolved oxygen boundary conditions. The melt serves as a common electrode for each of the electrochemical cells in this design, while independent reference electrodes are maintained at the outside surfaces of the electrolyte. By constructing isolated electrochemical cells at various locations along the container walls, oxygen is introduced or extracted by imposing a known electrical potential or passing a given current between the melt and the reference electrode. This programmed titration then establishes a known oxygen concentration boundary condition at the selected electrolyte-melt interface. Using the other cells, the concentration of oxygen at the electrolyte-melt interface is also monitored by measuring the open-circuit potentials developed between the melt and reference electrodes. Thus the electrochemical cells serve to both establish boundary conditions for the passive tracer and sense its path. Rayleigh-Benard convection was used to validate the electrochemical approach to flow visualization. Thus, a numerical characterization of the second critical Rayleigh numbers in liquid tin was conducted for a variety of Cartesian aspect ratios. The extremely low Prandtl number of tin represents the lowest value studied numerically. Additionally, flow field oscillations are visualized and the effect of tilt on convecting systems is quantified. Experimental studies of the effect of convection in liquid tin are presented. Three geometries are studied: (1) double electrochemical cell with vertical concentration gradients; (2) double cell with horizontal concentration gradients; and (3) multiple cells with vertical temperature gradients. The first critical Rayleigh number transition is detected with geometry (1) and it is concluded that current measurements are not as affected by convection as EMF measurements. The system is compared with numerical simulations in geometry (2), and oscillating convection is detected with geometry (3).

Studies of electrochemical interfaces by TOF neutron reflectometry at the IBR-2 reactor

NASA Astrophysics Data System (ADS)

Petrenko, V. I.; Gapon, I. V.; Rulev, A. A.; Ushakova, E. E.; Kataev, E. Yu; Yashina, L. V.; Itkis, D. M.; Avdeev, M. V.

2018-03-01

The operation performance of electrochemical energy conversion and storage systems such as supercapacitors and batteries depends on the processes occurring at the electrochemical interfaces, where charge separation and chemical reactions occur. Here, we report about the tests of the neutron reflectometry cells specially designed for operando studies of structural changes at the electrochemical interfaces between solid electrodes and liquid electrolytes. The cells are compatible with anhydrous electrolytes with organic solvents, which are employed today in all lithium ion batteries and most supercapacitors. The sensitivity of neutron reflectometry applied at the time-of-flight (TOF) reflectometer at the pulsed reactor IBR-2 is discussed regarding the effect of solid electrolyte interphase (SEI) formation on metal electrode surface.

Research and development of an electrochemical biocide reactor

NASA Technical Reports Server (NTRS)

See, G. G.; Bodo, C. A.; Glennon, J. P.

1975-01-01

An alternate disinfecting process to chemical agents, heat, or radiation in an aqueous media has been studied. The process is called an electrochemical biocide and employs cyclic, low-level voltages at chemically inert electrodes to pass alternating current through water and, in the process, to destroy microorganisms. The paper describes experimental hardware, methodology, and results with a tracer microorganism (Escherichia coli). The results presented show the effects on microorganism kill of operating parameters, including current density (15 to 55 mA/sq cm (14 to 51 ASF)), waveform of applied electrical signal (square, triangular, sine), frequency of applied electrical signal (0.5 to 1.5 Hz), process water flow rate (100 to 600 cc/min (1.6 to 9.5 gph)), and reactor resident time (0 to 4 min). Comparisons are made between the disinfecting property of the electrochemical biocide and chlorine, bromine, and iodine.

Preparation of superhydrophobic titanium surfaces via electrochemical etching and fluorosilane modification

NASA Astrophysics Data System (ADS)

Lu, Yao; Xu, Wenji; Song, Jinlong; Liu, Xin; Xing, Yingjie; Sun, Jing

2012-12-01

The preparation of superhydrophobic surfaces on hydrophilic metal substrates depends on both surface microstructures and low surface energy modification. In this study, a simple and inexpensive electrochemical method for preparing robust superhydrophobic titanium surfaces is reported. The neutral sodium chloride solution is used as electrolyte. Fluoroalkylsilane (FAS) was used to reduce the surface energy of the electrochemically etched surface. Scanning electron microscopy (SEM) images, energy-dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR) spectra, and contact angle measurement are performed to characterize the morphological features, chemical composition, and wettability of the titanium surfaces. Stability and friction tests indicate that the prepared titanium surfaces are robust. The analysis of electrolyte, reaction process, and products demonstrates that the electrochemical processing is very inexpensive and environment-friendly. This method is believed to be easily adaptable for use in large-scale industry productions to promote the application of superhydrophobic titanium surfaces in aviation, aerospace, shipbuilding, and the military industry.

The Impedance Response of Semiconductors: An Electrochemical Engineering Perspective.

ERIC Educational Resources Information Center

Orazem, Mark E.

1990-01-01

Shows that the principles learned in the study of mass transport, thermodynamics, and kinetics associated with electrochemical systems can be applied to the transport and reaction processes taking place within a semiconductor. Describes impedance techniques and provides several graphs illustrating impedance data for diverse circuit systems. (YP)

The Mathematical Modeling and Computer Simulation of Electrochemical Micromachining Using Ultrashort Pulses

NASA Astrophysics Data System (ADS)

Kozak, J.; Gulbinowicz, D.; Gulbinowicz, Z.

2009-05-01

The need for complex and accurate three dimensional (3-D) microcomponents is increasing rapidly for many industrial and consumer products. Electrochemical machining process (ECM) has the potential of generating desired crack-free and stress-free surfaces of microcomponents. This paper reports a study of pulse electrochemical micromachining (PECMM) using ultrashort (nanoseconds) pulses for generating complex 3-D microstructures of high accuracy. A mathematical model of the microshaping process with taking into consideration unsteady phenomena in electrical double layer has been developed. The software for computer simulation of PECM has been developed and the effects of machining parameters on anodic localization and final shape of machined surface are presented.

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. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Effects of Voltage and Concentration of Sodium Bicarbonate on Electrochemical Synthesis of Ethanol from Carbon Dioxide Using Brass as Cathode

NASA Astrophysics Data System (ADS)

Ramadan, Septian; Fariduddin, Sholah; Rizki Aminudin, Afianti; Kurnia Hayatri, Antisa; Riyanto

2017-11-01

The effects of voltage and concentration of sodium bicarbonate were investigated to determine the optimum conditions of the electrochemical synthesis process to convert carbon dioxide into ethanol. The conversion process is carried out using a sodium bicarbonate electrolyte solution in an electrochemical synthesis reactor equipped with a cathode and anode. As the cathode was used brass, while as the anode carbon was utilized. Sample of the electrochemical synthesis process was analyzed by gas chromatography to determine the content of the compounds produced. The optimum electrochemical synthesis conditions to convert carbon dioxide into ethanol are voltage and concentration of sodium bicarbonate are 3 volts and 0.4 M with ethanol concentration of 1.33%.

POM-assisted electrochemical delignification and bleaching of chemical pulp

Treesearch

Helene Laroche; Mohini Sain; Carl Houtman; Claude Daneault

2001-01-01

A polyoxometalate-catalyzed electrochemical process has shown good selectivity in delignifying pulp. This breakthrough in redox catalysis shows promise for the development of a new environmentally benign technology for pulp bleaching. The electrochemical process, applied with a mildly alkaline electrolyte solution containing trace amounts of a vanadium-based...

Superhydrophobic surfaces by electrochemical processes.

PubMed

Darmanin, Thierry; Taffin de Givenchy, Elisabeth; Amigoni, Sonia; Guittard, Frederic

2013-03-13

This review is an exhaustive representation of the electrochemical processes reported in the literature to produce superhydrophobic surfaces. Due to the intensive demand in the elaboration of superhydrophobic materials using low-cost, reproducible and fast methods, the use of strategies based on electrochemical processes have exponentially grown these last five years. These strategies are separated in two parts: the oxidation processes, such as oxidation of metals in solution, the anodization of metals or the electrodeposition of conducting polymers, and the reduction processed such as the electrodeposition of metals or the galvanic deposition. One of the main advantages of the electrochemical processes is the relative easiness to produce various surface morphologies and a precise control of the structures at a micro- or a nanoscale. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Menadione metabolism to thiodione in hepatoblastoma by scanning electrochemical microscopy

PubMed Central

Mauzeroll, Janine; Bard, Allen J.; Owhadian, Omeed; Monks, Terrence J.

2004-01-01

The cytotoxicity of menadione on hepatocytes was studied by using the substrate generation/tip collection mode of scanning electrochemical microscopy by exposing the cells to menadione and detecting the menadione-S-glutathione conjugate (thiodione) that is formed during the cellular detoxication process and is exported from the cell by an ATP-dependent pump. This efflux was electrochemically detected and allowed scanning electrochemical microscopy monitoring and imaging of single cells and groups of highly confluent live cells. Based on a constant flux model, ≈6 × 106 molecules of thiodione per cell per second are exported from monolayer cultures of Hep G2 cells. PMID:15601769

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.

Unravelling the electrochemical double layer by direct probing of the solid/liquid interface

PubMed Central

Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.; Yano, Junko; Hussain, Zahid; Liu, Zhi; Crumlin, Ethan J.

2016-01-01

The electrochemical double layer plays a critical role in electrochemical processes. Whilst there have been many theoretical models predicting structural and electrical organization of the electrochemical double layer, the experimental verification of these models has been challenging due to the limitations of available experimental techniques. The induced potential drop in the electrolyte has never been directly observed and verified experimentally, to the best of our knowledge. In this study, we report the direct probing of the potential drop as well as the potential of zero charge by means of ambient pressure X-ray photoelectron spectroscopy performed under polarization conditions. By analyzing the spectra of the solvent (water) and a spectator neutral molecule with numerical simulations of the electric field, we discern the shape of the electrochemical double layer profile. In addition, we determine how the electrochemical double layer changes as a function of both the electrolyte concentration and applied potential. PMID:27576762

Revealing metabolic storage processes in electrode respiring bacteria by differential electrochemical mass spectrometry.

PubMed

Kubannek, F; Schröder, U; Krewer, U

2018-06-01

In this work we employ differential electrochemical mass spectrometry (DEMS) in combination with static and dynamic electrochemical techniques for the study of metabolic processes of electrochemically active bacteria. CO 2 production during acetate oxidation by electrode respiring bacteria was measured, in-vivo and online with a sensitivity of 6.5 ⋅ 10 -13 mol/s. The correlation of ion current and electrical current provides insight into the interaction of metabolic processes and extra-cellular electron transfer. In low-turnover CVs, two competing potential dependent electron transfer mechanisms were observed and formal potentials of two redox systems that are involved in complete oxidation of acetate to CO 2 were determined. By balancing charge and carbon flows during dynamic measurements, two significant storage mechanisms in electrochemically active bacteria were identified: 1) a charge storage mechanism that allows substrate oxidation to proceed at a constant rate despite of external current flowing in cathodic direction. 2) a carbon storage mechanism that allows the biofilm to take up acetate at an unchanged rate at very low potentials even though the oxidation to CO 2 stops. These storage capabilities allow a limited decoupling of electrical current and CO 2 production rate. Copyright © 2018 Elsevier B.V. All rights reserved.

Development of a novel carbon-coating strategy for producing core-shell structured carbon coated LiFePO4 for an improved Li-ion battery performance.

PubMed

Pratheeksha, Parakandy Muzhikara; Mohan, Erabhoina Hari; Sarada, Bulusu Venkata; Ramakrishna, Mantripragada; Hembram, Kalyan; Srinivas, Pulakhandam Veera Venkata; Daniel, Paul Joseph; Rao, Tata Narasinga; Anandan, Srinivasan

2016-12-21

In the present study, LiFePO 4 (LFP) has been synthesized using a flame spray pyrolysis unit followed by carbon coating on LFP using a novel strategy of dehydration assisted polymerization process (DAP) in order to improve its electronic conductivity. Characterization studies revealed the presence of a pure LFP structure and the formation of a thin, uniform and graphitic carbon layer with a thickness of 6-8 nm on the surface of the LFP. A carbon coated LFP with 3 wt% of carbon, using a DAP process, delivered a specific capacity of 167 mA h g -1 at a 0.1C rate, whereas LFP carbon coated by a carbothermal process (CLFP-C) delivered a capacity of 145 mA h g -1 at 0.1C. Further carbon coated LFP by the DAP exhibited a good rate capability and cyclic stability. The enhanced electrochemical performance of C-LFP by DAP is attributed to the presence of a uniform, thin and ordered graphitic carbon layer with a core-shell structure, which greatly increased the electronic conductivity of LFP and thereby showed an improved electro-chemical performance. Interestingly, the developed carbon coating process has been extended to synthesize a bulk quantity (0.5 kg) of carbon coated LFP under optimized experimental conditions as a part of up-scaling and the resulting material electro-chemical performance has been evaluated and compared with commercial electrode materials. Bulk C-LFP showed a capacity of 131 mA h g -1 and 87 mA h g -1 at a rate of 1C and at 10C, respectively, illustrating that the developed DAP process greatly improved the electrochemical performance of LFP in terms of rate capability and cyclic stability, not only during the lab scale synthesis but also during the large scale synthesis. Benchmark studies concluded that the electro-chemical performance of C-LFP by DAP is comparable with that of TODA LFP and better than that of UNTPL LFP. The DAP process developed in the present study can be extended to other electrode materials as well.

Electrochemical investigations of Cr-Ni-Mo stainless steel used in urology

NASA Astrophysics Data System (ADS)

Przondziono, J.; Walke, W.

2011-05-01

The influence of chemical passivation process on physical and chemical characteristics of samples made of X2CrNiMo 17-7-2 steel with differentiated hardening, in the solution simulating the environment of human urine was analysed in the study. Wire obtained in cold drawing process is used for the production of stents and appliances in urological treatment. Proper roughness of the surface was obtained through mechanical working - grinding (Ra = 0,40 μn) and electrochemical polishing (Ra = 0,12 μn). Chemical passivation process was carried out in 40% solution of HN03 within 60 minutes in the temperature of 65°C. The tests of corrosion resistance were made on the ground of registered anodic polarisation curves and Stern method. For evaluation of phenomena occurring on the surface of tested steel, electrochemical impedance spectroscopy (EIS) was applied.

An overview on the removal of synthetic dyes from water by electrochemical advanced oxidation processes.

PubMed

Nidheesh, P V; Zhou, Minghua; Oturan, Mehmet A

2018-04-01

Wastewater containing dyes are one of the major threats to our environment. Conventional methods are insufficient for the removal of these persistent organic pollutants. Recently much attention has been received for the oxidative removal of various organic pollutants by electrochemically generated hydroxyl radical. This review article aims to provide the recent trends in the field of various Electrochemical Advanced Oxidation Processes (EAOPs) used for removing dyes from water medium. The characteristics, fundamentals and recent advances in each processes namely anodic oxidation, electro-Fenton, peroxicoagulation, fered Fenton, anodic Fenton, photoelectro-Fenton, sonoelectro-Fenton, bioelectro-Fenton etc. have been examined in detail. These processes have great potential to destroy persistent organic pollutants in aqueous medium and most of the studies reported complete removal of dyes from water. The great capacity of these processes indicates that EAOPs constitute a promising technology for the treatment of the dye contaminated effluents. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

PubMed

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

2014-01-01

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

Impact of the chemicals, essential for the purification process of strict Fe-hydrogenase, on the corrosion of mild steel.

PubMed

Rouvre, Ingrid; Gauquelin, Charles; Meynial-Salles, Isabelle; Basseguy, Régine

2016-06-01

The influence of additional chemical molecules, necessary for the purification process of [Fe]-hydrogenase from Clostridium acetobutylicum, was studied on the anaerobic corrosion of mild steel. At the end of the purification process, the pure [Fe-Fe]-hydrogenase was recovered in a Tris-HCl medium containing three other chemicals at low concentration: DTT, dithionite and desthiobiotin. Firstly, mild steel coupons were exposed in parallel to a 0.1 M pH7 Tris-HCl medium with or without pure hydrogenase. The results showed that hydrogenase and the additional molecules were in competition, and the electrochemical response could not be attributed solely to hydrogenase. Then, solutions with additional chemicals of different compositions were studied electrochemically. DTT polluted the electrochemical signal by increasing the Eoc by 35 mV 24 h after the injection of 300 μL of control solutions with DTT, whereas it drastically decreased the corrosion rate by increasing the charge transfer resistance (Rct 10 times the initial value). Thus, DTT was shown to have a strong antagonistic effect on corrosion and was removed from the purification process. An optimal composition of the medium was selected (0.5 mM dithionite, 7.5 mM desthiobiotin) that simultaneously allowed a high activity of hydrogenase and a lower impact on the electrochemical response for corrosion tests. Copyright © 2016 Elsevier B.V. All rights reserved.

Sol-gel derived electrode materials for supercapacitor applications

NASA Astrophysics Data System (ADS)

Lin, Chuan

1998-12-01

Electrochemical capacitors have been receiving increasing interest in recent years for use in energy storage systems because of their high energy and power density and long cycle lifes. Possible applications of electrochemical capacitors include high power pulsed lasers, hybrid power system for electric vehicles, etc. In this dissertation, the preparation of electrode materials for use as electrochemical capacitors has been studied using the sol-gel process. The high surface area electrode materials explored in this work include a synthetic carbon xerogel for use in a double-layer capacitor, a cobalt oxide xerogel for use in a pseudocapacitor, and a carbon-ruthenium xerogel composite, which utilizes both double-layer and faradaic capacitances. The preparation conditions of these materials were investigated in detail to maximize the surface area and optimize the pore size so that more energy could be stored while minimizing mass transfer limitations. The microstructures of the materials were also correlated with their performance as electrochemical capacitors to improve their energy and power densities. Finally, an idealistic mathematical model, including both double-layer and faradaic processes, was developed and solved numerically. This model can be used to perform the parametric studies of an electrochemical capacitor so as to gain a better understanding of how the capacitor works and also how to improve cell operations and electrode materials design.

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. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Electrochemically active biofilms: facts and fiction. A review

PubMed Central

Babauta, Jerome; Renslow, Ryan; Lewandowski, Zbigniew; Beyenal, Haluk

2014-01-01

This review examines the electrochemical techniques used to study extracellular electron transfer in the electrochemically active biofilms that are used in microbial fuel cells and other bioelectrochemical systems. Electrochemically active biofilms are defined as biofilms that exchange electrons with conductive surfaces: electrodes. Following the electrochemical conventions, and recognizing that electrodes can be considered reactants in these bioelectrochemical processes, biofilms that deliver electrons to the biofilm electrode are called anodic, ie electrode-reducing, biofilms, while biofilms that accept electrons from the biofilm electrode are called cathodic, ie electrode-oxidizing, biofilms. How to grow these electrochemically active biofilms in bioelec-trochemical systems is discussed and also the critical choices made in the experimental setup that affect the experimental results. The reactor configurations used in bioelectrochemical systems research are also described and the authors demonstrate how to use selected voltammetric techniques to study extracellular electron transfer in bioelectrochemical systems. Finally, some critical concerns with the proposed electron transfer mechanisms in bioelectrochemical systems are addressed together with the prospects of bioelectrochemical systems as energy-converting and energy-harvesting devices. PMID:22856464

Electrochemical force microscopy

DOEpatents

Kalinin, Sergei V.; Jesse, Stephen; Collins, Liam F.; Rodriguez, Brian J.

2017-01-10

A system and method for electrochemical force microscopy are provided. The system and method are based on a multidimensional detection scheme that is sensitive to forces experienced by a biased electrode in a solution. The multidimensional approach allows separation of fast processes, such as double layer charging, and charge relaxation, and slow processes, such as diffusion and faradaic reactions, as well as capturing the bias dependence of the response. The time-resolved and bias measurements can also allow probing both linear (small bias range) and non-linear (large bias range) electrochemical regimes and potentially the de-convolution of charge dynamics and diffusion processes from steric effects and electrochemical reactivity.

Plasmonic Imaging of Electrochemical Reactions of Single Nanoparticles.

PubMed

Fang, Yimin; Wang, Hui; Yu, Hui; Liu, Xianwei; Wang, Wei; Chen, Hong-Yuan; Tao, N J

2016-11-15

Electrochemical reactions are involved in many natural phenomena, and are responsible for various applications, including energy conversion and storage, material processing and protection, and chemical detection and analysis. An electrochemical reaction is accompanied by electron transfer between a chemical species and an electrode. For this reason, it has been studied by measuring current, charge, or related electrical quantities. This approach has led to the development of various electrochemical methods, which have played an essential role in the understanding and applications of electrochemistry. While powerful, most of the traditional methods lack spatial and temporal resolutions desired for studying heterogeneous electrochemical reactions on electrode surfaces and in nanoscale materials. To overcome the limitations, scanning probe microscopes have been invented to map local electrochemical reactions with nanometer resolution. Examples include the scanning electrochemical microscope and scanning electrochemical cell microscope, which directly image local electrochemical reaction current using a scanning electrode or pipet. The use of a scanning probe in these microscopes provides high spatial resolution, but at the expense of temporal resolution and throughput. This Account discusses an alternative approach to study electrochemical reactions. Instead of measuring electron transfer electrically, it detects the accompanying changes in the reactant and product concentrations on the electrode surface optically via surface plasmon resonance (SPR). SPR is highly surface sensitive, and it provides quantitative information on the surface concentrations of reactants and products vs time and electrode potential, from which local reaction kinetics can be analyzed and quantified. The plasmonic approach allows imaging of local electrochemical reactions with high temporal resolution and sensitivity, making it attractive for studying electrochemical reactions in biological systems and nanoscale materials with high throughput. The plasmonic approach has two imaging modes: electrochemical current imaging and interfacial impedance imaging. The former images local electrochemical current associated with electrochemical reactions (faradic current), and the latter maps local interfacial impedance, including nonfaradic contributions (e.g., double layer charging). The plasmonic imaging technique can perform voltammetry (cyclic or square wave) in an analogous manner to the traditional electrochemical methods. It can also be integrated with bright field, dark field, and fluorescence imaging capabilities in one optical setup to provide additional capabilities. To date the plasmonic imaging technique has found various applications, including mapping of heterogeneous surface reactions, analysis of trace substances, detection of catalytic reactions, and measurement of graphene quantum capacitance. The plasmonic and other emerging optical imaging techniques (e.g., dark field and fluorescence microscopy), together with the scanning probe-based electrochemical imaging and single nanoparticle analysis techniques, provide new capabilities for one to study single nanoparticle electrochemistry with unprecedented spatial and temporal resolutions. In this Account, we focus on imaging of electrochemical reactions at single nanoparticles.

Study on electrochemically deposited Mg metal

NASA Astrophysics Data System (ADS)

Matsui, Masaki

An electrodeposition process of magnesium metal from Grignard reagent based electrolyte was studied by comparing with lithium. The electrodeposition of magnesium was performed at various current densities. The obtained magnesium deposits did not show dendritic morphologies while all the lithium deposits showed dendritic products. Two different crystal growth modes in the electrodeposition process of magnesium metal were confirmed by an observation using scanning electron micro scope (SEM) and a crystallographic analysis using X-ray diffraction (XRD). An electrochemical study of the deposition/dissolution process of the magnesium showed a remarkable dependency of the overpotential of magnesium deposition on the electrolyte concentration compared with lithium. This result suggests that the dependency of the overpotential on the electrolyte concentration prevent the locally concentrated current resulting to form very uniform deposits.

Electrochemical Behavior of Pure Copper in Phosphate Buffer Solutions: A Comparison Between Micro- and Nano-Grained Copper

NASA Astrophysics Data System (ADS)

Imantalab, O.; Fattah-alhosseini, A.; Keshavarz, M. K.; Mazaheri, Y.

2016-02-01

In this work, electrochemical behavior of annealed (micro-) and nano-grained pure copper (fabricated by accumulative roll bonding process) in phosphate buffer solutions of various pH values ranging from 10.69 to 12.59 has been studied. Before any electrochemical measurements, evaluation of microstructure was obtained by optical microscope and transmission electron microscopy. To investigate the electrochemical behavior of the samples, the potentiodynamic polarization, Mott-Schottky analysis, and electrochemical impedance spectroscopy (EIS) were carried out. Potentiodynamic polarization plots and EIS measurements revealed that as a result of grain refinement, the passive behavior of the nano-grained sample was improved compared to that of annealed pure copper. Also, Mott-Schottky analysis indicated that the passive films behaved as p-type semiconductors and grain refinement did not change the semiconductor type of passive films.

Electrochemical atomic force microscopy: In situ monitoring of electrochemical processes

NASA Astrophysics Data System (ADS)

Reggente, Melania; Passeri, Daniele; Rossi, Marco; Tamburri, Emanuela; Terranova, Maria Letizia

2017-08-01

The in-situ electrodeposition of polyaniline (PANI), one of the most attractive conducting polymers (CP), has been monitored performing electrochemical atomic force microscopy (EC-AFM) experiments. The electropolymerization of PANI on a Pt working electrode has been observed performing cyclic voltammetry experiments and controlling the evolution of current flowing through the electrode surface, together with a standard AFM image. The working principle and the potentialities of this emerging technique are briefly reviewed and factors limiting the studying of the in-situ electrosynthesis of organic compounds discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li Hong.

A new technique was developed and demonstrated for combining carbon fibers with aromatic thermoplastic matrices to form a high-quality towpreg. The developed technique utilizes an in-situ electrochemical process (Electrochemical polymerization - ECP) to create the entire polymer matrix surrounding the fiber array by direct polymerization of monomer. Poly-paraxylylene (PPX) and derivatives are successfully polymerized in-situ on carbon fiber surfaces through ECP. A PPX/carbon-fiber towpreg with 40 vol % of matrix is achieved in a fairly short reaction time with a high polymer-coating efficiency. Vapor deposition polymerization (VDP) was also studied. PPX and carbon-fiber towpreg were made successfully by this process.more » A comparison between ECP and VDP was conducted. A study on electrochemical oxidation (ECO) of carbon fibers was also performed. The ECO treatment may be suitable for carbon fibers incorporated in composites with high-temperature curing resins and thermoplastic matrices.« less

Sol-gel Technology and Advanced Electrochemical Energy Storage Materials

NASA Technical Reports Server (NTRS)

Chu, Chung-tse; Zheng, Haixing

1996-01-01

Advanced materials play an important role in the development of electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. The sol-gel process is a versatile solution for use in the fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. This processing technique is particularly useful in producing porous materials with high surface area and low density, two of the most desirable characteristics for electrode materials. In addition,the porous surface of gels can be modified chemically to create tailored surface properties, and inorganic/organic micro-composites can be prepared for improved material performance device fabrication. Applications of several sol-gel derived electrode materials in different energy storage devices are illustrated in this paper. V2O5 gels are shown to be a promising cathode material for solid state lithium batteries. Carbon aerogels, amorphous RuO2 gels and sol-gel derived hafnium compounds have been studied as electrode materials for high energy density and high power density electrochemical capacitors.

Electrochemical processes of nucleation and growth of hydroxyapatite on titanium supported by real-time electrochemical atomic force microscopy.

PubMed

Eliaz, Noam; Eliyahu, Moshe

2007-03-01

Recently, interest in electrochemical formation of hydroxyapatite has evolved. In this work, highly crystalline hydroxyapatite is electrodeposited on pure titanium and Ti-6Al-4V alloy. In situ and ex situ imaging, coupled with potentiostatic and potentiodynamic measurements, is conducted by means of electrochemical atomic force microscopy. This allows for a study of the nucleation and growth of hydroxyapatite as well as of its near-atomic structure. Electrodeposition of hydroxyapatite is shown to result from precipitation in solution, following two stages: (1) instantaneous nucleation, two-dimensional growth; (2) progressive nucleation, three-dimensional growth. Although some nucleation occurs already at -842 mV, potentials that are more negative than -1.26 V versus SCE are required for enhanced growth. Mass transport is found to have only secondary effect on the deposition process. The conclusions of this work have implications in optimization of coatings on implants as well as in enhancement of the understanding of bone mineralization in vivo.

CFD analysis of a solid oxide fuel cell with internal reforming: Coupled interactions of transport, heterogeneous catalysis and electrochemical processes

NASA Astrophysics Data System (ADS)

Janardhanan, Vinod M.; Deutschmann, Olaf

Direct internal reforming in solid oxide fuel cell (SOFC) results in increased overall efficiency of the system. Present study focus on the chemical and electrochemical process in an internally reforming anode supported SOFC button cell running on humidified CH 4 (3% H 2 O). The computational approach employs a detailed multi-step model for heterogeneous chemistry in the anode, modified Butler-Volmer formalism for the electrochemistry and Dusty Gas Model (DGM) for the porous media transport. Two-dimensional elliptic model equations are solved for a button cell configuration. The electrochemical model assumes hydrogen as the only electrochemically active species. The predicted cell performances are compared with experimental reports. The results show that model predictions are in good agreement with experimental observation except the open circuit potentials. Furthermore, the steam content in the anode feed stream is found to have remarkable effect on the resulting overpotential losses and surface coverages of various species at the three-phase boundary.

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.

Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance.

PubMed

Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang

2018-02-12

Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization.

Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance

PubMed Central

Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang

2018-01-01

Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization. PMID:29439514

Mapping Ionic Currents and Reactivity on the Nanoscale: Electrochemical Strain Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalinin, S.V.

2010-10-19

Solid-state electrochemical processes in oxides underpin a broad spectrum of energy and information storage devices, ranging from Li-ion and Li-air batteries, to solid oxide fuel cells (SOFC) to electroresistive and memristive systems. These functionalities are controlled by the bias-driven diffusive and electromigration transport of mobile ionic species, as well as intricate a set of electrochemical and defect-controlled reactions at interfaces and in bulk. Despite the wealth of device-level and atomistic studies, little is known on the mesoscopic mechanisms of ion diffusion and electronic transport on the level of grain clusters, individual grains, and extended defects. The development of the capabilitymore » for probing ion transport on the nanometer scale is a key to deciphering complex interplay between structure, functionality, and performance in these systems. Here we introduce Electrochemical Strain Microscopy, a scanning probe microscopy technique based on strong strain-bias coupling in the systems in which local ion concentrations are changed by electrical fields. The imaging capability, as well as time- and voltage spectroscopies analogous to traditional current based electrochemical characterization methods are developed. The reversible intercalation of Li and mapping electrochemical activity in LiCoO2 is demonstrated, illustrating higher Li diffusivity at non-basal planes and grain boundaries. In Si-anode device structure, the direct mapping of Li diffusion at extended defects and evolution of Li-activity with charge state is explored. The electrical field-dependence of Li mobility is studied to determine the critical bias required for the onset of electrochemical transformation, allowing reaction and diffusion processes in the battery system to be separated at each location. Finally, the applicability of ESM for probing oxygen vacancy diffusion and oxygen reduction/evolution reactions is illustrated, and the high resolution ESM maps are correlated with aberration corrected scanning transmission electron microscopy imaging. The future potential for deciphering mechanisms of electrochemical transformations on an atomically-defined single-defect level is discussed.« less

High Power Electrochemical Capacitors

DTIC Science & Technology

2012-03-23

electrochemical properties of vanadium oxide aerogels prepared by a freeze-drying process. Journal of the Electrochemical Society, 2004. 151(5): p...Electrochemical Society, 2002. 149(1): p. A26-A30. 12. Rolison, D.R. and B. Dunn, Electrically conductive oxide aerogels : new materials in...surface area vanadium oxide aerogels . Electrochemical and Solid-State Letters, 2000. 3(10): p. 457-459. 14. Shembel, E., et al., Synthesis, investigation

Nanoscale electrochemical patterning reveals the active sites for catechol oxidation at graphite surfaces.

PubMed

Patel, Anisha N; McKelvey, Kim; Unwin, Patrick R

2012-12-19

Graphite-based electrodes (graphite, graphene, and nanotubes) are used widely in electrochemistry, and there is a long-standing view that graphite step edges are needed to catalyze many reactions, with the basal surface considered to be inert. In the present work, this model was tested directly for the first time using scanning electrochemical cell microscopy reactive patterning and shown to be incorrect. For the electro-oxidation of dopamine as a model process, the reaction rate was measured at high spatial resolution across a surface of highly oriented pyrolytic graphite. Oxidation products left behind in a pattern defined by the scanned electrochemical cell served as surface-site markers, allowing the electrochemical activity to be correlated directly with the graphite structure on the nanoscale. This process produced tens of thousands of electrochemical measurements at different locations across the basal surface, unambiguously revealing it to be highly electrochemically active, with step edges providing no enhanced activity. This new model of graphite electrodes has significant implications for the design of carbon-based biosensors, and the results are additionally important for understanding electrochemical processes on related sp(2)-hybridized materials such as pristine graphene and nanotubes.

Electrochemically assisted photocatalysis: Highly efficient treatment using thermal titanium oxides doped and non-doped electrodes for water disinfection.

PubMed

Dos Santos, Andreia Betina Kreuser; Claro, Elis Marina Turini; Montagnolli, Renato Nallin; Cruz, Jaqueline Matos; Lopes, Paulo Renato Matos; Bidoia, Ederio Dino

2017-12-15

Electrochemically assisted photocatalysis (by electronic drainage) is a highly promising method for disinfection of water. In this research, the efficiency of photolytic oxidation using UV-A radiation and electrochemically assisted photocatalysis (with electric potential of 1.5 V) was studied by using electrodes prepared by thermal treatment and doped with silver, for inactivation of Escherichia coli and Staphylococcus aureus. The Chick-Watson microorganism inactivation model was applied and the electrical energy consumption of the process was calculated. It was observed no significant inactivation of microorganisms when UV-A light or electric potential were applied separately. However, the electrochemically assisted photocatalytic process, with Ag-doped electrode completely inactivated the microbial population after 10 (E. coli) and 60 min (S. aureus). The best performing non-doped electrodes achieved 52.74% (E. coli) and 44.09% (S. aureus) inactivation rates after 60 min. Thus, electrochemically assisted photocatalytic activity was not only effective for the inactivation of microorganisms, but also notably low on electrical energy consumption during the treatment due to small current and low electric potential applied. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X-ray Absorption Spectroscopy Study.

PubMed

Jovanovič, Primož; Hodnik, Nejc; Ruiz-Zepeda, Francisco; Arčon, Iztok; Jozinović, Barbara; Zorko, Milena; Bele, Marjan; Šala, Martin; Šelih, Vid Simon; Hočevar, Samo; Gaberšček, Miran

2017-09-13

Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO 2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

Unravelling the electrochemical double layer by direct probing of the solid/liquid interface

DOE PAGES

Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.; ...

2016-08-31

The electrochemical double layer plays a critical role in electrochemical processes. Whilst there have been many theoretical models predicting structural and electrical organization of the electrochemical double layer, the experimental verification of these models has been challenging due to the limitations of available experimental techniques. The induced potential drop in the electrolyte has never been directly observed and verified experimentally, to the best of our knowledge. In this study, we report the direct probing of the potential drop as well as the potential of zero charge by means of ambient pressure X-ray photoelectron spectroscopy performed under polarization conditions. By analyzingmore » the spectra of the solvent (water) and a spectator neutral molecule with numerical simulations of the electric field, we discern the shape of the electrochemical double layer profile. In addition, we determine how the electrochemical double layer changes as a function of both the electrolyte concentration and applied potential.« less

Novel electrochemical process for coal conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farooque, M.

1989-07-01

The feasibility of two distinctly different routes to coal conversion at low severity conditions was investigated. An electrochemical approach utilizing both the electro-oxidation and electro-reduction routes was employed. The electro-oxidation route consists of an electrochemical reaction involving H{sub 2}O and coal, leading to the breakup of coal molecules. The observed reaction rate has been explained as a combination of the coal and pyrite electro-oxidation currents. Organic sulfur has been identified as the contributing factor for the observation of more than 100% H{sub 2} production current efficiency with several coal samples. Also, an attractive coal pre-treatment process has been identified whichmore » results in production of useful products and simultaneous upgrading of the coal. Electrochemical oxidation of coal with H{sub 2}O leads to the production of hydrogen, CO{sub 2}, simultaneous removal of pyritic sulfur, and significant reduction of ash content. There is also indirect evidence that the organic sulfur may be removed in the process. A preliminary economic evaluation of this process has projected a cost advantage of > $8 per ton of Illinois {number sign}2 coal. A lab-scale cell has been successfully employed in this study for generating process data useful for future design calculations. This study also explored the electro-reduction route of coal conversion and has successfully demonstrated production of liquid products from different coal types at low severity conditions. A variety of aliphatic and aromatic compounds have been identified in the products. Coal type appeared to be the most important parameter affecting the product spectrum. 32 refs., 26 figs., 19 tabs.« less

Electrochemical Processes for In-Situ Treatment of Contaminated Soils - Final Report - 09/15/1996 - 01/31/2001

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 reactormore » integrating the elector-osmosis and elector-Fantan processes will be used to study the treatment of contaminated soil in situ.« less

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.

Porous siliconformation and etching process for use in silicon micromachining

DOEpatents

Guilinger, Terry R.; Kelly, Michael J.; Martin, Jr., Samuel B.; Stevenson, Joel O.; Tsao, Sylvia S.

1991-01-01

A reproducible process for uniformly etching silicon from a series of micromechanical structures used in electrical devices and the like includes providing a micromechanical structure having a silicon layer with defined areas for removal thereon and an electrochemical cell containing an aqueous hydrofluoric acid electrolyte. The micromechanical structure is submerged in the electrochemical cell and the defined areas of the silicon layer thereon are anodically biased by passing a current through the electrochemical cell for a time period sufficient to cause the defined areas of the silicon layer to become porous. The formation of the depth of the porous silicon is regulated by controlling the amount of current passing through the electrochemical cell. The micromechanical structure is then removed from the electrochemical cell and submerged in a hydroxide solution to remove the porous silicon. The process is subsequently repeated for each of the series of micromechanical structures to achieve a reproducibility better than 0.3%.

Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production [Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production directly observed using environmental transmission electron microscopy

DOE PAGES

Lee, Sang Chul; Benck, Jesse D.; Tsai, Charlie; ...

2015-12-01

Amorphous MoS x is a highly active, earth-abundant catalyst for the electrochemical hydrogen evolution reaction. Previous studies have revealed that this material initially has a composition of MoS 3, but after electrochemical activation, the surface is reduced to form an active phase resembling MoS 2 in composition and chemical state. However, structural changes in the Mo Sx catalyst and the mechanism of the activation process remain poorly understood. In this study, we employ transmission electron microscopy (TEM) to image amorphous MoS x catalysts activated under two hydrogen-rich conditions: ex situ in an electrochemical cell and in situ in an environmentalmore » TEM. For the first time, we directly observe the formation of crystalline domains in the MoS x catalyst after both activation procedures as well as spatially localized changes in the chemical state detected via electron energy loss spectroscopy. Using density functional theory calculations, we investigate the mechanisms for this phase transformation and find that the presence of hydrogen is critical for enabling the restructuring process. Our results suggest that the surface of the amorphous MoS x catalyst is dynamic: while the initial catalyst activation forms the primary active surface of amorphous MoS 2, continued transformation to the crystalline phase during electrochemical operation could contribute to catalyst deactivation. Finally, these results have important implications for the application of this highly active electrocatalyst for sustainable H 2 generation.« less

Electrochemical Study and Applications of Selective Electrodeposition of Silver on Quantum Dots.

PubMed

Martín-Yerga, Daniel; Rama, Estefanía Costa; Costa-García, Agustín

2016-04-05

In this work, selective electrodeposition of silver on quantum dots is described. The particular characteristics of the nanostructured silver thus obtained are studied by electrochemical and microscopic techniques. On one hand, quantum dots were found to catalyze the silver electrodeposition, and on the other hand, a strong adsorption between electrodeposited silver and quantum dots was observed, indicated by two silver stripping processes. Nucleation of silver nanoparticles followed different mechanisms depending on the surface (carbon or quantum dots). Voltammetric and confocal microscopy studies showed the great influence of electrodeposition time on surface coating, and high-resolution transmission electron microscopy (HRTEM) imaging confirmed the initial formation of Janus-like Ag@QD nanoparticles in this process. By use of moderate electrodeposition conditions such as 50 μM silver, -0.1 V, and 60 s, the silver was deposited only on quantum dots, allowing the generation of localized nanostructured electrode surfaces. This methodology can also be employed for sensing applications, showing a promising ultrasensitive electrochemical method for quantum dot detection.

Feedback‐amplified electrochemical dual‐plate boron‐doped diamond microtrench detector for flow injection analysis

PubMed Central

Lewis, Grace E. M.; Gross, Andrew J.; Kasprzyk‐Hordern, Barbara; Lubben, Anneke T.

2015-01-01

An electrochemical flow cell with a boron‐doped diamond dual‐plate microtrench electrode has been developed and demonstrated for hydroquinone flow injection electroanalysis in phosphate buffer pH 7. Using the electrochemical generator‐collector feedback detector improves the sensitivity by one order of magnitude (when compared to a single working electrode detector). The diffusion process is switched from an analyte consuming “external” process to an analyte regenerating “internal” process with benefits in selectivity and sensitivity. PMID:25735831

Electro-oxidation of the dye azure B: kinetics, mechanism, and by-products.

PubMed

Olvera-Vargas, Hugo; Oturan, Nihal; Aravindakumar, C T; Paul, M M Sunil; Sharma, Virender K; Oturan, Mehmet A

2014-01-01

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals ((•)OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by (•)OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19 × 10(9) M(-1) s(-1). It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.

Electrochemical Treatment of Textile Dye Wastewater by Mild Steel Anode.

PubMed

Bhavya, J G; Rekha, H B; Murthy, Usha N

2014-04-01

This paper presents the results of the treatment of textile dye wastewater generated from a textile processing industry by electrochemical method. Experiments were conducted at current densities of 12, 24 and 48 A/m2 using mild steel as anode and cathode. During the various stages of electrolysis, parameters such as COD, color and BOD5 were determined in order to know the feasibility of electrochemical treatment. It was observed that increasing the electrolysis time and increased current density bring down the concentration of pollutants. Also COD removal rate and energy consumption during the electrolysis were calculated and presented in this paper. The present study proves the effectiveness of electrochemical treatment using MS as anode for TDW oxidation.

Real-Time Evaluation of Live Cancer Cells by an in Situ Surface Plasmon Resonance and Electrochemical Study.

PubMed

Wu, Changyu; Rehman, Fawad Ur; Li, Jingyuan; Ye, Jing; Zhang, Yuanyuan; Su, Meina; Jiang, Hui; Wang, Xuemei

2015-11-11

This work presents a new strategy of the combination of surface plasmon resonance (SPR) and electrochemical study for real-time evaluation of live cancer cells treated with daunorubicin (DNR) at the interface of the SPR chip and living cancer cells. The observations demonstrate that the SPR signal changes could be closely related to the morphology and mass changes of adsorbed cancer cells and the variation of the refractive index of the medium solution. The results of light microscopy images and 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide studies also illustrate the release or desorption of HepG2 cancer cells, which were due to their apoptosis after treatment with DNR. It is evident that the extracellular concentration of DNR residue can be readily determined through electrochemical measurements. The decreases in the magnitudes of SPR signals were linearly related to cell survival rates, and the combination of SPR with electrochemical study could be utilized to evaluate the potential therapeutic efficiency of bioactive agents to cells. Thus, this label-free, real-time SPR-electrochemical detection technique has great promise in bioanalysis or monitoring of relevant treatment processes in clinical applications.

Electrochemical in situ regeneration of granular activated carbon using a three-dimensional reactor.

PubMed

Sun, Hong; Liu, Zhigang; Wang, Ying; Li, Yansheng

2013-12-01

Electrochemical in situ regeneration of granular activated carbon (GAC) saturated with phenol was experimentally investigated using a three-dimensional electrode reactor with titanium filter electrode arrays. The feasibility of the electrochemical regeneration has been assessed by monitoring the regeneration efficiency and chemical oxygen demand (COD). The influence of the applied current, the effluent flow rate, and the effluent path of the electrochemical cell have been systematically studied. Under the optimum conditions, the regeneration efficiency of GAC could reach 94% in 2 hr, and no significant declination was observed after five-time continuous adsorption-regeneration cycles. The adsorption of organic pollutants was almost completely mineralized due to electrochemical oxidation, indicating that this regeneration process is much more potentially cost-effective for application. Copyright © 2013 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Intramolecular allyl transfer reaction from allyl ether to aldehyde groups: experimental and theoretical studies.

PubMed

Franco, Delphine; Wenger, Karine; Antonczak, Serge; Cabrol-Bass, Daniel; Duñach, Elisabet; Rocamora, Mercè; Gomez, Montserrat; Muller, Guillermo

2002-02-02

The intramolecular transfer of the allyl group of functionalized allyl aryl ethers to an aldehyde group in the presence of Ni0 complexes was studied from chemical, electrochemical and theoretical points of view. The chemical reaction involves the addition of Ni0 to the allyl ether followed by stoichiometric allylation. The electrochemical process is catalytic in nickel and involves the reduction of intermediate eta3-allylnickel(II) complexes.

Hydroxyl radical generation in electro-Fenton process with a gas-diffusion electrode: Linkages with electro-chemical generation of hydrogen peroxide and iron redox cycle.

PubMed

Yatagai, Tomonori; Ohkawa, Yoshiko; Kubo, Daichi; Kawase, Yoshinori

2017-01-02

The hydroxyl radical generation in an electro-Fenton process with a gas-diffusion electrode which is strongly linked with electro-chemical generation of hydrogen peroxide and iron redox cycle was studied. The OH radical generation subsequent to electro-chemical generations of H 2 O 2 was examined under the constant potential in the range of Fe 2+ dosage from 0 to 1.0 mM. The amount of generated OH radical initially increased and gradually decreased after the maximum was reached. The initial rate of OH radical generation increased for the Fe 2+ dosage <0.25 mM and at higher Fe 2+ dosages remained constant. At higher Fe 2+ dosages the precipitation of Fe might inhibit the enhancement of OH radical generation. The experiments for decolorization and total organic carbon (TOC) removal of azo-dye Orange II by the electro-Fenton process were conducted and the quick decolorization and slow TOC removal of Orange II were found. To quantify the linkages of OH radical generation with dynamic behaviors of electro-chemically generated H 2 O 2 and iron redox cycle and to investigate effects of OH radical generation on the decolorization and TOC removal of Orange II, novel reaction kinetic models were developed. The proposed models could satisfactory clarify the linkages of OH radical generation with electro-chemically generated H 2 O 2 and iron redox cycle and simulate the decolorization and TOC removal of Orange II by the electro-Fenton process.

Electrochemistry at Edge of Single Graphene Layer in a Nanopore

PubMed Central

Banerjee, Shouvik; Shim, Jiwook; Rivera, Jose; Jin, Xiaozhong; Estrada, David; Solovyeva, Vita; You, Xiuque; Pak, James; Pop, Eric; Aluru, Narayana; Bashir, Rashid

2013-01-01

We study the electrochemistry of single layer graphene edges using a nanopore-based structure consisting of stacked graphene and Al2O3 dielectric layers. Nanopores, with diameters ranging from 5 to 20 nm, are formed by an electron beam sculpting process on the stacked layers. This leads to unique edge structure which, along with the atomically thin nature of the embedded graphene electrode, demonstrates electrochemical current densities as high as 1.2 × 104 A/cm2. The graphene edge embedded structure offers a unique capability to study the electrochemical exchange at an individual graphene edge, isolated from the basal plane electrochemical activity. We also report ionic current modulation in the nanopore by biasing the embedded graphene terminal with respect to the electrodes in the fluid. The high electrochemical specific current density for a graphene nanopore-based device can have many applications in sensitive chemical and biological sensing, and energy storage devices. PMID:23249127

Investigating Li 2NiO 2–Li 2CuO 2 Solid Solutions as High-Capacity Cathode Materials for Li-Ion Batteries

DOE PAGES

Xu, Jing; Renfrew, Sara; Marcus, Matthew A.; ...

2017-05-11

Li 2Ni 1–xCu xO 2 solid solutions were prepared by a solid-state method to study the correlation between composition and electrochemical performance. Cu incorporation improved the phase purity of Li 2Ni 1–xCu xO 2 with orthorhombic Immm structure, resulting in enhanced capacity. However, the electrochemical profiles suggested Cu incorporation did not prevent irreversible phase transformation during the electrochemical process, instead, it likely influenced the phase transformation upon lithium removal. By combining ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and differential electrochemical mass spectrometry (DEMS) measurements, this study elucidates the relevant phase transformation (e.g., crystal structure, local environment, andmore » charge compensation) and participation of electrons from lattice oxygen during the first cycle in these complex oxides.« less

Comparative study of the effect of pharmaceutical additives on the elimination of antibiotic activity during the treatment of oxacillin in water by the photo-Fenton, TiO2-photocatalysis and electrochemical processes.

PubMed

Serna-Galvis, Efraim A; Silva-Agredo, Javier; Giraldo, Ana L; Flórez-Acosta, Oscar A; Torres-Palma, Ricardo A

2016-01-15

Synthetic pharmaceutical effluents loaded with the β-lactam antibiotic oxacillin were treated using advanced oxidation processes (the photo-Fenton system and TiO2 photocatalysis) and chloride mediated electrochemical oxidation (with Ti/IrO2 anodes). Combinations of the antibiotic with excipients (mannitol or tartaric acid), an active ingredient (calcium carbonate, i.e. bicarbonate ions due to the pH) and a cleaning agent (sodium lauryl ether sulfate) were considered. Additionally, urban wastewater that had undergone biological treatment was doped with oxacillin and treated with the tested systems. The evolution of antimicrobial activity was monitored as a parameter of processes efficiency. Although the two advanced oxidation processes (AOPs) differ only in the way they produce OH, marked differences were observed between them. There were also differences between the AOPs and the electrochemical system. Interestingly, each additive had a different effect on each treatment. For water loaded with mannitol, electrochemical treatment was the most suitable option because the additive did not significantly affect the efficiency of the system. Due to the formation of a complex with Fe(3+), tartaric acid accelerated the elimination of antibiotic activity during the photo-Fenton process. For TiO2 photocatalysis, the presence of bicarbonate ions contributed to antibiotic activity elimination through the possible formation of carbonate and bicarbonate radicals. Sodium lauryl ether sulfate negatively affected all of the processes. However, due to the higher selectivity of HOCl compared with OH, electrochemical oxidation showed the least inhibited efficiency. For the urban wastewater doped with oxacillin, TiO2 photocatalysis was the most efficient process. These results will help select the most suitable technology for the treatment of water polluted with β-lactam antibiotics. Copyright © 2015 Elsevier B.V. All rights reserved.

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 for the electrodissolution of anodes (first stage in electrocoagulation processes). This later model use a mixed macroscopic/maximum gradient approach to describe the chemical and electrochemical processes and it also assumes that the rates of all processes are very high, and that they can be successfully modeled using pseudoequilibrium approaches.

Nanoscale Electrochemistry of sp(2) Carbon Materials: From Graphite and Graphene to Carbon Nanotubes.

PubMed

Unwin, Patrick R; Güell, Aleix G; Zhang, Guohui

2016-09-20

Carbon materials have a long history of use as electrodes in electrochemistry, from (bio)electroanalysis to applications in energy technologies, such as batteries and fuel cells. With the advent of new forms of nanocarbon, particularly, carbon nanotubes and graphene, carbon electrode materials have taken on even greater significance for electrochemical studies, both in their own right and as components and supports in an array of functional composites. With the increasing prominence of carbon nanomaterials in electrochemistry comes a need to critically evaluate the experimental framework from which a microscopic understanding of electrochemical processes is best developed. This Account advocates the use of emerging electrochemical imaging techniques and confined electrochemical cell formats that have considerable potential to reveal major new perspectives on the intrinsic electrochemical activity of carbon materials, with unprecedented detail and spatial resolution. These techniques allow particular features on a surface to be targeted and models of structure-activity to be developed and tested on a wide range of length scales and time scales. When high resolution electrochemical imaging data are combined with information from other microscopy and spectroscopy techniques applied to the same area of an electrode surface, in a correlative-electrochemical microscopy approach, highly resolved and unambiguous pictures of electrode activity are revealed that provide new views of the electrochemical properties of carbon materials. With a focus on major sp(2) carbon materials, graphite, graphene, and single walled carbon nanotubes (SWNTs), this Account summarizes recent advances that have changed understanding of interfacial electrochemistry at carbon electrodes including: (i) Unequivocal evidence for the high activity of the basal surface of highly oriented pyrolytic graphite (HOPG), which is at least as active as noble metal electrodes (e.g., platinum) for outer-sphere redox processes. (ii) Demonstration of the high activity of basal plane HOPG toward other reactions, with no requirement for catalysis by step edges or defects, as exemplified by studies of proton-coupled electron transfer, redox transformations of adsorbed molecules, surface functionalization via diazonium electrochemistry, and metal electrodeposition. (iii) Rationalization of the complex interplay of different factors that determine electrochemistry at graphene, including the source (mechanical exfoliation from graphite vs chemical vapor deposition), number of graphene layers, edges, electronic structure, redox couple, and electrode history effects. (iv) New methodologies that allow nanoscale electrochemistry of 1D materials (SWNTs) to be related to their electronic characteristics (metallic vs semiconductor SWNTs), size, and quality, with high resolution imaging revealing the high activity of SWNT sidewalls and the importance of defects for some electrocatalytic reactions (e.g., the oxygen reduction reaction). The experimental approaches highlighted for carbon electrodes are generally applicable to other electrode materials and set a new framework and course for the study of electrochemical and interfacial processes.

A Demonstration of Simultaneous Electrochemiluminescence

ERIC Educational Resources Information Center

Ibanez, Jorge G.; Zavala-Araiza, Daniel; Sotomayor-Martinez Barranco, Biaani; Torres-Perez, Jonatan; Camacho-Zuniga, Claudia; Bohrmann-Linde, Claudia; Tausch, Michael W.

2013-01-01

Paired (simultaneous) electrochemical processes can increase energy savings in selected cases by using the reactions at both electrodes of an electrochemical cell to perform a desired process, as is the case in the commercially successful chlor-alkali process. In the demonstration described herein, simultaneous blue electrochemiluminescence (ECL)…

Formation of hazardous inorganic by-products during electrolysis of seawater as a disinfection process for desalination.

PubMed

Oh, Byung Soo; Oh, Sang Guen; Hwang, Youn Young; Yu, Hye-Weon; Kang, Joon-Wun; Kim, In S

2010-11-01

From our previous study, an electrochemical process was determined to be a promising tool for disinfection in a seawater desalination system, but an investigation on the production of several hazardous by-products is still required. In this study, a more intensive exploration of the formation patterns of perchlorate and bromate during the electrolysis of seawater was conducted. In addition, the rejection efficiencies of the targeted by-products by membrane processes (microfiltration and seawater reverse osmosis) were investigated to uncover the concentrations remaining in the final product from a membrane-based seawater desalination system for the production of drinking water. On the electrolysis of seawater, perchlorate did not provoke any problem due to the low concentrations formed, but bromate was produced at a much higher level, resulting in critical limitation in the application of the electrochemical process to the desalination of seawater. Even though the formed bromate was rejected via microfiltration and reverse osmosis during the 1st and 2nd passes, the residual concentration was a few orders of magnitude higher than the USEPA regulation. Consequently, it was concluded that the application of the electrochemical process to seawater desalination cannot be recommended without the control of bromate. Copyright © 2010 Elsevier B.V. All rights reserved.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater.

PubMed

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-03-15

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO 2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

PubMed Central

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-01-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process. PMID:28294180

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

NASA Astrophysics Data System (ADS)

Gu, Di; Gao, Simeng; Jiang, Tingting; Wang, Baohui

2017-03-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

Solar Thermo-coupled Electrochemical Oxidation of Aniline in Wastewater for the Complete Mineralization Beyond an Anodic Passivation Film.

PubMed

Yuan, Dandan; Tian, Lei; Li, Zhida; Jiang, Hong; Yan, Chao; Dong, Jing; Wu, Hongjun; Wang, Baohui

2018-02-15

Herein, we report the solar thermal electrochemical process (STEP) aniline oxidation in wastewater for totally solving the two key obstacles of the huge energy consumption and passivation film in the electrochemical treatment. The process, fully driven by solar energy without input of any other energies, sustainably serves as an efficient thermoelectrochemical oxidation of aniline by the control of the thermochemical and electrochemical coordination. The thermocoupled electrochemical oxidation of aniline achieved a fast rate and high efficiency for the full minimization of aniline to CO 2 with the stability of the electrode and without formation of polyaniline (PAN) passivation film. A clear mechanism of aniline oxidation indicated a switching of the reactive pathway by the STEP process. Due to the coupling of solar thermochemistry and electrochemistry, the electrochemical current remained stable, significantly improving the oxidation efficiency and mineralization rate by apparently decreasing the electrolytic potential when applied with high temperature. The oxidation rate of aniline and chemical oxygen demand (COD) removal rate could be lifted up to 2.03 and 2.47 times magnification compared to conventional electrolysis, respectively. We demonstrate that solar-driven STEP processes are capable of completely mineralizing aniline with high utilization of solar energy. STEP aniline oxidation can be utilized as a green, sustainable water treatment.

Electrochemical degradation, kinetics & performance studies of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Das, Debanjan

Linear and Non-linear electrochemical characterization techniques and equivalent circuit modelling were carried out on miniature and sub-commercial Solid Oxide Fuel Cell (SOFC) stacks as an in-situ diagnostic approach to evaluate and analyze their performance under the presence of simulated alternative fuel conditions. The main focus of the study was to track the change in cell behavior and response live, as the cell was generating power. Electrochemical Impedance Spectroscopy (EIS) was the most important linear AC technique used for the study. The distinct effects of inorganic components usually present in hydrocarbon fuel reformates on SOFC behavior have been determined, allowing identification of possible "fingerprint" impedance behavior corresponding to specific fuel conditions and reaction mechanisms. Critical electrochemical processes and degradation mechanisms which might affect cell performance were identified and quantified. Sulfur and siloxane cause the most prominent degradation and the associated electrochemical cell parameters such as Gerisher and Warburg elements are applied respectively for better understanding of the degradation processes. Electrochemical Frequency Modulation (EFM) was applied for kinetic studies in SOFCs for the very first time for estimating the exchange current density and transfer coefficients. EFM is a non-linear in-situ electrochemical technique conceptually different from EIS and is used extensively in corrosion work, but rarely used on fuel cells till now. EFM is based on exploring information obtained from non-linear higher harmonic contributions from potential perturbations of electrochemical systems, otherwise not obtained by EIS. The baseline fuel used was 3 % humidified hydrogen with a 5-cell SOFC sub-commercial planar stack to perform the analysis. Traditional methods such as EIS and Tafel analysis were carried out at similar operating conditions to verify and correlate with the EFM data and ensure the validity of the obtained information. The obtained values closely range from around 11 mA cm-2 - 16 mA cm -2 with reasonable repeatability and excellent accuracy. The potential advantages of EFM compared to traditional methods were realized and our primary aim at demonstrating this technique on a SOFC system are presented which can act as a starting point for future research efforts in this area. Finally, an approach based on in-situ State of Health tests by EIS was formulated and investigated to understand the most efficient fuel conditions for suitable long term operation of a solid oxide fuel cell stack under power generation conditions. The procedure helped to reflect the individual effects of three most important fuel characteristics CO/H2 volumetric ratio, S/C ratio and fuel utilization under the presence of a simulated alternative fuel at 0.4 A cm-2. Variation tests helped to identify corresponding electrochemical/chemical processes, narrow down the most optimum operating regimes considering practical behavior of simulated reformer-SOFC system arrangements. At the end, 8 different combinations of the optimized parameters were tested long term with the stack, and the most efficient blend was determined.

Following the electroreduction of uranium dioxide to uranium in LiCl-KCl eutectic in situ using synchrotron radiation

NASA Astrophysics Data System (ADS)

Brown, L. D.; Abdulaziz, R.; Jervis, R.; Bharath, V. J.; Atwood, R. C.; Reinhard, C.; Connor, L. D.; Simons, S. J. R.; Inman, D.; Brett, D. J. L.; Shearing, P. R.

2015-09-01

The electrochemical reduction of uranium dioxide to metallic uranium has been investigated in lithium chloride-potassium chloride eutectic molten salt. Laboratory based electrochemical studies have been coupled with in situ energy dispersive X-ray diffraction, for the first time, to deduce the reduction pathway. No intermediate phases were identified using the X-ray diffraction before, during or after electroreduction to form α-uranium. This suggests that the electrochemical reduction occurs via a single, 4-electron-step, process. The rate of formation of α-uranium is seen to decrease during electrolysis and could be a result of a build-up of oxygen anions in the molten salt. Slow transport of O2- ions away from the UO2 working electrode could impede the electrochemical reduction.

Carbon-Nanotube-Based Electrochemical Double-Layer Capacitor Technologies for Spaceflight Applications

NASA Technical Reports Server (NTRS)

Arepalli, S.; Fireman, H.; Huffman, C.; Maloney, P.; Nikolaev, P.; Yowell, L.; Kim, K.; Kohl, P. A.; Higgins, C. D.; Turano, S. P.

2005-01-01

Electrochemical double-layer capacitors, or supercapacitors, have tremendous potential as high-power energy sources for use in low-weight hybrid systems for space exploration. Electrodes based on single-wall carbon nanotubes (SWCNTs) offer exceptional power and energy performance due to the high surface area, high conductivity, and the ability to functionalize the SWCNTs to optimize capacitor properties. This paper will report on the preparation of electrochemical capacitors incorporating SWCNT electrodes and their performance compared with existing commercial technology. Preliminary results indicate that substantial increases in power and energy density are possible. The effects of nanotube growth and processing methods on electrochemical capacitor performance is also presented. The compatibility of different SWCNTs and electrolytes was studied by varying the type of electrolyte ions that accumulate on the high-surface-area electrodes.

Corrosion barriers processed by Al electroplating and their resistance against flowing Pb-15.7Li

NASA Astrophysics Data System (ADS)

Krauss, Wolfgang; Konys, Jürgen; Wulf, Sven-Erik

2014-12-01

In the HCLL blanket design, ferritic-martensitic steels are in direct contact with the flowing liquid breeder Pb-15.7Li and have to withstand severe corrosion attack. Beyond corrosion, T-permeation from the breeder into the RAFM-steels is also an important issue and has to be reduced significantly. Earlier work showed that Al-based coatings can act as barriers for both, however, applied processes e.g. HDA or VPS exhibited strong drawbacks in the past. Meanwhile new industrial relevant coating processes, using electroplating technology are under development and called ECA (electrochemical aluminization) and ECX (electrochemical deposition from ionic liquids) process. In this study electrochemically Al-coated and heat-treated Eurofer samples were tested in PICOLO loop for exposure times up to 12,000 h (ECA) and 2000 h (first results ECX) respectively to determine corrosion properties in flowing Pb-15.7Li (550 °C, 0.1 m/s). Cross section analysis afterward corrosion testing proved the ability of thin Al-based barriers made by electrochemical techniques to protect the bare Eurofer from corrosion attack even at exposure times of 12,000 h. Determined radial corrosion rates lay between 10 and 20 μm/a. First results for ECX coated samples (2000 h) revealed more homogeneous corrosion behavior of the barrier layer itself compared to ECA.

The Development of Non-Enzymatic Glucose Biosensors Based on Electrochemically Prepared Polypyrrole-Chitosan-Titanium Dioxide Nanocomposite Films.

PubMed

Al-Mokaram, Ali M A Abdul Amir; Yahya, Rosiyah; Abdi, Mahnaz M; Mahmud, Habibun Nabi Muhammad Ekramul

2017-05-31

The performance of a modified electrode of nanocomposite films consisting of polypyrrole-chitosan-titanium dioxide (Ppy-CS-TiO₂) has been explored for the developing a non-enzymatic glucose biosensors. The synergy effect of TiO₂ nanoparticles (NPs) and conducting polymer on the current responses of the electrode resulted in greater sensitivity. The incorporation of TiO₂ NPs in the nanocomposite films was confirmed by X-ray photoelectron spectroscopy (XPS) spectra. FE-SEM and HR-TEM provided more evidence for the presence of TiO₂ in the Ppy-CS structure. Glucose biosensing properties were determined by amperommetry and cyclic voltammetry (CV). The interfacial properties of nanocomposite electrodes were studied by electrochemical impedance spectroscopy (EIS). The developed biosensors showed good sensitivity over a linear range of 1-14 mM with a detection limit of 614 μM for glucose. The modified electrode with Ppy-CS nanocomposite also exhibited good selectivity and long-term stability with no interference effect. The Ppy-CS-TiO₂ nanocomposites films presented high electron transfer kinetics. This work shows the role of nanomaterials in electrochemical biosensors and describes the process of their homogeneous distribution in composite films by a one-step electrochemical process, where all components are taken in a single solution in the electrochemical cell.

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

2016-12-05

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). Copyright © 2016 Elsevier B.V. All rights reserved.

Dual-Mode Electro-Optical Techniques for Biosensing Applications: A Review

PubMed Central

Johnson, Steven

2017-01-01

The monitoring of biomolecular interactions is a key requirement for the study of complex biological processes and the diagnosis of disease. Technologies that are capable of providing label-free, real-time insight into these interactions are of great value for the scientific and clinical communities. Greater understanding of biomolecular interactions alongside increased detection accuracy can be achieved using technology that can provide parallel information about multiple parameters of a single biomolecular process. For example, electro-optical techniques combine optical and electrochemical information to provide more accurate and detailed measurements that provide unique insights into molecular structure and function. Here, we present a comparison of the main methods for electro-optical biosensing, namely, electrochemical surface plasmon resonance (EC-SPR), electrochemical optical waveguide lightmode spectroscopy (EC-OWLS), and the recently reported silicon-based electrophotonic approach. The comparison considers different application spaces, such as the detection of low concentrations of biomolecules, integration, the tailoring of light-matter interaction for the understanding of biomolecular processes, and 2D imaging of biointeractions on a surface. PMID:28880211

Dual-Mode Electro-Optical Techniques for Biosensing Applications: A Review.

PubMed

Juan-Colás, José; Johnson, Steven; Krauss, Thomas F

2017-09-07

The monitoring of biomolecular interactions is a key requirement for the study of complex biological processes and the diagnosis of disease. Technologies that are capable of providing label-free, real-time insight into these interactions are of great value for the scientific and clinical communities. Greater understanding of biomolecular interactions alongside increased detection accuracy can be achieved using technology that can provide parallel information about multiple parameters of a single biomolecular process. For example, electro-optical techniques combine optical and electrochemical information to provide more accurate and detailed measurements that provide unique insights into molecular structure and function. Here, we present a comparison of the main methods for electro-optical biosensing, namely, electrochemical surface plasmon resonance (EC-SPR), electrochemical optical waveguide lightmode spectroscopy (EC-OWLS), and the recently reported silicon-based electrophotonic approach. The comparison considers different application spaces, such as the detection of low concentrations of biomolecules, integration, the tailoring of light-matter interaction for the understanding of biomolecular processes, and 2D imaging of biointeractions on a surface.

Direct fabrication of 3D graphene on nanoporous anodic alumina by plasma-enhanced chemical vapor deposition

PubMed Central

Zhan, Hualin; Garrett, David J.; Apollo, Nicholas V.; Ganesan, Kumaravelu; Lau, Desmond; Prawer, Steven; Cervenka, Jiri

2016-01-01

High surface area electrode materials are of interest for a wide range of potential applications such as super-capacitors and electrochemical cells. This paper describes a fabrication method of three-dimensional (3D) graphene conformally coated on nanoporous insulating substrate with uniform nanopore size. 3D graphene films were formed by controlled graphitization of diamond-like amorphous carbon precursor films, deposited by plasma-enhanced chemical vapour deposition (PECVD). Plasma-assisted graphitization was found to produce better quality graphene than a simple thermal graphitization process. The resulting 3D graphene/amorphous carbon/alumina structure has a very high surface area, good electrical conductivity and exhibits excellent chemically stability, providing a good material platform for electrochemical applications. Consequently very large electrochemical capacitance values, as high as 2.1 mF for a sample of 10 mm3, were achieved. The electrochemical capacitance of the material exhibits a dependence on bias voltage, a phenomenon observed by other groups when studying graphene quantum capacitance. The plasma-assisted graphitization, which dominates the graphitization process, is analyzed and discussed in detail. PMID:26805546

Refurbishment of one-person regenerative air revitalization system

NASA Technical Reports Server (NTRS)

Powell, Ferolyn T.

1989-01-01

Regenerative processes for the revitalization of spacecraft atmospheres and reclamation of waste waters are essential for making long-term manned space missions a reality. Processes studied include: static feed water electrolysis for oxygen generation, Bosch carbon dioxide reduction, electrochemical carbon dioxide concentration, vapor compression distillation water recovery, and iodine monitoring. The objectives were to: provide engineering support to Marshall Space Flight Center personnel throughout all phases of the test program, e.g., planning through data analysis; fabricate, test, and deliver to Marshall Space Flight Center an electrochemical carbon dioxide module and test stand; fabricate and deliver an iodine monitor; evaluate the electrochemical carbon dioxide concentrator subsystem configuration and its ability to ensure safe utilization of hydrogen gas; evaluate techniques for recovering oxygen from a product oxygen and carbon dioxide stream; and evaluate the performance of an electrochemical carbon dioxide concentrator module to operate without hydrogen as a method of safe haven operation. Each of the tasks were related in that all focused on providing a better understanding of the function, operation, and performance of developmental pieces of environmental control and life support system hardware.

Direct fabrication of 3D graphene on nanoporous anodic alumina by plasma-enhanced chemical vapor deposition.

PubMed

Zhan, Hualin; Garrett, David J; Apollo, Nicholas V; Ganesan, Kumaravelu; Lau, Desmond; Prawer, Steven; Cervenka, Jiri

2016-01-25

High surface area electrode materials are of interest for a wide range of potential applications such as super-capacitors and electrochemical cells. This paper describes a fabrication method of three-dimensional (3D) graphene conformally coated on nanoporous insulating substrate with uniform nanopore size. 3D graphene films were formed by controlled graphitization of diamond-like amorphous carbon precursor films, deposited by plasma-enhanced chemical vapour deposition (PECVD). Plasma-assisted graphitization was found to produce better quality graphene than a simple thermal graphitization process. The resulting 3D graphene/amorphous carbon/alumina structure has a very high surface area, good electrical conductivity and exhibits excellent chemically stability, providing a good material platform for electrochemical applications. Consequently very large electrochemical capacitance values, as high as 2.1 mF for a sample of 10 mm(3), were achieved. The electrochemical capacitance of the material exhibits a dependence on bias voltage, a phenomenon observed by other groups when studying graphene quantum capacitance. The plasma-assisted graphitization, which dominates the graphitization process, is analyzed and discussed in detail.

Influence of thermomechanical processing on biomechanical compatibility and electrochemical behavior of new near beta alloy, Ti-20.6Nb-13.6Zr-0.5V

PubMed Central

Mohammed, Mohsin Talib; Khan, Zahid A; Manivasagam, Geetha; Siddiquee, Arshad N

2015-01-01

This paper presents the results for the effect of different methods of thermomechanical processing on the mechanical properties and electrochemical behavior of metastable β alloy Ti-20.6Nb-13.6Zr-0.5V (TNZV). The thermomechanical processing included hot working, solution heat treatments at different temperatures, and cooling rates in addition to aging. The thermomechanical processing conditions used in the study resulted in attainment of a wide range of microstructures with varying spatial distributions and morphologies of elongated/equiaxed α, β phases, or martensite, as a result of which several tensile properties were achieved. Aging treatment led to an increase in hardness, elastic modulus, and tensile strength and a decrease in ductility (elongation). Electrochemical tests indicated that the TNZV alloy undergoes spontaneous passivation due to spontaneous formation of an oxide film in the environment of the human body. Because the air-cooled samples possessed high hardness and also a fine grain size, they showed a lower corrosion rate than the samples treated under other conditions. PMID:26491324

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. Copyright © 2014 Elsevier B.V. All rights reserved.

Conversion of Carbon Dioxide into Ethanol by Electrochemical Synthesis Method Using Cu-Zn Electrode

NASA Astrophysics Data System (ADS)

Riyanto; Ramadan, S.; Fariduddin, S.; Aminudin, A. R.; Hayatri, A. K.

2018-01-01

Research on conversion of carbon dioxide into ethanol has been done. The conversion process is carried out in a sodium bicarbonate electrolyte solution in an electrochemical synthesis reactor. As cathode was used Cu-Zn, while as anode carbon was utilized. Variations of voltage, concentration of sodium bicarbonate electrolyte solution and time of electrolysis were performed to determine the optimum conditions to convert carbon dioxide into ethanol. Sample of the electrochemical synthesis process was analyzed by gas chromatography. From the result, it is found that the optimum conditions of the electrochemical synthesis process of carbon dioxide conversion into ethanol are voltage, concentration of sodium bicarbonate electrolyte solution and time of electrolysis are 3 volts, 0.4 M and 90 minutes with the ethanol concentration of 10.44%.

Morphological Study on Porous Silicon Carbide Membrane Fabricated by Double-Step Electrochemical Etching

NASA Astrophysics Data System (ADS)

Omiya, Takuma; Tanaka, Akira; Shimomura, Masaru

2012-07-01

The structure of porous silicon carbide membranes that peeled off spontaneously during electrochemical etching was studied. They were fabricated from n-type 6H SiC(0001) wafers by a double-step electrochemical etching process in a hydrofluoric electrolyte. Nanoporous membranes were obtained after double-step etching with current densities of 10-20 and 60-100 mA/cm2 in the first and second steps, respectively. Microporous membranes were also fabricated after double-step etching with current densities of 100 and 200 mA/cm2. It was found that the pore diameter is influenced by the etching current in step 1, and that a higher current is required in step 2 when the current in step 1 is increased. During the etching processes in steps 1 and 2, vertical nanopore and lateral crack formations proceed, respectively. The influx pathway of hydrofluoric solution, expansion of generated gases, and transfer limitation of positive holes to the pore surface are the key factors in the peeling-off mechanism of the membrane.

Light metal production

DOEpatents

Fan, Qinbai

2016-04-19

An electrochemical process for the production of light metals, particularly aluminum. Such a process involves contacting a light metal source material with an inorganic acid to form a solution containing the light metal ions in high concentration. The solution is fed to an electrochemical reactor assembly having an anode side containing an anode and a cathode side containing a cathode, with anode side and the cathode side separated by a bipolar membrane, with the solution being fed to the anode side. Light metal ions are electrochemically transferred through the bipolar membrane to the cathode side. The process further involves reducing the light metal ions to light metal powder. An associated processing system is also provided.

Synthesis of Magnetite Nanoparticles and Its Application As Electrode Material for the Electrochemical Oxidation of Methanol

NASA Astrophysics Data System (ADS)

Shah, Muhammad Tariq; Balouch, Aamna; Panah, Pirah; Rajar, Kausar; Mahar, Ali Muhammad; Khan, Abdullah; Jagirani, Muhammad Saqaf; Khan, Humaira

2018-06-01

In this study, magnetite (Fe3O4) nanoparticles were synthesized by a simple and facile chemical co-precipitation method at ambient laboratory conditions. The synthesized Fe3O4 nanostructures were characterized for their morphology, size, crystalline structure and component analysis using field emission scanning electron microscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, x-ray diffraction and electron dispersive x-ray spectroscopy. The Fe3O4 nanoparticles showed semi-spherical geometry with an average particle diameter up to 14 nm. The catalytic properties of Fe3O4 nanoparticles were evaluated for electrochemical oxidation of methanol. For this purpose, the magnetite NPs were coated on the surface of an indium tin oxide (ITO) electrode and used as a working electrode in the electrochemical oxidation of methanol. The effect of potential scan rate, the concentration of methanol, the volume of electrolyte and catalyst (Fe3O4 NPs) deposition volume was studied to get high peak current densities for methanol oxidation. The stability and selectivity of the fabricated electrode (Fe3O4/ITO) were also assessed during the electrochemical process. This study revealed that the Fe3O4/ITO electrode was highly stable and selective towards methanol electrochemical oxidation in basic (KOH) media. Bare ITO and Fe3O4 NPs modified glassy (Fe3O4/GCE) electrodes were also tested in the electro-oxidation study of methanol, but their peak current density responses were very low as compared to the Fe3O4/ITO electrode, which showed high electrocatalytic activity towards methanol oxidation under similar conditions. We hope that Fe3O4 nanoparticles (NPs) will be an alternative for methanol oxidation as compared to the expensive noble metals (Pt, Au, and Pd) for energy generation processes.

Metalized, three-dimensional structured oxygen cathode materials for lithium/air batteries and method for making and using the same

DOEpatents

Xing, Weibing; Buettner-Garrett, Josh

2017-04-18

This disclosure relates generally to cathode materials for electrochemical energy cells, more particularly to metal/air electrochemical energy cell cathode materials containing silver vanadium oxide and methods of making and using the same. The metal/air electrochemical energy cell can be a lithium/air electrochemical energy cell. Moreover the silver vanadium oxide can be a catalyst for one or more of oxidation and reduction processes of the electrochemical energy cell.

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.

Electrochemical push-pull probe: from scanning electrochemical microscopy to multimodal altering of cell microenvironment.

PubMed

Bondarenko, Alexandra; Cortés-Salazar, Fernando; Gheorghiu, Mihaela; Gáspár, Szilveszter; Momotenko, Dmitry; Stanica, Luciana; Lesch, Andreas; Gheorghiu, Eugen; Girault, Hubert H

2015-04-21

To understand biological processes at the cellular level, a general approach is to alter the cells' environment and to study their chemical responses. Herein, we present the implementation of an electrochemical push-pull probe, which combines a microfluidic system with a microelectrode, as a tool for locally altering the microenvironment of few adherent living cells by working in two different perturbation modes, namely electrochemical (i.e., electrochemical generation of a chemical effector compound) and microfluidic (i.e., infusion of a chemical effector compound from the pushing microchannel, while simultaneously aspirating it through the pulling channel, thereby focusing the flow between the channels). The effect of several parameters such as flow rate, working distance, and probe inclination angle on the affected area of adherently growing cells was investigated both theoretically and experimentally. As a proof of concept, localized fluorescent labeling and pH changes were purposely introduced to validate the probe as a tool for studying adherent cancer cells through the control over the chemical composition of the extracellular space with high spatiotemporal resolution. A very good agreement between experimental and simulated results showed that the electrochemical perturbation mode enables to affect precisely only a few living cells localized in a high-density cell culture.

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.

Glass composition and process for sealing void spaces in electrochemical devices

DOEpatents

Meinhardt, Kerry D [Richland, WA; Kirby, Brent W [Kennewick, WA

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.

A coupled Bio-EF process for mineralization of the pharmaceuticals furosemide and ranitidine: Feasibility assessment.

PubMed

Olvera-Vargas, Hugo; Oturan, Nihal; Buisson, Didier; Oturan, Mehmet A

2016-07-01

A coupled Bio-EF treatment has been applied as a reliable process for the degradation of the pharmaceuticals furosemide (FRSM) and ranitidine (RNTD) in aqueous medium, in order to reduce the high energy consumption related to electrochemical technology. In the first stage of this study, electrochemical degradation of the drugs was assessed by the electro-Fenton process (EF) using a BDD/carbon-felt cell. Biodegradability of the drugs solutions was enhanced reaching BOD5/COD ratios close to the biodegradability threshold of 0.4, evidencing the formation of bio-compatible by-products (mainly short-chain carboxylic acids) which are suitable for biological post-treatment. Moreover, toxicity evaluation by the Microtox(®) method revealed that EF pre-treatment was able of detoxifying both, FRSM and RNTD solutions, constituting another indicator of biodegradability of EF treated solutions. In the second stage, electrolyzed solutions were treated by means of an aerobic biological process. A significant part of the short-chain carboxylic acids formed during the electrochemical phase was satisfactorily removed by the used selected microorganisms. The results obtained demonstrate the efficiency and feasibility of the integrated Bio-EF process. Copyright © 2016 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larsen, G.

Research conducted in FY17 used photo-electrochemical methods to investigate the potential for radiationenhanced galvanic coupling in tritium-producing burnable absorber rod (TPBAR) materials. Specifically, a laboratory electrochemical cell was coupled with UV light in order to perform electrochemical opencircuit voltage and galvanic current measurements, techniques that have been used successfully in previous studies to replicate galvanic processes in reactor settings. UV irradiation can mimic reactor-like behavior because, similar to both directly and indirectly ionizing radiation, UV photons with energy greater than the band gap of the material will generate free charge carriers (electrons and holes) and can substantially alter the passivatingmore » effect of metal oxides.« less

Binder free MnO2/PIn electrode material for supercapacitor application

NASA Astrophysics Data System (ADS)

Purty, B.; Choudhary, R. B.; Kandulna, R.; Singh, R.

2018-05-01

Electrochemically stable MnO2/PIn nanocomposite was synthesized via in-situ chemical oxidative polymerization process. The structural and morphological properties were studied through FTIR and FESEM characterizing techniques. Sphere like PIn and MnO2 nanorods offers interacting surface for charge transfer action. The electrochemical properties were investigated through cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopic (EIS) techniques. The significant enhancement in capacitance value with 95% coulombic efficiency and relatively low equivalent series resistance (ESR)˜0.4 Ω proved that MnO2/PIn nanocomposite is an excellent performer as an electrode material in the spectrum of supercapcitors and optoelectronic devices.

Biocompatibility of Mg Ion Doped Hydroxyapatite Films on Ti-6Al-4V Surface by Electrochemical Deposition.

PubMed

Lee, Kang; Choe, Han-Cheol

2016-02-01

In this study, we prepared magnesium (Mg) doped nano-phase hydroxyapatite (HAp) films on the TiO2 nano-network surface using electrochemical deposition method. Ti-6Al-4V ELI surface was anodized in 5 M NaOH solution at 0.3 A for 10 min. Nano-network TiO2 surface were formed by these anodization steps which acted as templates and anchorage for growth of the Mg doped HAp during subsequent pulsed electrochemical deposition process at 85 degrees C. The phase and morphologies of HAp deposits were influenced by the Mg ion concentration.

ELECTROCHEMICAL REMEDIATION TECHNOLOGIES (ECRTS) DEMONSTRATION BULLETIN

EPA Science Inventory

The ElectroChemical Remediation Technologies (ECRTs) process was developed by P2-Soil Remediation, Inc. P-2 Soil Remediation, Inc. formed a partnership with Weiss Associates and ElectroPetroleum, Inc. to apply the technology to contaminated sites. The ECRTs process was evaluated ...

Methods and systems for in-situ electroplating of electrodes

DOEpatents

Zappi, Guillermo Daniel; Zarnoch, Kenneth Paul; Huntley, Christian Andrew; Swalla, Dana Ray

2015-06-02

The present techniques provide electrochemical devices having enhanced electrodes with surfaces that facilitate operation, such as by formation of a porous nickel layer on an operative surface, particularly of the cathode. The porous metal layer increases the surface area of the electrode, which may result in increasing the efficiency of the electrochemical devices. The formation of the porous metal layer is performed in situ, that is, after the assembly of the electrodes into an electrochemical device. The in situ process offers a number of advantages, including the ability to protect the porous metal layer on the electrode surface from damage during assembly of the electrochemical device. The enhanced electrode and the method for its processing may be used in any number of electrochemical devices, and is particularly well suited for electrodes in an electrolyzer useful for splitting water into hydrogen and oxygen.

A combined electrochemical-irradiation treatment of highly colored and polluted industrial wastewater

NASA Astrophysics Data System (ADS)

Barrera-Díaz, C.; Ureña-Nuñez, F.; Campos, E.; Palomar-Pardavé, M.; Romero-Romo, M.

2003-07-01

This study reports on the attainment of optimal conditions for two electrolytic methods to treat wastewater: namely, electrocoagulation and particle destabilization of a highly polluted industrial wastewater, and electrochemically induced oxidation induced by in situ generation of Fenton's reactive. Additionally, a combined method that consisted of electrochemical treatment plus γ-irradiation was carried out. A typical composition of the industrial effluent treated was COD 3400 mg/l, color 3750 Pt/Co units, and fecal coliforms 21000 MPN/ml. The best removal efficiency was obtained with electrochemical oxidation induced in situ , that resulted in the reduction of 78% for the COD, 86% color and 99.9% fecal coliforms removal. A treatment sequence was designed and carried out, such that after both electrochemical processes, a γ-irradiation technique was used to complete the procedure. The samples were irradiated with various doses in an ALC γ-cell unit provided with a Co-60 source. The removal efficiency obtained was 95% for the COD values, 90% color and 99.9% for fecal coliforms.

Electrochemical annealing of nanoporous gold by application of cyclic potential sweeps

PubMed Central

Sharma, Abeera; Bhattarai, Jay K.; Alla, Allan J.; Demchenko, Alexei V.; Stine, Keith J.

2015-01-01

An electrochemical method for annealing the pore sizes of nanoporous gold is reported. The pore sizes of nanoporous gold can be increased by electrochemical cycling with the upper potential limit being just at the onset of gold oxide formation. This study has been performed in electrolyte solutions including potassium chloride, sodium nitrate and sodium perchlorate. Scanning electron microscopy images have been used for ligament and pore size analysis. We examine the modifications of nanoporous gold due to annealing using electrochemical impedance spectroscopy, and cyclic voltammetry and offer a comparison of the surface coverage using the gold oxide stripping method as well as the method in which electrochemically accessible surface area is determined by using a diffusing redox probe. The effect of additives adsorbed on the nanoporous gold surface when subjected to annealing in different electrolytes as well as the subsequent structural changes in nanoporous gold are also reported. The effect of the annealing process on the application of nanoporous gold as a substrate for glucose electro-oxidation is briefly examined. PMID:25649027

Processing of Onion-like Carbon for Electrochemical Capacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Aken, Katherine L.; Maleski, Kathleen; Mathis, Tyler S.

Multi-shell fullerenes known as onion-like carbon (OLC) are especially attractive in applications relative to energy storage, such as electrochemical capacitors, due to a near-spherical shape of particles, their nanoscale diameters and high conductivity leading to fast rate performance. Because of this, onion-like carbon can be fabricated into electrodes, used as a conductive additive, and may have potential in composites and additive manufacturing. However due to agglomeration of OLC particles, creating a stable, aqueous dispersion for ink production or formulating composites proves challenging. Also, we explore how attrition milling, acid treatment, and probe sonication can be employed to decrease agglomeration andmore » provide colloidal stability in aqueous media. We also investigate how the electrochemical performance changes with each processing step as well as the treatments in succession. When tested in electrochemical capacitors, the processing increases the capacitance by a factor of three, due to an added pseudocapacitive contribution which is not present in untreated OLC. As a result, the processing of OLC proves to be advantageous for the production of stable, aqueous solutions, which also exhibit improved electrochemical properties suitable for functional inks, conductive additives, and fabrication of composite electrodes.« less

Processing of Onion-like Carbon for Electrochemical Capacitors

DOE PAGES

Van Aken, Katherine L.; Maleski, Kathleen; Mathis, Tyler S.; ...

2017-02-04

Multi-shell fullerenes known as onion-like carbon (OLC) are especially attractive in applications relative to energy storage, such as electrochemical capacitors, due to a near-spherical shape of particles, their nanoscale diameters and high conductivity leading to fast rate performance. Because of this, onion-like carbon can be fabricated into electrodes, used as a conductive additive, and may have potential in composites and additive manufacturing. However due to agglomeration of OLC particles, creating a stable, aqueous dispersion for ink production or formulating composites proves challenging. Also, we explore how attrition milling, acid treatment, and probe sonication can be employed to decrease agglomeration andmore » provide colloidal stability in aqueous media. We also investigate how the electrochemical performance changes with each processing step as well as the treatments in succession. When tested in electrochemical capacitors, the processing increases the capacitance by a factor of three, due to an added pseudocapacitive contribution which is not present in untreated OLC. As a result, the processing of OLC proves to be advantageous for the production of stable, aqueous solutions, which also exhibit improved electrochemical properties suitable for functional inks, conductive additives, and fabrication of composite electrodes.« less

Single-Molecule Sensing with Nanopore Confinement: From Chemical Reactions to Biological Interactions.

PubMed

Lin, Yao; Ying, Yi-Lun; Gao, Rui; Long, Yi-Tao

2018-03-25

The nanopore can generate an electrochemical confinement for single-molecule sensing that help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond-making and bond-breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single-molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this Concept article, we introduce and discuss the electrochemical confinement effects on single-molecule covalent reactions, conformational dynamics of individual molecules and host-guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid-state nanopores for developing new sensing mechanisms. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancement of electrochemical performance of LiFePO4 nanoparticles by direct nanocoating with conductive carbon layers

NASA Astrophysics Data System (ADS)

Świder, Joanna; Molenda, Marcin; Kulka, Andrzej; Molenda, Janina

2016-07-01

The results of simple and environmental-friendly method of the carbon nanocoatings on low-conductive cathode material have been shown in this work. The carbon nanocoatings were prepared during wet impregnation process of precursor derived from hydrophilic polymer based on poly(N-vinylformamide) modified by pyromellitic acid. The crystal structures and morphology of all composites were characterized by X-ray powder diffraction (XRD), low temperature nitrogen adsorption/desorption measurements (N2-BET) and transmission electronic microscopy (TEM). The electrical properties of the obtained composites were examined by EC studies. The electrochemical performance was carried out in galvanostatic mode with stable charge-discharge current and performed in Li/Li+/(CCL/LiFePO4) type cells. The process of formation CCL/LiFePO4 nanocomposite significantly enhances the electrical conductivity of the material and improves its capacity retention and electrochemical performance.

Methods for understanding microbial community structures and functions in microbial fuel cells: a review.

PubMed

Zhi, Wei; Ge, Zheng; He, Zhen; Zhang, Husen

2014-11-01

Microbial fuel cells (MFCs) employ microorganisms to recover electric energy from organic matter. However, fundamental knowledge of electrochemically active bacteria is still required to maximize MFCs power output for practical applications. This review presents microbiological and electrochemical techniques to help researchers choose the appropriate methods for the MFCs study. Pre-genomic and genomic techniques such as 16S rRNA based phylogeny and metagenomics have provided important information in the structure and genetic potential of electrode-colonizing microbial communities. Post-genomic techniques such as metatranscriptomics allow functional characterizations of electrode biofilm communities by quantifying gene expression levels. Isotope-assisted phylogenetic analysis can further link taxonomic information to microbial metabolisms. A combination of electrochemical, phylogenetic, metagenomic, and post-metagenomic techniques offers opportunities to a better understanding of the extracellular electron transfer process, which in turn can lead to process optimization for power output. Copyright © 2014 Elsevier Ltd. All rights reserved.

Comparative study for degradation of industrial dyes by electrochemical advanced oxidation processes with BDD anode in a laboratory stirred tank reactor.

PubMed

Alcocer, Salvador; Picos, Alain; Uribe, Agustín R; Pérez, Tzayam; Peralta-Hernández, Juan M

2018-08-01

Comparative degradation of the industrial dyes Blue BR, Violet SBL and Brown MF 50 mg L -1 has been studied by the electrochemical oxidation (EOx), electro-Fenton (EF), photoelectro-Fenton (PEF) process based on BDD electrode. Each dye was tested in 0.05 mM Na 2 SO 4 with 0.5 mM Fe 2+ at pH 3.0, and electrolyzed in a stirred tank reactor under galvanostatic conditions with 2.0, 5.0, 7.0, 11.0 and 18.0 mA cm -2 . Dyes were oxidized via hydroxyl radicals (OH) formed at the BDD anode from water oxidation coupled with Fenton's reaction cathodically produced hydrogen peroxide (H 2 O 2 ). Under Na 2 SO 4 medium close to 100% the decolorization was achieved. Through the color abatement rate the dyes behavior was analyzed at the beginning of the oxidation process. Dissolved Organic Carbon (DOC) was tested to evaluate the degradation. From DOC removal, it was established an increasing relative oxidation power of the EOx < EF < PEF, according with their decolorization trend. This study highlights the potential of the electrochemical/BDD process for the degradation of industrial dyes found in wastewaters under appropriate experimental conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Intense Electrochemical Oxidation on Graphitized Carbon Electrodes in the Presence of Ozone

NASA Astrophysics Data System (ADS)

Klochikhin, V. L.; Potapova, G. F.; Putilov, A. V.

2018-06-01

A new intense oxidation process for water treatment in which oxidation with ozone is coupled to electrochemical processes is described, and the results from its application to water purification are presented along with the discussion of its practical implementation. The use of graphitized carbon materials for this process is explained and tested experimentally. The use of glassy carbon for the anode enables us to achieve very high (up to 25 vol %) concentrations of ozone in the generated ozone-oxygen mixture. The material used for the cathode—graphitized carbon cloth (GCC) reinforced with Ni allows different electrocatalytic processes to proceed on its developed surface, and combines the high sorption capacity of this cathode and potentialcontrolled selectivity of cathodic electrochemical processes.

Electrochemical advanced oxidation processes as decentralized water treatment technologies to remediate domestic washing machine effluents.

PubMed

Dos Santos, Alexsandro Jhones; Costa, Emily Cintia Tossi de Araújo; da Silva, Djalma Ribeiro; Garcia-Segura, Sergi; Martínez-Huitle, Carlos Alberto

2018-03-01

Water scarcity is one of the major concerns worldwide. In order to secure this appreciated natural resource, management and development of water treatment technologies are mandatory. One feasible alternative is the consideration of water recycling/reuse at the household scale. Here, the treatment of actual washing machine effluent by electrochemical advanced oxidation processes was considered. Electrochemical oxidation and electro-Fenton technologies can be applied as decentralized small-scale water treatment devices. Therefore, efficient decolorization and total organic abatement have been followed. The results demonstrate the promising performance of solar photoelectro-Fenton process, where complete color and organic removal was attained after 240 min of treatment under optimum conditions by applying a current density of 66.6 mA cm -2 . Thus, electrochemical technologies emerge as promising water-sustainable approaches.

Mathematical modeling and hydrodynamics of Electrochemical deburring process

NASA Astrophysics Data System (ADS)

Prabhu, Satisha; Abhishek Kumar, K., Dr

2018-04-01

The electrochemical deburring (ECD) is a variation of electrochemical machining is considered as one of the efficient methods for deburring of intersecting features and internal parts. Since manual deburring costs are comparatively high one can potentially use this method in both batch production and flow production. The other advantage of this process is that time of deburring as is on the order of seconds as compared to other methods. In this paper, the mathematical modeling of Electrochemical deburring is analysed from its deburring time and base metal removal point of view. Simultaneously material removal rate is affected by electrolyte temperature and bubble formation. The mathematical model and hydrodynamics of the process throw limelight upon optimum velocity calculations which can be theoretically determined. The analysis can be the powerful tool for prediction of the above-mentioned parameters by experimentation.

Electrochemistry-mass spectrometry for in-vitro determination of selected chemotherapeutics and their electrochemical products in comparison to in-vivo approach.

PubMed

Szultka-Mlynska, Malgorzata; Buszewski, Boguslaw

2016-11-01

Chemotherapeutics are among the most frequently prescribed medications in modern medicine. They are widely prescribed; however, problems with organisms developing resistance to these drugs means that their efficacy may be lost, so care should be taken to avoid unnecessary prescription. It is therefore of great interest to study the detailed metabolism of these biologically active compounds. This study aimed at developing an efficient analytical protocol for the determination of in-vitro electrochemical products of selected antibiotic drugs (amoxicillin, cefotaxime, fluconazole, linezolid, metronidazole and moxifloxacin). Combination of electrochemistry (EC) and mass spectrometry (MS) was applied for the in-vitro determination of the studied antibiotics and their electrochemical products. To identify the structure of the detected electrochemical products, MS/MS experiments were performed. This was one of the first applications of the EC system for generation of electrochemical products produced from antibiotic drugs. Adjustment of appropriate conditions and such parameters as the potential value, mobile phase (pH), working electrode and temperature had significant influence on electrochemical simulations and the creation of selected derivatives. Consequently, several working electrodes were evaluated for this purpose. In most of the studied cases, mainly two types of products were observed. One corresponded to an increase in mass by 14Da, which can be explained by a process consisting of oxidation (+16 m/z) and dehydrogenation (-2 m/z); The second in turn showed mass reduction by 14Da, which can be attributed to the loss of -CH2 as a result of N-demethylation. The performed experiments consisted of two stages: electrochemical oxidation of the analyzed samples (phase I of metabolic transformation), and addition of glutathione (GSH) for follow-up reactions (phase II conjunction). The electrochemical results were compared to in-vivo experiments by analyzing urine samples from patients after antibiotic drugs have been administered.. Overall, the comparison of electrochemistry to in-vivo experiments shows the high potential of EC-MS as a fast analytical tool in the prediction of electrochemical conversion that could be applied to therapeutic drug monitoring and pharmacokinetic studies as well. Copyright © 2016 Elsevier B.V. All rights reserved.

Antitumor effects of electrochemical treatment

PubMed Central

González, Maraelys Morales; Zamora, Lisset Ortíz; Cabrales, Luis Enrique Bergues; Sierra González, Gustavo Victoriano; de Oliveira, Luciana Oliveira; Zanella, Rodrigo; Buzaid, Antonio Carlos; Parise, Orlando; Brito, Luciana Macedo; Teixeira, Cesar Augusto Antunes; Gomes, Marina das Neves; Moreno, Gleyce; Feo da Veiga, Venicio; Telló, Marcos; Holandino, Carla

2013-01-01

Electrochemical treatment is an alternative modality for tumor treatment based on the application of a low intensity direct electric current to the tumor tissue through two or more platinum electrodes placed within the tumor zone or in the surrounding areas. This treatment is noted for its great effectiveness, minimal invasiveness and local effect. Several studies have been conducted worldwide to evaluate the antitumoral effect of this therapy. In all these studies a variety of biochemical and physiological responses of tumors to the applied treatment have been obtained. By this reason, researchers have suggested various mechanisms to explain how direct electric current destroys tumor cells. Although, it is generally accepted this treatment induces electrolysis, electroosmosis and electroporation in tumoral tissues. However, action mechanism of this alternative modality on the tumor tissue is not well understood. Although the principle of Electrochemical treatment is simple, a standardized method is not yet available. The mechanism by which Electrochemical treatment affects tumor growth and survival may represent more complex process. The present work analyzes the latest and most important research done on the electrochemical treatment of tumors. We conclude with our point of view about the destruction mechanism features of this alternative therapy. Also, we suggest some mechanisms and strategies from the thermodynamic point of view for this therapy. In the area of Electrochemical treatment of cancer this tool has been exploited very little and much work remains to be done. Electrochemical treatment constitutes a good therapeutic option for patients that have failed the conventional oncology methods. PMID:23592904

Ferrocenyl-doped silica nanoparticles as an immobilized affinity support for electrochemical immunoassay of cancer antigen 15-3.

PubMed

Hong, Chenglin; Yuan, Ruo; Chai, Yaqin; Zhuo, Ying

2009-02-09

The aim of this study is to elaborate a simple and sensitive electrochemical immunoassay using ferrocenecarboxylic (Fc-COOH)-doped silica nanoparticles (SNPs) as an immobilized affinity support for cancer antigen 15-3 (CA 15-3) detection. The Fc-COOH-doped SNPs with redox-active were prepared by using a water-in-oil microemulsion method. The use of colloidal silica could prevent the leakage of Fc-COOH and were easily modified with trialkoxysilane reagents for covalent conjugation of CA 15-3 antibodies (anti-CA 15-3). The Fc-COOH-doped SNPs were characterized by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The fabrication process of the electrochemical immunosensor was demonstrated by using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Under optimal conditions, the developed immunosensor showed good linearity at the studied concentration range of 2.0-240 UmL(-1) with a coefficient 0.9986 and a detection limit of 0.64 UmL(-1) at S/N=3.

Electrochemical production and use of free chlorine for pollutant removal: an experimental design approach.

PubMed

Antonelli, Raissa; de Araújo, Karla Santos; Pires, Ricardo Francisco; Fornazari, Ana Luiza de Toledo; Granato, Ana Claudia; Malpass, Geoffroy Roger Pointer

2017-10-28

The present paper presents the study of (1) the optimization of electrochemical-free chlorine production using an experimental design approach, and (2) the application of the optimum conditions obtained for the application in photo-assisted electrochemical degradation of simulated textile effluent. In the experimental design the influence of inter-electrode gap, pH, NaCl concentration and current was considered. It was observed that the four variables studied are significant for the process, with NaCl concentration and current being the most significant variables for free chlorine production. The maximum free chlorine production was obtained at a current of 2.33 A and NaCl concentrations in 0.96 mol dm -3 . The application of the optimized conditions with simultaneous UV irradiation resulted in up to 83.1% Total Organic Carbon removal and 100% of colour removal over 180 min of electrolysis. The results indicate that a systematic (statistical) approach to the electrochemical treatment of pollutants can save time and reagents.

The Influence of Nanopore Dimensions on the Electrochemical Properties of Nanopore Arrays Studied by Impedance Spectroscopy

PubMed Central

Kant, Krishna; Priest, Craig; Shapter, Joe G.; Losic, Dusan

2014-01-01

The understanding of the electrochemical properties of nanopores is the key factor for better understanding their performance and applications for nanopore-based sensing devices. In this study, the influence of pore dimensions of nanoporous alumina (NPA) membranes prepared by an anodization process and their electrochemical properties as a sensing platform using impedance spectroscopy was explored. NPA with four different pore diameters (25 nm, 45 nm and 65 nm) and lengths (5 μm to 20 μm) was used and their electrochemical properties were explored using different concentration of electrolyte solution (NaCl) ranging from 1 to 100 μM. Our results show that the impedance and resistance of nanopores are influenced by the concentration and ion species of electrolytes, while the capacitance is independent of them. It was found that nanopore diameters also have a significant influence on impedance due to changes in the thickness of the double layer inside the pores. PMID:25393785

Electrochemistry and electron paramagnetic resonance spectroscopy of cytochrome c and its heme-disrupted analogs.

PubMed

Novak, David; Mojovic, Milos; Pavicevic, Aleksandra; Zatloukalova, Martina; Hernychova, Lenka; Bartosik, Martin; Vacek, Jan

2018-02-01

Cytochrome c (cyt c) is one of the most studied conjugated proteins due to its electron-transfer properties and ability to regulate the processes involved in homeostasis or apoptosis. Here we report an electrochemical strategy for investigating the electroactivity of cyt c and its analogs with a disrupted heme moiety, i.e. apocytochrome c (acyt c) and porphyrin cytochrome c (pcyt c). The electrochemical data are supplemented with low-temperature and spin-probe electron paramagnetic resonance (EPR) spectroscopy. The main contribution of this report is a complex evaluation of cyt c reduction and oxidation at the level of surface-localized amino acid residues and the heme moiety in a single electrochemical scan. The electrochemical pattern of cyt c is substantially different to both analogs acyt c and pcyt c, which could be applicable in further studies on the redox properties and structural stability of cytochromes and other hemeproteins. Copyright © 2017 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Huixiao; Lim, Cheolwoong; Li, Tianyi

The impact of calendering process on the geometric characteristics and electrochemical performance of LiNi1/3Mn1/3Co1/3O2 (NMC) electrode was investigated in this study. The geometric properties of NMC electrodes with different calendering conditions, such as porosity, pore size distribution, particle size distribution, specific surface area and tortuosity were calculated from the computed tomography data of the electrodes. A synchrotron transmission X-ray microscopy tomography system at the Advanced Photon Source of the Argonne National Laboratory was employed to obtain the tomography data. The geometric and electrochemical analysis show that calendering can increase the electrochemically active area, which improves rate capability. However, more calenderingmore » will result in crushing of NMC particles, which can reduce the electrode capacity at relatively high C rates. This study shows that the optimum electrochemical performance of NMC electrode at 94:3:3 weight ratio of NMC:binder:carbon black can be achieved by calendering to 3.0 g/cm3 NMC density.« less

Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

PubMed

Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

2016-10-26

Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

The Development of Non-Enzymatic Glucose Biosensors Based on Electrochemically Prepared Polypyrrole–Chitosan–Titanium Dioxide Nanocomposite Films

PubMed Central

AL-Mokaram, Ali M. A. Abdul Amir; Yahya, Rosiyah; Abdi, Mahnaz M.; Mahmud, Habibun Nabi Muhammad Ekramul

2017-01-01

The performance of a modified electrode of nanocomposite films consisting of polypyrrole–chitosan–titanium dioxide (Ppy-CS-TiO2) has been explored for the developing a non-enzymatic glucose biosensors. The synergy effect of TiO2 nanoparticles (NPs) and conducting polymer on the current responses of the electrode resulted in greater sensitivity. The incorporation of TiO2 NPs in the nanocomposite films was confirmed by X-ray photoelectron spectroscopy (XPS) spectra. FE-SEM and HR-TEM provided more evidence for the presence of TiO2 in the Ppy-CS structure. Glucose biosensing properties were determined by amperommetry and cyclic voltammetry (CV). The interfacial properties of nanocomposite electrodes were studied by electrochemical impedance spectroscopy (EIS). The developed biosensors showed good sensitivity over a linear range of 1–14 mM with a detection limit of 614 μM for glucose. The modified electrode with Ppy-CS nanocomposite also exhibited good selectivity and long-term stability with no interference effect. The Ppy-CS-TiO2 nanocomposites films presented high electron transfer kinetics. This work shows the role of nanomaterials in electrochemical biosensors and describes the process of their homogeneous distribution in composite films by a one-step electrochemical process, where all components are taken in a single solution in the electrochemical cell. PMID:28561760

SERS- and Electrochemically Active 3D Plasmonic Liquid Marbles for Molecular-Level Spectroelectrochemical Investigation of Microliter Reactions.

PubMed

Koh, Charlynn Sher Lin; Lee, Hiang Kwee; Phan-Quang, Gia Chuong; Han, Xuemei; Lee, Mian Rong; Yang, Zhe; Ling, Xing Yi

2017-07-17

Liquid marbles are emergent microreactors owing to their isolated environment and the flexibility of materials used. Plasmonic liquid marbles (PLMs) are demonstrated as the smallest spectroelectrochemical microliter-scale reactor for concurrent spectro- and electrochemical analyses. The three-dimensional Ag shell of PLMs are exploited as a bifunctional surface-enhanced Raman scattering (SERS) platform and working electrode for redox process modulation. The combination of SERS and electrochemistry (EC) capabilities enables in situ molecular read-out of transient electrochemical species, and elucidate the potential-dependent and multi-step reaction dynamics. The 3D configuration of our PLM-based EC-SERS system exhibits 2-fold and 10-fold superior electrochemical and SERS performance than conventional 2D platforms. The rich molecular-level electrochemical insights and excellent EC-SERS capabilities offered by our 3D spectroelectrochemical system are pertinent in charge transfer processes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

2016-06-08

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.

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

NASA Astrophysics Data System (ADS)

Wang, Zhijuan; Wu, Shixin; Zhang, Juan; Chen, Peng; Yang, Guocheng; Zhou, Xiaozhu; Zhang, Qichun; Yan, Qingyu; Zhang, Hua

2012-02-01

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.

Mechanistic Study of the Validity of Using Hydroxyl Radical Probes To Characterize Electrochemical Advanced Oxidation Processes.

PubMed

Jing, Yin; Chaplin, Brian P

2017-02-21

The detection of hydroxyl radicals (OH • ) is typically accomplished by using reactive probe molecules, but prior studies have not thoroughly investigated the suitability of these probes for use in electrochemical advanced oxidation processes (EAOPs), due to the neglect of alternative reaction mechanisms. In this study, we investigated the suitability of four OH • probes (coumarin, p-chlorobenzoic acid, terephthalic acid, and p-benzoquinone) for use in EAOPs. Experimental results indicated that both coumarin and p-chlorobenzoic acid are oxidized via direct electron transfer reactions, while p-benzoquinone and terephthalic acid are not. Coumarin oxidation to form the OH • adduct product 7-hydroxycoumarin was found at anodic potentials lower than that necessary for OH • formation. Density functional theory (DFT) simulations found a thermodynamically favorable and non-OH • mediated pathway for 7-hydroxycoumarin formation, which is activationless at anodic potentials > 2.10 V/SHE. DFT simulations also provided estimates of E° values for a series of OH • probe compounds, which agreed with voltammetry results. Results from this study indicated that terephthalic acid is the most appropriate OH • probe compound for the characterization of electrochemical and catalytic systems.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Development of Self-Powered Wireless-Ready High Temperature Electrochemical Sensors for In-Situ Corrosion Monitoring for Boiler Tubes in Next Generation Coal-based Power Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xingbo

The key innovation of this project is the synergy of the high temperature sensor technology based on the science of electrochemical measurement and state-of-the-art wireless communication technology. A novel self-powered wireless high temperature electrochemical sensor system has been developed for coal-fired boilers used for power generation. An initial prototype of the in-situ sensor demonstrated the capability of the wireless communication system in the laboratory and in a pilot plant (Industrial USC Boiler Setting) environment to acquire electrochemical potential and current signals during the corrosion process. Uniform and localized under-coal ash deposit corrosion behavior of Inconel 740 superalloy has been studiedmore » at different simulated coal ash hot corrosion environments using the developed sensor. Two typical potential noise patterns were found to correlate with the oxidation and sulfidation stages in the hot coal ash corrosion process. Two characteristic current noise patterns indicate the extent of the corrosion. There was a good correlation between the responses of electrochemical test data and the results from corroded surface analysis. Wireless electrochemical potential and current noise signals from a simulated coal ash hot corrosion process were concurrently transmitted and recorded. The results from the performance evaluation of the sensor confirm a high accuracy in the thermodynamic and kinetic response represented by the electrochemical noise and impedance test data.« less

Using porphyrin-amino acid pairs to model the electrochemistry of heme proteins: experimental and theoretical investigations.

PubMed

Samajdar, Rudra N; Manogaran, Dhivya; Yashonath, S; Bhattacharyya, Aninda J

2018-04-18

Quasi reversibility in electrochemical cycling between different oxidation states of iron is an often seen characteristic of iron containing heme proteins that bind dioxygen. Surprisingly, the system becomes fully reversible in the bare iron-porphyrin complex: hemin. This leads to the speculation that the polypeptide bulk (globin) around the iron-porphyrin active site in these heme proteins is probably responsible for the electrochemical quasi reversibility. To understand the effect of such polypeptide bulk on iron-porphyrin, we study the interaction of specific amino acids with the hemin center in solution. We choose three representative amino acids-histidine (a well-known iron coordinator in bio-inorganic systems), tryptophan (a well-known fluoroprobe for proteins), and cysteine (a redox-active organic molecule). The interactions of these amino acids with hemin are studied using electrochemistry, spectroscopy, and density functional theory. The results indicate that among these three, the interaction of histidine with the iron center is strongest. Further, histidine maintains the electrochemical reversibility of iron. On the other hand, tryptophan and cysteine interact weakly with the iron center but disturb the electrochemical reversibility by contributing their own redox active processes to the system. Put together, this study attempts to understand the molecular interactions that can control electrochemical reversibility in heme proteins. The results obtained here from the three representative amino acids can be scaled up to build a heme-amino acid interaction database that may predict the electrochemical properties of any protein with a defined polypeptide sequence.

Biomimetic Graphene-Based 3D Scaffold for Long-Term Cell Culture and Real-Time Electrochemical Monitoring.

PubMed

Hu, Xue-Bo; Liu, Yan-Ling; Wang, Wen-Jie; Zhang, Hai-Wei; Qin, Yu; Guo, Shan; Zhang, Xin-Wei; Fu, Lei; Huang, Wei-Hua

2018-01-16

Current achievements on electrochemical monitoring of cells are often gained on two-dimensional (2D) substrates, which fail in mimicking the cellular environments and accurately reproducing the cellular functions within a three-dimensional (3D) tissue. In this regard, 3D scaffold concurrently integrated with the function of cell culture and electrochemical sensing is conceivably a promising platform to monitor cells in real time under their in vivo-like 3D microenvironments. However, it is particularly challenging to construct such a multifunctional scaffold platform. Herein, we developed a 3-aminophenylboronic acid (APBA) functionalized graphene foam (GF) network, which combines the biomimetic property of APBA with the mechanical and electrochemical properties of GF. Hence, the GF network can serve as a 3D scaffold to culture cells for a long period with high viability and simultaneously as an electrode for highly sensitive electrochemical sensing. This allows monitoring of gaseous messengers H 2 S released from the cells cultured on the 3D scaffold in real time. This work represents considerable progress in fabricating 3D cell culture scaffold with electrochemical properties, thereby facilitating future studies of physiologically relevant processes.

Electrochemical Removal of Metal Cations from Wastewater Monitored by Differential Pulse Polarography

ERIC Educational Resources Information Center

Bruce, Delphine; Kuhn, Alexander; Sojic, Neso

2004-01-01

Electrodeposition eliminates wastewater pollutants such as electrochemically active metal cations, with different pulse polarography (DPP) scrutinizing the kinetics of the treatment process. These mechanisms produce qualitative and quantitative data about the removal process, while students appreciate the use of electrochemistry in resolving…

Belousov-Zhabotinsky oscillations during the chemical or electrochemical generation of Ag + ions

NASA Astrophysics Data System (ADS)

Treindl, Ludovit; Hemmingsen, Tor; Ruoff, Peter

1997-05-01

The oscillatory Belousov-Zhabotinsky reaction has been studied in the presence of Ag + ions using potentiometric and amperometric methods. Amperometrically the oscillations were followed by monitoring the anodic current at a potential of 1.0 V, which corresponds to the electrooxidation of Br - ions. In the Ag +-perturbed BZ reaction we still observe anodic current oscillations due to the electrooxidation of Br - ions more or less loosely bound in AgBr mono- or oligomers. Solid AgBr, however, has been found to be chemically and electrochemically inert in the BZ reaction. The timescale of producing electrochemically inactive AgBr precipitate is a second-order process with a rate constant of 256 M -1 s -1.

Splitting algorithm for numerical simulation of Li-ion battery electrochemical processes

NASA Astrophysics Data System (ADS)

Iliev, Oleg; Nikiforova, Marina A.; Semenov, Yuri V.; Zakharov, Petr E.

2017-11-01

In this paper we present a splitting algorithm for a numerical simulation of Li-ion battery electrochemical processes. Liion battery consists of three domains: anode, cathode and electrolyte. Mathematical model of electrochemical processes is described on a microscopic scale, and contains nonlinear equations for concentration and potential in each domain. On the interface of electrodes and electrolyte there are the Lithium ions intercalation and deintercalation processes, which are described by Butler-Volmer nonlinear equation. To approximate in spatial coordinates we use finite element methods with discontinues Galerkin elements. To simplify numerical simulations we develop the splitting algorithm, which split the original problem into three independent subproblems. We investigate the numerical convergence of the algorithm on 2D model problem.

Integration of MnO2 thin film and carbon nanotubes to three-dimensional carbon microelectrodes for electrochemical microcapacitors

NASA Astrophysics Data System (ADS)

Jiang, Shulan; Shi, Tielin; Liu, Dan; Long, Hu; Xi, Shuang; Wu, Fengshun; Li, Xiaoping; Xia, Qi; Tang, Zirong

2014-09-01

Large-scale three-dimensional (3D) hybrid microelectrodes have been fabricated through modified carbon microelectromechanical systems (Carbon-MEMS) process and electrochemical deposition method. Greatly improved electrochemical performance has been shown for the 3D photoresist-derived carbon microelectrodes with the integration of carbon nanotubes (CNTs) and manganese dioxide (MnO2). The electrochemical measurements of the microelectrodes indicate that the specific geometric capacitance can reach up to 238 mF cm-2 at the current density of 0.5 mA cm-2. The capacitance loss is less than 18.2% of the original value after 6000 charge-discharge cycles. This study shows that stacking of MnO2 film and integrating of CNTs to the 3D glassy carbon microelectrodes have great potential for on-chip microcapacitors as energy storage devices, and the presented approach is promising for large-scale and low-cost manufacturing.

Electrochemical capacitor materials based on carbon and luminophors doped with lanthanide ions

NASA Astrophysics Data System (ADS)

Kubasiewicz, Konrad; Slesinski, Adam; Gastol, Dominika; Lis, Stefan; Frackowiak, Elzbieta

2017-10-01

The described research is focused on the hybrid, bi-functional composite materials dedicated to the electrochemical capacitor electrodes. The novel material exhibits both luminescent and capacitive properties. The fabrication process of semi-products and the final composite is described. The structure and homogeneity of luminophors are confirmed with the XRD analysis. The morphology of materials is also determined by TEM and SEM images. The detailed spectroscopic characterization includes excitation and emission spectra, luminescence decay curves, emission lifetimes, CIE chromaticity indexes. The electrochemical studies of composite electrodes carried out by cyclic voltammetry and impedance spectroscopy exhibit good charge propagation. For the first time, inorganic luminophors containing doped LaF3 and GdVO4 have been successfully used for electrochemical capacitor. It is the primary stage to design a new generation of light emitting capacitors utilizing more stable inorganic luminophors than organic-based ones.

Synergetic effects of K + and Mg 2+ ion intercalation on the electrochemical and actuation properties of the two-dimensional Ti 3 C 2 MXene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Qiang; Come, Jeremy; Naguib, Michael

2017-01-01

Two-dimensional materials, such as MXenes, are attractive candidates for energy storage and electrochemical actuators due to their high volume changes upon ion intercalation. Of special interest for boosting energy storage is the intercalation of multivalent ions such as Mg 2+, which suffers from sluggish intercalation and transport kinetics due to its ion size. By combining traditional electrochemical characterization techniques with electrochemical dilatometry and contact resonance atomic force microscopy, the synergetic effects of the pre-intercalation of K +ions are demonstrated to improve the charge storage of multivalent ions, as well as tune the mechanical and actuation properties of the Ti 3Cmore » 2MXene. Our results have important implications for quantitatively understanding the charge storage processes in intercalation compounds and provide a new path for studying the mechanical evolution of energy storage materials.« less

Enhancement in photo-electrochemical efficiency by reducing recombination rate in branched TiO2 nanotube array on functionalizing with ZnO micro crystals

NASA Astrophysics Data System (ADS)

Boda, Muzaffar Ahmad; Ashraf Shah, Mohammad

2018-06-01

In this study, branched TiO2 nanotube array were fabricated through electrochemical anodization process at constant voltage using third generation electrolyte. On account of morphological advantage, these nanotubes shows significant enhancement in photo-electrochemical property than compact or conventional titania nanotube array. However, their photo-electrochemical efficiency intensifies on coating with ZnO micro-crystals. ZnO coated branched TiO2 nanotube array shows a photocurrent density of 27.8 mA cm‑2 which is 1.55 times the photocurrent density (17.2 mA cm‑2) shown by bare branched titania nanotubes. The significant enhancement in photocurrent density shown by the resulting ZnO/TiO2 hybrid structure is attributed to suppression in electron–hole recombination phenomenon by offering smooth pathway to photo generated excitons on account of staggered band edge positions in individual semiconductors.

Thermo-electrochemical instrumentation of cylindrical Li-ion cells

NASA Astrophysics Data System (ADS)

McTurk, Euan; Amietszajew, Tazdin; Fleming, Joe; Bhagat, Rohit

2018-03-01

The performance evaluation and optimisation of commercially available lithium-ion cells is typically based upon their full cell potential and surface temperature measurements, despite these parameters not being fully representative of the electrochemical processes taking place in the core of the cell or at each electrode. Several methods were devised to obtain the cell core temperature and electrode-specific potential profiles of cylindrical Li-ion cells. Optical fibres with Bragg Gratings were found to produce reliable core temperature data, while their small mechanical profile allowed for low-impact instrumentation method. A pure metallic lithium reference electrode insertion method was identified, avoiding interference with other elements of the cell while ensuring good contact, enabling in-situ observations of the per-electrode electrochemical responses. Our thermo-electrochemical instrumentation technique has enabled us to collect unprecedented cell data, and has subsequently been used in advanced studies exploring the real-world performance limits of commercial cells.

Humic acids as pseudocapacitive electrolyte additive for electrochemical double layer capacitors

NASA Astrophysics Data System (ADS)

Wasiński, Krzysztof; Walkowiak, Mariusz; Lota, Grzegorz

2014-06-01

Novel electrolyte additive for electrochemical capacitors has been reported. It has been demonstrated for the first time that addition of humic acids (HA) to KOH-based electrolyte significantly increases capacitance of symmetrical capacitors with electrodes made of activated carbon. Specific capacitances determined by means of galvanostatic charge/discharge, cyclic voltammetry and electrochemical impedance spectroscopy consistently showed increases for HA concentrations ranging from 2% w/w up to saturated solution with maximum positive effect observed for 5% w/w of the additive. The capacitance increase has been attributed to complex faradaic processes involving oxygen-containing groups of HA molecules. Due to abundant resources, low cost and easy processability the reported solution can find application in electrochemical capacitor technologies.

Electrochemical preparation of poly(methylene blue)/graphene nanocomposite thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erçarıkcı, Elif; Dağcı, Kader; Topçu, Ezgi

2014-07-01

Highlights: • Poly(MB)/graphene thin films are prepared by a simple electrochemical approach. • Graphene layers in the film show a broad band in visible region of absorbance spectra. • Morphology of composite films indicates both disordered and ordered regions. • XRD reveals that nanocomposite films include rGO layers after electropolymerization process. • Chemically prepared graphene is better than electrochemically prepared graphene for electrooxidation of nitrite. - Abstract: Poly(methylene blue)/graphene nanocomposite thin films were prepared by electropolymerization of methylene blue in the presence of graphene which have been synthesized by two different methods of a chemical oxidation process and an electrochemicalmore » approach. Synthesized nanocomposite thin films were characterized by using cyclic voltammetry, UV–vis. absorption spectroscopy, powder X-ray diffraction, and scanning tunneling microscopy techniques. Electrocatalytical properties of prepared poly(methylene blue)/graphene nanocomposite films were compared toward electrochemical oxidation of nitrite. Under optimized conditions, electrocatalytical effect of nanocomposite films of chemically prepared graphene through electrochemical oxidation of nitrite was better than that of electrochemically prepared graphene.« less

Microfluidic platform for studying the electrochemical reduction of carbon dioxide

NASA Astrophysics Data System (ADS)

Whipple, Devin Talmage

Diminishing supplies of conventional energy sources and growing concern over greenhouse gas emissions present significant challenges to supplying the world's rapidly increasing demand for energy. The electrochemical reduction of carbon dioxide has the potential to address many of these issues by providing a means of storing electricity in chemical form. Storing electrical energy as chemicals is beneficial for leveling the output of clean, but intermittent renewable energy sources such as wind and solar. Electrical energy stored as chemicals can also be used as carbon neutral fuels for portable applications allowing petroleum derived fuels in the transportation sector to be replaced by more environmentally friendly energy sources. However, to be a viable technology, the electrochemical reduction of carbon dioxide needs to have both high current densities and energetic efficiencies (Chapter 1). Although many researchers have studied the electrochemical reduction of CO2 including parameters such as catalysts, electrolytes and temperature, further investigation is needed to improve the understanding of this process and optimize the performance (Chapter 2). This dissertation reports the development and validation of a microfluidic reactor for the electrochemical reduction of CO2 (Chapter 3). The design uses a flowing liquid electrolyte instead of the typical polymer electrolyte membrane. In addition to other benefits, this flowing electrolyte gives the reactor great flexibility, allowing independent analysis of each electrode and the testing of a wide variety of conditions. In this work, the microfluidic reactor has been used in the following areas: • Comparison of different metal catalysts for the reduction of CO2 to formic acid and carbon monoxide (Chapter 4). • Investigation of the effects of the electrolyte pH on the reduction of CO2 to formic acid and carbon monoxide (Chapter 5). • Study of amine based electrolytes for lowering the overpotentials for CO2 reduction and suppressing undesirable hydrogen evolution (Chapter 6). • Investigation of the effects of reaction temperature on the Faradaic efficiency and current density for CO2 reduction on several catalysts (Chapter 7). These studies demonstrate the utility of this flexible reactor design and provide increased understanding of the electrochemical reduction of CO2 and the critical parameters for optimization of this process.

Development of an Electrochemistry Teaching Sequence using a Phenomenographic Approach

NASA Astrophysics Data System (ADS)

Rodriguez-Velazquez, Sorangel

Electrochemistry is the area of chemistry that studies electron transfer reactions across an interface. Chemistry education researchers have acknowledged that difficulties in electrochemistry instruction arise due to the level of abstraction of the topic, lack of adequate explanations and representations found in textbooks, and a quantitative emphasis in the application of concepts. Studies have identified conceptions (also referred to as misconceptions, alternative conceptions, etc.) about the electrochemical process that transcends academic and preparation levels (e.g., students and instructors) as well as cultural and educational settings. Furthermore, conceptual understanding of the electrochemical process requires comprehension of concepts usually studied in physics such as electric current, resistance and potential and often neglected in introductory chemistry courses. The lack of understanding of physical concepts leads to students. conceptions with regards to the relation between the concepts of redox reactions and electric circuits. The need for instructional materials to promote conceptual understanding of the electrochemical process motivated the development of the electrochemistry teaching sequence presented in this dissertation. Teaching sequences are educational tools that aim to bridge the gap between student conceptions and the scientific acceptable conceptions that instructors expect students to learn. This teaching sequence explicitly addresses known conceptions in electrochemistry and departs from traditional instruction in electrochemistry to reinforce students. previous knowledge in thermodynamics providing the foundation for the explicit relation of redox reactions and electric circuits during electrochemistry instruction. The scientific foundations of the electrochemical process are explained based on the Gibbs free energy (G) involved rather than on the standard redox potential values (E° ox/red) of redox half-reactions. Representations of the core concepts from discipline-specific models and theories serve as visual tools to describe reversible redox half-reactions at equilibrium, predict the spontaneity of the electrochemical process and explain interfacial equilibrium between redox species and electrodes in solution. The integration of physics concepts into electrochemistry instruction facilitated describing the interactions between the chemical system (e.g., redox species) and the external circuit (e.g., voltmeter). The "Two worlds" theoretical framework was chosen to anchor a robust educational design where the world of objects and events is deliberately connected to the world of theories and models. The core concepts in Marcus theory and density of states (DOS) provided the scientific foundations to connect both worlds. The design of this teaching sequence involved three phases; the selection of the content to be taught, the determination of a coherent and explicit connection among concepts and the development of educational activities to engage students in the learning process. The reduction-oxidation and electrochemistry chapters of three of the most popular general chemistry textbooks were revised in order to identify potential gaps during instruction, taking into consideration learning and teaching difficulties. The electrochemistry curriculum was decomposed into manageable sections contained in modules. Thirteen modules were developed and each module addresses specific conceptions with regard to terminology, redox reactions in electrochemical cells, and the function of the external circuit in electrochemical process. The electrochemistry teaching sequence was evaluated using a phenomenographic approach. This approach allows describing the qualitative variation in instructors' consciousness about the teaching of electrochemistry. A phenomenographic analysis revealed that the most relevant aspect of variation came from instructors' expertise. Participant A expertise (electrochemist) promoted in-depth discussions of fundamental theories and models that explain the electrochemical process while participant B expertise (general chemistry instruction) emphasized a coherent and explicit presentation of such theories and models to students. Other categories of variation were identified as: recognizing students' conceptions, the use of teaching resources and instructors' expectations for the teaching sequence. For example, while Participant B depended heavily on representations and explanations found in textbooks, participant A recognized misleading representations and oversimplified statements in general chemistry textbooks. Participant A was also more inclined to question the significance of some conceptions such as the correlation between the use of the term circuit and students' conceptions related to the movement of electrons in solution in an electrochemical cell. The electrochemistry teaching sequence in this dissertation fulfils each of the instructors' expectations with regards to the content that incorporated discipline-specific theories and models, explicit connections and flow among concepts, and addressing students' conceptions via the educational activities developed.

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)...

Conversion of raw carbonaceous fuels

DOEpatents

Cooper, John F [Oakland, CA

2007-08-07

Three configurations for an electrochemical cell are utilized to generate electric power from the reaction of oxygen or air with porous plates or particulates of carbon, arranged such that waste heat from the electrochemical cells is allowed to flow upwards through a storage chamber or port containing raw carbonaceous fuel. These configurations allow combining the separate processes of devolatilization, pyrolysis and electrochemical conversion of carbon to electric power into a single unit process, fed with raw fuel and exhausting high BTU gases, electric power, and substantially pure CO.sub.2 during operation.

Chronopotentiometry of refractory metals, actinides and oxyanions in molten salts: A review

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.

1992-01-01

The applications of chronopotentiometry to the study of electrochemical behavior of three technologically important areas of refractory metals, actinides, and oxyanions in molten salts are critically reviewed. Chronopotentiometry is a very versatile diagnostic tool to understand the reaction mechanism of the electrode processes for the electrochemical reduction/oxidation of these electroactive species in molten salt solutions. Well adherent, compact, and uniformly thick coatings of refractory metals may be electrodeposited from their solutions in molten salts.

Electrochemical synthesis of hard-alloy compositions based on tungsten carbide and an iron triad metal

NASA Astrophysics Data System (ADS)

Kushkhov, Kh. B.; Adamokova, M. N.; Kvashin, V. A.; Kardanov, A. L.

2010-08-01

Single and cyclic voltammetry is used to study the electrode processes that occur during electrochemical synthesis of hard-alloy compositions based on tungsten carbide and an iron triad metal in tungstate and tungstate-carbonate Na2WO4-Li2WO4-Li2CO3 (5.0-22.0 wt %) melts. The conditions of bringing the electroprecipitation potentials of tungsten, carbon, and an iron triad metal into coincidence are determined.

Effect of the synthesis conditions on the electrochemical properties of LiFePO{sub 4} obtained from NH{sub 4}FePO{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prosini, Pier Paolo, E-mail: pierpaolo.prosini@enea.it; Gislon, Paola; Cento, Cinzia

Graphical abstract: - Highlights: • Four different samples of FAP were synthesized by precipitation techniques. • The samples were used as precursors to synthesize electrochemical active LiFePO{sub 4}. • Their morphology, composition, structure and electrochemical performance were studied. • The LiFePO{sub 4} electrochemical performance resulted affected by the preparation method - Abstract: In this paper the morphological, structural and electrochemical properties of crystalline lithium iron phosphate (LiFePO{sub 4}) obtained from ferrous ammonium phosphate (FAP) have been studied. The FAP was obtained following four different processes, namely: (1) homogeneous phase precipitation, (2) heterogeneous phase precipitation from stoichiometric sodium phosphate, (3) heterogeneousmore » phase precipitation from stoichiometric ammonium phosphate, and (4) heterogeneous phase precipitation from over stoichiometric ammonium phosphate. Lithium iron phosphate was prepared by solid state reaction of FAP with lithium hydroxide. In order to evaluate the effect of reaction time and synthesis temperature the LiFePO{sub 4} was prepared varying the heating temperatures (550, 600 and 700 °C) and the reaction times (1 or 2 h). The morphology of the materials was evaluated by scanning electron microscopy while the chemical composition was determined by electron energy loss spectroscopy. X-ray diffraction was used to evaluate phase composition, crystal structure and crystallite size. The so obtained LiFePO{sub 4}'s were fully electrochemical characterized and a correlation was found between the crystal size and the electrochemical performance.« less

Silver deposition on titanium surface by electrochemical anodizing process reduces bacterial adhesion of Streptococcus sanguinis and Lactobacillus salivarius.

PubMed

Godoy-Gallardo, Maria; Rodríguez-Hernández, Ana G; Delgado, Luis M; Manero, José M; Javier Gil, F; Rodríguez, Daniel

2015-10-01

The aim of this study was to determine the antibacterial properties of silver-doped titanium surfaces prepared with a novel electrochemical anodizing process. Titanium samples were anodized with a pulsed process in a solution of silver nitrate and sodium thiosulphate at room temperature with stirring. Samples were processed with different electrolyte concentrations and treatment cycles to improve silver deposition. Physicochemical properties were determined by X-ray photoelectron spectroscopy, contact angle measurements, white-light interferometry, and scanning electron microscopy. Cellular cytotoxicity in human fibroblasts was studied with lactate dehydrogenase assays. The in vitro effect of treated surfaces on two oral bacteria strains (Streptococcus sanguinis and Lactobacillus salivarius) was studied with viable bacterial adhesion measurements and growth curve assays. Nonparametric statistical Kruskal-Wallis and Mann-Whitney U-tests were used for multiple and paired comparisons, respectively. Post hoc Spearman's correlation tests were calculated to check the dependence between bacteria adhesion and surface properties. X-ray photoelectron spectroscopy results confirmed the presence of silver on treated samples and showed that treatments with higher silver nitrate concentration and more cycles increased the silver deposition on titanium surface. No negative effects in fibroblast cell viability were detected and a significant reduction on bacterial adhesion in vitro was achieved in silver-treated samples compared with control titanium. Silver deposition on titanium with a novel electrochemical anodizing process produced surfaces with significant antibacterial properties in vitro without negative effects on cell viability. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Electroactive Au@Ag nanoparticles driven electrochemical sensor for endogenous H2S detection.

PubMed

Zhao, Yuan; Yang, Yaxin; Cui, Linyan; Zheng, Fangjie; Song, Qijun

2018-05-26

In this work, a novel and facile electrochemical sensor is reported for the highly selective and sensitive detection of dissolved hydrogen sulfide (H 2 S), attributing to the redox reaction between Au@Ag core-shell nanoparticles (Au@Ag NPs) and H 2 S. Electroactive Au@Ag NPs not only possess excellent conductivity, but exhibit great electrochemical reactivity at 0.26 V due to the electrochemical oxidation from Ag° to Ag + . In the presence of H 2 S, the Ag shell of Au@Ag NPs can be oxidized to Ag 2 S, resulting in the decrease of differential pulse voltammetry (DPV) peak at 0.26 V. The electrochemical sensor exhibits a wide linear response range from 0.1 nM to 500 nM. The limit of detection (LOD) for H 2 S is as low as 0.04 nM. The developed sensor shows significant prospects in the study of pathological processes related to the mechanism of H 2 S production. Copyright © 2018. Published by Elsevier B.V.

Polarization Resistance Measurement in Tap Water: The Influence of Rust Electrochemical Activity

NASA Astrophysics Data System (ADS)

Vasyliev, Georgii

2017-08-01

Corrosion rate of mild steel in tap water during 4300 h was estimated by LPR and weight-loss methods coupled with OCP measurements. The LPR results were found to be overestimated compared to the weight-loss data within initial 2000 h of exposure. The electrochemical activity of the rust separated from the metal surface was studied by cycling voltammetry using a home-built powder graphite electrode. High redox currents corresponding to the initial 2000 h of exposure were detected. Rust composition was characterized with IR and XRD, and the highest amounts of electrochemically active β- and γ-FeOOH were again detected for the initial 2000 h. Current consumption in rust transformation processes during LPR measurement in the galvanostatic mode accounts for overestimation of the corrosion rate. The time dependence of rust electrochemical activity correlates with OCP variation with time. During initial 2000 h, OCP values are shifted by 50 mV to cathodic side. For the period of a higher rust electrochemical activity, the use of a reduced B is suggested to increase accuracy of LPR technique in tap water.

Study of the Charge Transfer Process of LaNi5 Type Electrodes in Ni-MH Batteries

NASA Astrophysics Data System (ADS)

Le, Xuan Que; Nguyen, Phu Thuy

2002-12-01

As a result of the charge process of LaNi5 type electrode, hydrogen is reversibly absorbed on the electrode surface. The process consists two principal steps. During the both processes, the first reaction step occurs in the interface solid/liquid, negatively charged, with high static electric field, where the double layer structure became more compact. The transfer of charge under high electric field depends on many factors, principally on compositions of the electrode materials. Effects on that of Co, Fe, Mn substitutes, with different concentrations, have been comparatively studied using electrochemical technique. The analyse of interface C -.V study results has been realised, respecting Mott-Schottky relation. Optimal contents of some additives have been discussed. Some advantages of the applied electrochemical methods have been confirmed. The mechanism of the charges transfer and of the hydrogen reversible storage in the crystal structure in the batteries has been discussed. With the proposed mechanism, one can more explicitly understand the difference of the magnetic effect of the electrode materials before and after charge-discharge process can be explained.

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.

Electrochemical Oxidation of Resorcinol in Aqueous Medium Using Boron-Doped Diamond Anode: Reaction Kinetics and Process Optimization with Response Surface Methodology

PubMed Central

Körbahti, Bahadır K.; Demirbüken, Pelin

2017-01-01

Electrochemical oxidation of resorcinol in aqueous medium using boron-doped diamond anode (BDD) was investigated in a batch electrochemical reactor in the presence of Na2SO4 supporting electrolyte. The effect of process parameters such as resorcinol concentration (100–500 g/L), current density (2–10 mA/cm2), Na2SO4 concentration (0–20 g/L), and reaction temperature (25–45°C) was analyzed on electrochemical oxidation using response surface methodology (RSM). The optimum operating conditions were determined as 300 mg/L resorcinol concentration, 8 mA/cm2 current density, 12 g/L Na2SO4 concentration, and 34°C reaction temperature. One hundred percent of resorcinol removal and 89% COD removal were obtained in 120 min reaction time at response surface optimized conditions. These results confirmed that the electrochemical mineralization of resorcinol was successfully accomplished using BDD anode depending on the process conditions, however the formation of intermediates and by-products were further oxidized at much lower rate. The reaction kinetics were evaluated at optimum conditions and the reaction order of electrochemical oxidation of resorcinol in aqueous medium using BDD anode was determined as 1 based on COD concentration with the activation energy of 5.32 kJ/mol that was supported a diffusion-controlled reaction. PMID:29082225

In Situ Coating of Li[Ni0.33 Mn0.33 Co0.33 ]O2 Particles to Enable Aqueous Electrode Processing.

PubMed

Loeffler, Nicholas; Kim, Guk-Tae; Mueller, Franziska; Diemant, Thomas; Kim, Jae-Kwang; Behm, R Jürgen; Passerini, Stefano

2016-05-23

The aqueous processing of lithium-ion battery (LIB) electrodes has the potential to notably decrease the battery processing costs and paves the way for a sustainable and environmentally benign production (and recycling) of electrochemical energy storage devices. Although this concept has already been adopted for the industrial production of LIB graphite anodes, the performance decay of cathode electrodes based on transition metal oxides processed in aqueous environments is still an open issue. In this study, we show that the addition of small quantities of phosphoric acid into the cathodic slurry yields Li[Ni0.33 Mn0.33 Co0.33 ]O2 electrodes that have an outstanding electrochemical performance in lithium-ion cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical and spectroelectrochemical study on novel non-peripherally tetra 1,2,4-triazole substituted phthalocyanines

NASA Astrophysics Data System (ADS)

Demirbaş, Ümit; Akyüz, Duygu; Akçay, Hakkı Türker; Koca, Atıf; Bekircan, Olcay; Kantekin, Halit

2018-03-01

In the present study novel tetra 4-(4-fluorophenyl)-5-(4-methoxyphenyl)-4H-1,2,4-triazole-3-thio substituted non-peripherally metal free (4), zinc(II) (5), lead (II) (6) and copper(II) (7) phthalocyanines were synthesized. The obtained novel compounds were characterized by a combination of FT-IR, 1H NMR, UV-Vis and MALDI-TOF techniques. The redox properties of the complexes have been investigated via cyclic voltammetry, square wave voltammetry and in situ spectroelectrochemistry. The compounds displayed ring-based, reversible and/or quasi-reversible reduction and oxidation processes and aggregation of the complexes influenced the redox character of the processes. The color changes during the redox processes of metallo phthalocyanine were recorded by in-situ spectroelectrochemical measurements. In situ UV-vis spectroelectrochemical measurements, which was associated with color change of the complexes, showed their applicability in the fields of the electrochemical technologies.

Investigation of the degradation of different nickel anode types for alkaline fuel cells (AFCs)

NASA Astrophysics Data System (ADS)

Gülzow, E.; Schulze, M.; Steinhilber, G.

Alkaline fuel cells (AFCs) have the opportunity of becoming important for mobile energy systems as, in contrast to other low temperature fuel cells, the alkaline type requires neither noble metal catalysts nor an expensive polymer electrolyte. In AFCs, nickel is used as anode catalyst in gas diffusion electrodes. The metal catalyst was mixed with polytetraflourethylene (PTFE) as organic binder in a knife mile and rolled onto a metal web in a calendar to prepare the electrode. After an activation process with hydrogen evolution at 5 mA/cm 2 for 18 h, the electrodes were stressed at constant loading in a half cell equipment. During the fuel cell operation, the electrochemical performance decreased due to changes of the polymer (PTFE) and of the metal particles in the electrode, which is described in detail in another paper. In this study, three types of electrodes were investigated. The first type of electrode is composed of pure Raney-nickel and PTFE powder, the nickel particles in the second electrode type were selected according to particle size and in the third electrode copper powder was added to the nickel powder not selected by size. The size selected nickel particles show a better electrochemical performance related to the non-selected catalyst, but due to the electrochemically induced disintegration of the nickel particles the electrochemical performance decreases stronger. The copper powder in the third electrode is added to improve the electronic conductivity of the nickel catalyst, but the copper is not stable under the electrochemical conditions in fuel cell operation. With all three anode types long-term experiments have been performed. The electrodes have been characterized after the electrochemical stressing to investigate the degradation processes.

Corrosion resistance of premodeled wires made of stainless steel used for heart electrotherapy leaders

NASA Astrophysics Data System (ADS)

Przondziono, J.; Walke, W.; Młynarski, R.; Szatka, W.

2012-05-01

The purpose of the study is to evaluate resistance to electrochemical corrosion of wire made of X10CrNi18-8 stainless steel designed for use in cardiology treatment. The influence of strain formed in the premodeling process and methods of wire surface preparation to corrosive resistance in artificial plasma solution were analysed. Wire corrosion tests were carried out in the solution of artificial plasma. Resistance to electrochemical corrosion was evaluated on the ground of recorded curves of anodic polarization by means of potentiodynamic method. Potentiodynamic tests carried out enabled to determine how the resistance to pitting corrosion of wire changes, depending on strain formed in the premodeling process as well as on the method of wire surface preparation. For evaluation of phenomena occurring on the surface of tested steel, electrochemical impedance spectroscopy (EIS) was applied. Deterioration of corrosive properties of wire along with the increase in the formed strain hardening was observed.

Efficient fluorescence quenching in electrochemically exfoliated graphene decorated with gold nanoparticles

NASA Astrophysics Data System (ADS)

Hurtado-Morales, M.; Ortiz, M.; Acuña, C.; Nerl, H. C.; Nicolosi, V.; Hernández, Y.

2016-07-01

High surface area graphene sheets were obtained by electrochemical exfoliation of graphite in an acid medium under constant potential conditions. Filtration and centrifugation processes played an important role in order to obtain stable dispersions in water. Scanning electron microscopy and transmission electron microscopy imaging revealed highly exfoliated crystalline samples of ∼5 μm. Raman, Fourier transform infrared and x-ray photoelectron spectroscopy further confirmed the high quality of the exfoliated material. The electrochemically exfoliated graphene (EEG) was decorated with gold nanoparticles (AuNPs) using sodium cholate as a buffer layer. This approach allowed for a non-covalent functionalization without altering the desirable electronic properties of the EEG. The AuNP-EEG samples were characterized with various techniques including absorbance and fluorescence spectroscopy. These samples displayed a fluorescence signal using an excitation wavelength of 290 nm. The calculated quantum yield (Φ) for these samples was 40.04%, a high efficiency compared to previous studies using solution processable graphene.

A Study on Passive and Electrochemical Response of Pure Nickel in Borate Buffer Solutions: Effect of Cold Deformation

NASA Astrophysics Data System (ADS)

Fattah-alhosseini, Arash; Naseri, Majid; Gashti, Seyed Omid; Vafaeian, Saeed; Keshavarz, Mohsen K.

2018-06-01

In the present work, influences of the cold deformation on electrochemical and passive response of pure nickel in three solutions with adjusted pH values of 8.5, 9.0, and 9.5 at 298 ± 1 K (25 ± 1 °C) were investigated. A cold deformation process was applied by means of cold rolling. Implementation of the cold deformation process resulted in samples having a finer microstructure. Also, the cold work and grain refinement led to increased hardness. In addition, open-circuit potential and potentiodynamic polarization tests were performed and results showed that corrosion current density was reduced by applying the cold deformation. Moreover, the results of the electrochemical impedance spectroscopy and Mott-Schottky analyses indicated higher corrosion resistance of pure nickel after cold deformation. This behavior is attributed to the growth of much thicker, with less point defects, passive layer on the surface of cold-deformed samples.

Effect of Gas Pressure on Polarization of SOFC Cathode Prepared by Plasma Spray

NASA Astrophysics Data System (ADS)

Li, Cheng-Xin; Wang, Zhun-Zhun; Liu, Shuai; Li, Chang-Jiu

2013-06-01

A cermet-supported tubular SOFC was fabricated using thermal spray. The cell performance was investigated at temperatures from 750 to 900 °C and pressures from 0.1 to 0.5 MPa to examine the effect of operating gas pressure on the cell performance. The influence of gas pressure on the cathodic polarization was studied through the electrochemical impedance approach to examine the controlling electrochemical processes during cell operation. Results show that increasing the operating gas pressure improves the power output performance significantly. When the gas pressure is increased from 0.1 to 0.3 MPa, the maximum power density is increased by a factor of 32% at a temperature of 800 °C. The cathode polarization decreases significantly with the increase of the gas pressure. The electrochemical analysis shows that the main control processes of the cathode reaction are the oxygen species transfer at the three-phase boundary and oxygen diffusion on the surface or in the bulk of the cathode, which are enhanced with increasing gas pressure.

Thermo-electrochemical analysis of lithium ion batteries for space applications using Thermal Desktop

NASA Astrophysics Data System (ADS)

Walker, W.; Ardebili, H.

2014-12-01

Lithium-ion batteries (LIBs) are replacing the Nickel-Hydrogen batteries used on the International Space Station (ISS). Knowing that LIB efficiency and survivability are greatly influenced by temperature, this study focuses on the thermo-electrochemical analysis of LIBs in space orbit. Current finite element modeling software allows for advanced simulation of the thermo-electrochemical processes; however the heat transfer simulation capabilities of said software suites do not allow for the extreme complexities of orbital-space environments like those experienced by the ISS. In this study, we have coupled the existing thermo-electrochemical models representing heat generation in LIBs during discharge cycles with specialized orbital-thermal software, Thermal Desktop (TD). Our model's parameters were obtained from a previous thermo-electrochemical model of a 185 Amp-Hour (Ah) LIB with 1-3 C (C) discharge cycles for both forced and natural convection environments at 300 K. Our TD model successfully simulates the temperature vs. depth-of-discharge (DOD) profiles and temperature ranges for all discharge and convection variations with minimal deviation through the programming of FORTRAN logic representing each variable as a function of relationship to DOD. Multiple parametrics were considered in a second and third set of cases whose results display vital data in advancing our understanding of accurate thermal modeling of LIBs.

Electrochemical Biosensors: A Solution to Pollution Detection with Reference to Environmental Contaminants.

PubMed

Hernandez-Vargas, Gustavo; Sosa-Hernández, Juan Eduardo; Saldarriaga-Hernandez, Sara; Villalba-Rodríguez, Angel M; Parra-Saldivar, Roberto; Iqbal, Hafiz M N

2018-03-24

The increasing environmental pollution with particular reference to emerging contaminants, toxic heavy elements, and other hazardous agents is a serious concern worldwide. Considering this global issue, there is an urgent need to design and develop strategic measuring techniques with higher efficacy and precision to detect a broader spectrum of numerous contaminants. The development of precise instruments can further help in real-time and in-process monitoring of the generation and release of environmental pollutants from different industrial sectors. Moreover, real-time monitoring can also reduce the excessive consumption of several harsh chemicals and reagents with an added advantage of on-site determination of contaminant composition prior to discharge into the environment. With key scientific advances, electrochemical biosensors have gained considerable attention to solve this problem. Electrochemical biosensors can be an excellent fit as an analytical tool for monitoring programs to implement legislation. Herein, we reviewed the current trends in the use of electrochemical biosensors as novel tools to detect various contaminant types including toxic heavy elements. A particular emphasis was given to screen-printed electrodes, nanowire sensors, and paper-based biosensors and their role in the pollution detection processes. Towards the end, the work is wrapped up with concluding remarks and future perspectives. In summary, electrochemical biosensors and related areas such as bioelectronics, and (bio)-nanotechnology seem to be growing areas that will have a marked influence on the development of new bio-sensing strategies in future studies.

Submicron patterned metal hole etching

DOEpatents

McCarthy, Anthony M.; Contolini, Robert J.; Liberman, Vladimir; Morse, Jeffrey

2000-01-01

A wet chemical process for etching submicron patterned holes in thin metal layers using electrochemical etching with the aid of a wetting agent. In this process, the processed wafer to be etched is immersed in a wetting agent, such as methanol, for a few seconds prior to inserting the processed wafer into an electrochemical etching setup, with the wafer maintained horizontal during transfer to maintain a film of methanol covering the patterned areas. The electrochemical etching setup includes a tube which seals the edges of the wafer preventing loss of the methanol. An electrolyte composed of 4:1 water: sulfuric is poured into the tube and the electrolyte replaces the wetting agent in the patterned holes. A working electrode is attached to a metal layer of the wafer, with reference and counter electrodes inserted in the electrolyte with all electrodes connected to a potentiostat. A single pulse on the counter electrode, such as a 100 ms pulse at +10.2 volts, is used to excite the electrochemical circuit and perform the etch. The process produces uniform etching of the patterned holes in the metal layers, such as chromium and molybdenum of the wafer without adversely effecting the patterned mask.

Facile route to covalently-jointed graphene/polyaniline composite and it's enhanced electrochemical performances for supercapacitors

NASA Astrophysics Data System (ADS)

Qiu, Hanxun; Han, Xuebin; Qiu, Feilong; Yang, Junhe

2016-07-01

A polyaniline/graphene composite with covalently-bond is synthesized by a novel approach. In this way, graphene oxide is functionalized firstly by introducing amine groups onto the surface with the reduction of graphene oxide in the process and then served as the anchor sites for the growth of polyaniline (PANI) via in-situ polymerization. The composite material is characterized by electron microscopy, the resonant Raman spectra, X-ray diffraction, transform infrared spectroscopy and X-ray photoelectron spectroscopy. The electrochemical properties of the composite are measured by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charging/discharging. With the functionalization process, the graphene/polyaniline composite electrode exhibits remarkably enhanced electrochemical performance with specific capacitance of 489 F g-1 at 0.5 A g-1, which is superior to those of its individual components. The outstanding electrochemical performance of the hybrid can be attributed to its covalently synergistic effect between graphene and polyaniline, suggesting promising potentials for supercapacitors.

Biologically Derived Nanoparticle Arrays via a Site-Specific Reconstitution of Ferritin and their Electrochemistry

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; King, Glen C.; Elliott, James R.; Chu, Sang-Hyon; Park, Yeonjoon; Watt, Gerald D.

2004-01-01

Nanoparticle arrays biologically derived from an electrochemically-controlled site-specific biomineralization were fabricated on a gold substrate through the immobilization process of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, the fabrication of self-assembled arrays with the immobilized ferritin, and the electrochemical characterization of various core materials. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of electrochemical site-specific biomineralization with a protein cage loads ferritins with different core materials such as Pt, Co, Mn, and Ni. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. The nano-sized metalcored ferritins on a gold substrate displayed a good electrochemical activity for the electron transport and storage, which is suitable for bioelectronics applications such as biofuel cell, bionanobattery, biosensors, etc. Keywords: Ferritin, immobilization, site-specific reconstitution, biomineralization, and bioelectronics

Electrochemical studies on niobium triselenide cathode material for lithium rechargeable cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ratnakumar, B.V.; Ni, C.L.; DiStefano, S.

1989-01-01

Niobium triselenide offers promise as a high energy density cathode material for ambient temperature lithium rechargeable cells. The electrochemical behavior of NbSe/sub 3/ in the battery electrolyte, i.e., 1.5m LiAsF/sub 6//2 Me-THF is reported here. A detailed study has been carried out using various ac and dc electrochemical techniques to establish the mechanism of intercalation of three equivalents of Li with NbSe/sub 3/ as well as the rate governing processes in the reduction of NbSe/sub 3/. Based on the experimental data, an equivalent circuit has been formulated to represent the NbSe/sub 3/-solution interface. The kinetic parameters for the reduction ofmore » NbSe/sub 3/ were evaluated from the ac and dc measurements. Finally, the structural change in NbSe/sub 3/ on lithiation during initial discharge which results in higher cell voltages and different electrochemical response as compared to virgin NbSe/sub 3/ was identified to be a loss of crystallographic order, i.e., amorphous by x-ray diffraction.« less

Active sites of ligand-protected Au{sub 25} nanoparticle catalysts for CO{sub 2} electroreduction to CO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alfonso, Dominic R., E-mail: alfonso@netl.doe.gov; Kauffman, Douglas; Matranga, Christopher

2016-05-14

Recent experimental studies have reported the electrochemical reduction of carbon dioxide (CO{sub 2}) into CO at atomically precise negatively charged Au{sub 25}{sup −} nanoclusters. The studies showed CO{sub 2} conversion at remarkably low overpotentials, but the exact mechanisms and nature of the active sites remain unclear. We used first-principles density functional theory and continuum solvation models to examine the role of the cluster during electrochemical CO{sub 2} reduction and analyze the free energies of proposed intermediate species. Contrary to previous assumptions, our results show that the fully ligand protected cluster is not an active CO{sub 2} reduction catalyst because formationmore » of the crucial carboxyl intermediate required very high electrochemical potentials. Instead, our calculations suggest that the reduction process likely occurs on a dethiolated gold site, and adsorbed carboxyl intermediate formation was significantly stabilized at dethiolated gold sites. These findings point to the crucial role of exposed metal sites during electrochemical CO{sub 2} reduction at gold nanocluster catalysts.« less

Characterization of electrochemically deposited polypyrrole using magnetoelastic material transduction elements

NASA Technical Reports Server (NTRS)

Ersoz, Arzu; Ball, J. Christopher; Grimes, Craig A.; Bachas, Leonidas G.

2002-01-01

Magnetoelastic alloy films have been used as a working electrode in an electrochemical cell. This material allows magnetic interrogation of electrochemical deposition. This technique was used to monitor the electrochemical deposition of polypyrrole by multisweep (CV) and potentiostatic methods. Since the determination of the mass-sensitive magnetoelastic film's resonance frequency is based on magnetic transduction, an inherent advantage of this method is that it requires no electrical connections other than the working lead of the potentiostat. Increases in pyrrole deposition correlated with a decrease in the peak resonance frequency of the magnetoelastic alloy. This technique provides a novel approach by which one can monitor electrochemical processes.

Space Electrochemical Research and Technology

NASA Technical Reports Server (NTRS)

1991-01-01

The proceedings of NASA's third Space Electrochemical Research and Technology (SERT) conference are presented. The objective of the conference was to assess the present status and general thrust of research and development in those areas of electrochemical technology required to enable NASA missions in the next century. The conference provided a forum for the exchange of ideas and opinions of those actively involved in the field, in order to define new opportunities for the application of electrochemical processes in future NASA missions. Papers were presented in three technical areas: the electrochemical interface, the next generation in aerospace batteries and fuel cells, and electrochemistry for nonenergy storage applications.

Modeling of Electrochemical Copying in a Finite-Width Cell

NASA Astrophysics Data System (ADS)

Zhitnikov, V. P.; Sherykhalina, N. M.; Zaripov, A. A.

2017-11-01

The problem of modeling of electrochemical machining is reduced to the solution of the Schwartz problem on a parametrical rectangle with the use of theta-functions. Various conditions (non-equipotentiality of electrodes and inconstancy of current efficiency) at the boundary of a processed surface are considered. Nonstationary, quasistationary, stationary, and limit solutions are studied. Results of machining of surfaces by tool electrodes of various shapes are given. It is shown that machining mode parameters significantly affect the dissolved layer size necessary for obtaining high-precision copying.

Production of hydrogen by electron transfer catalysis using conventional and photochemical means

NASA Technical Reports Server (NTRS)

Rillema, D. P.

1981-01-01

Alternate methods of generating hydrogen from the sulfuric acid thermal or electrochemical cycles are presented. A number of processes requiring chemical, electrochemical or photochemical methods are also presented. These include the design of potential photoelectrodes and photocatalytic membranes using Ru impregnated nafion tubing, and the design of experiments to study the catalyzed electrolytic formation of hydrogen and sulfuric acid from sulfur dioxide and water using quinones as catalysts. Experiments are carried out to determine the value of these approaches to energy conversion.

Electrochemical studies on the performance of SS316L electrode in electrokinetics

NASA Astrophysics Data System (ADS)

Choi, Jeong-Hee; Maruthamuthu, Sundaram; Lee, Hyun-Goo; Ha, Tae-Hyun; Bae, Jeong-Hyo

2009-10-01

Organic and trace metal pollutants are removed by employing various electrodes in an electrokinetic (EK) process. Stainless steel was used either as an anode or a cathode by various investigators in electroremediation systems. In the present study, the role of SS316L as an anode and cathode in EK system was studied by the measurements of pH, conductivity of electrolyte, and potential of the anode and cathode at different current densities. The weight loss of the anode and cathode and the leaching of chromium, iron, and nickel at different current densities were measured and discussed with an electroosmosis process. The electrochemical behavior of SS316L electrode in neutral, acidic and alkaline pH in soil environment was studied by an electrochemical technique viz. polarization study. Surface analysis of SS316L after EK was done by XPS and SEM. The higher conductivity was noticed at anolyte when compared to catholyte. The weight loss of the anode was in the following order 0.615 > 0.307 > 0.123 mA/cm2 and the cathode corrosion rate was vice versa. Peroxide production was also noticed at the anolyte, which may encourage the degradation of the total organic content (TOC) in the soil. The OCP (open circuit potential) of SS316L was about +75 mV vs SCE in the soil extract; while adding acetic acid, the potential shifted to the positive side, to about +380 mV vs SCE. The breakdown potential and the range of passivation potential were higher in acetic acid added system when compared to other systems. Pitting was observed on both the anode and cathode within 48 h during the EK process. The present study concludes that SS is not a proper electrode material for the EK process.

Electrochemically modified dissolved organic matter accelerates the combining photodegradation and biodegradation of 17α-ethinylestradiol in natural aquatic environment.

PubMed

He, Huan; Huang, Bin; Fu, Gen; Xiong, Dan; Xu, Zhixiang; Wu, Xinhao; Pan, Xuejun

2018-06-15

The photochemical conversion and microbial transformation of pollutants mediated by dissolved organic matter (DOM), including 17α-ethinylestradiol (EE2), are often accompanied in natural water. However, there are few studies to explore the connection and mechanism between the two processes. This research aims to investigate the mechanism of DOM after electrochemically modification mediated EE2 combining photodegradation and biodegradation in the environment and it want to explain the natural phenomena of DOM after electrochemical advanced treatment entering the water environment mediated EE2 natural degradation. The results showed that combining photodegradation with biodegradation rates of EE2 mediated by DOM and electrochemically modified DOM (E-DOM) were promoted obviously. The efficiency of EE2 biodegradation was shown to be strongly correlated with electron accepting capacity (EAC) of DOM. Electrochemical modification can increase the EAC of DOM leading to EE2 biodegradation accelerated, and it also can form more triplet-state DOM moieties to promote the EE2 photodegradation in irradiation conditions, due to the increasing of quinone-type structures in DOM. Moreover, cell polymeric secretion (CPS) secreted from the microorganism could be stimulated to an excited state by irradiation, and that also accelerated EE2 degradation. Photolysis combined with biochemical degradation yielded less toxic degradation products. This study shows that the emission of DOM in wastewater after electrochemical treatment could accelerate estrogen degradation and play a positive role on the pollutant transformation in the environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Dissecting anode swelling in commercial lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Ningxin; Tang, Huaqiong

2012-11-01

An innovative method is applied to investigate anode swelling during electrochemical processes in commercial lithium-ion batteries. Cathode surface is partially covered with a piece of paste to block the transportation of lithium ion from active material during charging/discharging, and the corresponding part on the anode film shows no formation of Li-graphite compounds during different electrochemical processes, which is confirmed by XRD analysis. The increases of anode thickness within and outside lithiated zone are measured, and defined as electrochemical swelling and physical swelling respectively. The microscopic lattice expansion of graphite due to lithiation process correlates to mesoscopic electrochemical swelling synchronically, while physical swelling tends to decrease steadily with time. The relationship among the microscopic stress due to lithium-ion intercalation, the mesoscopic stress resulting in anode swelling, and the macroscopic rippling of pouch cell after a large number of cycle test, is analyzed and correlated in terms of stress evolution across different scales, and suggestions for solving anode swelling are provided.

Electrochemical characterization of monoclinic and orthorhombic Li3CrF6 as positive electrodes in lithium-ion batteries synthesized by a sol-gel process with environmentally benign chemicals

NASA Astrophysics Data System (ADS)

Lieser, Georg; Winkler, Volker; Geßwein, Holger; de Biasi, Lea; Glatthaar, Sven; Hoffmann, M. J.; Ehrenberg, Helmut; Binder, Joachim R.

2015-10-01

Lithium transition metal fluorides (Li3MF6; M = Fe, V) with cryolite structure are investigated as positive electrode materials for lithium-ion batteries. A novel sol-gel process with trifluoroacetic acid as fluorine source was used to synthesize monoclinic and orthorhombic Li3CrF6. A ball milling process with Li3CrF6, binder, and conductive agent was applied to form a Li3CrF6 composite, which was electrochemically characterized against lithium metal for the first time. The electrochemical properties of two different modifications are quite similar, with a reversible specific capacity of 111 mAhg-1 for monoclinic Li3CrF6 and 106 mAhg-1 for orthorhombic Li3CrF6 (1 eq. Li ≙ 143 mAhg-1). The electrochemically active redox couple CrIII/CrII was confirmed by X-ray photoelectron spectroscopy.

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

PubMed

Batisse, Nicolas; Raymundo-Piñero, Encarnación

2017-11-29

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

Electrochemical properties in a seawater environment of 5456-H116 aluminum alloy subjected to optimal friction stir processing

NASA Astrophysics Data System (ADS)

Park, Jae-Cheul; Kim, Seong-Jong

2010-05-01

The mechanical properties of aluminum alloy may be enhanced by modifying the microstructure of the metal by friction stir processing (FSP). Previous studies have demonstrated that the mechanical characteristics of 5456-H116 Al alloy subjected to FSP, at 250 rpm and 15 mm min-1 using a full screw probe, are similar to those of the original alloy. In the present work, the same alloy was processed under these optimal conditions, and the range of favorable protection potentials with regard to hydrogen embrittlement and stress corrosion cracking was determined to lie between -1.3 and -0.7 V (versus Ag/AgCl). The electrochemical behavior of the specimens subjected to FSP was superior to that of the original 5456-H116 Al alloy.

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.

An Easy-to-Machine Electrochemical Flow Microreactor: Efficient Synthesis of Isoindolinone and Flow Functionalization.

PubMed

Folgueiras-Amador, Ana A; Philipps, Kai; Guilbaud, Sébastien; Poelakker, Jarno; Wirth, Thomas

2017-11-27

Flow electrochemistry is an efficient methodology to generate radical intermediates. An electrochemical flow microreactor has been designed and manufactured to improve the efficiency of electrochemical flow reactions. With this device only little or no supporting electrolytes are needed, making processes less costly and enabling easier purification. This is demonstrated by the facile synthesis of amidyl radicals used in intramolecular hydroaminations to produce isoindolinones. The combination with inline mass spectrometry facilitates a much easier combination of chemical steps in a single flow process. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Main chemical species and molecular structure of deep eutectic solvent studied by experiments with DFT calculation: a case of choline chloride and magnesium chloride hexahydrate.

PubMed

Zhang, Chao; Jia, Yongzhong; Jing, Yan; Wang, Huaiyou; Hong, Kai

2014-08-01

The infrared spectrum of deep eutectic solvent of choline chloride and magnesium chloride hexahydrate was measured by the FTIR spectroscopy and analyzed with the aid of DFT calculations. The main chemical species and molecular structure in deep eutectic solvent of [MgClm(H2O)6-m]2-m and [ChxCly]x+y complexes were mainly identified and the active ion of magnesium complex during the electrochemical process was obtained. The mechanism of the electrochemical process of deep eutectic solvent of choline chloride and magnesium chloride hexahydrate was well explained by combination theoretical calculations and experimental. Besides, based on our results we proposed a new system for the dehydration study of magnesium chloride hexahydrate.

Single bead-based electrochemical biosensor.

PubMed

Liu, Changchun; Schrlau, Michael G; Bau, Haim H

2009-12-15

A simple, robust, single bead-based electrochemical biosensor was fabricated and characterized. The sensor's working electrode consists of an electrochemically etched platinum wire, with a nominal diameter of 25 microm, hermetically heat-fusion sealed in a pulled glass capillary (micropipette). The sealing process does not require any epoxy or glue. A commercially available, densely functionalized agarose bead was mounted on the tip of the etched platinum wire. The use of a pre-functionalized bead eliminates the tedious and complicated surface functionalization process that is often the bottleneck in the development of electrochemical biosensors. We report on the use of a biotin agarose bead-based, micropipette, electrochemical (Bio-BMP) biosensor to monitor H(2)O(2) concentration and the use of a streptavidin bead-based, micropipette, electrochemical (SA-BMP) biosensor to detect DNA amplicons. The Bio-BMP biosensor's response increased linearly as the H(2)O(2) concentration increased in the range from 1 x 10(-6) to 1.2 x10(-4)M with a detection limit of 5 x 10(-7)M. The SA-BMP was able to detect the amplicons of 1pg DNA template of B. Cereus bacteria, thus providing better detection sensitivity than conventional gel-based electropherograms.

Electrochemical analyses of redox-active iron minerals: a review of nonmediated and mediated approaches.

PubMed

Sander, Michael; Hofstetter, Thomas B; Gorski, Christopher A

2015-05-19

Redox-active minerals are ubiquitous in the environment and are involved in numerous electron transfer reactions that significantly affect biogeochemical processes and cycles as well as pollutant dynamics. As a consequence, research in different scientific disciplines is devoted to elucidating the redox properties and reactivities of minerals. This review focuses on the characterization of mineral redox properties using electrochemical approaches from an applied (bio)geochemical and environmental analytical chemistry perspective. Establishing redox equilibria between the minerals and working electrodes is a major challenge in electrochemical measurements, which we discuss in an overview of traditional electrochemical techniques. These issues can be overcome with mediated electrochemical analyses in which dissolved redox mediators are used to increase the rate of electron transfer and to facilitate redox equilibration between working electrodes and minerals in both amperometric and potentiometric measurements. Using experimental data on an iron-bearing clay mineral, we illustrate how mediated electrochemical analyses can be employed to derive important thermodynamic and kinetic data on electron transfer to and from structural iron. We summarize anticipated methodological advancements that will further contribute to advance an improved understanding of electron transfer to and from minerals in environmentally relevant redox processes.

Removal of antibiotic cloxacillin by means of electrochemical oxidation, TiO2 photocatalysis, and photo-Fenton processes: analysis of degradation pathways and effect of the water matrix on the elimination of antimicrobial activity.

PubMed

Serna-Galvis, Efraim A; Giraldo-Aguirre, Ana L; Silva-Agredo, Javier; Flórez-Acosta, Oscar A; Torres-Palma, Ricardo A

2017-03-01

This study evaluates the treatment of the antibiotic cloxacillin (CLX) in water by means of electrochemical oxidation, TiO 2 photocatalysis, and the photo-Fenton system. The three treatments completely removed cloxacillin and eliminated the residual antimicrobial activity from synthetic pharmaceutical wastewater containing the antibiotic, commercial excipients, and inorganic ions. However, significant differences in the degradation routes were found. In the photo-Fenton process, the hydroxyl radical was involved in the antibiotic removal, while in the TiO 2 photocatalysis process, the action of both the holes and the adsorbed hydroxyl radicals degraded the pollutant. In the electrochemical treatment (using a Ti/IrO 2 anode in sodium chloride as supporting electrolyte), oxidation via HClO played the main role in the removal of CLX. The analysis of initial by-products showed five different mechanistic pathways: oxidation of the thioether group, opening of the central β-lactam ring, breakdown of the secondary amide, hydroxylation of the aromatic ring, and decarboxylation. All the oxidation processes exhibited the three first pathways. Moreover, the aromatic ring hydroxylation was found in both photochemical treatments, while the decarboxylation of the pollutant was only observed in the TiO 2 photocatalysis process. As a consequence of the degradation routes and mechanistic pathways, the elimination of organic carbon was different. After 480 and 240 min, the TiO 2 photocatalysis and photo-Fenton processes achieved ∼45 and ∼15 % of mineralization, respectively. During the electrochemical treatment, 100 % of the organic carbon remained even after the antibiotic was treated four times the time needed to degrade it. In contrast, in all processes, a natural matrix (mineral water) did not considerably inhibit pollutant elimination. However, the presence of glucose in the water significantly affected the degradation of CLX by means of TiO 2 photocatalysis.

Opto-electrochemical spectroscopy of metals in aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Habib, K., E-mail: khaledhabib@usa.net

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

Synthesis and electrochemical properties of Ti-doped DLC films by a hybrid PVD/PECVD process

NASA Astrophysics Data System (ADS)

Jo, Yeong Ju; Zhang, Teng Fei; Son, Myoung Jun; Kim, Kwang Ho

2018-03-01

Low electrical conductivity and poor adhesion to metallic substrates are the main drawbacks of diamond-like carbon (DLC) films when used in electrode applications. In this study, Ti-doped DLC films with various Ti contents were synthesized on metal Ti substrates by a hybrid PVD/PECVD process, where PECVD was used for deposition of DLC films and PVD was used for Ti doping. The effects of the Ti doping ratio on the microstructure, adhesion strength, and electrical and electrochemical properties of the DLC films were systematically investigated. An increase in the Ti content led to increased surface roughness and a higher sp2/sp3 ratio of the Ti-DLC films. Ti atoms existed as amorphous-phase Ti carbide when the Ti doping ratio was less than 2.8 at.%, while the nanocrystalline TiC phase was formed in DLC films when the Ti doping ratio was exceeded 4.0 at.%. The adhesion strength, electrical resistivity, electrochemical activity and reversibility of the DLC films were greatly improved by Ti doping. The influence of Ti doping ratio on the electrical and electrochemical properties of the DLC films were also investigated and the best performance was obtained at a Ti content of 2.8 at.%.

Electroplating of polyaniline on carbon fiber cloth in a simple two electrode system: Application for the electrochemical filter in wastewater treatment

NASA Astrophysics Data System (ADS)

Tran, Thien Khanh; Tran, Hoai Nam; Nguyen, Thuy Linh; Leu, Hoang Jyn

2018-04-01

Nowadays, the pollution of water environment has become a significant problem that really requires a long term solution to deal with. In this study, we provide a simple method to create a capable electrode for electrochemical treatment of wastewater or even can be used as a filter by a physical method. Carbon fiber clothes 300×700 mm were chosen to carry on experiments of Polyaniline (PANI) electrodeposition. Generally, PANI was used to be deposited by three electrodes electrochemical system, however, our samples we obtained here are created by a simple two-electrode electrochemical system. Nevertheless, the product fiber cloth is controlled with a thickness of 0.19 mm and the mass density of 0.44g/cm3, the whole process was carried out under simple lab scale condition at Ton Duc Thang University. To clarify the properties of our products, there was some measurement applied, such as SEM for surface monographic investigation, thermal conductivity by DSC, electrical conductivity by CV and material properties by XRD and EDS measurement. In that manner, we believe that there is still more room for this method to improve in the near future and a bright chance to apply to industrial processes.

Electrochemical Behavior of Sn-9Zn-xTi Lead-Free Solders in Neutral 0.5M NaCl Solution

NASA Astrophysics Data System (ADS)

Wang, Zhenghong; Chen, Chuantong; Jiu, Jinting; Nagao, Shijo; Nogi, Masaya; Koga, Hirotaka; Zhang, Hao; Zhang, Gong; Suganuma, Katsuaki

2018-03-01

Electrochemical techniques were employed to study the electrochemical corrosion behavior of Sn-9Zn-xTi (x = 0, 0.05, 0.1, 0.2 wt.%) lead-free solders in neutral 0.5M NaCl solution, aiming to figure out the effect of Ti content on the corrosion properties of Sn-9Zn, providing information for the composition design of Sn-Zn-based lead-free solders from the perspective of corrosion. EIS results reveal that Ti addition was involved in the corrosion product layer and changed electrochemical interface behavior from charge transfer control process to diffusion control process. The trace amount of Ti addition (0.05 wt.%) can refine the microstructure and improve the corrosion resistance of Sn-9Zn solder, evidenced by much lower corrosion current density (i corr) and much higher total resistance (R t). Excess Ti addition (over 0.1 wt.%) led to the formation of Ti-containing IMCs, which were confirmed as Sn3Ti2 and Sn5Ti6, deteriorating the corrosion resistance of Sn-9Zn-xTi solders. The main corrosion products were confirmed as Sn3O(OH)2Cl2 mixed with small amount of chlorine/oxide Sn compounds.

New Secondary Batteries Utilizing Electronically Conductive Polypyrrole Cathode. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Yeu, Taewhan

1991-01-01

To gain a better understanding of the dynamic behavior in electronically conducting polypyrroles and to provide guidance toward designs of new secondary batteries based on these polymers, two mathematical models are developed; one for the potentiostatically controlled switching behavior of polypyrrole film, and one for the galvanostatically controlled charge/discharge behavior of lithium/polypyrrole secondary battery cell. The first model is used to predict the profiles of electrolyte concentrations, charge states, and electrochemical potentials within the thin polypyrrole film during switching process as functions of applied potential and position. Thus, the detailed mechanisms of charge transport and electrochemical reaction can be understood. Sensitivity analysis is performed for independent parameters, describing the physical and electrochemical characteristic of polypyrrole film, to verify their influences on the model performance. The values of independent parameters are estimated by comparing model predictions with experimental data obtained from identical conditions. The second model is used to predict the profiles of electrolyte concentrations, charge state, and electrochemical potentials within the battery system during charge and discharge processes as functions of time and position. Energy and power densities are estimated from model predictions and compared with existing battery systems. The independent design criteria on the charge and discharge performance of the cell are provided by studying the effects of design parameters.

Electrochemical Behavior of Sn-9Zn- xTi Lead-Free Solders in Neutral 0.5M NaCl Solution

NASA Astrophysics Data System (ADS)

Wang, Zhenghong; Chen, Chuantong; Jiu, Jinting; Nagao, Shijo; Nogi, Masaya; Koga, Hirotaka; Zhang, Hao; Zhang, Gong; Suganuma, Katsuaki

2018-05-01

Electrochemical techniques were employed to study the electrochemical corrosion behavior of Sn-9Zn- xTi ( x = 0, 0.05, 0.1, 0.2 wt.%) lead-free solders in neutral 0.5M NaCl solution, aiming to figure out the effect of Ti content on the corrosion properties of Sn-9Zn, providing information for the composition design of Sn-Zn-based lead-free solders from the perspective of corrosion. EIS results reveal that Ti addition was involved in the corrosion product layer and changed electrochemical interface behavior from charge transfer control process to diffusion control process. The trace amount of Ti addition (0.05 wt.%) can refine the microstructure and improve the corrosion resistance of Sn-9Zn solder, evidenced by much lower corrosion current density ( i corr) and much higher total resistance ( R t). Excess Ti addition (over 0.1 wt.%) led to the formation of Ti-containing IMCs, which were confirmed as Sn3Ti2 and Sn5Ti6, deteriorating the corrosion resistance of Sn-9Zn- xTi solders. The main corrosion products were confirmed as Sn3O(OH)2Cl2 mixed with small amount of chlorine/oxide Sn compounds.

In situ electrochemical and photo-electrochemical generation of the fenton reagent: a potentially important new water treatment technology.

PubMed

Peralta-Hernández, J M; Meas-Vong, Yunny; Rodríguez, Francisco J; Chapman, Thomas W; Maldonado, Manuel I; Godínez, Luis A

2006-05-01

In this work, the design and construction of an annular tube reactor for the electrochemical and photo-electrochemical in situ generation of H2O2 are described. By cathodic reduction of dissolved oxygen and the coupled oxidation of water at a UV-illuminated nanocrystalline-TiO2 semiconductor anode, it was found that the electrochemically generated H2O2 can be employed to readily oxidize the model compound Direct Yellow-52 in dilute acidic solution at high rates in the presence of small quantities of dissolved iron(II). Although, the model organic compound is chemically stable under UV radiation, its electrochemical oxidation rate increases substantially when the semiconductor anode is illuminated as compared to the same processes carried out in the dark.

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.

Electrochemical removal of tannins from aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buso, A.; Balbo, L.; Giomo, M.

2000-02-01

The application of electrochemical methods to remove tannins from wastewater was investigated. Gallotannic acid was used as the reference substance. Electrochemical experiments were performed using platinum electrodes. Macroscale potentiostatic or galvanostatic electrolyses were carried out with sodium sulfate or sodium chloride as supporting electrolytes, to analyze direct and indirect oxidation processes. Operating variables such as pH and chloride concentration were considered to determine their influence on the efficiency and energy consumption of the process. The simulation of a pilot plant was carried out with a mathematical model, the parameters of which were determined by fitting of experimental profiles. The resultsmore » of a preliminary investigation on the oxidation-coagulation process using sacrificial electrodes are also reported.« less

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators.

PubMed

Badalyan, Artavazd; Stahl, Shannon S

2016-07-21

The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1–2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2′-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2′-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators

NASA Astrophysics Data System (ADS)

Badalyan, Artavazd; Stahl, Shannon S.

2016-07-01

The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1-2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2‧-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2‧-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

Low-Cost alpha Alane for Hydrogen Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fabian, Tibor; Petrie, Mark; Crouch-Baker, Steven

This project was directed towards the further development of the Savannah River National Laboratory (SRNL) lab-scale electrochemical synthesis of the hydrogen storage material alpha-alane and Ardica Technologies-SRI International (SRI) chemical downstream processes that are necessary to meet DoE cost metrics and transition alpha-alane synthesis to an industrial scale. Ardica has demonstrated the use of alpha-alane in a fuel-cell system for the U.S. Army WFC20 20W soldier power system that has successfully passed initial field trials with individual soldiers. While alpha-alane has been clearly identified as a desirable hydrogen storage material, cost-effective means for its production and regeneration on a scalemore » of use applicable to the industry have yet to be established. We focused on three, principal development areas: 1. The construction of a comprehensive engineering techno-economic model to establish the production costs of alpha-alane by both electrochemical and chemical routes at scale. 2. The identification of critical, cost-saving design elements of the electrochemical cell and the quantification of the product yields of the primary electrochemical process. A moving particle-bed reactor design was constructed and operated. 3. The experimental quantification of the product yields of candidate downstream chemical processes necessary to produce alpha-alane to complete the most cost-effective overall manufacturing process. Our techno-economic model shows that under key assumptions most 2015 and 2020 DOE hydrogen storage system cost targets for low and medium power can be achieved using the electrochemical alane synthesis process. To meet the most aggressive 2020 storage system cost target, $1/g, our model indicates that 420 metric tons per year (MT/y) production of alpha-alane is required. Laboratory-scale experimental work demonstrated that the yields of two of the three critical component steps within the overall “electrochemical process” were sufficiently high to meet this production target. In the case of the yield of the third step, the crystallization of alpha-alane from the primary alane-related product of the electrochemical reaction, further development is required.« less

Electrochemical oxidation for landfill leachate treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

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.

Electrochemistry in hollow-channel paper analytical devices.

PubMed

Renault, Christophe; Anderson, Morgan J; Crooks, Richard M

2014-03-26

In the present article we provide a detailed analysis of fundamental electrochemical processes in a new class of paper-based analytical devices (PADs) having hollow channels (HCs). Voltammetry and amperometry were applied under flow and no flow conditions yielding reproducible electrochemical signals that can be described by classical electrochemical theory as well as finite-element simulations. The results shown here provide new and quantitative insights into the flow within HC-PADs. The interesting new result is that despite their remarkable simplicity these HC-PADs exhibit electrochemical and hydrodynamic behavior similar to that of traditional microelectrochemical devices.

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...

Kinetic and thermodynamic studies of AISI 4130 steel alloy corrosion in ethylene glycol-water mixture in presence of inhibitors

NASA Astrophysics Data System (ADS)

Khomami, M. Niknejad; Danaee, I.; Attar, A. A.; Peykari, M.

2013-05-01

The electrochemical behavior of steel alloy in ethylene glycol-water mixture was investigated by electrochemical methods. The results obtained showed that corrosion rate was decreased with increasing ethylene glycol concentration. The effect of inorganic inhibitors including NO3 -, NO2 -, Cr2O7 2- and CrO4 2- were studied using electrochemical techniques where the highest inhibition efficiency was obtained for CrO4 2-. In the presence of chromate the inhibitor efficiency increased with its concentration. The inhibiting effect of the chromate was explained on the basis of the competitive adsorption between the inorganic anions and the aggressive Cl- ions, and the adsorption isotherm basically obeys the Langmuir adsorption isotherm. Thermodynamic parameters for steel corrosion and inhibitor adsorption were determined and reveal that the adsorption process is spontaneous. Also, a phenomenon of both physical and chemical adsorption is proposed.

Electrocatalytic Transformation of Carbon Dioxide into Low Carbon Compounds on Conducting Polymers Derived from Multimetallic Porphyrins.

PubMed

Dreyse, Paulina; Honores, Jessica; Quezada, Diego; Isaacs, Mauricio

2015-11-01

The electrochemical reduction of carbon dioxide is studied herein by using conducting polymers based on metallotetraruthenated porphyrins (MTRPs). The polymers on glassy carbon electrodes were obtained by electropolymerization processes of the monomeric MTRP. The linear sweep voltammetry technique resulted in polymeric films that showed electrocatalytic activity toward carbon dioxide reduction with an onset potential of -0.70 V. The reduction products obtained were hydrogen, formic acid, formaldehyde, and methanol, with a tendency for a high production of methanol with a maximum value of turnover frequency equal to 15.07 when using a zinc(II) polymeric surface. Studies of the morphology (AFM) and electrochemical impedance spectroscopy results provide an adequate background to explain that the electrochemical reduction is governed by the roughness of the polymer, for which the possible mechanism involves a series of one-electron reduction reactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface phenomenon in Electrochemical Systems

NASA Astrophysics Data System (ADS)

Gupta, Tanya

Interfaces play a critical role in the performance of electrochemical systems. This thesis focusses on interfaces in batteries and covers aspects of interfacial morphologies of metal anodes, including Silicon, Lithium and Zinc. Growth and cycling of electrochemically grown Lithium and Zinc metal structures is investigated. A new morphology of Zinc, called Hyper Dendritic Zinc is introduced. It is cycled against Prussian Blue Analogues and is shown to improve the performance of this couple significantly. Characterization of materials is done using various electron microscopy techniques ranging from Low Energy Electron Microscope (LEEM), to high energy Transmission Electron Microscope (TEM). LEEM is used for capturing subtle surface phenomenon occurring during epitaxial process of electrolyte on anode. The system studied is Silicon (100) during Chemical Vapor Deposition of Ethylene Carbonate. A strain driven relaxation theory is modeled to explain the unusual restructuring of Si substrate. The other extreme, TEM, is often used to study electrochemical processes, without clear understanding of how the high-energy electron beam can influence the sample under investigation. Here, we study the radiolysis in liquid cell TEM and emphasize on the enhancement of radiation dose at interfaces of the liquid due to generation of secondary and backscattered electrons from adjoining materials. It is shown that this effect is localized in a 10 nm region around the interface and can play a dominating role if there is an interface of liquid with heavy metals like Gold and Platinum which are frequently used as electrode materials. This analysis can be used to establish guidelines for experimentalists to follow, for accurate interpretation of their results.

Investigation into Generation of Micro Features by Localised Electrochemical Deposition

NASA Astrophysics Data System (ADS)

Debnath, Subhrajit; Laskar, Hanimur Rahaman; Bhattacharyya, B.

2017-11-01

With the fast advancement of technology, localised electrochemical deposition (LECD) is becoming very advantageous in generating high aspect ratio micro features to meet the steep demand in modern precision industries of the present world. Except many other advantages, this technology is highly uncomplicated and economical for fabricating metal micro-parts with in micron ranges. In the present study, copper micro-columns have been fabricated utilizing LECD process. Different process parameters such as voltage, frequency, duty ratio and electrolyte concentration, which affect the deposition performance have been identified and their effects on deposition performances such as deposition rate, height and diameter of the micro-columns have been experimentally investigated. Taguchi's methodology has been used to study the effects as well as to obtain the optimum values of process parameters so that localised deposition with best performance can be achieved. Moreover, the generated micro-columns were carefully observed under optical and scanning electron microscope from where the surface quality of the deposited micro-columns has been studied qualitatively. Also, an array of copper micro-columns has been fabricated on stainless steel (SS-304) substrate for further exploration of LECD process capability.

Multilayer porous structures of HVPE and MOCVD grown GaN for photonic applications

NASA Astrophysics Data System (ADS)

Braniste, T.; Ciers, Joachim; Monaico, Ed.; Martin, D.; Carlin, J.-F.; Ursaki, V. V.; Sergentu, V. V.; Tiginyanu, I. M.; Grandjean, N.

2017-02-01

In this paper we report on a comparative study of electrochemical processes for the preparation of multilayer porous structures in hydride vapor phase epitaxy (HVPE) and metal organic chemical vapor phase deposition (MOCVD) grown GaN. It was found that in HVPE-grown GaN, multilayer porous structures are obtained due to self-organization processes leading to a fine modulation of doping during the crystal growth. However, these processes are not totally under control. Multilayer porous structures with a controlled design have been produced by optimizing the technological process of electrochemical etching in MOCVD-grown samples, consisting of five pairs of thin layers with alternating-doping profiles. The samples have been characterized by SEM imaging, photoluminescence spectroscopy, and micro-reflectivity measurements, accompanied by transfer matrix analysis and simulations by a method developed for the calculation of optical reflection spectra. We demonstrate the applicability of the produced structures for the design of Bragg reflectors.

Comparison of diffusivity data derived from electrochemical and NMR investigations of the SeCN¯/(SeCN)2/(SeCN)3¯ system in ionic liquids.

PubMed

Solangi, Amber; Bond, Alan M; Burgar, Iko; Hollenkamp, Anthony F; Horne, Michael D; Rüther, Thomas; Zhao, Chuan

2011-06-02

Electrochemical studies in room temperature ionic liquids are often hampered by their relatively high viscosity. However, in some circumstances, fast exchange between participating electroactive species has provided beneficial enhancement of charge transport. The iodide (I¯)/iodine (I(2))/triiodide (I(3)¯) redox system that introduces exchange via the I¯ + I(2) ⇌ I(3)¯ process is a well documented example because it is used as a redox mediator in dye-sensitized solar cells. To provide enhanced understanding of ion movement in RTIL media, a combined electrochemical and NMR study of diffusion in the {SeCN¯-(SeCN)(2)-(SeCN)(3)¯} system has been undertaken in a selection of commonly used RTILs. In this system, each of the Se, C and N nuclei is NMR active. The electrochemical behavior of the pure ionic liquid, [C(4)mim][SeCN], which is synthesized and characterized here for the first time, also has been investigated. Voltammetric studies, which yield readily interpreted diffusion-limited responses under steady-state conditions by means of a Random Assembly of Microdisks (RAM) microelectrode array, have been used to measure electrochemically based diffusion coefficients, while self-diffusion coefficients were measured by pulsed field gradient NMR methods. The diffusivity data, derived from concentration and field gradients respectively, are in good agreement. The NMR data reveal that exchange processes occur between selenocyanate species, but the voltammetric data show the rates of exchange are too slow to enhance charge transfer. Thus, a comparison of the iodide and selenocyanate systems is somewhat paradoxical in that while the latter give RTILs of low viscosity, sluggish exchange kinetics prevent any significant enhancement of charge transfer through direct electron exchange. In contrast, faster exchange between iodide and its oxidation products leads to substantial electron exchange but this effect does not compensate sufficiently for mass transport limitations imposed by the higher viscosity of iodide RTILs.

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.

Electrochemical behavior of Al in a non-aqueous alkyl carbonate solution containing LiBOB salt

NASA Astrophysics Data System (ADS)

Myung, Seung-Taek; Natsui, Hiroshi; Sun, Yang-Kook; Yashiro, Hitoshi

Aluminum was studied as a current collector for rechargeable lithium batteries to understand electrochemical and passivation behavior. Electrochemical polarization tests, in situ scratch polarization tests and time-of-flight secondary ion mass spectroscopy (ToF-SIMS) analysis in lithium bis-oxalato borate (LiBOB)-containing alkyl carbonate solution were conducted. The Al foil did not follow the alloy and de-alloy process with the LiBOB salt in electrolyte at 0 V vs. Li/Li + in the cathodic sweep. During the anodic scan to the noble direction, the absence of an oxidation peak up to 3 V vs. Li/Li + indicated that the air-formed oxide layer of Al was not reduced to metal. Oxide-free Al surfaces made by the in situ scratch test during the electrochemical polarization resulted in abrupt alloy formation with Li at 0 V vs. Li/Li +, but the newly formed surface formed passive films at higher potential with oxygen, namely, Al-O compound, as confirmed by ToF-SIMS.

Favoring the unfavored: Selective electrochemical nitrogen fixation using a reticular chemistry approach

PubMed Central

Lee, Hiang Kwee; Koh, Charlynn Sher Lin; Lee, Yih Hong; Liu, Chong; Phang, In Yee; Han, Xuemei; Tsung, Chia-Kuang; Ling, Xing Yi

2018-01-01

Electrochemical nitrogen-to-ammonia fixation is emerging as a sustainable strategy to tackle the hydrogen- and energy-intensive operations by Haber-Bosch process for ammonia production. However, current electrochemical nitrogen reduction reaction (NRR) progress is impeded by overwhelming competition from the hydrogen evolution reaction (HER) across all traditional NRR catalysts and the requirement for elevated temperature/pressure. We achieve both excellent NRR selectivity (~90%) and a significant boost to Faradic efficiency by 10 percentage points even at ambient operations by coating a superhydrophobic metal-organic framework (MOF) layer over the NRR electrocatalyst. Our reticular chemistry approach exploits MOF’s water-repelling and molecular-concentrating effects to overcome HER-imposed bottlenecks, uncovering the unprecedented electrochemical features of NRR critical for future theoretical studies. By favoring the originally unfavored NRR, we envisage our electrocatalytic design as a starting point for high-performance nitrogen-to-ammonia electroconversion directly from water vapor–abundant air to address increasing global demand of ammonia in (bio)chemical and energy industries. PMID:29536047

Tunneling Mode of Scanning Electrochemical Microscopy: Probing Electrochemical Processes at Single Nanoparticles.

PubMed

Sun, Tong; Wang, Dengchao; Mirkin, Michael V

2018-06-18

Electrochemical experiments at individual nanoparticles (NPs) can provide new insights into their structure-activity relationships. By using small nanoelectrodes as tips in a scanning electrochemical microscope (SECM), we recently imaged individual surface-bound 10-50 nm metal NPs. Herein, we introduce a new mode of SECM operation based on tunneling between the tip and a nanoparticle immobilized on the insulating surface. The obtained current vs. distance curves show the transition from the conventional feedback response to electron tunneling between the tip and the NP at separation distances of less than about 3 nm. In addition to high-resolution imaging of the NP topography, the tunneling mode enables measurement of the heterogeneous kinetics at a single NP without making an ohmic contact with it. The developed method should be useful for studying the effects of nanoparticle size and geometry on electrocatalytic activity in real-world applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Origin of Capacity Fading in Nano-Sized Co3O4 Electrodes: Electrochemical Impedance Spectroscopy Study

NASA Astrophysics Data System (ADS)

Kang, Jin-Gu; Ko, Young-Dae; Park, Jae-Gwan; Kim, Dong-Wan

2008-10-01

Transition metal oxides have been suggested as innovative, high-energy electrode materials for lithium-ion batteries because their electrochemical conversion reactions can transfer two to six electrons. However, nano-sized transition metal oxides, especially Co3O4, exhibit drastic capacity decay during discharge/charge cycling, which hinders their practical use in lithium-ion batteries. Herein, we prepared nano-sized Co3O4 with high crystallinity using a simple citrate-gel method and used electrochemical impedance spectroscopy method to examine the origin for the drastic capacity fading observed in the nano-sized Co3O4 anode system. During cycling, AC impedance responses were collected at the first discharged state and at every subsequent tenth discharged state until the 100th cycle. By examining the separable relaxation time of each electrochemical reaction and the goodness-of-fit results, a direct relation between the charge transfer process and cycling performance was clearly observed.

Establishment of dsDNA/GNs/chit/GCE biosensor and electrochemical study on interaction between 6-mercaptopurine and DNA.

PubMed

Tang, Wenwei; Zhang, Min; Zeng, Xinping

2014-01-01

In this paper, the anti-cancer drug 6-mercaptopurine (6-MP) was taken as the detection object. The biosensor of dsDNA/GNs/chit/GCE was established using the grapheme (GNs) and chitosan (chit) as the compound modified material. The electrochemical behavior of 6-MP on the sensor was discussed, and the damage and its mechanism of 6-MP on DNA were studied. The experimental result showed that, after the modification of GNs-chit, the electrode activation area of GNs/chit/GCE increased remarkably, which was improved from 1.76cm2 to 8.64 cm2, and the responsive oxidation peak current of GNs/chit/GCE to K3[Fe(CN)6] also increased remarkably. At the meantime, it was demonstrated that DNA was effectively fixed on the GNs/chit/GCE electrode;6-MP caused obvious damage to dsDNA, and the damage degree on the adenine was bigger than that on the guanine; the interaction between 6-MP and dsDNA was preliminarily deduced as the intercalation, and its electrochemical oxidation process was an irreversible process controlled by the adsorption.

Monitoring dynamic electrochemical processes with in situ ptychography

NASA Astrophysics Data System (ADS)

Kourousias, George; Bozzini, Benedetto; Jones, Michael W. M.; Van Riessen, Grant A.; Dal Zilio, Simone; Billè, Fulvio; Kiskinova, Maya; Gianoncelli, Alessandra

2018-03-01

The present work reports novel soft X-ray Fresnel CDI ptychography results, demonstrating the potential of this method for dynamic in situ studies. Specifically, in situ ptychography experiments explored the electrochemical fabrication of Co-doped Mn-oxide/polypyrrole nanocomposites for sustainable and cost-effective fuel-cell air-electrodes. Oxygen-reduction catalysts based on Mn-oxides exhibit relatively high activity, but poor durability: doping with Co has been shown to improve both reduction rate and stability. In this study, we examine the chemical state distribution of the catalytically crucial Co dopant to elucidate details of the Co dopant incorporation into the Mn/polymer matrix. The measurements were performed using a custom-made three-electrode thin-layer microcell, developed at the TwinMic beamline of Elettra Synchrotron during a series of experiments that were continued at the SXRI beamline of the Australian Synchrotron. Our time-resolved ptychography-based investigation was carried out in situ after two representative growth steps, controlled by electrochemical bias. In addition to the observation of morphological changes, we retrieved the spectroscopic information, provided by multiple ptychographic energy scans across Co L3-edge, shedding light on the doping mechanism and demonstrating a general approach for the molecular-level investigation complex multimaterial electrodeposition processes.

Synthesis, spectroscopic and electrochemical performance of pasted β-nickel hydroxide electrode in alkaline electrolyte

NASA Astrophysics Data System (ADS)

Shruthi, B.; Bheema Raju, V.; Madhu, B. J.

2015-01-01

β-Nickel hydroxide (β-Ni(OH)2) was successfully synthesized using precipitation method. The structure and property of the β-Ni(OH)2 were characterized by X-ray diffraction (XRD), Fourier Transform infra-red (FT-IR), Raman spectra and thermal gravimetric-differential thermal analysis (TG-DTA). The results of the FTIR spectroscopy and TG-DTA studies indicate that the β-Ni(OH)2 contains water molecules and anions. The microstructural and composition studies have been performed using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) analysis. A pasted-type electrode is prepared using β-Ni(OH)2 powder as the active material on a nickel sheet as a current collector. Cyclic voltammetry (CV) and Electrochemical impedance spectroscopy (EIS) studies were performed to evaluate the electrochemical performance of the β-Ni(OH)2 electrode in 6 M KOH electrolyte. CV curves showed a pair of strong redox peaks as a result of the Faradaic redox reactions of β-Ni(OH)2. The proton diffusion coefficient (D) for the present β-Ni(OH)2 electrode material is found to be 1.44 × 10-12 cm2 s-1. Further, electrochemical impedance studies confirmed that the β-Ni(OH)2 electrode reaction processes are diffusion controlled.

Synthesis, spectroscopic and electrochemical performance of pasted β-nickel hydroxide electrode in alkaline electrolyte.

PubMed

Shruthi, B; Bheema Raju, V; Madhu, B J

2015-01-25

β-Nickel hydroxide (β-Ni(OH)2) was successfully synthesized using precipitation method. The structure and property of the β-Ni(OH)2 were characterized by X-ray diffraction (XRD), Fourier Transform infra-red (FT-IR), Raman spectra and thermal gravimetric-differential thermal analysis (TG-DTA). The results of the FTIR spectroscopy and TG-DTA studies indicate that the β-Ni(OH)2 contains water molecules and anions. The microstructural and composition studies have been performed using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) analysis. A pasted-type electrode is prepared using β-Ni(OH)2 powder as the active material on a nickel sheet as a current collector. Cyclic voltammetry (CV) and Electrochemical impedance spectroscopy (EIS) studies were performed to evaluate the electrochemical performance of the β-Ni(OH)2 electrode in 6M KOH electrolyte. CV curves showed a pair of strong redox peaks as a result of the Faradaic redox reactions of β-Ni(OH)2. The proton diffusion coefficient (D) for the present β-Ni(OH)2 electrode material is found to be 1.44×10(-12) cm(2) s(-1). Further, electrochemical impedance studies confirmed that the β-Ni(OH)2 electrode reaction processes are diffusion controlled. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrochemical Applications in Metal Bioleaching.

PubMed

Tanne, Christoph Kurt; Schippers, Axel

2017-12-10

Biohydrometallurgy comprises the recovery of metals by biologically catalyzed metal dissolution from solids in an aqueous solution. The application of this kind of bioprocessing is described as "biomining," referring to either bioleaching or biooxidation of sulfide metal ores. Acidophilic iron- and sulfur-oxidizing microorganisms are the key to successful biomining. However, minerals such as primary copper sulfides are recalcitrant to dissolution, which is probably due to their semiconductivity or passivation effects, resulting in low reaction rates. Thus, further improvements of the bioleaching process are recommendable. Mineral sulfide dissolution is based on redox reactions and can be accomplished by electrochemical technologies. The impact of electrochemistry on biohydrometallurgy affects processing as well as analytics. Electroanalysis is still the most widely used electrochemical application in mineralogical research. Electrochemical processing can contribute to bioleaching in two ways. The first approach is the coupling of a mineral sulfide to a galvanic partner or electrocatalyst (spontaneous electron transfer). This approach requires only low energy consumption and takes place without technical installations by the addition of higher redox potential minerals (mostly pyrite), carbonic material, or electrocatalytic ions (mostly silver ions). Consequently, the processed mineral (often chalcopyrite) is preferentially dissolved. The second approach is the application of electrolytic bioreactors (controlled electron transfer). The electrochemical regulation of electrolyte properties by such reactors has found most consideration. It implies the regulation of ferrous and ferric ion ratios, which further results in optimized solution redox potential, less passivation effects, and promotion of microbial activity. However, many questions remain open and it is recommended that reactor and electrode designs are improved, with the aim of finding options for simplified biohydrometallurgical processing. This chapter focuses on metal sulfide dissolution via bioleaching and does not include other biohydrometallurgical processes such as microbial metal recovery from solution.

Electrochemical treatment of concentrate from reverse osmosis of sanitary landfill leachate.

PubMed

Labiadh, Lazhar; Fernandes, Annabel; Ciríaco, Lurdes; Pacheco, Maria José; Gadri, Abdellatif; Ammar, Salah; Lopes, Ana

2016-10-01

Conventional sanitary landfill leachate treatment has recently been complemented and, in some cases, completely replaced by reverse osmosis technology. Despite the good quality of treated water, the efficiency of the process is low and a large volume of reverse osmosis concentrate has to be either discharged or further treated. In this study, the use of anodic oxidation combined with electro-Fenton processes to treat the concentrate obtained in the reverse osmosis of sanitary landfill leachate was evaluated. The anodic oxidation pretreatment was performed in a pilot plant using an electrochemical cell with boron-doped diamond electrodes. In the electro-Fenton experiments, a boron-doped diamond anode and carbon-felt cathode were used, and the influence of the initial pH and iron concentration were studied. For the experimental conditions, the electro-Fenton assays performed at an initial pH of 3 had higher organic load removal levels, whereas the best nitrogen removal was attained when the electrochemical process was performed at the natural pH of 8.8. The increase in the iron concentration had an adverse impact on treatment under natural pH conditions, but it enhanced the nitrogen removal in the electro-Fenton assays performed at an initial pH of 3. The combined anodic oxidation and electro-Fenton process is useful for treating the reverse osmosis concentrate because it is effective at removing the organic load and nitrogen-containing species. Additionally, this process potentiates the increase in the biodegradability index of the treated effluent. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Review--Interactions between diatoms and stainless steel: focus on biofouling and biocorrosion.

PubMed

Landoulsi, J; Cooksey, K E; Dupres, V

2011-11-01

There is a considerable body of information regarding bacterially enhanced corrosion, however, this review focuses on diatoms (unicellular algae) whose contribution to biocorrosion is less well studied. The reasons why diatoms have been neglected in studies of biocorrosion in natural waters are discussed and the question whether diatoms should be considered as inert with respect of electrochemical processes is considered. A particular focus is given to the case of stainless steels (SS), which are widely used in variety of applications in natural waters. Basic information on the cell biology of diatoms is included in the review, particularly with respect to their ability to 'sense' and adhere to surfaces. Investigations at the nanoscale are reviewed as these studies provide information about the behavior of cells at interfaces. Recent advances include the use of atomic force microscopy (AFM), although only a few studies have been applied to diatoms. Regarding the electrochemical behavior of SS, the mechanisms by which diatoms influence the potential ennoblement process is discussed. Such studies reveal the association of diatoms, in addition to bacteria, with biocorrosion processes.

Porous TiO2-ZrO2 thin film formed by electrochemical technique to improve the biocompatibility of titanium alloy in physiological environment

NASA Astrophysics Data System (ADS)

Benea, L.; Dănăilă, E.; Ponthiaux, P.

2017-02-01

Porous Ti and Ti alloys have received increasing research interest for bone tissue engineering, especially for dental and orthopaedic implants because they provide cell ingrowths and vascularization, improving of adhesion and osseointegration. The tribocorrosion process is encountered in orthopaedic and dentistry applications, since it is known that the implants are often exposed to simultaneous chemical/electrochemical and mechanical stresses. The purpose of this study was to carry out a systematic investigation of the tribo-electrochemical performance of porous TiO2-ZrO2 thin film formed by anodization of Ti-10Zr alloy surface in an artificial saliva solution and to compare the resulted performance with that of the untreated Ti-10Zr alloy surface in order to be applied for biomedical use. The in situ electrochemical technique used for investigation of tribo-electrochemical degradation was the open circuit potential (OCP) measurement performed before, during and after sliding tests. The results presented herein show that controlled anodic oxidation method can significantly improve the tribocorrosion and friction performances of Ti-10Zr alloy surface intended for biomedical applications.

Electrochemical Behavior Assessment of Micro- and Nano-Grained Commercial Pure Titanium in H2SO4 Solutions

NASA Astrophysics Data System (ADS)

Fattah-alhosseini, Arash; Ansari, Ali Reza; Mazaheri, Yousef; Karimi, Mohsen

2017-02-01

In this study, the electrochemical behavior of commercial pure titanium with both coarse-grained (annealed sample with the average grain size of about 45 µm) and nano-grained microstructure was compared by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and Mott-Schottky analysis. Nano-grained Ti, which typically has a grain size of about 90 nm, is successfully made by six-cycle accumulative roll-bonding process at room temperature. Potentiodynamic polarization plots and impedance measurements revealed that as a result of grain refinement, the passive behavior of the nano-grained sample was improved compared to that of annealed pure Ti in H2SO4 solutions. Mott-Schottky analysis indicated that the passive films behaved as n-type semiconductors in H2SO4 solutions and grain refinement did not change the semiconductor type of passive films. Also, Mott-Schottky analysis showed that the donor densities decreased as the grain size of the samples reduced. Finally, all electrochemical tests showed that the electrochemical behavior of the nano-grained sample was improved compared to that of annealed pure Ti, mainly due to the formation of thicker and less defective oxide film.

Isolation of high quality graphene from Ru by solution phase intercalation

NASA Astrophysics Data System (ADS)

Koren, E.; Sutter, E.; Bliznakov, S.; Ivars-Barcelo, F.; Sutter, P.

2013-09-01

We introduce a method for isolating graphene grown on epitaxial Ru(0001)/α-Al2O3. The strong graphene/Ru(0001) coupling is weakened by electrochemically driven intercalation of hydrogen underpotentially deposited in aqueous KOH solution, which allows the penetration of water molecules at the graphene/Ru(0001) interface. Following these electrochemically driven processes, the graphene can be isolated by electrochemical hydrogen evolution and transferred to arbitrary supports. Raman and transport measurements demonstrate the high quality of the transferred graphene. Our results show that intercalation, typically carried out in vacuum, can be extended to solution environments for graphene processing under ambient conditions.

Highly Stretchable and Transparent Supercapacitor by Ag-Au Core-Shell Nanowire Network with High Electrochemical Stability.

PubMed

Lee, Habeom; Hong, Sukjoon; Lee, Jinhwan; Suh, Young Duk; Kwon, Jinhyeong; Moon, Hyunjin; Kim, Hyeonseok; Yeo, Junyeob; Ko, Seung Hwan

2016-06-22

Stretchable and transparent electronics have steadily attracted huge attention in wearable devices. Although Ag nanowire is the one of the most promising candidates for transparent and stretchable electronics, its electrochemical instability has forbidden its application to the development of electrochemical energy devices such as supercapacitors. Here, we introduce a highly stretchable and transparent supercapacitor based on electrochemically stable Ag-Au core-shell nanowire percolation network electrode. We developed a simple solution process to synthesize the Ag-Au core-shell nanowire with excellent electrical conductivity as well as greatly enhanced chemical and electrochemical stabilities compared to pristine Ag nanowire. The proposed core-shell nanowire-based supercapacitor still possesses fine optical transmittance and outstanding mechanical stability up to 60% strain. The Ag-Au core-shell nanowire can be a strong candidate for future wearable electrochemical energy devices.

Electrochemical behavior of triflusal, aspirin and their metabolites at glassy carbon and boron doped diamond electrodes.

PubMed

Enache, Teodor Adrian; Fatibello-Filho, Orlando; Oliveira-Brett, Ana Maria

2010-08-01

The electrochemical behavior of triflusal (TRF) and aspirin (ASA), before and after hydrolysis in water and in alkaline medium using two different electrode surfaces, glassy carbon and boron doped diamond, was study by differential pulse voltammetry over a wide pH range. The hydrolysis products are 2-(hydroxyl)-4-(trifluoromethyl)-benzoic acid (HTB) for triflusal and salicylic acid (SA) for aspirin, which in vivo represent their main metabolites. The hydrolysis processes were also followed by spectrophotometry. The UV results showed complete hydrolysis after one hour for TRF and after two hours for ASA in alkaline solution. The glassy carbon electrode enables only indirect determination of TRF and ASA through the electrochemical detection of their hydrolysis products HTB and SA, respectively. The oxidation processes of HTB and SA are pH dependent and involve different numbers of electrons and protons. Moreover, the difference between the oxidation peak potential of SA and HTB was equal to 100 mV in the studied pH range from 1 to 8 due to the CF3 of the aromatic ring of HTB molecule. Due to its wider oxidation potential range, the boron doped diamond electrode was used to study the direct oxidation of TRF and ASA, as well as of their respective metabolites HTB and SA.

In Situ Mass Spectrometric Monitoring of the Dynamic Electrochemical Process at the Electrode–Electrolyte Interface: a SIMS Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhaoying; Zhang, Yanyan; Liu, Bingwen

The in situ molecular characterization of reaction intermediates and products at electrode-electrolyte interfaces is central to mechanistic studies of complex electrochemical processes, yet a great challenge. The coupling of electrochemistry (EC) and mass spectrometry (MS) has seen rapid development and found broad applicability in tackling challenges in analytical and bioanalytical chemistry. However, few truly in situ and real-time EC-MS studies have been reported at electrode-electrolyte interfaces. An innovative EC-MS coupling method named in situ liquid secondary ion mass spectrometry (SIMS) was recently developed by combining SIMS with a vacuum compatible microfluidic electrochemical device. Using this novel capability we report themore » first in situ elucidation of the electro-oxidation mechanism of a biologically significant organic compound, ascorbic acid (AA), at the electrode-electrolyte interface. The short-lived radical intermediate was successfully captured, which had not been detected directly before. Moreover, we demonstrated the power of this new technique in real-time monitoring of the formation and dynamic evolution of electrical double layers at the electrode-electrolyte interface. This work suggests further promising applications of in situ liquid SIMS in studying more complex chemical and biological events at the electrode-electrolyte interface.« less

Carbon-neutral energy cycles using alcohols.

PubMed

Fukushima, Takashi; Kitano, Sho; Hata, Shinichi; Yamauchi, Miho

2018-01-01

We demonstrated carbon-neutral (CN) energy circulation using glycolic acid ( GC )/oxalic acid ( OX ) redox couple. Here, we report fundamental studies on both catalyst search for power generation process, i.e. GC oxidation, and elemental steps for fuel generation process, i.e. OX reduction, in CN cycle. The catalytic activity test on various transition metals revealed that Rh, Pd, Ir, and Pt have preferable features as a catalyst for electrochemical oxidation of GC . A carbon-supported Pt catalyst in alkaline conditions exhibited higher activity, durability, and product selectivity for electrooxidation of GC rather than those in acidic media. The kinetic study on OX reduction clearly indicated that OX reduction undergoes successive two-electron reductions to form GC . Furthermore, application of TiO 2 catalysts with large specific area for electrochemical reduction of OX facilitates the selective formation of GC .

Carbon-neutral energy cycles using alcohols

PubMed Central

Fukushima, Takashi; Kitano, Sho; Hata, Shinichi; Yamauchi, Miho

2018-01-01

Abstract We demonstrated carbon-neutral (CN) energy circulation using glycolic acid (GC)/oxalic acid (OX) redox couple. Here, we report fundamental studies on both catalyst search for power generation process, i.e. GC oxidation, and elemental steps for fuel generation process, i.e. OX reduction, in CN cycle. The catalytic activity test on various transition metals revealed that Rh, Pd, Ir, and Pt have preferable features as a catalyst for electrochemical oxidation of GC. A carbon-supported Pt catalyst in alkaline conditions exhibited higher activity, durability, and product selectivity for electrooxidation of GC rather than those in acidic media. The kinetic study on OX reduction clearly indicated that OX reduction undergoes successive two-electron reductions to form GC. Furthermore, application of TiO2 catalysts with large specific area for electrochemical reduction of OX facilitates the selective formation of GC. PMID:29511392

Constructing the magnetic bifunctional graphene/titania nanosheet-based composite photocatalysts for enhanced visible-light photodegradation of MB and electrochemical ORR from polluted water.

PubMed

Zhang, Qian; Zhang, Yihe; Meng, Zilin; Tong, Wangshu; Yu, Xuelian; An, Qi

2017-09-25

Photocatalysis is a promising strategy to address the global environmental and energy challenges. However, the studies on the application of the photocatalytically degraded dye-polluted water and the multi-purpose use of one type of catalyst have remained sparse. In this report, we try to demonstrate a concept of multiple and cyclic application of materials and resources in environmentally relevant catalyst reactions. A magnetic composite catalyst prepared from exfoliated titania nanosheets, graphene, the magnetic iron oxide nanoparticles, and a polyelectrolyte enabled such a cyclic application. The composite catalyst decomposed a methylene blue-polluted water under visible light, and then the catalyst was collected and removed from the treated water using a magnet. The photocatalytically treated water was then used to prepare the electrolyte in electrochemical reductive reactions and presented superior electrochemical performance compared with the dye-polluted water. The composite catalyst was once again used as the cathode catalyst in the electrochemical reaction. Each component in the composite catalyst was indispensable in its catalytic activity, but each component played different roles in the photochemical, magnetic recycling, and electrochemical processes. We expect the report inspire the study on the multi-functional catalyst and cyclic use of the catalytically cleaned water, which should contribute for the environmental and energy remedy from a novel perspective.

Poly(vinyl Alcohol) Borate Gel Polymer Electrolytes Prepared by Electrodeposition and Their Application in Electrochemical Supercapacitors.

PubMed

Jiang, Mengjin; Zhu, Jiadeng; Chen, Chen; Lu, Yao; Ge, Yeqian; Zhang, Xiangwu

2016-02-10

Gel polymer electrolytes (GPEs) have been studied for preparing flexible and compact electrochemical energy storage devices. However, the preparation and use of GPEs are complex, and most GPEs prepared through traditional methods do not have good wettability with the electrodes, which retard them from achieving their performance potential. In this study, these problems are addressed by conceiving and implementing a simple, but effective, method of electrodepositing poly(vinyl alcohol) potassium borate (PVAPB) GPEs directly onto the surfaces of active carbon electrodes for electrochemical supercapacitors. PVAPB GPEs serve as both the electrolyte and the separator in the assembled supercapacitors, and their scale and shape are determined solely by the geometry of the electrodes. PVAPB GPEs have good bonding to the active electrode materials, leading to excellent and stable electrochemical performance of the supercapacitors. The electrochemical performance of PVAPB GPEs and supercapacitors can be manipulated simply by adjusting the concentration of KCl salt used during the electrodeposition process. With a 0.9 M KCl concentration, the as-prepared supercapacitors deliver a specific capacitance of 65.9 F g(-1) at a current density of 0.1 A g(-1) and retain more than 95% capacitance after 2000 charge/discharge cycles at a current density of 1 A g(-1). These supercapacitors also exhibit intelligent high voltage self-protection function due to the electrolysis-induced cross-linking effect of PVAPB GPEs.

Influence of humic substances on electrochemical degradation of trichloroethylene in limestone aquifers

PubMed Central

Rajic, Ljiljana; Fallahpour, Noushin; Nazari, Roya; Alshawabkeh, Akram N.

2015-01-01

In this study we investigate the influence of humic substances (HS) on electrochemical transformation of trichloroethylene (TCE) in groundwater from limestone aquifers. A laboratory flow-through column with an electrochemical reactor that consists of a palladized iron foam cathode followed by a MMO anode was used to induce TCE electro-reduction in groundwater. Up to 82.9% TCE removal was achieved in the absence of HS. Presence of 1, 2, 5, and 10 mgTOC L−1 reduced TCE removal to 70.9%, 61.4%, 51.8% and 19.5%, respectively. The inverse correlation between HS content and TCE removal was linear. Total organic carbon (TOC), dissolved organic carbon (DOC) and absorption properties (A=254 nm, 365 nm and 436 nm) normalized to DOC, were monitored during treatment to understand the behavior and impacts of HS under electrochemical processes. Changes in all parameters occurred mainly after contact with the cathode, which implies that the HS are reacting either directly with electrons from the cathode or with H2 formed at the cathode surface. Since hydrodechlorination is the primary TCE reduction mechanism in this setup, reactions of the HS with the cathode limit transformation of TCE. The presence of limestone gravel reduced the impact of HS on TCE removal. The study concludes that presence of humic substances adversely affects TCE removal from contaminated groundwater by electrochemical reduction using palladized cathodes. PMID:26549889

Solid oxide membrane-assisted controllable electrolytic fabrication of metal carbides in molten salt.

PubMed

Zou, Xingli; Zheng, Kai; Lu, Xionggang; Xu, Qian; Zhou, Zhongfu

2016-08-15

Silicon carbide (SiC), titanium carbide (TiC), zirconium carbide (ZrC), and tantalum carbide (TaC) have been electrochemically produced directly from their corresponding stoichiometric metal oxides/carbon (MOx/C) precursors by electrodeoxidation in molten calcium chloride (CaCl2). An assembled yttria stabilized zirconia solid oxide membrane (SOM)-based anode was employed to control the electrodeoxidation process. The SOM-assisted controllable electrochemical process was carried out in molten CaCl2 at 1000 °C with a potential of 3.5 to 4.0 V. The reaction mechanism of the electrochemical production process and the characteristics of these produced metal carbides (MCs) were systematically investigated. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses clearly identify that SiC, TiC, ZrC, and TaC carbides can be facilely fabricated. SiC carbide can be controlled to form a homogeneous nanowire structure, while the morphologies of TiC, ZrC, and TaC carbides exhibit porous nodular structures with micro/nanoscale particles. The complex chemical/electrochemical reaction processes including the compounding, electrodeoxidation, dissolution-electrodeposition, and in situ carbonization processes in molten CaCl2 are also discussed. The present results preliminarily demonstrate that the molten salt-based SOM-assisted electrodeoxidation process has the potential to be used for the facile and controllable electrodeoxidation of MOx/C precursors to micro/nanostructured MCs, which can potentially be used for various applications.

Electrochemical Upgrading of Bio-Oil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elangovan, S.; Larsen, Dennis; Bay, Insoo

Bio-oil produced by fast pyrolysis of biomass is a potential source of low carbon, renewable hydrocarbon fuel. However, the properties such as low heating value, incomplete volatility, acidity, instability, and incompatibility with standard fuels restrict its use. The undesirable properties of pyrolysis oil result from its chemical composition that mostly consists of different classes of oxygenated organic compounds. Current process of Hydrodeoxygenation to remove oxygen involves high-temperature, high-pressure processing in the presence of hydrogen and catalyst. An alternative process of deoxygenation of bio-oil using solid-state, oxygen conductor based electrochemical cell is under investigation. The electrolysis process removes oxygen from themore » oxygenated organic molecule as well from steam to produce hydrogen in-situ allowing for a distributed, small scale integrated upgrading unit. Mixtures of model compounds and a slip stream of pyrolysis vapor were tested. The results show the potential for integrating a pyrolyzer and an electrochemical device for stabilizing pyrolysis oil.« less

Positive electrodes of nickel-cadmium batteries

NASA Technical Reports Server (NTRS)

Wabner, D. W.; Kandler, L.; Krienke, W.

1985-01-01

Ni hydroxide sintered electrodes which are filled electrochemically are superior to chemically treated electrodes. In the electrochemical process, the hydroxide grows on the Ni grains and possesses a well-defined porous structure. Diffusion and conducting mechanisms are therefore facilitated.

Titanium dioxide@polypyrrole core-shell nanowires for all solid-state flexible supercapacitors

NASA Astrophysics Data System (ADS)

Yu, Minghao; Zeng, Yinxiang; Zhang, Chong; Lu, Xihong; Zeng, Chenghui; Yao, Chenzhong; Yang, Yangyi; Tong, Yexiang

2013-10-01

Herein, we developed a facile two-step process to synthesize TiO2@PPy core-shell nanowires (NWs) on carbon cloth and reported their improved electrochemical performance for flexible supercapacitors (SCs). The fabricated solid-state SC device based on TiO2@PPy core-shell NWs not only has excellent flexibility, but also exhibits remarkable electrochemical performance.Herein, we developed a facile two-step process to synthesize TiO2@PPy core-shell nanowires (NWs) on carbon cloth and reported their improved electrochemical performance for flexible supercapacitors (SCs). The fabricated solid-state SC device based on TiO2@PPy core-shell NWs not only has excellent flexibility, but also exhibits remarkable electrochemical performance. Electronic supplementary information (ESI) available: Experimental details, XRD pattern, FT-IR absorption spectrum and CV curves of TiO2@PPy NWs, and SEM images of the PPy. See DOI: 10.1039/c3nr03578f

Simultaneous removal of NOx and SO2 from flue gas using combined Na2SO3 assisted electrochemical reduction and direct electrochemical reduction.

PubMed

Guo, Qingbin; He, Yi; Sun, Tonghua; Wang, Yalin; Jia, Jinping

2014-07-15

A method combining Na2SO3 assisted electrochemical reduction and direct electrochemical reduction using Fe(II)(EDTA) solution was proposed to simultaneously remove NOx and SO2 from flue gas. Activated carbon was used as catalyst to accelerate the process. This new system features (a) direct conversion of NOx and SO2 to harmless N2 and SO4(2-); (b) fast regeneration of Fe(II)(EDTA); (c) minimum use of chemical reagents; and (d) recovery of the reduction by-product (Na2SO4). Fe(II)(EDTA) solution was continuously recycled and reused during entire process, and no harmful waste was generated. Approximately 99% NOx and 98% SO2 were removed under the optimal condition. The stability test showed that the system operation was reliable. Copyright © 2014 Elsevier B.V. All rights reserved.

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2000-01-01

The present invention is directed to an improved electrochemical energy storage device. The electrochemical energy storage device includes a number of solid-state, thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. In one embodiment, a sheet of conductive material is processed by employing a known milling, stamping, or chemical etching technique to include a connection pattern which provides for flexible and selective interconnecting of individual electrochemical cells within the housing, which may be a hermetically sealed housing. Fuses and various electrical and electro-mechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

Optical Detection of Ketoprofen by Its Electropolymerization on an Indium Tin Oxide-Coated Optical Fiber Probe.

PubMed

Bogdanowicz, Robert; Niedziałkowski, Paweł; Sobaszek, Michał; Burnat, Dariusz; Białobrzeska, Wioleta; Cebula, Zofia; Sezemsky, Petr; Koba, Marcin; Stranak, Vitezslav; Ossowski, Tadeusz; Śmietana, Mateusz

2018-04-27

In this work an application of optical fiber sensors for real-time optical monitoring of electrochemical deposition of ketoprofen during its anodic oxidation is discussed. The sensors were fabricated by reactive magnetron sputtering of indium tin oxide (ITO) on a 2.5 cm-long core of polymer-clad silica fibers. ITO tuned in optical properties and thickness allows for achieving a lossy-mode resonance (LMR) phenomenon and it can be simultaneously applied as an electrode in an electrochemical setup. The ITO-LMR electrode allows for optical monitoring of changes occurring at the electrode during electrochemical processing. The studies have shown that the ITO-LMR sensor’s spectral response strongly depends on electrochemical modification of its surface by ketoprofen. The effect can be applied for real-time detection of ketoprofen. The obtained sensitivities reached over 1400 nm/M (nm·mg −1 ·L) and 16,400 a.u./M (a.u.·mg −1 ·L) for resonance wavelength and transmission shifts, respectively. The proposed method is a valuable alternative for the analysis of ketoprofen within the concentration range of 0.25⁻250 μg mL −1 , and allows for its determination at therapeutic and toxic levels. The proposed novel sensing approach provides a promising strategy for both optical and electrochemical detection of electrochemical modifications of ITO or its surface by various compounds.

Electrochemical oxidation of ampicillin antibiotic at boron-doped diamond electrodes and process optimization using response surface methodology.

PubMed

Körbahti, Bahadır K; Taşyürek, Selin

2015-03-01

Electrochemical oxidation and process optimization of ampicillin antibiotic at boron-doped diamond electrodes (BDD) were investigated in a batch electrochemical reactor. The influence of operating parameters, such as ampicillin concentration, electrolyte concentration, current density, and reaction temperature, on ampicillin removal, COD removal, and energy consumption was analyzed in order to optimize the electrochemical oxidation process under specified cost-driven constraints using response surface methodology. Quadratic models for the responses satisfied the assumptions of the analysis of variance well according to normal probability, studentized residuals, and outlier t residual plots. Residual plots followed a normal distribution, and outlier t values indicated that the approximations of the fitted models to the quadratic response surfaces were very good. Optimum operating conditions were determined at 618 mg/L ampicillin concentration, 3.6 g/L electrolyte concentration, 13.4 mA/cm(2) current density, and 36 °C reaction temperature. Under response surface optimized conditions, ampicillin removal, COD removal, and energy consumption were obtained as 97.1 %, 92.5 %, and 71.7 kWh/kg CODr, respectively.

Electrochemically Controlled Reconstitution of Immobilized Ferritins for Bioelectronic Applications

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; Chu, Sang-Hong; King, Glen C.; Watt, Gerald D.

2007-01-01

Site-specific reconstituted nanoparticles were fabricated via electrochemically-controlled biomineralization through the immobilization of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, and the electrocatalytic reduction of oxygen on the reconstituted Pt-cored ferritins. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of site-specific electrochemical biomineralization with a protein cage loads ferritins with different core materials. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This first demonstration of electrochemically controlled site-specific reconstitution of biomolecules provides a new tool for biomineralization and opens the way to produce the bio-templated nanoparticles by electrochemical control. The nanosized platinum-cored ferritins on gold displayed good catalytic activity for the electrochemical reduction of oxygen, which is applicable to biofuel cell applications. This results in a smaller catalyst loading on the electrodes for fuel cells or other bioelectronic devices.

Influence of the Surface Layer on the Electrochemical Deposition of Metals and Semiconductors into Mesoporous Silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chubenko, E. B., E-mail: eugene.chubenko@gmail.com; Redko, S. V.; Sherstnyov, A. I.

2016-03-15

The influence of the surface layer on the process of the electrochemical deposition of metals and semiconductors into porous silicon is studied. It is shown that the surface layer differs in structure and electrical characteristics from the host porous silicon bulk. It is established that a decrease in the conductivity of silicon crystallites that form the surface layer of porous silicon has a positive effect on the process of the filling of porous silicon with metals and semiconductors. This is demonstrated by the example of nickel and zinc oxide. The effect can be used for the formation of nanocomposite materialsmore » on the basis of porous silicon and nanostructures with a high aspect ratio.« less

Performance of electrochemical oxidation and photocatalysis in terms of kinetics and energy consumption. New insights into the p-cresol degradation.

PubMed

Escudero, Carlos J; Iglesias, Olalla; Dominguez, Sara; Rivero, Maria J; Ortiz, Inmaculada

2017-06-15

This work reports the comparative performance of two Advanced Oxidation Processes (AOPs), electrochemical oxidation and photocatalysis, as individual technological alternatives for the treatment of effluents containing p-cresol. First, the influence of operating parameters in the oxidation and mineralization yield was carried out together with kinetic analysis. Boron Doped Diamond (BDD), RuO 2 and Pt as anodic materials, Na 2 SO 4 and NaCl as supporting electrolytes and different current densities were evaluated in electrochemical oxidation whereas the effect of TiO 2 concentration and radiation was studied in the photocatalytic degradation. Then, the parameter Electrical Energy per Order (E EO ) was calculated to compare the energy consumption in both AOPs, concluding that under the studied conditions the electrochemical treatment with BDD, Na 2 SO 4 and 125 A m -2 showed the best energy efficiency, with an E EO of 5.83 kW h m -3 order -1 for p-cresol and 58.05 kW h m -3 order -1 for DOC removal, respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Self-Limiting Electro-Ablation Technique for the Top-Down Synthesis of Large-Area Monolayer Flakes of 2D Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Saptarshi; Bera, Mrinal K.; Tong, Sheng

2016-06-21

We report the discovery of an electrochemical process that converts two dimensional layered materials of arbitrary thicknesses into monolayers. The lateral dimensions of the monolayers obtained by the process within a few seconds time at room temperature were as large as 0.5 mm. The temporal and spatial dynamics of this physical phenomenon, studied on MoS2 flakes using ex-situ AFM imaging, Raman mapping, and photoluminescence measurements trace the origin of monolayer formation to a substrate-assisted self-limiting electrochemical ablation process. Electronic structure and atomistic calculations point to the interplay between three essential factors in the process: (1) strong covalent interaction of monolayermore » MoS2 with the substrate; (2) electric-field induced differences in Gibbs free energy of exfoliation; (3) dispersion of MoS2 in aqueous solution of hydrogen peroxide. This process was successful in obtaining monolayers of other 2D transition metal dichalcogenides, like WS2 and MoTe2 as well.« less

Inheritance of Crystallographic Orientation during Lithiation/Delithiation Processes of Single-Crystal α-Fe2O3 Nanocubes in Lithium-Ion Batteries.

PubMed

Ma, Xiaowei; Zhang, Manyu; Liang, Chongyun; Li, Yuesheng; Wu, Jingjing; Che, Renchao

2015-11-04

Iron oxides are very promising anode materials based on conversion reactions for lithium-ion batteries (LIBs). During conversion processes, the crystal structure and composition of the electrode material are drastically changed. Surprisingly, in our study, inheritance of a crystallographic orientation was found during lithiation/delithiation processes of single-crystal α-Fe2O3 nanocubes by ex situ transmission electron microscopy. Single-crystal α-Fe2O3 was first transformed into numerous Fe nanograins embedded in a Li2O matrix, and then the conversion between Fe and FeO nanograins became the main reversible electrochemical reaction for energy storage. Interestingly, these Fe/FeO nanograins had almost the same crystallographic orientation, indicating that the lithiated/delithiated products can inherit the crystallographic orientation of single-crystal α-Fe2O3. This finding is important for understanding the detailed electrochemical conversion processes of iron oxides, and this feature may also exist during lithiation/delithiation processes of other transition-metal oxides.

In operando spectroscopic studies of high temperature electrocatalysts used for energy conversion

NASA Astrophysics Data System (ADS)

McIntyre, Melissa Dawn

Solid-state electrochemical cells are efficient energy conversion devices that can be used for clean energy production or for removing air pollutants from exhaust gas emitted by combustion processes. For example, solid oxide fuel cells generate electricity with low emissions from a variety of fuel sources; solid oxide electrolysis cells produce zero-emission H2 fuel; and solid-state DeNOx cells remove NOx gases from diesel exhaust. In order to maintain high conversion efficiencies, these systems typically operate at temperatures ≥ 500°C. The high operating temperatures, however, accelerate chemical and mechanical cell degradation. To improve device durability, a mechanistic understanding of the surface chemistry occurring at the cell electrodes (anode and cathode) is critical in terms of refining cell design, material selection and operation protocols. The studies presented herein utilized in operando Raman spectroscopy coupled with electrochemical measurements to directly correlate molecular/material changes with device performance in solid oxide cells under various operating conditions. Because excessive carbon accumulation with carbon-based fuels destroys anodes, the first three studies investigated strategies for mitigating carbon accumulation on Ni cermet anodes. Results from the first two studies showed that low amounts of solid carbon stabilized the electrical output and improved performance of solid oxide fuel cells operating with syn-gas (H 2/CO fuel mixture). The third study revealed that infiltrating anodes with Sn or BaO suppressed carbon accumulation with CH4 fuel and that H2O was the most effective reforming agent facilitating carbon removal. The last two studies explored how secondary phases formed in traditional solid oxide cell materials doped with metal oxides improve electrochemical performance. Results from the fourth study suggest that the mixed ion-electron conducting Zr5Ti7O24 secondary phase can expand the electrochemically active region and increase electrochemical activity in cermet electrodes. The final study of lanthanum strontium manganite cathodes infiltrated with BaO revealed the reversible decomposition/formation of a Ba3Mn2O8 secondary phase under applied potentials and proposed mechanisms for the enhanced electrocatalytic oxygen reduction associated with this compound under polarizing conditions. Collectively, these studies demonstrate that mechanistic information obtained from molecular/material specific techniques coupled with electrochemical measurements can be used to help optimize materials and operating conditions in solid-state electrochemical cells.

Detailed studies of a high-capacity electrode material for rechargeable batteries, Li2MnO3-LiCo(1/3)Ni(1/3)Mn(1/3)O2.

PubMed

Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek; Nakai, Izumi; Komaba, Shinichi

2011-03-30

Lithium-excess manganese layered oxides, which are commonly described by the chemical formula zLi(2)MnO(3)-(1-z)LiMeO(2) (Me = Co, Ni, Mn, etc.), are of great importance as positive electrode materials for rechargeable lithium batteries. In this Article, Li(x)Co(0.13)Ni(0.13)Mn(0.54)O(2-δ) samples are prepared from Li(1.2)Ni(0.13)Co(0.13)Mn(0.54)O(2) (or 0.5Li(2)MnO(3)-0.5LiCo(1/3)Ni(1/3)Mn(1/3)O(2)) by an electrochemical oxidation/reduction process in an electrochemical cell to study a reaction mechanism in detail before and after charging across a voltage plateau at 4.5 V vs Li/Li(+). Changes of the bulk and surface structures are examined by synchrotron X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (SIMS). SXRD data show that simultaneous oxygen and lithium removal at the voltage plateau upon initial charge causes the structural rearrangement, including a cation migration process from metal to lithium layers, which is also supported by XAS. This is consistent with the mechanism proposed in the literature related to the Li-excess manganese layered oxides. Oxygen removal associated with the initial charge on the high voltage plateau causes oxygen molecule generation in the electrochemical cells. The oxygen molecules in the cell are electrochemically reduced in the subsequent discharge below 3.0 V, leading to the extra capacity. Surface analysis confirms the formation of the oxygen containing species, such as lithium carbonate, which accumulates on the electrode surface. The oxygen containing species are electrochemically decomposed upon second charge above 4.0 V. The results suggest that, in addition to the conventional transition metal redox reactions, at least some of the reversible capacity for the Li-excess manganese layered oxides originates from the electrochemical redox reaction of the oxygen molecules at the electrode surface.

Influence of oxalic acid on the dissolution kinetics of manganese oxide

NASA Astrophysics Data System (ADS)

Godunov, E. B.; Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.

2012-11-01

The kinetics and electrochemical processes of the dissolution of manganese oxides with various oxidation states in sulfuric acid solutions containing oxalate ion additives is studied under variable conditions (concentration, pH, temperature). The parameters favoring a higher degree of the dissolution of manganese oxides in acidic media are determined. The optimal conditions are found for the dissolution of manganese oxides in acidic media in the presence of oxalate ions. The mechanism proposed for the dissolution of manganese oxides in sulfuric acid solutions containing oxalic acid is based on the results of kinetic and electrochemical studies. The steps of the dissolution mechanism are discussed.

Process for removal of hydrogen halides or halogens from incinerator gas

DOEpatents

Huang, Hann S.; Sather, Norman F.

1988-01-01

A process for reducing the amount of halogens and halogen acids in high temperature combustion gases and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

Process for removal of hydrogen halides or halogens from incinerator gas

DOEpatents

Huang, H.S.; Sather, N.F.

1987-08-21

A process for reducing the amount of halogens and halogen acids in high temperature combustion gas and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

Economic evaluation of an electrochemical process for the recovery of metals from electronic waste.

PubMed

Diaz, Luis A; Lister, Tedd E

2018-04-01

As the market of electronic devices continues to evolve, the waste stream generated from antiquated technology is increasingly view as an alternative to substitute primary sources of critical a value metals. Nevertheless, the sustainable recovery of materials can only be achieved by environmentally friendly processes that are economically competitive with the extraction from mineral ores. Hence, This paper presents the techno-economic assessment for a comprehensive process for the recovery of metals and critical materials from e-waste, which is based in an electrochemical recovery (ER) technology. Economic comparison is performed with the treatment of e-waste via smelting, which is currently the primary route for recycling metals from electronics. Results indicate that the electrochemical recovery process is a competitive alternative for the recovery of value from electronic waste when compared with the traditional black Cu smelting process. A significantly lower capital investment, 2.9 kg e-waste per dollar of capital investment, can be achieved with the ER process vs. 1.3 kg per dollar in the black Cu smelting process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sensing Properties of Multiwalled Carbon Nanotubes Grown in MW Plasma Torch: Electronic and Electrochemical Behavior, Gas Sensing, Field Emission, IR Absorption

PubMed Central

Majzlíková, Petra; Sedláček, Jiří; Prášek, Jan; Pekárek, Jan; Svatoš, Vojtěch; Bannov, Alexander G.; Jašek, Ondřej; Synek, Petr; Eliáš, Marek; Zajíčková, Lenka; Hubálek, Jaromír

2015-01-01

Vertically aligned multi-walled carbon nanotubes (VA-MWCNTs) with an average diameter below 80 nm and a thickness of the uniform VA-MWCNT layer of about 16 μm were grown in microwave plasma torch and tested for selected functional properties. IR absorption important for a construction of bolometers was studied by Fourier transform infrared spectroscopy. Basic electrochemical characterization was performed by cyclic voltammetry. Comparing the obtained results with the standard or MWCNT‐modified screen-printed electrodes, the prepared VA-MWCNT electrodes indicated their high potential for the construction of electrochemical sensors. Resistive CNT gas sensor revealed a good sensitivity to ammonia taking into account room temperature operation. Field emission detected from CNTs was suitable for the pressure sensing application based on the measurement of emission current in the diode structure with bending diaphragm. The advantages of microwave plasma torch growth of CNTs, i.e., fast processing and versatility of the process, can be therefore fully exploited for the integration of surface-bound grown CNTs into various sensing structures. PMID:25629702

A novel fullerene lipoic acid derivative: Synthesis and preparation of self-assembled monolayers on gold

NASA Astrophysics Data System (ADS)

Viana, A. S.; Leupold, S.; Eberle, C.; Shokati, T.; Montforts, F.-P.; Abrantes, L. M.

2007-11-01

Synthesis and preparation of self-assembled monolayers of a novel fullerene lipoic acid derivative on gold are reported. The presence of densely packed SAMs was confirmed by ellipsometry and cyclic voltammetry. The electrochemical response of the modified electrode in organic media exhibits the first two redox peaks characteristic of the extended π-electron system of fullerene. C 60 surface coverage (1.4 × 10 -10 mol cm -2) has been electrochemically determined by the redox process of the adsorbed fullerene moiety and by reductive desorption of the SAM in strong alkaline solution. Electrochemical data indicate that all four sulphur atoms are involved in the self-assembly process, providing an increase of SAM stability in comparison to mono or di-thiolated appended molecules. Visualisation of discrete fullerene molecules by scanning tunnelling microscopy supplied further evidence for gold modification and molecular distribution on the surface. Mixed monolayers of hexanethiol and fullerene derivatives in a proportion of 1:2 have been also studied with the purpose of controlling the amount and distribution of fullerene units on the gold surface.

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.

Titanium Carbide Bipolar Plate for Electrochemical Devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

LaConti, Anthony B.; Griffith, Arthur E.; Cropley, Cecelia C.

Titanium carbide comprises a corrosion resistant, electrically conductive, non-porous bipolar plate for use in an electrochemical device. The process involves blending titanium carbide powder with a suitable binder material, and molding the mixture, at an elevated temperature and pressure.

Inhibitory effect of glutamic acid on the scale formation process using electrochemical methods.

PubMed

Karar, A; Naamoune, F; Kahoul, A; Belattar, N

2016-08-01

The formation of calcium carbonate CaCO3 in water has some important implications in geoscience researches, ocean chemistry studies, CO2 emission issues and biology. In industry, the scaling phenomenon may cause technical problems, such as reduction in heat transfer efficiency in cooling systems and obstruction of pipes. This paper focuses on the study of the glutamic acid (GA) for reducing CaCO3 scale formation on metallic surfaces in the water of Bir Aissa region. The anti-scaling properties of glutamic acid (GA), used as a complexing agent of Ca(2+) ions, have been evaluated by the chronoamperometry and electrochemical impedance spectroscopy methods in conjunction with a microscopic examination. Chemical and electrochemical study of this water shows a high calcium concentration. The characterization using X-ray diffraction reveals that while the CaCO3 scale formed chemically is a mixture of calcite, aragonite and vaterite, the one deposited electrochemically is a pure calcite. The effect of temperature on the efficiency of the inhibitor was investigated. At 30 and 40°C, a complete scaling inhibition was obtained at a GA concentration of 18 mg/L with 90.2% efficiency rate. However, the efficiency of GA decreased at 50 and 60°C.

Correlation of surface site formation to nanoisland growth in the electrochemical roughening of Pt(111)

NASA Astrophysics Data System (ADS)

Jacobse, Leon; Huang, Yi-Fan; Koper, Marc T. M.; Rost, Marcel J.

2018-03-01

Platinum plays a central role in a variety of electrochemical devices and its practical use depends on the prevention of electrode degradation. However, understanding the underlying atomic processes under conditions of repeated oxidation and reduction inducing irreversible surface structure changes has proved challenging. Here, we examine the correlation between the evolution of the electrochemical signal of Pt(111) and its surface roughening by simultaneously performing cyclic voltammetry and in situ electrochemical scanning tunnelling microscopy (EC-STM). We identify a `nucleation and early growth' regime of nanoisland formation, and a `late growth' regime after island coalescence, which continues up to at least 170 cycles. The correlation analysis shows that each step site that is created in the `late growth' regime contributes equally strongly to both the electrochemical and the roughness evolution. In contrast, in the `nucleation and early growth' regime, created step sites contribute to the roughness, but not to the electrochemical signal.

Electric terminal performance and characterization of solid oxide fuel cells and systems

NASA Astrophysics Data System (ADS)

Lindahl, Peter Allan

Solid Oxide Fuel Cells (SOFCs) are electrochemical devices which can effect efficient, clean, and quiet conversion of chemical to electrical energy. In contrast to conventional electricity generation systems which feature multiple discrete energy conversion processes, SOFCs are direct energy conversion devices. That is, they feature a fully integrated chemical to electrical energy conversion process where the electric load demanded of the cell intrinsically drives the electrochemical reactions and associated processes internal to the cell. As a result, the cell's electric terminals provide a path for interaction between load side electric demand and the conversion side processes. The implication of this is twofold. First, the magnitude and dynamic characteristics of the electric load demanded of the cell can directly impact the long-term efficacy of the cell's chemical to electrical energy conversion. Second, the electric terminal response to dynamic loads can be exploited for monitoring the cell's conversion side processes and used in diagnostic analysis and degradation-mitigating control schemes. This dissertation presents a multi-tier investigation into this electric terminal based performance characterization of SOFCs through the development of novel test systems, analysis techniques and control schemes. First, a reference-based simulation system is introduced. This system scales up the electric terminal performance of a prototype SOFC system, e.g. a single fuel cell, to that of a full power-level stack. This allows realistic stack/load interaction studies while maintaining explicit ability for post-test analysis of the prototype system. Next, a time-domain least squares fitting method for electrochemical impedance spectroscopy (EIS) is developed for reduced-time monitoring of the electrochemical and physicochemical mechanics of the fuel cell through its electric terminals. The utility of the reference-based simulator and the EIS technique are demonstrated through their combined use in the performance testing of a hybrid-source power management (HSPM) system designed to allow in-situ EIS monitoring of a stack under dynamic loading conditions. The results from the latter study suggest that an HSPM controller allows an opportunity for in-situ electric terminal monitoring and control-based mitigation of SOFC degradation. As such, an exploration of control-based SOFC degradation mitigation is presented and ideas for further work are suggested.

In vivo monitor oxidative burst induced by Cd2+ stress for the oilseed rape (Brassica napus L.) based on electrochemical microbiosensor.

PubMed

Xu, Qiao; Wei, Fang; Wang, Zhan; Yang, Qin; Zhao, Yuan-Di; Chen, Hong

2010-01-01

Since the mechanism of Cd(2+) stress for plants is not clear, an in vivo method to monitor Cd(2+) stress for plants is necessary. However, oxidative burst (OB) is a signal messenger in the process of Cd(2+) stress for plants. To establish an electrochemical method with poly-o-phenylenediamine and Pt microparticle modified Pt electrode (POPD-Pt-MP-Pt) as a microbiosensor for the in vivo detection of oxidative burst induced by Cd(2+) stress in oilseed rape (Brassica napus L.). The optimal fabrication of POPD-Pt-MP-Pt biosensor was achieved. Electrochemical signal was collected by amperometry. After oilseed rape was exposed to 84.9 mM CdCl(2) stress, three oxidative bursts were observed in oilseed rape by amperometry at 3.3 h, 8.4 h and 13.2 h, respectively. However, there was no obvious signal observed in the controlled assay. This contribution presents the in vivo monitoring of the OB process induced by Cd(2+) stress in oilseed rape by POPD-Pt-MP-Pt microbiosensor in real-time. The novel electrochemical microbiosensor not only facilitates the real-time study in plant self-defence response to the adverse environment such as Cd(2+) stress, but also provides an effective tool for probing the self-defence mechanism in plants.

Insights on Microbial Activity from Reduction Potential: Electrochemical Noise Analysis of a Pristine Aquifer

NASA Astrophysics Data System (ADS)

Enright, A. M.; Shirokova, V.; Ferris, G.

2012-12-01

Reduction potential was measured in a shallow, till-hosted, pristine aquifer. A previous study* characterized the microbial community of the aquifer, and geochemical analysis of water from the aquifer from 2010, 2011, and 2012 indicates persistent localized geochemical gradients of ferrous, ferric, sulphate, and sulphide ions. The chemical plume changes oxidation state from a reduced centre to oxidized outer boundaries, and microbial activity is responsible for the shift in redox state. Analysis of reduction potential as electrochemical noise in both the frequency and time domains provides insight into the manipulation of dissolved ions by the microbial community. Analysis of electrochemical noise is sensitive enough to distinguish the rates and magnitude of influence of the mechanisms which contribute to the redox state of a system. Self-similarity has been suggested to arise in any system where electrochemical noise is the result of a multitude of contributory processes, and this type of noise signature has been reported for many biological and abiotic natural processes. This observed ubiquity is not well understood. Reduction potential data is analyzed using detrended fluctuation analysis in the frequency domain and detrended moving average analysis in the time domain to characterize the Hurst exponent and fractal dimension of this physiological time series. *V.L. Shirokova and F.G. Ferris. (2012). Microbial Diversity and Biogeochemistry of a Pristine Canadian Shield Groundwater System. Geomicrobiology Journal.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dang-Long, T., E-mail: 3TE14098G@kyushu-u.ac.jp; Quang-Tuyen, T., E-mail: tran.tuyen.quang.314@m.kyushu-u.ac.jp; Shiratori, Y., E-mail: shiratori.yusuke.500@m.kyushu-u.ac.jp

2016-06-03

Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH{sub 4} and CO{sub 2} 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 candidatemore » for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO{sub 2} reforming of CH{sub 4} and electrochemical oxidation of the produced syngas (H{sub 2}–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 CH{sub 4}–CO{sub 2} mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO{sub 2} had strong influences on both reaction processes. The increase in CO{sub 2} 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 CH{sub 4}−CO{sub 2} mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.« less

Study on the Electrochemical Reaction Mechanism of ZnFe2O4 by In Situ Transmission Electron Microscopy

PubMed Central

Su, Qingmei; Wang, Shixin; Yao, Libing; Li, Haojie; Du, Gaohui; Ye, Huiqun; Fang, Yunzhang

2016-01-01

A family of mixed transition–metal oxides (MTMOs) has great potential for applications as anodes for lithium ion batteries (LIBs). However, the reaction mechanism of MTMOs anodes during lithiation/delithiation is remain unclear. Here, the lithiation/delithiation processes of ZnFe2O4 nanoparticles are observed dynamically using in situ transmission electron microscopy (TEM). Our results suggest that during the first lithiation process the ZnFe2O4 nanoparticles undergo a conversion process and generate a composite structure of 1–3 nm Fe and Zn nanograins within Li2O matrix. During the delithiation process, volume contraction and the conversion of Zn and Fe take place with the disappearance of Li2O, followed by the complete conversion to Fe2O3 and ZnO not the original phase ZnFe2O4. The following cycles are dominated by the full reversible phase conversion between Zn, Fe and ZnO, Fe2O3. The Fe valence evolution during cycles evidenced by electron energy–loss spectroscopy (EELS) techniques also exhibit the reversible conversion between Fe and Fe2O3 after the first lithiation, agreeing well with the in situ TEM results. Such in situ TEM observations provide valuable phenomenological insights into electrochemical reaction of MTMOs, which may help to optimize the composition of anode materials for further improved electrochemical performance. PMID:27306189

Investigation of the electrochemically active surface area and lithium diffusion in graphite anodes by a novel OsO4 staining method

NASA Astrophysics Data System (ADS)

Pfaffmann, Lukas; Birkenmaier, Claudia; Müller, Marcus; Bauer, Werner; Mitsch, Tim; Feinauer, Julian; Krämer, Yvonne; Scheiba, Frieder; Hintennach, Andreas; Schleid, Thomas; Schmidt, Volker; Ehrenberg, Helmut

2016-03-01

Negative electrodes of lithium-ion batteries generally consist of graphite-based active materials. In order to realize batteries with a high current density and therefore accelerated charging processes, the intercalation of lithium and the diffusion processes of these carbonaceous materials must be understood. In this paper, we visualized the electrochemical active surface area for three different anode materials using a novel OsO4 staining method in combination with scanning electron microscopy techniques. The diffusion behavior of these three anode materials is investigated by potentiostatic intermittent titration technique measurements. From those we determine the diffusion coefficient with and without consideration of the electrochemical active surface area.

Principles and Applications of Solid Polymer Electrolyte Reactors for Electrochemical Hydrodehalogenation of Organic Pollutants

NASA Astrophysics Data System (ADS)

Cheng, Hua; Scott, Keith

The ability to re-cycle halogenated liquid wastes, based on electrochemical hydrodehalogenation (EHDH), will provide a significant economic advantage and will reduce the environmental burden in a number of processes. The use of a solid polymer electrolyte (SPE) reactor is very attractive for this purpose. Principles and features of electrochemical HDH technology and SPE EHDH reactors are described. The SPE reactor enables selective dehalogenation of halogenated organic compounds in both aqueous and non-aqueous media with high current efficiency and low energy consumption. The influence of operating conditions, including cathode material, current density, reactant concentration and temperature on the HDH process and its stability are examined.

Electrochemical sensing platform based on the highly ordered mesoporous carbon-fullerene system.

PubMed

Zhou, Ming; Guo, Jidong; Guo, Li-ping; Bai, Jing

2008-06-15

In this paper, we report a novel all-carbon two-dimensionally ordered nanocomposite electrode system on the basis of the consideration of host-guest chemistry, which utilizes synergistic interactions between a nanostructured matrix of ordered mesoporous carbon (OMC) and an excellent electron acceptor of nanosized fullerene (C 60) to facilitate heterogeneous electron-transfer processes. The integration of OMC-C 60 by covalent interaction, especially its electrochemical applications for electrocatalysis, has not been explored thus far. Such integration may even appear to be counterintuitive because OMC and C 60 provide opposite electrochemical benefits in terms of facilitating heterogeneous electron-transfer processes. Nevertheless, the present work demonstrates the integration of OMC and C 60 can provide a remarkable synergistic augmentation of the current. To illuminate the concept, eight kinds of inorganic and organic electroactive compounds were employed to study the electrochemical response at an OMC-C 60 modified glassy carbon (OMC-C 60/GC) electrode for the first time, which shows more favorable electron-transfer kinetics than OMC/GC, carbon nanotube modified GC, C 60/GC, and GC electrodes. Such electrocatalytic behavior at OMC-C 60/GC electrode could be attributed to the unique physicochemical properties of OMC and C 60, especially the unusual host-guest synergy of OMC-C 60, which induced a substantial decrease in the overvoltage for NADH oxidation compared with GC electrode. The ability of OMC-C 60 to promote electron transfer not only suggests a new platform for the development of dehydrogenase-based bioelectrochemical devices but also indicates a potential of OMC-C 60 to be of a wide range of sensing applications because the electrocatalysis of different electroactive compounds at the OMC-C 60/GC electrode in this work should be a good model for constructing a novel and promising electrochemical sensing platform for further electrochemical detection of other biomolecules.

Chlor-Alkali Technology.

ERIC Educational Resources Information Center

Venkatesh, S.; Tilak, B. V.

1983-01-01

Chlor-alkali technology is one of the largest electrochemical industries in the world, the main products being chlorine and caustic soda (sodium hydroxide) generated simultaneously by the electrolysis of sodium chloride. This technology is reviewed in terms of electrochemical principles and manufacturing processes involved. (Author/JN)

ELECTROCHEMICAL REMEDIATION TECHNOLOGIES (ECRTS) - IN SITU REMEDIATION OF CONTAMINATED MARINE SEDIMENTS

EPA Science Inventory

This Innovative Technology Evaulation Report summarizes the results of the evaluation of the Electrochemical Remediation Technologies (ECRTs) process, developed by P2-Soil Remediation, Inc. (in partnership with Weiss Associates and Electro-Petroleum, Inc.). This evaluation was co...

Electrochemical Doping of Halide Perovskites with Ion Intercalation.

PubMed

Jiang, Qinglong; Chen, Mingming; Li, Junqiang; Wang, Mingchao; Zeng, Xiaoqiao; Besara, Tiglet; Lu, Jun; Xin, Yan; Shan, Xin; Pan, Bicai; Wang, Changchun; Lin, Shangchao; Siegrist, Theo; Xiao, Qiangfeng; Yu, Zhibin

2017-01-24

Halide perovskites have recently been investigated for various solution-processed optoelectronic devices. The majority of studies have focused on using intrinsic halide perovskites, and the intentional incoporation of dopants has not been well explored. In this work, we discovered that small alkali ions, including lithium and sodium ions, could be electrochemically intercalated into a variety of halide and pseudohalide perovskites. The ion intercalation caused a lattice expansion of the perovskite crystals and resulted in an n-type doping of the perovskites. Such electrochemical doping improved the conductivity and changed the color of the perovskites, leading to an electrochromism with more than 40% reduction of transmittance in the 450-850 nm wavelength range. The doped perovskites exhibited improved electron injection efficiency into the pristine perovskite crystals, resulting in bright light-emitting diodes with a low turn-on voltage.

Preparation of Ti/IrO2 Anode with Low Iridium Content by Thermal Decomposition Process: Electrochemical removal of organic pollutants in water

NASA Astrophysics Data System (ADS)

Yaqub, Asim; Isa, Mohamed Hasnain; Ajab, Huma; Kutty, S. R. M.; Ezechi, Ezerie H.; Farooq, Robina

2018-04-01

In this study IrO2 (Iridium oxide) was coated onto a titanium plate anode from a dilute (50 mg/10 ml) IrCl3×H2O salt solution. Coating was done at high temperature (550∘C) using thermal decomposition. Surface morphology and characteristics of coated surface of Ti/IrO2 anode were examined by FESEM and XRD. The coated anode was applied for electrochemical removal of organic pollutants from synthetic water samples in 100 mL compartment of batch electrochemical cell. About 50% COD removal was obtained at anode prepared with low Ir content solution while 72% COD removal was obtained with anode prepared at high Ir content. Maximum COD removal was obtained at 10 mA/cm2 current density.

Electrochemical decomposition of fluorinated wetting agents in plating industry waste water.

PubMed

Fath, Andreas; Sacher, Frank; McCaskie, John E

2016-01-01

Electrochemical decomposition of fluorinated surfactants (PFAS, perfluorinated alkyl substances) used in the plating industry was analyzed and the decomposition process parameters optimized at the laboratory scale and production scale of a 500-liter reactor using lead electrodes. The method and system was successfully demonstrated under production conditions to treat PFAS) with up to 99% efficiency in the concentration range of 1,000-20,000 μg/l (1 ppm-20 ppm). The treatment also reduced hexavalent chromium (Cr(6+)) ions to trivalent chromium (Cr(3+)) ions in the wastewater. If the PFAS-containing wastewater is mixed with other wastewater streams, specifically from nickel plating drag out solution or when pH values >5, the treatment process is ineffective. For the short chain PFAS, (perfluorobutylsulfonate) the process was less efficient than C6-C8 PFAS. The process is automated and has safety procedures and controls to prevent hazards. The PFAS were decomposed to hydrogen fluoride (HF) under the strong acid electrochemical operating conditions. Analytical tests showed no evidence of organic waste products remaining from the process. Conventional alternative PFAS removal systems were tested on the waste streams and compared with each other and with the-E-destruct (electrochemical oxidation) process. For example, ion exchange resin (IX resin) treatment of wastewater to complex and remove PFAS was found to be seven times more efficient when compared to the conventional activated carbon absorption (C-treat) process. However, the E-destruct process is higher in capacity, exhibits longer service life and lower operating costs than either IX or C-treat methods for elimination of PFAS from these electroplating waste streams.

Probing Local Ionic Dynamics in Functional Oxides: From Nanometer to Atomic Scale

NASA Astrophysics Data System (ADS)

Kalinin, Sergei

2014-03-01

Vacancy-mediated electrochemical reactions in oxides underpin multiple applications ranging from electroresistive memories, to chemical sensors to energy conversion systems such as fuel cells. Understanding the functionality in these systems requires probing reversible (oxygen reduction/evolution reaction) and irreversible (cathode degradation and activation, formation of conductive filaments) electrochemical processes. In this talk, I summarize recent advances in probing and controlling these transformations locally on nanometer level using scanning probe microscopy. The localized tip concentrates the electric field in the nanometer scale volume of material, inducing local transition. Measured simultaneously electromechanical response (piezoresponse) or current (conductive AFM) provides the information on the bias-induced changes in material. Here, I illustrate how these methods can be extended to study local electrochemical transformations, including vacancy dynamics in oxides such as titanates, LaxSr1-xCoO3, BiFeO3, and YxZr1-xO2. The formation of electromechanical hysteresis loops and their bias-, temperature- and environment dependences provide insight into local electrochemical mechanisms. In materials such as lanthanum-strontium cobaltite, mapping both reversible vacancy motion and vacancy ordering and static deformation is possible, and can be corroborated by post mortem STEM/EELS studies. In ceria, a broad gamut of electrochemical behaviors is observed as a function of temperature and humidity. The possible strategies for elucidation ionic motion at the electroactive interfaces in oxides using high-resolution electron microscopy and combined ex-situ and in-situ STEM-SPM studies are discussed. In the second part of the talk, probing electrochemical phenomena on in-situ grown surfaces with atomic resolution is illustrated. I present an approach based on the multivariate statistical analysis of the coordination spheres of individual atoms to reveal preferential structures and symmetries. The relevant statistical techniques including k-means clustering, principal component analysis, and Baesian unmixing are briefly intriduced. This approach is illustrated for several systems, including chemical phase identification, mapping ferroic variants, and probing topological and structural defects, and provides real space view on surface atomic processes. Research supported (SVK) by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division and partially performed at the Center for Nanophase Materials Sciences (AK, SJ), a DOE-BES user facility.

Use of a Corona Discharge to Selectively Pattern a Hydrophilic/Hydrophobic Interface for Integrating Segmented Flow with Microchip Electrophoresis and Electrochemical Detection

PubMed Central

Filla, Laura A.; Kirkpatrick, Douglas C.; Martin, R. Scott

2011-01-01

Segmented flow in microfluidic devices involves the use of droplets that are generated either on- or off-chip. When used with off-chip sampling methods, segmented flow has been shown to prevent analyte dispersion and improve temporal resolution by periodically surrounding an aqueous flow stream with an immiscible carrier phase as it is transferred to the microchip. To analyze the droplets by methods such as electrochemistry or electrophoresis, a method to “desegment” the flow into separate aqueous and immiscible carrier phase streams is needed. In this paper, a simple and straightforward approach for this desegmentation process was developed by first creating an air/water junction in natively hydrophobic and perpendicular PDMS channels. The air-filled channel was treated with a corona discharge electrode to create a hydrophilic/hydrophobic interface. When a segmented flow stream encounters this interface, only the aqueous sample phase enters the hydrophilic channel, where it can be subsequently analyzed by electrochemistry or microchip-based electrophoresis with electrochemical detection. It is shown that the desegmentation process does not significantly degrade the temporal resolution of the system, with rise times as low as 12 s reported after droplets are recombined into a continuous flow stream. This approach demonstrates significant advantages over previous studies in that the treatment process takes only a few minutes, fabrication is relatively simple, and reversible sealing of the microchip is possible. This work should enable future studies where off-chip processes such as microdialysis can be integrated with segmented flow and electrochemical-based detection. PMID:21718004

New insights into the interface between a single-crystalline metal electrode and an extremely pure ionic liquid: slow interfacial processes and the influence of temperature on interfacial dynamics.

PubMed

Drüschler, Marcel; Borisenko, Natalia; Wallauer, Jens; Winter, Christian; Huber, Benedikt; Endres, Frank; Roling, Bernhard

2012-04-21

Ionic liquids are of high interest for the development of safe electrolytes in modern electrochemical cells, such as batteries, supercapacitors and dye-sensitised solar cells. However, electrochemical applications of ionic liquids are still hindered by the limited understanding of the interface between electrode materials and ionic liquids. In this article, we first review the state of the art in both experiment and theory. Then we illustrate some general trends by taking the interface between the extremely pure ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and an Au(111) electrode as an example. For the study of this interface, electrochemical impedance spectroscopy was combined with in situ STM and in situ AFM techniques. In addition, we present new results for the temperature dependence of the interfacial capacitance and dynamics. Since the interfacial dynamics are characterised by different processes taking place on different time scales, the temperature dependence of the dynamics can only be reliably studied by recording and carefully analysing broadband capacitance spectra. Single-frequency experiments may lead to artefacts in the temperature dependence of the interfacial capacitance. We demonstrate that the fast capacitive process exhibits a Vogel-Fulcher-Tamman temperature dependence, since its time scale is governed by the ionic conductivity of the ionic liquid. In contrast, the slower capacitive process appears to be Arrhenius activated. This suggests that the time scale of this process is determined by a temperature-independent barrier, which may be related to structural reorganisations of the Au surface and/or to charge redistributions in the strongly bound innermost ion layer. This journal is © the Owner Societies 2012

Laser irradiation of Mg-Al-Zn alloy: Reduced electrochemical kinetics and enhanced performance in simulated body fluid.

PubMed

Florian, David C; Melia, Michael A; Steuer, Fritz W; Briglia, Bruce F; Purzycki, Michael K; Scully, John R; Fitz-Gerald, James M

2017-05-11

As a lightweight metal with mechanical properties similar to natural bone, Mg and its alloys are great prospects for biodegradable, load bearing implants. However, rapid degradation and H 2 gas production in physiological media has prevented widespread use of Mg alloys. Surface heterogeneities in the form of intermetallic particles dominate the corrosion response. This research shows that surface homogenization significantly improved the biological corrosion response observed during immersion in simulated body fluid (SBF). The laser processed Mg alloy exhibited a 50% reduction in mass loss and H 2 evolution after 24 h of immersion in SBF when compared to the wrought, cast alloy. The laser processed samples exhibited increased wettability as evident from wetting angle studies, further suggesting improved biocompatibility. Electrochemical analysis by potentiodynamic polarization measurements showed that the anodic and cathodic kinetics were reduced following laser processing and are attributed to the surface chemical homogeneity.

Guided evolution of bulk metallic glass nanostructures: A platform for designing three-dimensional electrocatalytic surfaces

DOE PAGES

Doubek, Gustavo; Sekol, Ryan C.; Li, Jinyang; ...

2015-12-22

Precise control over catalyst surface composition and structure is necessary to improve the function of electrochemical systems. To that end, bulk metallic glass (BMG) alloys with atomically dispersed elements provide a highly processable, nanoscale platform for electrocatalysis and surface modification. Here we report on nanostructures of Pt-based BMGs that are modified with various subtractive and additive processes to improve their electrochemical performance.

Optimization of an integrated electrodisinfection/electrocoagulation process with Al bipolar electrodes for urban wastewater reclamation.

PubMed

Cotillas, Salvador; Llanos, Javier; Cañizares, Pablo; Mateo, Sara; Rodrigo, Manuel A

2013-04-01

In this work, a novel integrated electrochemical process for urban wastewater regeneration is described. The electrochemical cell consists in a Boron Doped Diamond (BDD) or a Dimensionally Stable Anode (DSA) as anode, a Stainless Steel (SS) as cathode and a perforated aluminum plate, which behaves as bipolar electrode, between anode and cathode. Thus, in this cell, it is possible to carry out, at the same time, two different electrochemical processes: electrodisinfection (ED) and electrocoagulation (EC). The treatment of urban wastewater with different anodes and different operating conditions is studied. First of all, in order to check the process performance, experiments with synthetic wastewaters were carried out, showing that it is possible to achieve a 100% of turbidity removal by the electrodissolution of the bipolar electrode. Next, the effect of the current density and the anode material are studied during the ED-EC process of actual effluents. Results show that it is possible to remove Escherichia coli and turbidity simultaneously of an actual effluent from a WasteWater Treatment Facility (WWTF). The use of BDD anodes allows to remove the E. coli completely at an applied electric charge of 0.0077 A h dm(-3) when working with a current density of 6.65 A m(-2). On the other hand, with DSA anodes, the current density necessary to achieve the total removal of E. coli is higher (11.12 A m(-2)) than that required with BDD anodes. Finally, the influence of cell flow path and flow rate have been studied. Results show that the performance of the process strongly depends on the characteristics of the initial effluent (E. coli concentration and Cl(-)/NH(4)(+) initial ratio) and that a cell configuration cathode (inlet)-anode (outlet) and a higher flow rate enhance the removal of the turbidity from the treated effluent. Copyright © 2013 Elsevier Ltd. All rights reserved.

Space Electrochemical Research and Technology. Abstracts

NASA Technical Reports Server (NTRS)

1995-01-01

This document contains abstracts of the proceedings of NASA's fifth Space Electrochemical Research and Technology (SERT) Conference, held at the NASA Lewis Research Center on May 1-3, 1995. The objective of the conference was to assess the present status and general thrust of research and development in those areas of electrochemical technology required to enable NASA missions into the next century. The conference provided a forum for the exchange of ideas and opinions of those actively involved in the field, in order to define new opportunities for the application of electrochemical processes in future NASA missions. Papers were presented in three technical areas: (1) the electrochemical interface, (2) the next generation in aerospace batteries and fuel cells, and (3) electrochemistry for non-energy storage applications. This document contains the abstracts of the papers presented.

Electrochemical quartz crystal microbalance study of polyelectrolyte film growth under anodic conditions

NASA Astrophysics Data System (ADS)

Nilsson, Sara; Björefors, Fredrik; Robinson, Nathaniel D.

2013-09-01

Coating hard materials such as Pt with soft polymers like poly-L-lysine is a well-established technique for increasing electrode biocompatibility. We have combined quartz crystal microgravimetry with dissipation with electrochemistry (EQCM-D) to study the deposition of PLL onto Pt electrodes under anodic potentials. Our results confirm the change in film growth over time previously reported by others. However, the dissipation data suggest that, after the short initial phase of the process, the rigidity of the film increases with time, rather than decreasing, as previously proposed. In addition to these results, we discuss how gas evolution from water electrolysis and Pt etching in electrolytes containing Cl- affect EQCM-D measurements, how to recognize these effects, and how to reduce them. Despite the challenges of using Pt as an anode in this system, we demonstrate that the various electrochemical processes can be understood and that PLL coatings can be successfully electrodeposited.

A comparative study of electrochemical machining process parameters by using GA and Taguchi method

NASA Astrophysics Data System (ADS)

Soni, S. K.; Thomas, B.

2017-11-01

In electrochemical machining quality of machined surface strongly depend on the selection of optimal parameter settings. This work deals with the application of Taguchi method and genetic algorithm using MATLAB to maximize the metal removal rate and minimize the surface roughness and overcut. In this paper a comparative study is presented for drilling of LM6 AL/B4C composites by comparing the significant impact of numerous machining process parameters such as, electrolyte concentration (g/l),machining voltage (v),frequency (hz) on the response parameters (surface roughness, material removal rate and over cut). Taguchi L27 orthogonal array was chosen in Minitab 17 software, for the investigation of experimental results and also multiobjective optimization done by genetic algorithm is employed by using MATLAB. After obtaining optimized results from Taguchi method and genetic algorithm, a comparative results are presented.

Aqueous Electrochemical Mechanisms in Actinide Residue Processing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morris, David E.; Burns, Carol J.; Smith, Wayne H.

2000-12-31

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 Energy's (DOE) legacy waste from fifty years of nuclear weapons production activities. Much of this material is presently in storage at sites throughout the DOE weapons production complex (most notably Rocky Flats, Savannah River and Hanford) awaiting further processing and/or final disposition. The chemical and physical stability of much of this material has been called into question recently by the Defense Nuclearmore » Facility Safety Board (DNFSB) and resulted in the issuance of a mandate by the DNFSB to undertake a program to stabilize these materials [1]. The ultimate disposition for much of these materials is anticipated to be geologic repositories such as the proposed Waste Isolation Pilot Plant in New Mexico. However, in light of the mandate to stabilize existing residues and the probable concomitant increase in the volume of material to be disposed as a result of stabilization (e.g., from repackaging at lower residue densities), the projected storage volume for these wastes within anticipated geologic repositories will likely be exceeded simply to handle existing wastes. Additional processing of some of these residue waste streams to reduce radionuclide activity levels, matrix volume, or both is a potentially important strategy to achieve both stabilization and volume reduction so that the anticipated geologic repositories will provide adequate storage volume. In general, the plutonium and uranium that remains in solid residue materials exists in a very stable chemical form (e.g., as binary oxides), and the options available to remove the actinides are limited. However, there have been some demonstrated successes in this vain using aqueous phase electrochemical methods such as the Catalyzed Electrochemical Plutonium Oxide Dissolution (CEPOD) process pioneered by workers at Pacific Northwest National Laboratory in the mid-1970s [2]. The basis for most of these mediated electrochemical oxidation/reduction (MEO/R) processes is the generation of a dissolved electrochemical catalyst, such as Ag2+, which is capable of oxidizing or reducing solid-phase actinide species or actinide sorbates via 7 heterogeneous electron transfer to oxidation states that have significantly greater solubilities (e.g., PuO2(s) to PuO2 2+ (dissolved)). The solubilized actinide can then be recovered by ion exchange or other mechanisms. These aqueous electrochemical methods for residue treatment have been considered in many of the ''trade studies'' to evaluate options for stabilization of the various categories of residue materials. While some concerns generally arise (e.g., large secondary waste volumes could results since the process stream normally goes th rough anion exchange or precipitation steps to remove the actinide), the real utility and versatility of these methods should not be overlooked. They are low temperature, ambient pressure processes that operate in a non-corrosive environment. In principle, they can be designed to be highly selective for the actinides (i.e., no substrate degradation occurs), they can be utilized for many categories of residue materials with little or no modification in hardware or operating conditions, and they can conceivably be engineered to minimize secondary waste stream volume. However, some fundamental questions remain concerning the mechanisms through which these processes act, and how the processes might be optimized to maximize efficiency while minimizing secondary waste. In addition, given the success achieved to date on the limited set of residues, further research is merited to extend the range of applicability of these electrochemical methods to other residue and waste streams. The principal goal of the work described here is to develop a fundamental understanding of the heterogeneous electron transfer thermodynamics and kinetics that lie at the heart of the MEO/R processes for actinide solids and actinide species entrained in or surface-bound to residue substrates. This has been accomplished as described in detail below through spectroscopic characterization of actinide-bearing substrates and electrochemical investigations of electron transfer reactions between uranium- and plutonium- (or surrogates) bearing solids (dispersed actinide solid phases and actinides sorbed to inorganic and organic colloids) and polarizable electrode materials. In general, the actinide solids or substrate-supported species were chosen to represent relevant residue materials (e.g., incinerator ash, sand/slag/crucible, and combustibles).« less

Layered double hydroxide materials coated carbon electrode: New challenge to future electrochemical power devices

NASA Astrophysics Data System (ADS)

Djebbi, Mohamed Amine; Braiek, Mohamed; Namour, Philippe; Ben Haj Amara, Abdesslem; Jaffrezic-Renault, Nicole

2016-11-01

Layered double hydroxides (LDHs) have been widely used in the past years due to their unique physicochemical properties and promising applications in electroanalytical chemistry. The present paper is going to focus exclusively on magnesium-aluminum and zinc-aluminum layered double hydroxides (MgAl & ZnAl LDHs) in order to investigate the property and structure of active cation sites located within the layer structure. The MgAl and ZnAl LDH nanosheets were prepared by the constant pH co-precipitation method and uniformly supported on carbon-based electrode materials to fabricate an LDH electrode. Characterization by powder x-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy revealed the LDH form and well-crystallized materials. Wetting surface properties (hydrophilicity and hydrophobicity) of both prepared LDHs were recorded by contact angle measurement show hydrophilic character and basic property. The electrochemical performance of these hybrid materials was investigated by mainly cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry techniques to identify the oxidation/reduction processes at the electrode/electrolyte interface and the effect of the divalent metal cations in total reactivity. The hierarchy of the modified electrode proves that the electronic conductivity of the bulk material is considerably dependent on the divalent cation and affects the limiting parameter of the overall redox process. However, MgAl LDH shows better performance than ZnAl LDH, due to the presence of magnesium cations in the layers. Following the structural, morphological and electrochemical behavior studies of both synthesized LDHs, the prepared LDH modified electrodes were tested through microbial fuel cell configuration, revealing a remarkable, potential new pathway for high-performance and cost-effective electrode use in electrochemical power devices.

Recognized Leader in Electrochemical Purification

ScienceCinema

Hoppe, Eric

2018-01-16

PNNL scientists developed an electrochemical method for purifying copper, a key material that makes possible radiation detection systems of unprecedented sensitivity. The method begins with the purest copper materials available, and results in the lowest-background copper in the world. Chemist Eric Hoppe explains the process.

Design of a dual-mode electrochemical measurement and analysis system.

PubMed

Yang, Jr-Fu; Wei, Chia-Ling; Wu, Jian-Fu; Liu, Bin-Da

2013-01-01

A dual-mode electrochemical measurement and analysis system is proposed. This system includes a dual-mode chip, which was designed and fabricated by using TSMC 0.35 µm 3.3 V/5 V 2P4M mixed-signal CMOS process. Two electrochemical measurement and analysis methods, chronopotentiometry and voltammetry, can be performed by using the proposed chip and system. The proposed chip and system are verified successfully by performing voltammetry and chronopotentiometry on solutions.

Preparation of Al-Ti Master Alloy by Electrochemical Recovery of Titanium-Reducing Slag in Molten Salts

NASA Astrophysics Data System (ADS)

Zhao, Kun; Wang, Yaowu; Feng, Naixiang

2018-02-01

An electrochemical method for the preparation of an Al-Ti master alloy in Al electrolysis melts of Na3AlF6-Al2O3-LiF at 980°C was investigated. The Ti-reducing slag (5.24 wt.% Ti in the Ti-reducing slag) was obtained from the aluminothermic reduction of Na2TiF6. The cold test (i.e., the aluminothermic reduction process without applying any voltages) result revealed the capability of the Al cathode to reduce the Ti slag, and the recovery rate could reach 45.8% at 980°C over 3.5 h with the addition of 10 wt.% Ti-reducing slag. In contrast, the recovery rate of Ti after electrolysis at 3.0 V could reach 99.2%. Thus, the electrochemical treatment for Ti-reducing slag is a cooperative process involving aluminothermic and electrochemical reduction reactions. Electrochemical analysis indicated that the Ti ions are reduced to metallic Ti according to Ti4+ → Ti3+ → Ti. An Al-Ti alloy layer could be prepared on the external surface of the Mo electrode after electrolysis with the addition of 12 wt.% Ti-reducing slag.

Graphene-Selenium Hybrid Microballs as Cathode Materials for High-performance Lithium-Selenium Secondary Battery Applications.

PubMed

Youn, Hee-Chang; Jeong, Jun Hui; Roh, Kwang Chul; Kim, Kwang-Bum

2016-08-02

In this study, graphene-selenium hybrid microballs (G-SeHMs) are prepared in one step by aerosol microdroplet drying using a commercial spray dryer, which represents a simple, scalable continuous process, and the potential of the G-SeHMs thus prepared is investigated for use as cathode material in applications of lithium-selenium secondary batteries. These morphologically unique graphene microballs filled with Se particles exhibited good electrochemical properties, such as high initial specific capacity (642 mA h g(-1) at 0.1 C, corresponding to Se electrochemical utilisation as high as 95.1%), good cycling stability (544 mA h g(-1) after 100 cycles at 0.1 C; 84.5% retention) and high rate capability (specific capacity of 301 mA h g(-1) at 5 C). These electrochemical properties are attributed to the fact that the G-SeHM structure acts as a confinement matrix for suppressing the dissolution of polyselenides in the organic electrolyte, as well as an electron conduction path for increasing the transport rate of electrons for electrochemical reactions. Notably, based on the weight of hybrid materials, electrochemical performance is considerably better than that of previously reported Se-based cathode materials, attributed to the high Se loading content (80 wt%) in hybrid materials.

Electrochemical growth of CoNi and Pt-CoNi soft magnetic composites on an alkanethiol monolayer-modified ITO substrate.

PubMed

Escalera-López, D; Gómez, E; Vallés, E

2015-07-07

CoNi and Pt-CoNi magnetic layers on indium-tin oxide (ITO) substrates modified by an alkanethiol self-assembled monolayer (SAM) have been electrochemically obtained as an initial stage to prepare semiconducting layer-SAM-magnetic layer hybrid structures. The best conditions to obtain the maximum compactness of adsorbed layers of dodecanethiol (C12-SH) on ITO substrate have been studied using contact angle, AFM, XPS and electrochemical tests. The electrochemical characterization (electrochemical probe or voltammetric response in blank solutions) is fundamental to ensure the maximum blocking of the substrate. Although the electrodeposition process on the SAM-modified ITO substrate is very slow if the blocking of the surface is significant, non-cracked metallic layers of CoNi, with or without a previously electrodeposited seed-layer of platinum, have been obtained by optimizing the deposition potentials. Initial nucleation is expected to take place at the pinhole defects of the C12-SH SAM, followed by a mushroom-like growth regime through the SAM interface that allows the formation of a continuous metallic layer electrically connected to the ITO surface. Due to the potential of the methodology, the preparation of patterned metallic deposits on ITO substrate using SAMs with different coverage as templates is feasible.

In operando neutron diffraction study of LaNdMgNi9H13 as a metal hydride battery anode

NASA Astrophysics Data System (ADS)

Nazer, N. S.; Denys, R. V.; Yartys, V. A.; Hu, Wei-Kang; Latroche, M.; Cuevas, F.; Hauback, B. C.; Henry, P. F.; Arnberg, L.

2017-03-01

La2MgNi9-related alloys are superior metal hydride battery anodes as compared to the commercial AB5 alloys. Nd-substituted La2-yNdyMgNi9 intermetallics are of particular interest because of increased diffusion rate of hydrogen and thus improved performance at high discharge currents. The present work presents in operando characterization of the LaNdMgNi9 intermetallic as anode for the nickel metal hydride (Ni-MH) battery. We have studied the structural evolution of LaNdMgNi9 during its charge and discharge using in situ neutron powder diffraction. The work included experiments using deuterium gas and electrochemical charge-discharge measurements. The alloy exhibited a high electrochemical discharge capacity (373 mAh/g) which is 20% higher than the AB5 type alloys. A saturated β-deuteride synthesized by solid-gas reaction at PD2 = 1.6 MPa contained 12.9 deuterium atoms per formula unit (D/f.u.) which resulted in a volume expansion of 26.1%. During the electrochemical charging, the volume expansion (23.4%) and D-contents were found to be slightly reduced. The reversible electrochemical cycling is performed through the formation of a two-phase mixture of the α-solid solution and β-hydride phases. Nd substitution contributes to the high-rate dischargeability, while maintaining a good cyclic stability. Electrochemical Impedance Spectroscopy (EIS) was used to characterize the anode electrode on cycling. A mathematical model for the impedance response of a porous electrode was utilized. The EIS showed a decreased hydrogen transport rate during the long-term cycling, which indicated a corresponding slowing down of the electrochemical processes at the surface of the metal hydride anode.

Shape Effect of Electrochemical Chloride Extraction in Structural Reinforced Concrete Elements Using a New Cement-Based Anodic System

PubMed Central

Carmona, Jesús; Climent, Miguel-Ángel; Antón, Carlos; de Vera, Guillem; Garcés, Pedro

2015-01-01

This article shows the research carried out by the authors focused on how the shape of structural reinforced concrete elements treated with electrochemical chloride extraction can affect the efficiency of this process. Assuming the current use of different anode systems, the present study considers the comparison of results between conventional anodes based on Ti-RuO2 wire mesh and a cement-based anodic system such as a paste of graphite-cement. Reinforced concrete elements of a meter length were molded to serve as laboratory specimens, to closely represent authentic structural supports, with circular and rectangular sections. Results confirm almost equal performances for both types of anode systems when electrochemical chloride extraction is applied to isotropic structural elements. In the case of anisotropic ones, such as rectangular sections with no uniformly distributed rebar, differences in electrical flow density were detected during the treatment. Those differences were more extreme for Ti-RuO2 mesh anode system. This particular shape effect is evidenced by obtaining the efficiencies of electrochemical chloride extraction in different points of specimens.

Directing Stem Cell Differentiation via Electrochemical Reversible Switching between Nanotubes and Nanotips of Polypyrrole Array.

PubMed

Wei, Yan; Mo, Xiaoju; Zhang, Pengchao; Li, Yingying; Liao, Jingwen; Li, Yongjun; Zhang, Jinxing; Ning, Chengyun; Wang, Shutao; Deng, Xuliang; Jiang, Lei

2017-06-27

Control of stem cell behaviors at solid biointerfaces is critical for stem-cell-based regeneration and generally achieved by engineering chemical composition, topography, and stiffness. However, the influence of dynamic stimuli at the nanoscale from solid biointerfaces on stem cell fate remains unclear. Herein, we show that electrochemical switching of a polypyrrole (Ppy) array between nanotubes and nanotips can alter surface adhesion, which can strongly influence mechanotransduction activation and guide differentiation of mesenchymal stem cells (MSCs). The Ppy array, prepared via template-free electrochemical polymerization, can be reversibly switched between highly adhesive hydrophobic nanotubes and poorly adhesive hydrophilic nanotips through an electrochemical oxidation/reduction process, resulting in dynamic attachment and detachment to MSCs at the nanoscale. Multicyclic attachment/detachment of the Ppy array to MSCs can activate intracellular mechanotransduction and osteogenic differentiation independent of surface stiffness and chemical induction. This smart surface, permitting transduction of nanoscaled dynamic physical inputs into biological outputs, provides an alternative to classical cell culture substrates for regulating stem cell fate commitment. This study represents a general strategy to explore nanoscaled interactions between stem cells and stimuli-responsive surfaces.

Symposium on High Power, Ambient Temperature Lithium Batteries, 180th Meeting of the Electrochemical Society, Phoenix, AZ, Oct. 13-17, 1991, Proceedings

NASA Technical Reports Server (NTRS)

Clark, W. D. K. (Editor); Halpert, Gerald (Editor)

1992-01-01

Papers presented in these proceedings are on the state of the art in high-power lithium batteries, a design analysis of high-power Li-TiS2 battery, the performance and safety features of spiral wound lithium/thionyl chloride cells, the feasibility of a superhigh energy density battery of the Li/BrF3 electrochemical system, and an enhanced redox process of disulfide compounds and their application in high energy storage. Attention is also given to the structure and charge-discharge characteristics of mesophase-pitch based carbons, a study of carbons and graphites as anodes for lithium rechargeable cells, Li metal-free rechargeable Li(1+x)Mn2O4/carbon cells, and rechargeable lithium batteries using V6O13/V5O5 as the positive electrode material. Other papers discuss the electrochemical stability of organic electrolytes in contact with solid inorganic cathode materials, the electrochemical behavior of methyl formate solutions, and the interface between a solid polymer electrolyte and lithium anode.

Ce(III, IV)-MOF electrocatalyst as signal-amplifying tag for sensitive electrochemical aptasensing.

PubMed

Yu, Hua; Han, Jing; An, Shangjie; Xie, Gang; Chen, Sanping

2018-06-30

Metal-organic frameworks (MOFs) as a new class of porous materials have attracted increasing attention in the field of biomimetic catalysis. This study firstly reports a mixed valence state Ce-MOF possessing intrinsic catalytic activity towards thionine (Thi), and its application in constructing an amplified electrochemical aptasensor for thrombin detection. As noticed, the novel catalytic process combines the advantages of 3D infinite extension of the Ce(III, IV)-MOF skeleton containing large amounts of catalytic sites and spontaneous recycling of the Ce(III)/Ce(IV) for electrochemical reduction of Thi, thereby presenting amplified electrochemical signals. To further improve the aptasensor performance, the high selectivity of proximity binding-induced DNA strand displacement and high efficiency of exonuclease III-assisted recycling amplification were incorporated into the assay. The aptasensor was employed to detect thrombin in complex serum samples, which shows high sensitivity, specificity, stability and reproducibility. This work offers an opportunity to develop MOF-based electrocatalyst as signal-amplifying tag for versatile bioassays and catalytic applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Differential Electrochemical Conductance Imaging at the Nanoscale.

PubMed

López-Martínez, Montserrat; Artés, Juan Manuel; Sarasso, Veronica; Carminati, Marco; Díez-Pérez, Ismael; Sanz, Fausto; Gorostiza, Pau

2017-09-01

Electron transfer in proteins is essential in crucial biological processes. Although the fundamental aspects of biological electron transfer are well characterized, currently there are no experimental tools to determine the atomic-scale electronic pathways in redox proteins, and thus to fully understand their outstanding efficiency and environmental adaptability. This knowledge is also required to design and optimize biomolecular electronic devices. In order to measure the local conductance of an electrode surface immersed in an electrolyte, this study builds upon the current-potential spectroscopic capacity of electrochemical scanning tunneling microscopy, by adding an alternating current modulation technique. With this setup, spatially resolved, differential electrochemical conductance images under bipotentiostatic control are recorded. Differential electrochemical conductance imaging allows visualizing the reversible oxidation of an iron electrode in borate buffer and individual azurin proteins immobilized on atomically flat gold surfaces. In particular, this method reveals submolecular regions with high conductance within the protein. The direct observation of nanoscale conduction pathways in redox proteins and complexes enables important advances in biochemistry and bionanotechnology. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The influence of current collector corrosion on the performance of electrochemical capacitors

NASA Astrophysics Data System (ADS)

Wojciechowski, Jarosław; Kolanowski, Łukasz; Bund, Andreas; Lota, Grzegorz

2017-11-01

This paper discusses the effect of current collector (stainless steel 316L) corrosion on the performance of electrochemical capacitors operated in aqueous electrolytes. This topic seems to be often neglected in scientific research. The studied electrolytes were 1 M H2SO4, 1 M KI, 1 M Na2SO4, 1 M KOH and 6 M KOH. The corrosion process was investigated by means of selected direct and alternating current techniques. The surface of the current collectors as well as the corrosion products were characterised using scanning electron microscopy, energy-dispersive X-ray spectroscopy, Raman spectroscopy and atomic force microscopy. Stainless steel 316L in alkaline solutions is characterised by the lowest values of corrosion potentials whereas the potentials in acidic media become the most noble. Our studies show that corrosion potentials increase with decreasing pH value. This phenomenon can be explained with the formation of passive oxide films on the stainless steel current collectors. The passive oxide films are usually thicker and more porous in alkaline solutions than that in the other electrolytes. The processes occurring at the electrode/electrolyte interfaces strongly influence the working parameters of electrochemical capacitors such as voltage, working potentials of single electrodes, self-discharge as well as the internal resistance and cycling stability.

Influence of Pore Characteristics on Electrochemical and Biological Behavior of Ti Foams

NASA Astrophysics Data System (ADS)

Salehi, Akram; Barzegar, Faezeh; Amini Mashhadi, Hossein; Nokhasteh, Samira; Abravi, Mohammad Sadegh

2017-08-01

This study reports on titanium (Ti) foams produced using the powder metallurgy technique. During the investigation, the cross-sectional area and perimeter distributions of the pores within the foam were measured. Metallographic image processing analysis software combined with scanning electron microscopic images demonstrated that the pore size and circularity were affected by varying the volume percentage of the space-holder material. The corrosion resistance was investigated using electrochemical impedance spectroscopy and cyclic polarization tests. MG-63 osteoblast-like cells were used to study the biocompatibility and to evaluate the cell attachment, viability, and alkaline phosphatase activity. Analytical results indicated that 50 and 60 vol.% samples were suitable for biomedical applications. Because of the high degree of interconnectivity in the 60 and 70% porosity samples, the electrochemical parameters produced similar results. The corrosion rate of the porous samples showed that the amount of dissolved Ti was at an acceptable level that can be ejected by the body. Applying a fluoridated hydroxyapatite coating significantly increased the osteoblast cell functions on the porous surface.

A numerical study on electrochemical transport of ions in calcium fluoride slag

NASA Astrophysics Data System (ADS)

Karimi-Sibaki, E.; Kharicha, A.; Wu, M.; Ludwig, A.

2016-07-01

Electrically resistive CaF 2-based slags are widely used in electroslag remelting (ESR) process to generate Joule heat for the melting of electrode. The electric current is conducted by ions (electrolyte) such as Ca +2 or F -, thus it is necessary to establish electrochemical models to study electrical behavior of slag. This paper presents a numerical model on electrochemical transport of ions in an arbitrary symmetrical (ZZ) and non-symmetrical (CaF2) stagnant electrolytes blocked by two parallel, planar electrodes. The dimensionless Poisson-Nernst-Planck (PNP) equations are solved to model electro-migration and diffusion of ions. The ions are considered to be inert that no Faradic reactions occur. Spatial variations of concentrations of ions, charge density and electric potential across the electrolyte are analyzed. It is shown that the applied potential has significant influence on the system response. At high applied voltage, the anodic potential drop near the electrode is significantly larger than cathodic potential drop in fully dissociated CaF2 electrolyte.

A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis

DOE PAGES

Zhang, Linan; Mallikarjun Sharada, Shaama; Singh, Aayush R.; ...

2018-01-17

We report that ammonia synthesis is one of the most studied reactions in heterogeneous catalysis. To date, however, electrochemical N 2 reduction in aqueous systems has proven to be extremely difficult, mainly due to the competing hydrogen evolution reaction (HER). Recently, it has been shown that transition metal complexes based on molybdenum can reduce N 2 to ammonia at room temperature and ambient pressure in a non-aqueous system, with a relatively small amount of hydrogen output. We demonstrate that the non-aqueous proton donor they have chosen, 2,6-lutidinium (LutH +), is a viable substitute for hydronium in the electrochemical process atmore » a solid surface, since this donor can suppress the HER rate. Finally, we also show that the presence of LutH + can selectively stabilize the *NNH intermediate relative to *NH or *NH 2via the formation of hydrogen bonds, indicating that the use of non-aqueous solvents can break the scaling relationship between limiting potential and binding energies.« less

A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Linan; Mallikarjun Sharada, Shaama; Singh, Aayush R.

We report that ammonia synthesis is one of the most studied reactions in heterogeneous catalysis. To date, however, electrochemical N 2 reduction in aqueous systems has proven to be extremely difficult, mainly due to the competing hydrogen evolution reaction (HER). Recently, it has been shown that transition metal complexes based on molybdenum can reduce N 2 to ammonia at room temperature and ambient pressure in a non-aqueous system, with a relatively small amount of hydrogen output. We demonstrate that the non-aqueous proton donor they have chosen, 2,6-lutidinium (LutH +), is a viable substitute for hydronium in the electrochemical process atmore » a solid surface, since this donor can suppress the HER rate. Finally, we also show that the presence of LutH + can selectively stabilize the *NNH intermediate relative to *NH or *NH 2via the formation of hydrogen bonds, indicating that the use of non-aqueous solvents can break the scaling relationship between limiting potential and binding energies.« less

Electrochemical and microstructural characterization of magnetron-sputtered ATO thin films as Li–ion storage materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ouyang, Pan; Zhang, Hong; Chen, Wenhao

2015-01-15

Highlights: • Nano-structured ATO thin films prepared by RF magnetron sputtering at 25 °C, 100 °C and 200 °C, respectively. • ATO thin films show a high reversible capacity and high rate performance. • Electrochemical reaction mechanism of the ATO thin film was revealed by transmission electron microscopy. - Abstract: Sb-doped SnO{sub 2} (ATO) nanostructured thin films were prepared by using radio frequency magnetron sputtering at the substrate temperatures of 25 °C, 100 °C and 200 °C, respectively. All the ATO thin films have the similar redox characteristics in the cyclic voltammetry measurements. The ATO thin film sputtered at 200more » °C shows the lowest charge transfer resistance and best electrochemical performance, and has a high reversible capacity of 679 mA h g{sup −1} at 100 mA g{sup −1} after 200 charge–discharge cycles and high rate performance of 483 mA h g{sup −1} at 800 mA g{sup −1}. The electrochemical mechanisms were investigated by analyzing the phase evolution of the ATO electrodes that had been electrochemically induced at various stages. The results reveal that the ATO underwent reversible lithiation/delithiation processes during the electrochemical cycles, i.e., the SnO{sub 2} reacted with Li{sup +} to produce metallic Sn and followed by the formation of the Li{sub x}Sn alloys during discharge process, and then Li{sub x}Sn alloys de-alloyed, Sn reacted with Li{sub 2}O, and even partially formed SnO{sub 2} during charge process.« less

Nonradical oxidation from electrochemical activation of peroxydisulfate at Ti/Pt anode: Efficiency, mechanism and influencing factors.

PubMed

Song, Haoran; Yan, Linxia; Ma, Jun; Jiang, Jin; Cai, Guangqiang; Zhang, Wenjuan; Zhang, Zhongxiang; Zhang, Jiaming; Yang, Tao

2017-06-01

Electrochemical activation of peroxydisulfate (PDS) at Ti/Pt anode was systematically investigated for the first time in this work. The synergistic effect produced from the combination of electrolysis and the addition of PDS demonstrates that PDS can be activated at Ti/Pt anode. The selective oxidation towards carbamazepine (CBZ), sulfamethoxazole (SMX), propranolol (PPL), benzoic acid (BA) rather than atrazine (ATZ) and nitrobenzene (NB) was observed in electrochemical activation of PDS process. Moreover, addition of excess methanol or tert-butanol had negligible impact on CBZ (model compound) degradation, demonstrating that neither sulfate radical (SO 4 - ) nor hydroxyl radical (HO) was produced in electrochemical activation of PDS process. Direct oxidation (PDS oxidation alone and electrolysis) and nonradical oxidation were responsible for the degradation of contaminants. The results of linear sweep voltammetry (LSV) and chronoamperometry suggest that electric discharge may integrate PDS molecule with anode surface into a unique transition state structure, which is responsible for the nonradical oxidation in electrochemical activation of PDS process. Adjustment of the solution pH from 1.0 to 7.0 had negligible effect on CBZ degradation. Increase of either PDS concentration or current density facilitated the degradation of CBZ. The presence of chloride ion (Cl - ) significantly enhanced CBZ degradation, while addition of bicarbonate (HCO 3 - ), phosphate (PO 4 3- ) and humic acid (HA) all inhibited CBZ degradation with the order of HA > HCO 3 -  > PO 4 3- . The degradation products of CBZ and chlorinated products were also identified. Electrochemical activation of PDS at Ti/Pt anode may serve as a novel technology for selective oxidation of organic contaminants in water and soil. Copyright © 2017. Published by Elsevier Ltd.

Performance Optimization Control of ECH using Fuzzy Inference Application

NASA Astrophysics Data System (ADS)

Dubey, Abhay Kumar

Electro-chemical honing (ECH) is a hybrid electrolytic precision micro-finishing technology that, by combining physico-chemical actions of electro-chemical machining and conventional honing processes, provides the controlled functional surfaces-generation and fast material removal capabilities in a single operation. Process multi-performance optimization has become vital for utilizing full potential of manufacturing processes to meet the challenging requirements being placed on the surface quality, size, tolerances and production rate of engineering components in this globally competitive scenario. This paper presents an strategy that integrates the Taguchi matrix experimental design, analysis of variances and fuzzy inference system (FIS) to formulate a robust practical multi-performance optimization methodology for complex manufacturing processes like ECH, which involve several control variables. Two methodologies one using a genetic algorithm tuning of FIS (GA-tuned FIS) and another using an adaptive network based fuzzy inference system (ANFIS) have been evaluated for a multi-performance optimization case study of ECH. The actual experimental results confirm their potential for a wide range of machining conditions employed in ECH.

Decolorization and degradation of reactive yellow HF aqueous solutions by electrochemical advanced oxidation processes.

PubMed

Bedolla-Guzman, A; Feria-Reyes, R; Gutierrez-Granados, S; Peralta-Hernández, Juan M

2017-05-01

Textile manufacturing is the one responsible for water bodies' contamination through the discharge of colored wastes. This work presents the study of reactive yellow HF (RYHF) dye degradation under two different electrochemical advanced oxidation processes (EAOP), namely anodic oxidation (AO) and electro-Fenton (EF)/boron-doped diamond (BDD) process. For the AO, 100 and 300 mg/L solutions using Pt and BDD as anodes in a 100 mL stirred tank cell were used, with a supporting electrolyte of 0.05 mol/L of Na 2 SO 4 at pH 3 under 30 and 50 mA/cm 2 current density. The EF/BDD process was carried out in a flow reactor at 4 and 7 L/min to degrade 100, 200, and 300 mg/L RYHF solutions under 50 and 80 mA/cm 2 . UV-Vis determinations were used for decolorization evaluation, while high-performance liquid chromatography (HPLC) method provided information on dye degradation rate.

Electrochemical sensing and biosensing platform based on chemically reduced graphene oxide.

PubMed

Zhou, Ming; Zhai, Yueming; Dong, Shaojun

2009-07-15

In this paper, the characterization and application of a chemically reduced graphene oxide modified glassy carbon (CR-GO/GC) electrode, a novel electrode system, for the preparation of electrochemical sensing and biosensing platform are proposed. Different kinds of important inorganic and organic electroactive compounds (i.e., probe molecule (potassium ferricyanide), free bases of DNA (guanine (G), adenine (A), thymine (T), and cytosine (C)), oxidase/dehydrogenase-related molecules (hydrogen peroxide (H2O2)/beta-nicotinamide adenine dinucleotide (NADH)), neurotransmitters (dopamine (DA)), and other biological molecules (ascorbic acid (AA), uric acid (UA), and acetaminophen (APAP)) were employed to study their electrochemical responses at the CR-GO/GC electrode, which shows more favorable electron transfer kinetics than graphite modified glassy carbon (graphite/GC) and glassy carbon (GC) electrodes. The greatly enhanced electrochemical reactivity of the four free bases of DNA at the CR-GO/GC electrode compared with that at graphite/GC and GC electrodes makes the CR-GO/GC electrode a better choice for the electrochemical biosensing of four DNA bases in both the single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA) at physiological pH without a prehydrolysis step. This allows us to detect a single-nucleotide polymorphism (SNP) site for short oligomers with a particular sequence at the CR-GO/GC electrode without any hybridization or labeling processes in this work, suggesting the potential applications of CR-GO in the label-free electrochemical detection of DNA hybridization or DNA damage for further research. Based on the greatly enhanced electrochemical reactivity of H2O2 and NADH at the CR-GO/GC electrode, CR-GO/GC electrode-based bioelectrodes (in connection with glucose oxidase (GOD) and alcohol dehydrogenase (ADH)) show a better analytical performance for the detection of glucose and ethanol compared with graphite/GC- or GC-based bioelectrodes. By comparing the electrochemical performance of CR-GO with that of the conventional graphite and GC, we reveal that CR-GO with the nature of a single sheet showing favorable electrochemical activity should be a kind of more robust and advanced carbon electrode material which may hold great promise for electrochemical sensors and biosensors design.

Effective anodic oxidation of naproxen by platinum nanoparticles coated FTO glass.

PubMed

Chin, Ching-Ju Monica; Chen, Tsan-Yao; Lee, Menshan; Chang, Chiung-Fen; Liu, Yu-Ting; Kuo, Yu-Tsun

2014-07-30

This study investigated applications of the electrochemical anodic oxidation process with Pt-FTO and Pt/MWCNTs-FTO glasses as anodes on the treatment of one of the most important emerging contaminants, naproxen. The anodes used in this study have been synthesized using commercial FTO, MWCNTs and Pt nanoparticles (PtNP). XRD patterns of Pt nanoparticles coated on FTO and MWCNTs revealed that MWCNTs can prevent the surface of PtNPs from sintering and thus provide a greater reaction sites density to interact with naproxen, which have also been confirmed by higher degradation and mineralization efficiencies in the Pt/MWCNTs-FTO system. Results from the CV analysis showed that the Pt-FTO and Pt/MWCNTs-FTO electrodes possessed dual functions of decreasing activation energy and interactions between hydroxyl radicals to effectively degrade naproxen. The lower the solution pH value, the better the degradation efficiency. The existence of humic acid indeed inhibited the degradation ability of naproxen due to the competitions in the multiple-component system. The electrochemical degradation processes were controlled by diffusion mechanism and two major intermediates of 2-acetyl-6-methoxynaphthalene and 2-(6-Hydroxy-2-naphthyl)propanoic acid were identified. This study has successfully demonstrated new, easy, flexible and effective anodic materials which can be feasibly applied to the electrochemical oxidation of naproxen. Copyright © 2014 Elsevier B.V. All rights reserved.

Direct Electrophoretic Deposition of Binder-Free Co3O4/Graphene Sandwich-Like Hybrid Electrode as Remarkable Lithium Ion Battery Anode.

PubMed

Yang, Yang; Huang, Jingxin; Zeng, Jing; Xiong, Jian; Zhao, Jinbao

2017-09-27

Co 3 O 4 is emerging as a promising anode candidate for lithium ion batteries (LIBs) with high theoretical capacity (890 mAh g -1 ) but suffers from poor electrochemical cycling stability resulting from the inferior intrinsic electronic conductivity and large volume changes during electrochemical cycling. Here, a new electrophoretic deposition Co 3 O 4 /graphene (EPD Co 3 O 4 /G) hybrid electrode is developed to improve the electrochemical performance. Through EPD, Co 3 O 4 nanocubes can be homogeneously embedded between graphene sheets to form a sandwich-like structure. Owing to the excellent flexibility of graphene and a large number of voids in this sandwich-like structure, the structural integrity and unobstructed conductive network can be maintained during cycling. Moreover, the electrode kinetics has proved to be a fast surface-controlled lithium storage process. As a result, the Co 3 O 4 /G hybrid electrode exhibits high specific capacity and excellent electrochemical cycling performance. The Co 3 O 4 /G hybrid electrode was also further studied by in situ electrochemical XRD to understand the relationship of its structure and performance: (1) The observed Li x Co 3 O 4 indicates an intermediate of possible small volume change in the first discharging. (2) The theoretical capacity achievement of the Co 3 O 4 in hybrid electrode was evidenced. (3) The correlation between the electrochemical performance and the structural evolution of the Co 3 O 4 /G hybrid electrode was discussed detailedly.

Nucleation and growth of thin films of the organic conductor TTF-iodide over glassy carbon. Electrochemical and spectroelectrochemical study.

PubMed

Gómez, L; Rodríguez-Amaro, R

2009-04-21

On the basis of the electrochemical and spectroelectrochemical behavior of thin films of TTF over a glassy carbon electrode in iodide media, a new, more complete mechanism for the electrode processes involved is proposed. The voltammetric and chronoamperometric results for the films can be explained in light of a recently developed nucleation-growth model involving a layer-by-layer mechanism. Also, their in situ UV-vis spectral data expand the available knowledge about the overall mechanism and the nature of the compound formed over the glassy carbon electrode.

Vapor-Phase Atomic Layer Deposition of Co9S8 and Its Application for Supercapacitors.

PubMed

Li, Hao; Gao, Yuanhong; Shao, Youdong; Su, Yantao; Wang, Xinwei

2015-10-14

Atomic layer deposition (ALD) of cobalt sulfide (Co9S8) is reported. The deposition process uses bis(N,N'-diisopropylacetamidinato)cobalt(II) and H2S as the reactants and is able to produce high-quality Co9S8 films with an ideal layer-by-layer ALD growth behavior. The Co9S8 films can also be conformally deposited into deep narrow trenches with aspect ratio of 10:1, which demonstrates the high promise of this ALD process for conformally coating Co9S8 on high-aspect-ratio 3D nanostructures. As Co9S8 is a highly promising electrochemical active material for energy devices, we further explore its electrochemical performance by depositing Co9S8 on porous nickel foams for supercapacitor electrodes. Benefited from the merits of ALD for making high-quality uniform thin films, the ALD-prepared electrodes exhibit remarkable electrochemical performance, with high specific capacitance, great rate performance, and long-term cyclibility, which highlights the broad and promising applications of this ALD process for energy-related electrochemical devices, as well as for fabricating complex 3D nanodevices in general.

Highly branched RuO2 Nanorods on Electrospun TiO2 Nanofibers toward Electrochemical Catalysts

NASA Astrophysics Data System (ADS)

Cho, Yukyung; Kim, Su-Jin; Lee, Nam-Suk; Kim, Myung Hwa; Lee, Youngmi

2014-03-01

We report a facile growth route to synthesize hierarchically grown single crystalline metallic RuO2 nanorods on electrospun TiO2 nanofibers via a combination of a simple vapour phase transport process with an electrospinning process. This synthetic strategy could be very useful to design a variety of highly branched network architectures of the functional hetero-nanostructures for electrochemical applications. Particularly, Ruthenium oxide (RuO2) 1-dimensional nanostructures can be used as the effective catalysts or electrochemical electrode materials. Thus, we first synthesize TiO2 nanofibers from mixture of titanium isopropoxide precursor and polymer and then ruthenium hydroxide precursor on TiO2 nanofibers are transformed into RuO2 nanorods by thermal treatment at 250oC in air. The crystalline structures of products are confirmed using scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) spectrum, Raman spectroscopy, and high resolution electron microscopy (HRTEM). The fundamental electrochemical performances are examined using cyclic voltammetry (CV).

Surface Modifications of Materials by Electrochemical Methods to Improve the Properties for Industrial and Medical Applications

NASA Astrophysics Data System (ADS)

Benea, Lidia

2018-06-01

There are two applied electrochemical methods in our group in order to obtain advanced functional surfaces on materials: (i) direct electrochemical synthesis by electro-codeposition process and (ii) anodization of materials to form nanoporous oxide layers followed by electrodeposition of hydroxyapatite or other bioactive molecules and compounds into porous film. Electrodeposition is a process of low energy consumption, and therefore very convenient for the surface modification of various types of materials. Electrodeposition is a powerful method compared with other methods, which led her to be adopted and spread rapidly in nanotechnology to obtain nanostructured layers and films. Nanoporous thin oxide layers on titanum alloys as support for hydroxyapatite or other biomolecules electrodeposition in view of biomedical applications could be obtained by electrochemical methods. For surface modification of titanium or titanium alloys to improve the biocompatibility or osseointegration, the two steps must be fulfilled; the first is controlled growth of oxide layer followed by second being biomolecule electrodeposition into nanoporous formed titanium oxide layer.

Effects of H2S/HS- on Stress Corrosion Cracking Behavior of X100 Pipeline Steel Under Simulated Sulfate-Reducing Bacteria Metabolite Conditions

NASA Astrophysics Data System (ADS)

Liu, Q.; Li, Z.; Liu, Z. Y.; Li, X. G.; Wang, S. Q.

2017-04-01

The effect of H2S/HS-, which simulates the main metabolites of sulfate-reducing bacteria (SRB), on the electrochemical and stress corrosion cracking (SCC) behaviors of X100 steel was investigated in a near-neutral solution. The results showed that different H2S/HS- contents mainly affected the cathodic process of X100 electrochemical corrosion. As the concentration of H2S/HS- increased, the corrosion potential was shifted negatively, the corrosion current density was considerably increased, and the corrosion rate was linearly increased. Different rust layers with shifting structures were formed under different conditions and had different effects on electrochemical behaviors. However, sulfide mainly promoted local corrosion processes. With the synergistic effects of stress and H2S/HS-, SCC susceptibility was considerably enhanced. The accelerated process of hydrogen evolution by sulfide was crucial in enhancing SCC processes. In brief, the trace H2S/HS- generated by SRB metabolites played a positive role in promoting SCC.

Electroslag Treatment of Liquid Cast Iron

NASA Astrophysics Data System (ADS)

Grachev, V. A.

2018-01-01

The processes that occur in the liquid metal-slag system during electroslag treatment of cast iron are studied from an electrochemical standpoint. The role of electrolysis in the electroslag process is shown, and a method for producing high-strength cast iron with globular graphite using electrolysis of a slag containing magnesium oxides and fluorides is proposed and tested.

Silica decorated on porous activated carbon nanofiber composites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Kim, So Yeun; Kim, Bo-Hye

2016-10-01

A hybrid of silica decorated on porous activated carbon nanofibers (ACNFs) is fabricated in the form of a web via electrospinning and an activation process as an electrode material for electrochemical capacitors in an organic electrolyte. The introduction of PhSiH3 (PS) into the polyacrylonitrile (PAN) solution induces a porous ACNF structure containing silica nanoparticles (NPs) via the spontaneous sol-gel process of PS by steam in the subsequent physical activation process. These inorganic-organic hybrid composites of porous ACNF containing silica NPs show superior specific capacitance and energy density in electrochemical tests, along with good rate capability and excellent cycle life in an organic electrolyte, which is attributed to the combination of ACNF's high surface area and silica's hydrophilicity. The electrochemical performance decreases with increasing PS concentration, and this trend is consistent with the specific surface area results, which reveal the rapid formation of a double layer.

Enabling high areal capacitance in electrochemical double layer capacitors by means of the environmentally friendly starch binder

NASA Astrophysics Data System (ADS)

Varzi, Alberto; Passerini, Stefano

2015-12-01

Potatoes starch (PS), a natural polymer obtainable from non-edible sources, is for the first time evaluated as alternative water-processable binder for Electrochemical Double-Layer Capacitor (EDLC) electrodes. Morphological and electrochemical properties of activated carbon (AC)-based electrodes are investigated and compared to those achieved with the state-of-the-art aqueous binder (CMC, i.e. Na-carboxymethyl cellulose). The obtained results suggest substantial benefits of PS, in particular regarding the electrode fabrication process. As a matter of fact, owing to its amylopectin content (moderately branched polysaccharide), PS displays only minimal shrinkage upon drying, resulting on rather homogeneous electrodes not presenting the dramatic surface cracking observed with CMC. Furthermore, owing to the smaller volume of water required for the processing, much higher active material loading per area unit can be achieved. This is reflected on improvements of up to 60% in terms of areal capacitance.

Studies on the preparation of Caro’s acid by ultrasonic enhanced electrochemistry

NASA Astrophysics Data System (ADS)

Li, Linbo; Yu, Zeli; Hong, Tao; Fang, Zhao; Peng, Jishi; Yang, Zhao

2017-06-01

Ultrasonic cavitation effects can generate hydroxyl radicals and high energy, which is widely applied in the field of oxidation currently. Ultrasound-enhanced electrochemical is used to prepare Caro’s acid, which improves the generate rate of Caro’s acid. In this article, the influences of ultrasonic frequency and ultrasonic power on the electrolysis voltage, electrolyte temperature, electrolyte concentration and the concentration of additive in the process of electrochemical preparation of Caro’s acid was studied. And the optimal production conditions were determined. The research results showed that ultrasonic can significantly improve the production of Caro’s acid and the product can increase by about 20 g/L under the best condition.

All silicon electrode photocapacitor for integrated energy storage and conversion.

PubMed

Cohn, Adam P; Erwin, William R; Share, Keith; Oakes, Landon; Westover, Andrew S; Carter, Rachel E; Bardhan, Rizia; Pint, Cary L

2015-04-08

We demonstrate a simple wafer-scale process by which an individual silicon wafer can be processed into a multifunctional platform where one side is adapted to replace platinum and enable triiodide reduction in a dye-sensitized solar cell and the other side provides on-board charge storage as an electrochemical supercapacitor. This builds upon electrochemical fabrication of dual-sided porous silicon and subsequent carbon surface passivation for silicon electrochemical stability. The utilization of this silicon multifunctional platform as a combined energy storage and conversion system yields a total device efficiency of 2.1%, where the high frequency discharge capability of the integrated supercapacitor gives promise for dynamic load-leveling operations to overcome current and voltage fluctuations during solar energy harvesting.

Electrochemical and theoretical characterization of the electro-oxidation of dimethoxycurcumin

NASA Astrophysics Data System (ADS)

Arrue, Lily; Barra, Tomas; Camarada, María Belén; Zarate, Ximena; Schott, Eduardo

2017-06-01

Dimethoxycurcumin (DMC) ((1E,6E)-1-(3,4-dimethoxycyclohexyl)-7-(3,4-dimethoxyphenyl) hepta-1,6- diene-3,5-dione) is a natural polyphenolic compound that appears together with curcumin in turmeric. Both molecules have wide range biological activities as antioxidant, anti-inflammatory and anti-carcinogenic agent. To evaluate the oxidation process and kinetics for DMC, the rate constant, electron transfer and diffusion coefficients for the electrochemical oxidation were determined. Therefore, its electrochemical behavior over a platinum electrode in anhydrous media was investigated. Furthermore, DFT calculations were performed to give a rational explanation to the obtained results. All the results support the fact that the central sbnd CH2sbnd group is the most reactive against an oxidation process.

Prioritized List of Research Needs to support MRWFD Case Study Flowsheet Advancement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Law, Jack Douglas; Soelberg, Nicholas Ray

In FY-13, a case study evaluation was performed of full recycle technologies for both the processing of light-water reactor (LWR) used nuclear fuels as well as fast reactor (FR) fuel in the full recycle option. This effort focused on the identification of the case study processes and the initial preparation of material balance flowsheets for the identified technologies. In identifying the case study flowsheets, it was decided that two cases would be developed: one which identifies the flowsheet as currently developed and another near-term target flowsheet which identifies the flowsheet as envisioned within two years, pending the results of ongoingmore » research. The case study focus is on homogeneous aqueous recycle of the U/TRU resulting from the processing of LWR fuel as feed for metal fuel fabrication. The metal fuel is utilized in a sodium-cooled fast reactor, and the used fast reactor fuel is processed using electrochemical separations. The recovered U/TRU from electrochemical separations is recycled to fuel fabrication and the fast reactor. Waste streams from the aqueous and electrochemical processing are treated and prepared for disposition. Off-gas from the separations and waste processing are also treated. As part of the FY-13 effort, preliminary process unknowns and research needs to advance the near-term target flowsheets were identified. In FY-14, these research needs were updated, expanded and prioritized. This report again updates the prioritized list of research needs based upon results to date in FY-15. The research needs are listed for each of the main portions of the flowsheet: 1) Aqueous headend, 2) Headend tritium pretreatment off-gas, 3) Aqueous U/Pu/Np recovery, 4) Aqueous TRU product solidification, 5) Aqueous actinide/lanthanide separation, 6) Aqueous off-gas treatment, 7) Aqueous HLW management, 8) Treatment of aqueous process wastes, 9) E-chem actinide separations, 10) E-chem off-gas, 11) E-chem HLW management. The identified research needs were prioritized within each of these areas. No effort was made to perform an overall prioritization. This information will be used by the MRWFD Campaign leadership in research planning for FY-16. Additionally, this information will be incorporated into the next version of the Case Study Report scheduled to be issued September 2015.« less

Application of Electro Chemical Machining for materials used in extreme conditions

NASA Astrophysics Data System (ADS)

Pandilov, Z.

2018-03-01

Electro-Chemical Machining (ECM) is the generic term for a variety of electrochemical processes. ECM is used to machine work pieces from metal and metal alloys irrespective of their hardness, strength or thermal properties, through the anodic dissolution, in aerospace, automotive, construction, medical equipment, micro-systems and power supply industries. The Electro Chemical Machining is extremely suitable for machining of materials used in extreme conditions. General overview of the Electro-Chemical Machining and its application for different materials used in extreme conditions is presented.

Electrochemical research on corrosion behavior of A3 steel in compound sodium molybadate and organic inhibitor solution

NASA Astrophysics Data System (ADS)

Sun, C. X.; Chen, Y. M.; Xu, H. W.; Zhang, M.; Chen, M.; Xue, M.; Wu, J. Y.; Huang, C. S.

2015-07-01

The electrochemical corrosion behavior of A3 in compound sodium molybdate and organic inhibitor solution was tested by the electrochemical workstation method. The concentration of the compound inhibitor set to range 250 mg/L to 3000 mg/L. The polarization curve results of A3 in different concentration inhibitor solutions show that the inhibitor markedly represses the anodic processes. The EIS has two time constant. The extreme concentration is 1500 mg/L.

A Novel of Multi-wall Carbon Nanotubes/Chitosan Electrochemical Sensor for Determination of Cupric ion

NASA Astrophysics Data System (ADS)

Tan, Funeng; Li, Lei

2018-03-01

A multi-wall carbon nanotubes/Chitosan electrochemical sensor had been fabricated by dropping CHS/MWNT solution directly onto the GC surface. The sensor was charactered by cyclic voltammetry and AC impedance with K3Fe(CN)6 as a electrochemical probe; Cyclic voltammograms(CV) and electrochemical impedance spectroscopy(EIS) indicated that the active area and electrochemical behavior of the sensor increased and improved significantly after the electrode was modified by carbon nanotubes dispersed by the chitosan. The sensor showed good electrocatalytic activity of K3Fe(CN)6. Also, from the cyclic voltammograms, we can see the process was diffusion controlled on the bare electrode and kinetics and diffusion controlled on the modified electrode. Finally Cu2+ responsed sensitively at the sensor which supplied a new method for the detection of Cu2+.

Facile synthesis of NiAl-layered double hydroxide/graphene hybrid with enhanced electrochemical properties for detection of dopamine

NASA Astrophysics Data System (ADS)

Li, Meixia; Zhu, Jun E.; Zhang, Lili; Chen, Xu; Zhang, Huimin; Zhang, Fazhi; Xu, Sailong; Evans, David G.

2011-10-01

Layered double hydroxides (LDHs), also known as hydrotalcite-like anionic clays, have been investigated widely as promising electrochemical active materials. Due to the inherently weak conductivity, the electrochemical properties of LDHs were improved typically by utilization of either functional molecules intercalated between LDH interlayer galleries, or proteins confined between exfoliated LDH nanosheets. Here, we report a facile protocol to prepare NiAl-LDH/graphene (NiAl-LDH/G) nanocomposites using a conventional coprecipitation process under low-temperature conditions and subsequent reduction of the supporting graphene oxide. Electrochemical tests showed that the NiAl-LDH/G modified electrode exhibited highly enhanced electrochemical performance of dopamine electrooxidation in comparison with the pristine NiAl-LDH modified electrode. Results of high-resolution transmission electron microscopy and Raman spectra provide convincing information on the nanostructure and composition underlying the enhancement. Our results of the NiAl-LDH/G modified electrodes with the enhanced electrochemical performance may allow designing a variety of promising hybrid sensors via a simple and feasible approach.Layered double hydroxides (LDHs), also known as hydrotalcite-like anionic clays, have been investigated widely as promising electrochemical active materials. Due to the inherently weak conductivity, the electrochemical properties of LDHs were improved typically by utilization of either functional molecules intercalated between LDH interlayer galleries, or proteins confined between exfoliated LDH nanosheets. Here, we report a facile protocol to prepare NiAl-LDH/graphene (NiAl-LDH/G) nanocomposites using a conventional coprecipitation process under low-temperature conditions and subsequent reduction of the supporting graphene oxide. Electrochemical tests showed that the NiAl-LDH/G modified electrode exhibited highly enhanced electrochemical performance of dopamine electrooxidation in comparison with the pristine NiAl-LDH modified electrode. Results of high-resolution transmission electron microscopy and Raman spectra provide convincing information on the nanostructure and composition underlying the enhancement. Our results of the NiAl-LDH/G modified electrodes with the enhanced electrochemical performance may allow designing a variety of promising hybrid sensors via a simple and feasible approach. Electronic supplementary information (ESI) available: Fig. S1 showing 2D fast Fourier transform (FFT) image of NiAl-LDH phase in NiAl-LDH/G composites, and Fig. S2 showing CV curve of the pristine G modified electrode. See DOI: 10.1039/c1nr10592b.

A novel in situ electrochemical NMR cell with a palisade gold film electrode

NASA Astrophysics Data System (ADS)

Ni, Zu-Rong; Cui, Xiao-Hong; Cao, Shuo-Hui; Chen, Zhong

2017-08-01

In situ electrochemical nuclear magnetic resonance (EC-NMR) has attracted considerable attention because of its ability to directly observe real-time electrochemical processes. Therefore, minimizing the incompatibility between the electrochemical device and NMR detection has become an important challenge. A circular thin metal film deposited on the outer surface of a glass tube with a thickness considerably less than the metal skin depth is considered to be the ideal working electrode. In this study, we demonstrate that such a thin film electrode still has a great influence on the radio frequency field homogeneity in the detective zone of the NMR spectrometer probe and provide theoretical and experimental confirmation of its electromagnetic shielding. Furthermore, we propose a novel palisade gold film device to act as the working electrode. The NMR nutation behavior of protons shows that the uniformity of the radio frequency field is greatly improved, increasing the sensitivity in NMR detection. Another advantage of the proposed device is that an external reference standard adapted to the reaction compound can be inserted as a probe to determine the fluctuation of the physico-chemical environment and achieve high-accuracy quantitative NMR analysis. A three-chamber electrochemical device based on the palisade gold film design was successfully fabricated and the in situ electrochemical NMR performance was validated in a standard 5 mm NMR probe by acquiring voltammograms and high-resolution NMR spectra to characterize the electrochemically generated species. The evolution of in situ EC-NMR spectrum monitoring of the redox transformation between p-benzoquinone and hydroquinone demonstrates the ability of the EC-NMR device to simultaneously quantitatively determine the reactants and elucidate the reaction mechanism at the molecular level.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Low-dimensional carbon and MXene-based electrochemical capacitor electrodes.

PubMed

Yoon, Yeoheung; Lee, Keunsik; Lee, Hyoyoung

2016-04-29

Due to their unique structure and outstanding intrinsic physical properties such as extraordinarily high electrical conductivity, large surface area, and various chemical functionalities, low-dimension-based materials exhibit great potential for application in electrochemical capacitors (ECs). The electrical properties of electrochemical capacitors are determined by the electrode materials. Because energy charge storage is a surface process, the surface properties of the electrode materials greatly influence the electrochemical performance of the cell. Recently, graphene, a single layer of sp(2)-bonded carbon atoms arrayed into two-dimensional carbon nanomaterial, has attracted wide interest as an electrode material for electrochemical capacitor applications due to its unique properties, including a high electrical conductivity and large surface area. Several low-dimensional materials with large surface areas and high conductivity such as onion-like carbons (OLCs), carbide-derived carbons (CDCs), carbon nanotubes (CNTs), graphene, metal hydroxide, transition metal dichalcogenides (TMDs), and most recently MXene, have been developed for electrochemical capacitors. Therefore, it is useful to understand the current issues of low-dimensional materials and their device applications.

Remediation of water pollution caused by pharmaceutical residues based on electrochemical separation and degradation technologies: a review.

PubMed

Sirés, Ignasi; Brillas, Enric

2012-04-01

In the last years, the decontamination and disinfection of waters by means of direct or integrated electrochemical processes are being considered as a very appealing alternative due to the significant improvement of the electrode materials and the coupling with low-cost renewable energy sources. Many electrochemical technologies are currently available for the remediation of waters contaminated by refractory organic pollutants such as pharmaceutical micropollutants, whose presence in the environment has become a matter of major concern. Recent reviews have focused on the removal of pharmaceutical residues upon the application of other important methods like ozonation and advanced oxidation processes. Here, we present an overview on the electrochemical methods devised for the treatment of pharmaceutical residues from both, synthetic solutions and real pharmaceutical wastewaters. Electrochemical separation technologies such as membrane technologies, electrocoagulation and internal micro-electrolysis, which only isolate the pollutants from water, are firstly introduced. The fundamentals and experimental set-ups involved in technologies that allow the degradation of pharmaceuticals, like anodic oxidation, electro-oxidation with active chlorine, electro-Fenton, photoelectro-Fenton and photoelectrocatalysis among others, are further discussed. Progress on the promising solar photoelectro-Fenton process devised and further developed in our laboratory is especially highlighted and documented. The abatement of total organic carbon or reduction of chemical oxygen demand from contaminated waters allows the comparison between the different methods and materials. The routes for the degradation of the some pharmaceuticals are also presented. Copyright © 2011 Elsevier Ltd. All rights reserved.

Optimization of the Electrochemical Extraction and Recovery of Metals from Electronic Waste Using Response Surface Methodology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diaz, Luis A.; Clark, Gemma G.; Lister, Tedd E.

The rapid growth of the electronic waste can be viewed both as an environmental threat and as an attractive source of minerals that can reduce the mining of natural resources, and stabilize the market of critical materials, such as rare earths. Here in this article surface response methodology was used to optimize a previously developed electrochemical recovery process for base metals from electronic waste using a mild oxidant (Fe 3+). Through this process an effective extraction of base metals can be achieved enriching the concentration of precious metals and significantly reducing environmental impacts and operational costs associated with the wastemore » generation and chemical consumption. The optimization was performed using a bench-scale system specifically designed for this process. Operational parameters such as flow rate, applied current density and iron concentration were optimized to reduce the specific energy consumption of the electrochemical recovery process to 1.94 kWh per kg of metal recovered at a processing rate of 3.3 g of electronic waste per hour.« less

Optimization of the Electrochemical Extraction and Recovery of Metals from Electronic Waste Using Response Surface Methodology

DOE PAGES

Diaz, Luis A.; Clark, Gemma G.; Lister, Tedd E.

2017-06-08

The rapid growth of the electronic waste can be viewed both as an environmental threat and as an attractive source of minerals that can reduce the mining of natural resources, and stabilize the market of critical materials, such as rare earths. Here in this article surface response methodology was used to optimize a previously developed electrochemical recovery process for base metals from electronic waste using a mild oxidant (Fe 3+). Through this process an effective extraction of base metals can be achieved enriching the concentration of precious metals and significantly reducing environmental impacts and operational costs associated with the wastemore » generation and chemical consumption. The optimization was performed using a bench-scale system specifically designed for this process. Operational parameters such as flow rate, applied current density and iron concentration were optimized to reduce the specific energy consumption of the electrochemical recovery process to 1.94 kWh per kg of metal recovered at a processing rate of 3.3 g of electronic waste per hour.« less

Catalytic Hydrogenation of Organic Compounds without H2 Supply: An Electrochemical System

ERIC Educational Resources Information Center

Navarro, Daniela Maria do Amaral Ferraz; Navarro, Marcelo

2004-01-01

An experiment developed for an undergraduate organic chemistry laboratory course that can be used to introduce the catalytic hydrogenation reaction, catalysis electrochemical principles and gas chromatography is presented. The organic compounds hydrogenated by the electrocatalytic hydrogenation (ECH) process were styrene, benzaldehyde and…

THE ELECTROCHEMISTRY OF ANTIBODY-MODIFIED CONDUCTING POLYMER ELECTRODES. (R825323)

EPA Science Inventory

Abstract

The modification of conducting polymer electrodes with antibodies (i.e. proteins) by means of electrochemical polymerization is a simple step that can be used to develop an immunological sensor. However, the electrochemical processes involved leading to the ge...

Stabilized TiN nanowire arrays for high-performance and flexible supercapacitors.

PubMed

Lu, Xihong; Wang, Gongming; Zhai, Teng; Yu, Minghao; Xie, Shilei; Ling, Yichuan; Liang, Chaolun; Tong, Yexiang; Li, Yat

2012-10-10

Metal nitrides have received increasing attention as electrode materials for high-performance supercapacitors (SCs). However, most of them are suffered from poor cycling stability. Here we use TiN as an example to elucidate the mechanism causing the capacitance loss. X-ray photoelectron spectroscopy analyses revealed that the instability is due to the irreversible electrochemical oxidation of TiN during the charging/discharging process. Significantly, we demonstrate for the first time that TiN can be stabilized without sacrificing its electrochemical performance by using poly(vinyl alcohol) (PVA)/KOH gel as the electrolyte. The polymer electrolyte suppresses the oxidation reaction on electrode surface. Electrochemical studies showed that the TiN solid-state SCs exhibit extraordinary stability up to 15,000 cycles and achieved a high volumetric energy density of 0.05 mWh/cm(3). The capability of effectively stabilizing nitride materials could open up new opportunities in developing high-performance and flexible SCs.

Spine-like Nanostructured Carbon Interconnected by Graphene for High-performance Supercapacitors

NASA Astrophysics Data System (ADS)

Park, Sang-Hoon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Han, Joong Tark; Park, Hae-Woong; Han, Joah; Yun, Seok-Min; Jeong, Han Gi; Roh, Kwang Chul; Kim, Kwang-Bum

2014-08-01

Recent studies on supercapacitors have focused on the development of hierarchical nanostructured carbons by combining two-dimensional graphene and other conductive sp2 carbons, which differ in dimensionality, to improve their electrochemical performance. Herein, we report a strategy for synthesizing a hierarchical graphene-based carbon material, which we shall refer to as spine-like nanostructured carbon, from a one-dimensional graphitic carbon nanofiber by controlling the local graphene/graphitic structure via an expanding process and a co-solvent exfoliation method. Spine-like nanostructured carbon has a unique hierarchical structure of partially exfoliated graphitic blocks interconnected by thin graphene sheets in the same manner as in the case of ligaments. Owing to the exposed graphene layers and interconnected sp2 carbon structure, this hierarchical nanostructured carbon possesses a large, electrochemically accessible surface area with high electrical conductivity and exhibits high electrochemical performance.

Spine-like nanostructured carbon interconnected by graphene for high-performance supercapacitors.

PubMed

Park, Sang-Hoon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Han, Joong Tark; Park, Hae-Woong; Han, Joah; Yun, Seok-Min; Jeong, Han Gi; Roh, Kwang Chul; Kim, Kwang-Bum

2014-08-19

Recent studies on supercapacitors have focused on the development of hierarchical nanostructured carbons by combining two-dimensional graphene and other conductive sp(2) carbons, which differ in dimensionality, to improve their electrochemical performance. Herein, we report a strategy for synthesizing a hierarchical graphene-based carbon material, which we shall refer to as spine-like nanostructured carbon, from a one-dimensional graphitic carbon nanofiber by controlling the local graphene/graphitic structure via an expanding process and a co-solvent exfoliation method. Spine-like nanostructured carbon has a unique hierarchical structure of partially exfoliated graphitic blocks interconnected by thin graphene sheets in the same manner as in the case of ligaments. Owing to the exposed graphene layers and interconnected sp(2) carbon structure, this hierarchical nanostructured carbon possesses a large, electrochemically accessible surface area with high electrical conductivity and exhibits high electrochemical performance.

Spine-like Nanostructured Carbon Interconnected by Graphene for High-performance Supercapacitors

PubMed Central

Park, Sang-Hoon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Han, Joong Tark; Park, Hae-Woong; Han, Joah; Yun, Seok-Min; Jeong, Han Gi; Roh, Kwang Chul; Kim, Kwang-Bum

2014-01-01

Recent studies on supercapacitors have focused on the development of hierarchical nanostructured carbons by combining two-dimensional graphene and other conductive sp2 carbons, which differ in dimensionality, to improve their electrochemical performance. Herein, we report a strategy for synthesizing a hierarchical graphene-based carbon material, which we shall refer to as spine-like nanostructured carbon, from a one-dimensional graphitic carbon nanofiber by controlling the local graphene/graphitic structure via an expanding process and a co-solvent exfoliation method. Spine-like nanostructured carbon has a unique hierarchical structure of partially exfoliated graphitic blocks interconnected by thin graphene sheets in the same manner as in the case of ligaments. Owing to the exposed graphene layers and interconnected sp2 carbon structure, this hierarchical nanostructured carbon possesses a large, electrochemically accessible surface area with high electrical conductivity and exhibits high electrochemical performance. PMID:25134517

Probing electrokinetics in microchannels and nanochannels with electrochemical measurements

NASA Astrophysics Data System (ADS)

Schiffbauer, Jarrod; Park, Sinwook; Yossifon, Gilad

2013-11-01

We present a brief review of recent experimental and theoretical results concerning the use of electrochemical impedance spectroscopy (EIS), in conjunction with other electrochemical measurements (chronoamperometry, linear sweep voltammetry), to characterize the response of micro- and nanofluidic systems. Using these techniques, the interplay between conduction, diffusion, and convection are probed across a range of time- and length scales. The resulting information permits characterization of the respective roles of processes in both micro- and nanchannel regions of a fluidic device. Such techniques provide a useful probe of transient behavior at the micro-nanochannel interface, have great potential in biomolecular sensing applications, and may be useful in the study of surface properties at the fluid-solid interface. We wish to acknowledge Israel Science Foundation, grant number 2015240, the Technion Russel-Berrie Nanotechnology Institute (RBNI) and a fellowship grant from the Techion Faculty of Mechanical Engineering.

Electrolytic Generation of Nano-Scale Carbon Phases with Framework Structures in Molten Salts on Metal Cathodes

NASA Astrophysics Data System (ADS)

Novoselova, Inessa A.; Oliinyk, Nikolai F.; Voronina, Anastasiya B.; Volkov, Sergei V.

2008-08-01

An electrochemical study of mechanisms of electrodeposition of carbon solid phases from halide melts (Na,K|Cl; Na,K,Cs|Cl), saturated with carbon dioxide under an excessive pressure of up to 1.5 MPa, has been carried out in the temperature range 550 - 850 °C by cyclic voltammetry. It has been found that the cathode process occurs in three steps at sweep rates of less than 0.1 Vs-1, and its electrochemical-chemical-electrochemical (ECE) mechanism is suggested. It has furthermore been found that cathodic deposits contain nano-sized carbon particles of different forms and structure: blocks of amorphous carbon, crystalline graphite, carbon nanotubes (CNT), and nanofibres. The outer diameter of the tubes is 5 - 250 nm, and the internal diameter is 2 - 140 nm. A correlation between the product structure and yield against electrolysis conditions and regimes has been established.

pH-dependent ammonia removal pathways in microbial fuel cell system.

PubMed

Kim, Taeyoung; An, Junyeong; Lee, Hyeryeong; Jang, Jae Kyung; Chang, In Seop

2016-09-01

In this work, ammonia removal paths in microbial fuel cells (MFCs) under different initial pH conditions (pH 7.0, 8.0, and 8.6) were investigated. At a neutral pH condition (pH 7.0), MFC used an electrical energy of 27.4% and removed 23.3% of total ammonia by electrochemical pathway for 192h. At the identical pH condition, 36.1% of the total ammonia was also removed by the biological path suspected to be biological ammonia oxidation process (e.g., Anammox). With the initial pH increased, the electrochemical removal efficiency decreased to less than 5.0%, while the biological removal efficiency highly increased to 61.8%. In this study, a neutral pH should be maintained in the anode to utilize MFCs for ammonia recovery via electrochemical pathways from wastewater stream. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fluorinated graphenes as advanced biosensors - effect of fluorine coverage on electron transfer properties and adsorption of biomolecules

NASA Astrophysics Data System (ADS)

Urbanová, Veronika; Karlický, František; Matěj, Adam; Šembera, Filip; Janoušek, Zbyněk; Perman, Jason A.; Ranc, Václav; Čépe, Klára; Michl, Josef; Otyepka, Michal; Zbořil, Radek

2016-06-01

Graphene derivatives are promising materials for the electrochemical sensing of diverse biomolecules and development of new biosensors owing to their improved electron transfer kinetics compared to pristine graphene. Here, we report complex electrochemical behavior and electrocatalytic performance of variously fluorinated graphene derivatives prepared by reaction of graphene with a nitrogen-fluorine mixture at 2 bars pressure. The fluorine content was simply controlled by varying the reaction time and temperature. The studies revealed that electron transfer kinetics and electrocatalytic activity of CFx strongly depend on the degree of fluorination. The versatility of fluorinated graphene as a biosensor platform was demonstrated by cyclic voltammetry for different biomolecules essential in physiological processes, i.e. NADH, ascorbic acid and dopamine. Importantly, the highest electrochemical performance, even higher than pristine graphene, was obtained for fluorinated graphene with the lowest fluorine content (CF0.084) due to its high conductivity and enhanced adsorption properties combining π-π stacking interaction with graphene regions with hydrogen-bonding interaction with fluorine atoms.Graphene derivatives are promising materials for the electrochemical sensing of diverse biomolecules and development of new biosensors owing to their improved electron transfer kinetics compared to pristine graphene. Here, we report complex electrochemical behavior and electrocatalytic performance of variously fluorinated graphene derivatives prepared by reaction of graphene with a nitrogen-fluorine mixture at 2 bars pressure. The fluorine content was simply controlled by varying the reaction time and temperature. The studies revealed that electron transfer kinetics and electrocatalytic activity of CFx strongly depend on the degree of fluorination. The versatility of fluorinated graphene as a biosensor platform was demonstrated by cyclic voltammetry for different biomolecules essential in physiological processes, i.e. NADH, ascorbic acid and dopamine. Importantly, the highest electrochemical performance, even higher than pristine graphene, was obtained for fluorinated graphene with the lowest fluorine content (CF0.084) due to its high conductivity and enhanced adsorption properties combining π-π stacking interaction with graphene regions with hydrogen-bonding interaction with fluorine atoms. Electronic supplementary information (ESI) available: SEM, HRTEM, and AFM images the sheet in pristine graphene sample, survey XPS spectrum, high resolution C 1s XPS spectrum, and Raman spectrum of pristine graphene precursor used for controlled fluorination, survey and high resolution F 1s XPS spectra of the CF0.084, CF0.158, and CF0.218 samples, EDS chemical mapping of fluorine in CF0.158, contact angle measurement of CF0.084, CF0.158, CF0.218, and HOPG, and additional electrochemical data. See DOI: 10.1039/c6nr00353b

Investigating effectiveness of activated carbons of natural sources on various supercapacitors

NASA Astrophysics Data System (ADS)

Faisal, Md. Shahnewaz Sabit; Rahman, Muhammad M.; Asmatulu, Ramazan

2016-04-01

Activated carbon can be produced from natural sources, such as pistachio and acorn shells, which can be an inexpensive and sustainable sources of natural wastes for the energy storage devices, such as supercapacitors. The carbonaceous materials used in this study were carbonized at the temperatures of 700°C and 900°C after the stabilization process at 240°C for two hours. These shells showed approximately 60% carbon yield. Carbonized nutshells were chemically activated using1wt% potassium hydroxide (KOH). Activated carbon powders with polyvinylidene fluoride (PVdF) were used to construct carbon electrodes. A 1M of tetraethylammonium tetrafluoroborate (TEABF4) and propylene carbonate (PC) were used as electrolytes. Electrochemical techniques, such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used for the characterization of the supercapacitors. Scanning electron microscopy (SEM) was used to inspect the surface texture of the activated carbons. Activated pistachio shells carbonized at 700°C showed more porous surface texture than those carbonized at 900°C. Effects of the carbonization temperatures were studied for their electrochemical characteristics. The shells carbonized at 700°C showed better electrochemical characteristics compared to those carbonized at 900°C. The test results provided about 27,083 μF/g specific capacitance at a scan rate of 10mV/s. This study showed promising results for using these activated carbons produced from the natural wastes for supercapacitor applications.

Space Electrochemical Research and Technology

NASA Technical Reports Server (NTRS)

1993-01-01

This document contains the proceedings of NASA's fourth Space Electrochemical Research and Technology (SERT) Conference, held at the NASA Lewis Research Center on April 14-15, 1993. The objective of the conference was to assess the present status and general thrust of research and development in those areas of electrochemical technology required to enable NASA missions into the next century. The conference provided a forum for the exchange of ideas and opinions of those actively involved in the field, in order to define new opportunities for the application of electrochemical processes in future NASA missions. Papers were presented in three technical areas: advanced secondary batteries, fuel cells, and advanced concepts for space power. This document contains the papers presented.

Improvement of diamond-like carbon electrochemical corrosion resistance by addition of nanocrystalline diamond.

PubMed

Marciano, F R; Almeida, E C; Bonetti, L F; Corat, E J; Trava-Airoldi, V J

2010-02-15

Nanocrystalline diamond (NCD) particles were incorporated into diamond-like carbon (DLC) films in order to investigate NCD-DLC electrochemical corrosion resistance. The films were grown over 304 stainless steel using plasma-enhanced chemical vapor deposition. NCD particles were incorporated into DLC during the deposition process. The investigation of NCD-DLC electrochemical corrosion behavior was performed using potentiodynamic polarization against NaCl. NCD-DLC films presented more negative corrosion potential and lower anodic and cathodic current densities. The electrochemical analysis indicated that NCD-DLC films present superior impedance and polarization resistance compared to the pure DLC, which indicate that they are promising corrosion protective coatings in aggressive solutions. Copyright 2009 Elsevier Inc. All rights reserved.

In-vitro bioactivity and electrochemical behavior of polyaniline encapsulated titania nanotube arrays for biomedical applications

NASA Astrophysics Data System (ADS)

Agilan, P.; Rajendran, N.

2018-05-01

Titania nanotube arrays (TNTA) have attracted increasing attention due to their outstanding properties and potential applications in biomedical field. Fabrication of titania nanotubes on titanium surface enhances the biocompatibility. Polyaniline (PANI) is one of the best conducting polymers with remarkable corrosion resistance and reasonable biocompatibility. In this work, the corrosion resistance and biocompatibility of polyaniline encapsulated TiO2 nanotubes for orthopaedic applications were investigated. The vertically oriented, highly ordered TiO2 nanotubes were fabricated on titanium by electrochemical anodization process using fluoride containing electrolytes. The anodization parameters viz., voltage, pH, time and electrolyte concentration were optimized to get orderly arranged TNTA. Further, the conducting polymer PANI was encapsulated on TNTA by electropolymerization process to enhance the corrosion resistance. The nanostructure of the fabricated TNTA and polyaniline encapsulated titania nanotube arrays (PANI-TNTA) were investigated by HR SEM analysis. The formed phases and functional groups were find using XRD, ATR-FTIR. The hydrophilic surface of TNTA and PANI-TNTA was identified by water contact angle studies. The corrosion behavior of specimens was evaluated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization studies. In-vitro immersion studies were carried out in simulated body fluid solution (Hanks' solution) to evaluate the bioactivity of the TNTA and PANI-TNTA. The surface morphological studies revealed the formation of PANI on the TNTA surface. Formation of hydroxyapatite (HAp) on the surfaces of TNTA and PANI-TNTA enhanced the bioactivity and corrosion resistance.

Treatment of textile wastewater by a hybrid electrocoagulation/nanofiltration process.

PubMed

Aouni, Anissa; Fersi, Cheïma; Ben Sik Ali, Mourad; Dhahbi, Mahmoud

2009-09-15

Untreated effluents from textile industries are usually highly coloured and contain a considerable amount of contaminants and pollutants. Stringent environmental regulation for the control of textile effluents is enforced in several countries. Previous studies showed that many techniques have been used for the treatment of textile wastewater, such as adsorption, biological treatment, oxidation, coagulation and/or flocculation, among them coagulation is one of the most commonly used techniques. Electrocoagulation is a process consisting in creating metallic hydroxide flocks within the wastewater by the electrodissolution of soluble anodes, usually made of iron or aluminium. This method has been practiced for most of the 20th century with limited success. In recent years, however, it started to regain importance with the progress of the electrochemical processes and the increase in environmental restrictions in effluent wastewater. This paper examines the use of electrocoagulation treatment process followed by nanofiltration process of a textile effluent sample. The electrocoagulation process was studied under several conditions such as various current densities and effect of experimental tense. Efficiencies of COD and turbidity reductions and colour removal were studied for each experiment. The electrochemical treatment was indented primarily to remove colour and COD of wastewater while nanofiltration was used to further improve the removal efficiency of the colour, COD, conductivity, alkalinity and total dissolved solids (TDS). The experimental results, throughout the present study, have indicated that electrocoagulation treatment followed by nanofiltration processes were very effective and were capable of elevating quality of the treated textile wastewater effluent.

The Synergistic Effect of Proteins and Reactive Oxygen Species on Electrochemical Behaviour of 316L Stainless Steel for Biomedical Applications

NASA Astrophysics Data System (ADS)

Simionescu, N.; Benea, L.; Dumitrascu, V. M.

2018-06-01

The stainless steels, especially 316L type is the most used metallic biomaterials for biomedical applications due to their good biocompatibility, low price, excellent corrosion resistance, availability, easy processing and high strength. Due to these favorable properties 316L stainless steel has become the most attractive biomaterial for dental implants, stents and orthopedic implants. However an implant material in the human body is exposed to an action effect of other molecules, including proteins (such as albumin) and reactive oxygen species (such as hydrogen peroxide - H2O2 ) produced by bacteria and immune cells. In the literature there are few studies to follow the effect of proteins and reactive oxygen species on 316L stainless steel used as implant material and are still unclear. The degree of corrosion resistance is the first criterion in the use of a metallic biomaterial in the oral or body environment. The aim of this research work is to investigate the influence of proteins (albumin) and reactive oxygen species (H2O2 ) in combination, taking into account the synergistic effect of these two factors on 316L stainless steel. Albumin is present in the body near implants and reactive oxygen species could appear in inflammatory processes as well. The study shows that the presence of albumin and reactive species influences the corrosion resistance of 316L stainless steel in biological solutions. In this research work the corrosion behavior of 316L stainless steel is analyzed by electrochemical methods such as: open circuit potential (OCP), Electrochemical Impedance Spectroscopy (EIS). It was found that, the electrochemical results are in a good agreement with micro photographs taken before and after corrosion assays. The albumin and reactive oxygen species have influence on 316L stainless steel behavior.

Activated carbon electrode from banana-peel waste for supercapacitor applications

NASA Astrophysics Data System (ADS)

Taer, E.; Taslim, R.; Aini, Z.; Hartati, S. D.; Mustika, W. S.

2017-01-01

Seven types of activated carbon electrode (ACM) have been produced from the banana peel waste for supercapacitor application. The difference type of the electrode was synthesized by the various conditions of carbonization and activation. The production of the ACM was begun by the milling process and molded by a solution casting technique. The next step was followed by drying, carbonization and activation process. Physical properties of the ACM were studied by the N2 gas absorption-desorption method to characterize the specific surface area of the sample. On the other side, the electrochemical properties such as specific capacitance (Csp), specific energy (E) and specific power (P) were resulted by calculating the current (I) and voltage (V) data from the cyclic voltammetry testing. Based on the data obtained the surface area of the ACM has a significant relationship with the electrochemical properties. The specific surface area (SBET), Csp, E and P were found the maximum value as high as 581m2 / g, 68 F/g, 0.75 Wh/kg and 31 W/kg, respectively. Further more, this paper were also analyzed the relationship between electrochemical properties of supercapacitor with the degree of crystallization of the ACM.

Hierarchical Ti-Nb oxide microspheres with synergic multiphase structure as ultra-long-life anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, Guanqin; Wen, Zhongsheng; Du, Lulu; Yang, Yan-E.; Li, Song; Sun, Juncai; Ji, Shijun

2017-11-01

Titanium/niobium oxides have drawn wide attention due to their attractive high lithium-intercalation voltage avoiding the formation of solid electrochemical interface. However, their poor electronic conductivity hinders the commercial applications because of the low electrochemical kinetics in lithiating and de-lithiating process. In the study, new approach to improving the low conductivity of the conventional oxides in micrometers are tactically proposed via the synergic effect of highly mixed multiphase oxide nanocrystals. Ti-Nb oxide composite microspheres with hierarchical microstructure are fabricated successfully via a very facile method combined solvothermal process and calcination. Interconnected crystalline nanoparticles of TiO2, Nb2O5 and TiNb2O7 nanocrystals are involved in the obtained Ti-Nb oxides, demonstrating high structure stability during electrochemical reaction. Meanwhile, the ionic/electronic conductivity is remarkably enhanced by the defects of O2- vacancies and Ti3+/Nb4+ ions. The remained specific capacity of the multiphase Ti-Nb oxides is up to 185.3 mAh g-1 at 5 C with very weak capacity fade of 5.3% after 1800 cycles, showing a very long cycling stability.

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.

Alkaline electrochemical advanced oxidation process for chromium oxidation at graphitized multi-walled carbon nanotubes.

PubMed

Xue, Yudong; Zheng, Shili; Sun, Zhi; Zhang, Yi; Jin, Wei

2017-09-01

Alkaline electrochemical advanced oxidation processes for chromium oxidation and Cr-contaminated waste disposal were reported in this study. The highly graphitized multi-walled carbon nanotubes g-MWCNTs modified electrode was prepared for the in-situ electrochemical generation of HO 2 - . RRDE test results illustrated that g-MWCNTs exhibited much higher two-electron oxygen reduction activity than other nanocarbon materials with peak current density of 1.24 mA cm -2 , %HO 2 - of 77.0% and onset potential of -0.15 V (vs. Hg/HgO). It was originated from the highly graphitized structure and good electrical conductivity as illustrated from the Raman, XRD and EIS characterizations, respectively. Large amount of reactive oxygen species (HO 2 - and ·OH) were in-situ electro-generated from the two-electron oxygen reduction and chromium-induced alkaline electro-Fenton-like reaction. The oxidation of Cr(III) was efficiently achieved within 90 min and the conversion ratio maintained more than 95% of the original value after stability test, offering an efficient and green approach for the utilization of Cr-containing wastes. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

2014-12-21

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

Superstructure ZrV2O7 nanofibres: thermal expansion, electronic and lithium storage properties.

PubMed

Li, Qidong; Zhao, Yanming; Kuang, Quan; Fan, Qinghua; Dong, Youzhong; Liu, Xudong

2016-11-30

ZrV 2 O 7 has attracted much attention as a negative thermal expansion (NTE) material due to its isotropic negative structure. However, rarely has investigation of the lithium storage behaviors been carried out except our first report on it. Meanwhile, the electrochemical behaviors and energy storage characteristics have not been studied in depth and will be explored in this article. Herein, we report on the synthesis, characterization and lithium intercalation mechanism of superstructure ZrV 2 O 7 nanofibres that were prepared through a facile solution-based method with a subsequent annealing process. The thermal in situ XRD technique combined with the Rietveld refinement method is adopted to analyze the change in the temperature-dependent crystal structure. Benefiting from the nanostructured morphology and relatively high electronic conductivity, it presents acceptable cyclic stability and rate capability. According to the operando evolution of the XRD patterns obtained from electrochemical in situ measurements, the Li intercalation mechanism of the solid solution process with a subsequent conversion reaction can be concluded. Finally, the amorphous state of the electrodes after the initial fully discharged state can effectively enhance the electrochemical performances.

Basolateral choline transport in isolated rabbit renal proximal tubules.

PubMed

Dantzler, W H; Evans, K K; Wright, S H

1998-11-01

Choline can undergo both net secretion and net reabsorption by renal proximal tubules, but at physiological plasma levels net reabsorption occurs. During this process, choline enters the cells at the luminal side down an electrochemical gradient via a specific transporter with a high affinity for choline. It appeared likely that choline was then transported out of the cells against an electrochemical gradient at the basolateral membrane by countertransport for another organic cation. This possibility was examined by studying net transepithelial reabsorption and basolateral uptake and efflux of [14C]choline in isolated S2 segments of rabbit renal proximal tubules. Basolateral uptake, which was inhibited by other organic cations such as tetraethylammonium (TEA), appeared to occur by the standard organic cation transport pathway. However, the addition of TEA to the bathing medium not only failed to trans-stimulate net transepithelial reabsorption and basolateral efflux of [14C]choline but it actually inhibited transepithelial reabsorption by @60%. The results do not support the presence of a countertransport step for choline against an electrochemical gradient at the basolateral membrane. Instead, they suggest that choline crosses this membrane by some form of carrier-mediated diffusion even during the reabsorptive process.

In situ fabrication of electrochemically grown mesoporous metallic thin films by anodic dissolution in deep eutectic solvents.

PubMed

Renjith, Anu; Roy, Arun; Lakshminarayanan, V

2014-07-15

We describe here a simple electrodeposition process of forming thin films of noble metallic nanoparticles such as Au, Ag and Pd in deep eutectic solvents (DES). The method consists of anodic dissolution of the corresponding metal in DES followed by the deposition on the cathodic surface. The anodic dissolution process in DES overcomes the problems associated with copious hydrogen and oxygen evolution on the electrode surface when carried out in aqueous medium. The proposed method utilizes the inherent abilities of DES to act as a reducing medium while simultaneously stabilizing the nanoparticles that are formed. The mesoporous metal films were characterized by SEM, XRD and electrochemical techniques. Potential applications of these substrates in surface enhanced Raman spectroscopy and electrocatalysis have been investigated. A large enhancement of Raman signal of analyte was achieved on the mesoporous silver substrate after removing all the stabilizer molecules from the surface by calcination. The highly porous texture of the electrodeposited film provides superior electro catalytic performance for hydrogen evolution reaction (HER). The mechanisms of HER on the fabricated substrates were studied by Tafel analysis and electrochemical impedance spectroscopy (EIS). Copyright © 2014 Elsevier Inc. All rights reserved.

An Electrochemical Study on the Copolymer Formed from Piperazine and Aniline Monomers.

PubMed

Dkhili, Samiha; López-Bernabeu, Sara; Kedir, Chahineze Nawel; Huerta, Francisco; Montilla, Francisco; Besbes-Hentati, Salma; Morallon, Emilia

2018-06-14

A study on the electrochemical oxidation of piperazine and its electrochemical copolymerization with aniline in acidic medium is presented. It was found that the homopolymerization of piperazine cannot be achieved under electrochemical conditions. A combination of electrochemistry, in situ Fourier transform infrared (FTIR), and ex situ X-ray photoelectron spectroscopy (XPS) spectroscopies was used to characterize both the chemical structure and the redox behavior of an electrochemically synthesized piperazine⁻aniline copolymer. The electrochemical sensing properties of the deposited material were also tested against ascorbic acid and dopamine as redox probes.

Single-step direct fabrication of pillar-on-pore hybrid nanostructures in anodizing aluminum for superior superhydrophobic efficiency.

PubMed

Jeong, Chanyoung; Choi, Chang-Hwan

2012-02-01

Conventional electrochemical anodizing processes of metals such as aluminum typically produce planar and homogeneous nanopore structures. If hydrophobically treated, such 2D planar and interconnected pore structures typically result in lower contact angle and larger contact angle hysteresis than 3D disconnected pillar structures and, hence, exhibit inferior superhydrophobic efficiency. In this study, we demonstrate for the first time that the anodizing parameters can be engineered to design novel pillar-on-pore (POP) hybrid nanostructures directly in a simple one-step fabrication process so that superior surface superhydrophobicity can also be realized effectively from the electrochemical anodization process. On the basis of the characteristic of forming a self-ordered porous morphology in a hexagonal array, the modulation of anodizing voltage and duration enabled the formulation of the hybrid-type nanostructures having controlled pillar morphology on top of a porous layer in both mild and hard anodization modes. The hybrid nanostructures of the anodized metal oxide layer initially enhanced the surface hydrophilicity significantly (i.e., superhydrophilic). However, after a hydrophobic monolayer coating, such hybrid nanostructures then showed superior superhydrophobic nonwetting properties not attainable by the plain nanoporous surfaces produced by conventional anodization conditions. The well-regulated anodization process suggests that electrochemical anodizing can expand its usefulness and efficacy to render various metallic substrates with great superhydrophilicity or -hydrophobicity by directly realizing pillar-like structures on top of a self-ordered nanoporous array through a simple one-step fabrication procedure.

Electrochemical performance of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ electrolyte based proton-conducting SOFC solid oxide fuel cell with layered perovskite PrBaCo2O5+δ cathode

NASA Astrophysics Data System (ADS)

Ding, Hanping; Xie, Yuanyuan; Xue, Xingjian

2011-03-01

BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb) exhibits adequate protonic conductivity as well as sufficient chemical and thermal stability over a wide range of SOFC operating conditions, while layered perovskite PrBaCo2O5+δ (PBCO) has advanced electrochemical properties. This research fully takes advantage of these advanced properties and develops a novel protonic ceramic membrane fuel cell (PCMFC) of Ni-BZCYYb|BZCYYb|PBCO. The performance of the button cell was tested under intermediate-temperature range from 600 to 700 °C with humified H2 (∼3% H2O) as fuel and ambient air as oxidant. The results show that the open circuit potential of 0.983 V and the maximal power density of 490 mW cm-2 were achieved at 700 °C. By co-doping barium zirconate-cerate with Y and Yb, the conductivity of electrolyte was significantly improved. The polarization processes of the button cell were characterized using the complicated electrochemical impedance spectroscopy technique. The results indicate that the polarization resistances contributed from both charge migration processes and mass transfer processes increase with decreasing cell voltage loads. However the polarization resistance induced by mass transfer processes is negligible in the studied button cell.

Modularized Production of Value-Added Products and Fuels from Distributed Waste Carbon-Rich Feedstocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weber, Robert S.; Holladay, Johnathan E.

Here, we have adapted and characterized electrolysis reactors to complement the conversion of regional- and community-scale quantities of waste into fuel or chemicals. The overall process must be able to contend with a wide range of feedstocks, must be inherently safe, and should not rely on external facilities for co-reactants or heat rejection and supply. Our current approach is based on the upgrading of bio-oil produced by the hydrothermal liquefaction (HTL) of carbon-containing waste feedstocks. HTL can convert a variety of feedstocks into a bio-oil that requires much less upgrading than the products of other ways of deconstructing biomass. Wemore » are now investigating the use of electrochemical processes for the further conversions needed to transform the bio-oil from HTL into fuel or higher value chemicals. We, and others, have shown that electrochemical reduction can offer adequate reaction rates and at least some of the necessary generality. In addition, an electrochemical reactor necessarily both oxidizes (removes electrons) on one side of the reactor and reduces (adds electrons) on the other side. Therefore, the two types of reactions could, in principle, be coupled to upgrade the bio-oil and simultaneously polish the water that is employed as a reactant and a carrier in the upstream HTL. Here, we overview a notional process, the possible conversion chemistry, and the economics of an HTL-electrochemical process.« less

Modularized Production of Value-Added Products and Fuels from Distributed Waste Carbon-Rich Feedstocks

DOE PAGES

Weber, Robert S.; Holladay, Johnathan E.

2018-05-22

Here, we have adapted and characterized electrolysis reactors to complement the conversion of regional- and community-scale quantities of waste into fuel or chemicals. The overall process must be able to contend with a wide range of feedstocks, must be inherently safe, and should not rely on external facilities for co-reactants or heat rejection and supply. Our current approach is based on the upgrading of bio-oil produced by the hydrothermal liquefaction (HTL) of carbon-containing waste feedstocks. HTL can convert a variety of feedstocks into a bio-oil that requires much less upgrading than the products of other ways of deconstructing biomass. Wemore » are now investigating the use of electrochemical processes for the further conversions needed to transform the bio-oil from HTL into fuel or higher value chemicals. We, and others, have shown that electrochemical reduction can offer adequate reaction rates and at least some of the necessary generality. In addition, an electrochemical reactor necessarily both oxidizes (removes electrons) on one side of the reactor and reduces (adds electrons) on the other side. Therefore, the two types of reactions could, in principle, be coupled to upgrade the bio-oil and simultaneously polish the water that is employed as a reactant and a carrier in the upstream HTL. Here, we overview a notional process, the possible conversion chemistry, and the economics of an HTL-electrochemical process.« less

Carbon-Based Materials for Lithium-Ion Batteries, Electrochemical Capacitors, and Their Hybrid Devices.

PubMed

Yao, Fei; Pham, Duy Tho; Lee, Young Hee

2015-07-20

A rapidly developing market for portable electronic devices and hybrid electrical vehicles requires an urgent supply of mature energy-storage systems. As a result, lithium-ion batteries and electrochemical capacitors have lately attracted broad attention. Nevertheless, it is well known that both devices have their own drawbacks. With the fast development of nanoscience and nanotechnology, various structures and materials have been proposed to overcome the deficiencies of both devices to improve their electrochemical performance further. In this Review, electrochemical storage mechanisms based on carbon materials for both lithium-ion batteries and electrochemical capacitors are introduced. Non-faradic processes (electric double-layer capacitance) and faradic reactions (pseudocapacitance and intercalation) are generally explained. Electrochemical performance based on different types of electrolytes is briefly reviewed. Furthermore, impedance behavior based on Nyquist plots is discussed. We demonstrate the influence of cell conductivity, electrode/electrolyte interface, and ion diffusion on impedance performance. We illustrate that relaxation time, which is closely related to ion diffusion, can be extracted from Nyquist plots and compared between lithium-ion batteries and electrochemical capacitors. Finally, recent progress in the design of anodes for lithium-ion batteries, electrochemical capacitors, and their hybrid devices based on carbonaceous materials are reviewed. Challenges and future perspectives are further discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical and AFM Characterization of G-Quadruplex Electrochemical Biosensors and Applications

PubMed Central

2018-01-01

Guanine-rich DNA sequences are able to form G-quadruplexes, being involved in important biological processes and representing smart self-assembling nanomaterials that are increasingly used in DNA nanotechnology and biosensor technology. G-quadruplex electrochemical biosensors have received particular attention, since the electrochemical response is particularly sensitive to the DNA structural changes from single-stranded, double-stranded, or hairpin into a G-quadruplex configuration. Furthermore, the development of an increased number of G-quadruplex aptamers that combine the G-quadruplex stiffness and self-assembling versatility with the aptamer high specificity of binding to a variety of molecular targets allowed the construction of biosensors with increased selectivity and sensitivity. This review discusses the recent advances on the electrochemical characterization, design, and applications of G-quadruplex electrochemical biosensors in the evaluation of metal ions, G-quadruplex ligands, and other small organic molecules, proteins, and cells. The electrochemical and atomic force microscopy characterization of G-quadruplexes is presented. The incubation time and cations concentration dependence in controlling the G-quadruplex folding, stability, and nanostructures formation at carbon electrodes are discussed. Different G-quadruplex electrochemical biosensors design strategies, based on the DNA folding into a G-quadruplex, the use of G-quadruplex aptamers, or the use of hemin/G-quadruplex DNAzymes, are revisited. PMID:29666699

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

PubMed

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

2018-06-12

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

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 density at solid/liquid interface.

Surface morphology and electrochemical studies on polyaniline/CuO nano composites

NASA Astrophysics Data System (ADS)

Ashokkumar, S. P.; Vijeth, H.; Yesappa, L.; Niranjana, M.; Vandana, M.; Basappa, M.; Devendrappa, H.

2018-05-01

An electrochemically synthesized Polyaniline (PANI) and Polyaniline/copper oxide (PCN) nano composite have studied the morphology and electrochemical properties. The composite is characterized by X-ray diffraction (XRD) and surface morphology was studied using FESEM and electrochemical behavior is studied using cyclic voltammetry (CV) technique. The CV curves shows rectangular shaped curve and they have contribution to electrical double layer capacitance (EDCL).

Effect of processing parameters on the corrosion behaviour of friction stir processed AA 2219 aluminum alloy

NASA Astrophysics Data System (ADS)

Surekha, K.; Murty, B. S.; Prasad Rao, K.

2009-04-01

The effect of processing parameters (rotation speed and traverse speed) on the corrosion behaviour of friction stir processed high strength precipitation hardenable AA 2219-T87 alloy was investigated. The results indicate that the rotation speed has a major influence in determining the rate of corrosion, which is attributed to the breaking down and dissolution of the intermetallic particles. Corrosion resistance of friction stir processed alloy was studied by potentiodynamic polarization, electrochemical impedance spectroscopy, salt spray and immersion tests.

In Situ TEM Investigation of the Electrochemical Behavior in CNTs/MnO2-Based Energy Storage Devices.

PubMed

Tsai, Tsung-Chun; Huang, Guan-Min; Huang, Chun-Wei; Chen, Jui-Yuan; Yang, Chih-Chieh; Tseng, Tseung-Yuen; Wu, Wen-Wei

2017-09-19

Transition metal oxides have attracted much interest owing to their ability to provide high power density in lithium batteries; therefore, it is important to understand the electrochemical behavior and mechanism of lithiation-delithiation processes. In this study, we successfully and directly observed the structural evolution of CNTs/MnO 2 during the lithiation process using transmission electron microscopy (TEM). CNTs/MnO 2 were selected due to their high surface area and capacitance effect, and the lithiation mechanism of the CNT wall expansion was systematically analyzed. Interestingly, the wall spacings of CNTs/MnO 2 and CNTs were obviously expanded by 10.92% and 2.59%, respectively. The MnO 2 layer caused structural defects on the CNTs surface that could allow penetration of Li + and Mn 4+ through the tube wall and hence improve the ionic transportation speed. This study provided direct evidence for understanding the role of CNTs/MnO 2 in the lithiation process used in lithium ion batteries and also offers potential benefits for applications and development of supercapacitors.

Flower-like NiO structures: Controlled hydrothermal synthesis and electrochemical characteristic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chai, Hui; Chen, Xuan; Key Laboratory of Advanced Functional Materials, Institute of Applied Chemistry, Xinjiang University, Urumqi 830046, Xinjiang

Graphical abstract: Flower-like porous NiO was obtained via thermal decomposition of the precursor prepared by a hydrothermal process using hexamethylenetetramine and polyethylene glycol as hydrolysis-controlling agent and surfactant, respectively. The morphology and microstructure of as-synthesized NiO were characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results of electrochemical measurements demonstrated that the flower-like porous NiO has high capacity (340 F g{sup −1}) with excellent cycling performance as electrode materials of electrochemical capacitors (ECs), which may be attributed to the unique microstrcture of NiO. Data analyses indicated that NiO with novel porousmore » structure attractive for practical and large-scale applications in electrochemical capacitors. Display Omitted Highlights: ► Synthesis and characterization of NiO with novel porous structure is presented in this work. ► The electrochemical performance of product was examined. ► NiO with excellent performance as electrode materials may be due to the unique microstrcture. ► NiO with novel porous structure attractive for practical with high capacity (340 F g{sup −1}). -- Abstract: Flower-like porous NiO was obtained by thermal decomposition of the precursor prepared by a hydrothermal process with hexamethylenetetramine and polyethylene glycol as hydrolysis-controlling agent and surfactant, respectively. The morphology and microstructure of as-synthesized NiO were characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The resulting structures of NiO exhibited porous like petal building blocks. The electrochemical measurements’ results demonstrated that flower-like porous NiO has high capacity (340 F g{sup −1}) with excellent cycling performance as electrode materials for electrochemical capacitors, which may be attributed to the unique structure of NiO. The results indicated that NiO with novel porous structure has been attractive for practical and large-scale applications in electrochemical capacitors.« less

Electrochemical characteristics of calcium-phosphatized AZ31 magnesium alloy in 0.9 % NaCl solution.

PubMed

Hadzima, Branislav; Mhaede, Mansour; Pastorek, Filip

2014-05-01

Magnesium alloys suffer from their high reactivity in common environments. Protective layers are widely created on the surface of magnesium alloys to improve their corrosion resistance. This article evaluates the influence of a calcium-phosphate layer on the electrochemical characteristics of AZ31 magnesium alloy in 0.9 % NaCl solution. The calcium phosphate (CaP) layer was electrochemically deposited in a solution containing 0.1 M Ca(NO3)2, 0.06 M NH4H2PO4 and 10 ml l(-1) of H2O2. The formed surface layer was composed mainly of brushite [(dicalcium phosphate dihidrate (DCPD)] as proved by energy-dispersive X-ray analysis. The surface morphology was observed by scanning electron microscopy. Immersion test was performed in order to observe degradation of the calcium phosphatized surfaces. The influence of the phosphate layer on the electrochemical characteristics of AZ31, in 0.9 % NaCl solution, was evaluated by potentiodynamic measurements and electrochemical impedance spectroscopy. The obtained results were analysed by the Tafel-extrapolation method and equivalent circuits method. The results showed that the polarization resistance of the DCPD-coated surface is about 25 times higher than that of non-coated surface. The CaP electro-deposition process increased the activation energy of corrosion process.

A Twice Electrochemical-Etching Method to Fabricate Superhydrophobic-Superhydrophilic Patterns for Biomimetic Fog Harvest.

PubMed

Yang, Xiaolong; Song, Jinlong; Liu, Junkai; Liu, Xin; Jin, Zhuji

2017-08-18

Superhydrophobic-superhydrophilic patterned surfaces have attracted more and more attention due to their great potential applications in the fog harvest process. In this work, we developed a simple and universal electrochemical-etching method to fabricate the superhydrophobic-superhydrophilic patterned surface on metal superhydrophobic substrates. The anti-electrochemical corrosion property of superhydrophobic substrates and the dependence of electrochemical etching potential on the wettability of the fabricated dimples were investigated on Al samples. Results showed that high etching potential was beneficial for efficiently producing a uniform superhydrophilic dimple. Fabrication of long-term superhydrophilic dimples on the Al superhydrophobic substrate was achieved by combining the masked electrochemical etching and boiling-water immersion methods. A long-term wedge-shaped superhydrophilic dimple array was fabricated on a superhydrophobic surface. The fog harvest test showed that the surface with a wedge-shaped pattern array had high water collection efficiency. Condensing water on the pattern was easy to converge and depart due to the internal Laplace pressure gradient of the liquid and the contact angle hysteresis contrast on the surface. The Furmidge equation was applied to explain the droplet departing mechanism and to control the departing volume. The fabrication technique and research of the fog harvest process may guide the design of new water collection devices.

Formation of Sn–M (M=Fe, Al, Ni) alloy nanoparticles by DC arc-discharge and their electrochemical properties as anodes for Li-ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Song; Huang, Hao, E-mail: huanghao@dlut.edu.cn; Wu, Aimin

2016-10-15

A direct current arc-discharge method was applied to prepare the Sn–M (M=Fe, Al, Ni) bi-alloy nanoparticles. Thermodynamic is introduced to analyze the energy circumstances for the formation of the nanoparticles during the physical condensation process. The electrochemical properties of as-prepared Sn–M alloy nanoparticles are systematically investigated as anodes of Li-ion batteries. Among them, Sn–Fe nanoparticles electrode exhibits high Coulomb efficiency (about 71.2%) in the initial charge/discharge (257.9 mA h g{sup −1}/366.6 mA h g{sup −1}) and optimal cycle stability (a specific reversible capacity of 240 mA h g{sup −1} maintained after 20 cycles) compared with others. Large differences in themore » electrochemical behaviors indicate that the chemical composition and microstructure of the nanoparticles determine the lithium-ion storage properties and the long-term cyclic stability during the charge/discharge process. - Graphical abstract: The growth mechanism and electrochemical performance of Sn-based alloy nanoparticles. - Highlights: • Thermodynamic analyses of oxides on Sn-M nanoparticles surface. • The relationship between chemical components and electrochemical responses. • Sn-Fe nanoparticles show excellent electrode performance.« less

Reduced Graphene Oxide/Carbon Nanotube Composites as Electrochemical Energy Storage Electrode Applications.

PubMed

Yang, Wenyao; Chen, Yan; Wang, Jingfeng; Peng, Tianjun; Xu, Jianhua; Yang, Bangchao; Tang, Ke

2018-06-15

We demonstrate an electrochemical reduction method to reduce graphene oxide (GO) to electrochemically reduced graphene oxide (ERGO) with the assistance of carbon nanotubes (CNTs). The faster and more efficient reduction of GO can be achieved after proper addition of CNTs into GO during the reduction process. This nanotube/nanosheet composite was deposited on electrode as active material for electrochemical energy storage applications. It has been found that the specific capacitance of the composite film was strongly affected by the mass ratio of GO/CNTs and the scanning ratio of cyclic voltammetry. The obtained ERGO/CNT composite electrode exhibited a 279.4 F/g-specific capacitance and showed good cycle rate performance with the evidence that the specific capacitance maintained above 90% after 6000 cycles. The synergistic effect between ERGO and CNTs as well as crossing over of CNTs into ERGO is attributed to the high electrochemical performance of composite electrode.

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.

Enhanced catalytic and dopamine sensing properties of electrochemically reduced conducting polymer nanocomposite doped with pure graphene oxide.

PubMed

Wang, Wenting; Xu, Guiyun; Cui, Xinyan Tracy; Sheng, Ge; Luo, Xiliang

2014-08-15

Significantly enhanced catalytic activity of a nanocomposite composed of conducting polymer poly (3,4-ethylenedioxythiophene) (PEDOT) doped with graphene oxide (GO) was achieved through a simple electrochemical reduction process. The nanocomposite (PEDOT/GO) was electrodeposited on an electrode and followed by electrochemical reduction, and the obtained reduced nanocomposite (PEDOT/RGO) modified electrode exhibited lowered electrochemical impedance and excellent electrocatalytic activity towards the oxidation of dopamine. Based on the excellent catalytic property of PEDOT/RGO, an electrochemical sensor capable of sensitive and selective detection of DA was developed. The fabricated sensor can detect DA in a wide linear range from 0.1 to 175μM, with a detection limit of 39nM, and it is free from common interferences such as uric acid and ascorbic acid. Copyright © 2014 Elsevier B.V. All rights reserved.

A New PC and LabVIEW Package Based System for Electrochemical Investigations

PubMed Central

Stević, Zoran; Andjelković, Zoran; Antić, Dejan

2008-01-01

The paper describes a new PC and LabVIEW software package based system for electrochemical research. An overview of well known electrochemical methods, such as potential measurements, galvanostatic and potentiostatic method, cyclic voltammetry and EIS is given. Electrochemical impedance spectroscopy has been adapted for systems containing large capacitances. For signal generation and recording of the response of investigated electrochemical cell, a measurement and control system was developed, based on a PC P4. The rest of the hardware consists of a commercially available AD-DA converter and an external interface for analog signal processing. The interface is a result of authors own research. The software platform for desired measurement methods is LabVIEW 8.2 package, which is regarded as a high standard in the area of modern virtual instruments. The developed system was adjusted, tested and compared with commercially available system and ORCAD simulation. PMID:27879794

Electrochemical Performance Estimation of Anodized AZ31B Magnesium Alloy as Function of Change in the Current Density

NASA Astrophysics Data System (ADS)

Girón, L.; Aperador, W.; Tirado, L.; Franco, F.; Caicedo, J. C.

2017-08-01

The anodized AZ31B magnesium alloys were synthesized via electrodeposition processes. The aim of this work was to determine the electrochemical behavior of magnesium alloys by using anodized alloys as a protective coating. The anodized alloys were characterized by x-ray diffraction, exhibiting the crystallography orientation for Mg and MgO phases. The x-ray photoelectron spectroscopy was used to determine the chemical composition of anodized magnesium alloys. By using electrochemical impedance spectroscopy and Tafel curves, it was possible to estimate the electrochemical behavior of anodized AZ31B magnesium alloys in Hank's balanced salt solution (HBSS). Scanning electron microscopy was performed to analyze chemical changes and morphological surface changes on anodized Mg alloys due to the reaction in HBSS/anodized magnesium surface interface. Electrochemical behavior in HBSS indicates that the coatings may be a promising material for biomedical industry.

XPS-nanocharacterization of organic layers electrochemically grafted on the surface of SnO2 thin films to produce a new hybrid material coating

NASA Astrophysics Data System (ADS)

Drevet, R.; Dragoé, D.; Barthés-Labrousse, M. G.; Chaussé, A.; Andrieux, M.

2016-10-01

This work presents the synthesis and the characterization of hybrid material thin films obtained by the combination of two processes. The electrochemical grafting of organic layers made of carboxyphenyl moieties is carried out from the reduction of a diazonium salt on tin dioxide (SnO2) thin films previously deposited on Si substrates by metal organic chemical vapor deposition (MOCVD). Since the MOCVD experimental parameters impact the crystal growth of the SnO2 layer (i.e. its morphology and its texturation), various electrochemical grafting models can occur, producing different hybrid materials. In order to evidence the efficiency of the electrochemical grafting of the carboxyphenyl moieties, X-ray Photoelectron Spectroscopy (XPS) is used to characterize the first nanometers in depth of the synthesized hybrid material layer. Then three electrochemical grafting models are proposed.

Spin-Dependent Processes Measured without a Permanent Magnet.

PubMed

Fontanesi, Claudio; Capua, Eyal; Paltiel, Yossi; Waldeck, David H; Naaman, Ron

2018-05-07

A novel Hall circuit design that can be incorporated into a working electrode, which is used to probe spin-selective charge transfer and charge displacement processes, is reviewed herein. The general design of a Hall circuit based on a semiconductor heterostructure, which forms a shallow 2D electron gas and is used as an electrode, is described. Three different types of spin-selective processes have been studied with this device in the past: i) photoinduced charge exchange between quantum dots and the working electrode through chiral molecules is associated with spin polarization that creates a local magnetization and generates a Hall voltage; ii) charge polarization of chiral molecules by an applied voltage is accompanied by a spin polarization that generates a Hall voltage; and iii) cyclic voltammetry (current-voltage) measurements of electrochemical redox reactions that can be spin-analyzed by the Hall circuit to provide a third dimension (spin) in addition to the well-known current and voltage dimensions. The three studies reviewed open new doors into understanding both the spin current and the charge current in electronic materials and electrochemical processes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental Studies of Selected Aqueous Electrochemical Systems Relevant for Materials Processing in the Fabrications of Microelectronic Components and Direct Alcohol Fuel Cells

NASA Astrophysics Data System (ADS)

Shi, Xingzhao

A broad range of electrochemical techniques are employed in this dissertation to investigate a selected set of aqueous electrochemical systems that are relevant for materials processing in the fabrication of microelectronic devices and direct alcohol fuel cells. In terms of technical applications, this work covers three main experimental systems: (i) chemical mechanical planarization (CMP), (ii) electro-less nickel deposition, and (iii) direct alkaline glycerol fuel cells. The first two areas are related to electronic device fabrications and the third topic is related to cost-effective energy conversion. The common electrochemical aspect of these different systems is that, in all these cases the active material characteristics are governed by complex (often multi-step) reactions occurring at metal-liquid (aqueous) interfaces. Electro-analytical techniques are ideally suited for studying the detailed mechanisms of such reactions, and the present investigation is largely focused on developing adequate analytical strategies for probing these reaction mechanisms. In the fabrication of integrated circuits, certain steps of materials processing involve CMP of Al deposited on thin layers of diffusion barrier materials like Ta/TaN, Co, or Ti/TiN. A specific example of this situation is found in the processing of replacement metal gates used for high-k/metal-gate transistors. Since the commonly used barrier materials are nobler than Al, the Al interface in contact with the barrier can become prone to galvanic corrosion in the wet CMP environment. Using model systems of coupon electrodes and two specific barrier metals, Ta and Co, the electrochemical factors responsible for these corrosion effects are investigated here in a moderately acidic (pH = 4.0) abrasive-free solution. The techniques of cyclic voltammetry and impedance spectroscopy are combined with strategic measurements of galvanic currents and open circuit potentials (OCPs). L-ascorbic acid (AA) is employed as a surface modifying agent for controlling galvanic corrosions of Al in the Ta-Al and Co-Al bimetallic combinations. The results elaborate the chemical and electrochemical mechanisms responsible for activating and suppressing the corrosion processes in these systems. Defect-control is a critical requirement for CMP of the ultrathin diffusion barriers considered for the new Cu-interconnects. The challenging task of developing advanced CMP slurries for such systems can be aided by electrochemical evaluations of model CMP schemes under tribological conditions. The present work uses this strategy to characterize an alkaline slurry formulation aimed at minimizing galvanic corrosion in the CMP systems involving Ru, Ta (barrier metals) and Cu (wiring metal). This slurry is based on percarbonate and guanidine additives, and the test metals are polycrystalline disc samples. A particular goal of this study is to explore the essential analytical aspects of evaluating CMP systems in the tribo-electrochemical approach. The CMP specific surface reactions are characterized by potentiodynamic polarization and open circuit voltage measurements, performed both in the presence and in the absence of polishing, and by employing abrasive free as well as abrasive (colloidal SiO 2) added solutions. The findings of these experiments are further checked by using impedance spectroscopy. The electrochemical mixed potential steps of the CMP promoting reactions are analyzed, and the removable surface species formed by these reactions are discussed. Electro-oxidation of hypophosphite plays an important role in the electro-less deposition of Ni used to fabricate surface engineered films, alloys, and coatings for a variety of applications. At the same time, the kinetic details of this oxidation reaction comprise an ideal framework for studying many general mechanistic aspects of electrocatalysis on transition metal substrates. The present study utilizes these specific attributes of hypophosphite oxidation to probe the underlying function of the incipient hydrous oxide of Ni in promoting the catalytic properties of this metal in an alkaline medium. The experiments reported here use time-resolved Fourier-transform electrochemical impedance spectroscopy (FT-EIS), strategically coupled with scan-rate controlled voltammetry. The results suggest that the incipient hydrous oxide Ni(OH)ad formed at the onset of hypophosphite oxidation catalytically promotes the latter's precursor de-hydrogenation step. While voltammetry provides suggestive evidence for these Ni(OH)ad induced effects, the FT-EIS data serve to gather more direct signatures of the catalytic function of Ni(OH)ad. The mechanism of energy conversion in a direct glycerol fuel cell (DGFC) is governed by the anode-supported heterogeneous steps of glycerol electro-oxidation. In aerated alkaline electrolytes, glycerol also participates in a base catalyzed process, which can release certain species mixing with the anode catalyzed surface products. As a result, selective probing of the surface catalytic reactions involving such systems can be difficult. The present work addresses this issue for a gold anode by using the analytical capability of cyclic voltammetry (CV). In addition, surface plasmon resonance measurements are used to optically probe the adsorption characteristics of the electrolyte species. The net exchange current of the oxidation process and the transfer coefficient of the rate determining step are evaluated by analyzing the CV data. The interfacial reactions and their products on Au are identified by measuring the number of electrons released during the electro-oxidation of glycerol. The results indicate that these reactions are facilitated by the surface bound hydroxyl species on Au (chemisorbed OH-- and faradaically formed Au-OH). By comparing the findings for stationary and rotating electrodes, it is shown that, convective mass transport is critical to maintaining efficient progression of the consecutive oxidation steps of glycerol. In the absence of hydrodynamic support, the main surface products of glycerol oxidation appear to be glyceraldehyde, glycerate and malonate, formed through a net six-electron route. In the presence of controlled convection, a ten-electron process is activated, where mesaxolate is the likely additional product.

Preparation of Nickel Cobalt Sulfide Hollow Nanocolloids with Enhanced Electrochemical Property for Supercapacitors Application

PubMed Central

Chen, Zhenhua; Wan, Zhanghui; Yang, Tiezhu; Zhao, Mengen; Lv, Xinyan; Wang, Hao; Ren, Xiuli; Mei, Xifan

2016-01-01

Nanostructured functional materials with hollow interiors are considered to be good candidates for a variety of advanced applications. However, synthesis of uniform hollow nanocolloids with porous texture via wet chemistry method is still challenging. In this work, nickel cobalt precursors (NCP) in sub-micron sized spheres have been synthesized by a facile solvothermal method. The subsequent sulfurization process in hydrothermal system has changed the NCP to nickel cobalt sulfide (NCS) with porous texture. Importantly, the hollow interiors can be tuned through the sulfurization process by employing different dosage of sulfur source. The derived NCS products have been fabricated into supercapacitor electrodes and their electrochemical performances are measured and compared, where promising results were found for the next-generation high-performance electrochemical capacitors. PMID:27114165

Electrochemically-driven large amplitude pH cycling for acid-base driven DNA denaturation and renaturation.

PubMed

Wang, Yong-Chun; Lin, Cong-Bin; Su, Jian-Jia; Ru, Ying-Ming; Wu, Qiao; Chen, Zhao-Bin; Mao, Bing-Wei; Tian, Zhao-Wu

2011-06-15

In this paper, we present an electrochemically driven large amplitude pH alteration method based on a serial electrolytic cell involving a hydrogen permeable bifacial working electrode such as Pd thin foil. The method allows solution pH to be changed periodically up to ±4~5 units without additional alteration of concentration and/or composition of the system. Application to the acid-base driven cyclic denaturation and renaturation of 290 bp DNA fragments is successfully demonstrated with in situ real-time UV spectroscopic characterization. Electrophoretic analysis confirms that the denaturation and renaturation processes are reversible without degradation of the DNA. The serial electrolytic cell based electrochemical pH alteration method presented in this work would promote investigations of a wide variety of potential-dependent processes and techniques.

ESM of ionic and electrochemical phenomena on the nanoscale

DOE PAGES

Kalinin, Sergei V.; Kumar, Amit; Balke, Nina; ...

2011-01-01

Operation of energy storage and conversion devices is ultimately controlled by series of intertwined ionic and electronic transport processes and electrochemical reactions at surfaces and interfaces, strongly mediated by strain and mechanical processes. In a typical fuel cell, these include chemical species transport in porous cathode and anode materials, gas-solid electrochemical reactions at grains and triple-phase boundaries (TPBs), ionic and electronic flows in multicomponent electrodes, and chemical and electronic potential drops at internal interfaces in electrodes and electrolytes. Furthermore, all these phenomena are sensitively affected by the microstructure of materials from device level to the atomic scales. Similar spectrum ofmore » length scales and phenomena underpin operation of other energy systems including primary and secondary batteries, as well as hybrid systems such flow and metal-air/water batteries.« less

Effect of Thermal Shock During Legionella Bacteria Removal on the Corrosion Properties of Zinc-Coated Steel Pipes

NASA Astrophysics Data System (ADS)

Orlikowski, Juliusz; Ryl, Jacek; Jazdzewska, Agata; Krakowiak, Stefan

2016-07-01

The purpose of this investigation was to conduct the failure analysis of a water-supply system made from zinc-coated steel. The observed corrosion process had an intense and complex character. The brownish deposits and perforations were present after 2-3 years of exploitation. The electrochemical study based on the Tafel polarization, corrosion potential monitoring, and electrochemical impedance spectroscopy together with microscopic analysis via SEM and EDX were performed in order to identify the cause of such intense corrosion. The performed measurements allowed us to determine that thermal shock was the source of polarity-reversal phenomenon. This process had begun the corrosion of steel which later led to the formation of deposits and perforations in the pipes. The work includes appropriate action in order to efficiently identify the described corrosion threat.

Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free, zinc(II), copper(II) and cobalt(II) phthalocyanines

NASA Astrophysics Data System (ADS)

Demirbaş, Ümit; Akçay, Hakkı Türker; Koca, Atıf; Kantekin, Halit

2017-08-01

In this study novel peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free phthalocyanine (4) and its zinc(II) (5), copper(II) (6) and cobalt(II) (7) derivatives were synthesized and characterized by a combination of various spectroscopic techniques such as FT-IR, 1H-NMR, UV-vis and MALDI-TOF mass. Electrochemical characterizations of metallo-phthalocyanine complexes were conducted by voltammetric and in situ spectroelectrochemical measurements. CoIIPc went [CoIIPc-2]/[CoIPc-2]1-, [CoIPc-2]1-/[CoIPc-3]2-, [CoIPc-3]2-/[CoIPc-4]3- and [CoIIPc-2]/[CoIIPc-2]1+ reduction and oxidation processes respectively. Differently ZnIIPc only showed four ligand-based reductions and two ligand based oxidation processes.

Real-Time XRD Studies of Li-O2 Electrochemical Reaction in Nonaqueous Lithium-Oxygen Battery.

PubMed

Lim, Hyunseob; Yilmaz, Eda; Byon, Hye Ryung

2012-11-01

Understanding of electrochemical process in rechargeable Li-O2 battery has suffered from lack of proper analytical tool, especially related to the identification of chemical species and number of electrons involved in the discharge/recharge process. Here we present a simple and straightforward analytical method for simultaneously attaining chemical and quantified information of Li2O2 (discharge product) and byproducts using in situ XRD measurement. By real-time monitoring of solid-state Li2O2 peak area, the accurate efficiency of Li2O2 formation and the number of electrons can be evaluated during full discharge. Furthermore, by observation of sequential area change of Li2O2 peak during recharge, we found nonlinearity of Li2O2 decomposition rate for the first time in ether-based electrolyte.

Bio and nanomaterials in tribocorrosion systems

NASA Astrophysics Data System (ADS)

Benea, Lidia

2017-02-01

The growing attention that the scientific community has paid in the last decades to the corrosion phenomena, including tribocorrosion is related to the huge economic, social and environmental losses (3,5 % GDP in industrialized countries as USA, UK, Japan and Germany), that result from the spread of damage of several metal constructions and devices. Tribocorrosion is defined as the chemical-electrochemical-mechanical process leading to a degradation of materials in sliding, rolling or erosion contacts immersed in a corrosive environment or even in water. That degradation results from the combined action of corrosion and wear are higher compared with addition of corrosion and wear degradation separately. This synergism between chemical, electrochemical, and mechanical processes on materials in sliding, abrasive or erosive contacts immersed in a liquid requires a multi-disciplinary approach (material science, electrochemistry, tribology, mechanics, and surface engineering). This paper presents few summary results obtained by studying the materials degradation by complex tribocorrosion processes in terms of two broad categories of applications: tribocorrosion in industrial systems with improved behaviour of nanomaterials as hybrid and nanocomposite layers and tribocorrosion in living systems with improved behaviour by surface modifications of biomaterials applying electrochemical techniques. The purpose of this paper is to provide information on the surface conditions of materials in sliding contacts and also on the kinetics of reactions that control the corrosion component in the material loss during tribocorrosion tests.

Removal of bisphenol A by electrochemical carbon-nanotube filter: Influential factors and degradation pathway.

PubMed

Bakr, Ahmed Refaat; Rahaman, Md Saifur

2017-10-01

Bisphenol A is a chemical with hazardous health effects that is largely used in the manufacture of extensively used products including adhesives, plastics, powder paints, thermal paper and paper coatings, and epoxy resin, and is reported to exist in nature in an accumulative manner. In this study, both pristine and boron-doped multiwalled carbon nanotubes (MWNTs) were employed as filtration and electrochemical filtration materials, resulting in a significant removal of bisphenol A with identical performance for both MWNTs types. It was shown that the presence of salt is not critical for the greatest contaminant removal efficiency, likely due to the vital role of other electroactive species (e.g. reactive oxygen species). Near complete removal of 1 mg L -1 bisphenol A at 2 and 3 V of applied DC potentials was achieved, indicating that the electrochemical filtration process is voltage dependent at both 2 and 3 V. Increasing the residence time by 7.4 fold (from 2.0 to 14.9 s) resulted in a significant removal of bisphenol A and its toxic byproducts, up to 424 min of electrochemical filtration time at 3 V of applied potential. Based on these results, electrochemical filtration using MWNTs is considered a promising technology for the removal of the accumulative bisphenol A and the reduction of its hazardous effects in waters. Copyright © 2017. Published by Elsevier Ltd.

Electrochemical evaluation of antibacterial drugs as environment-friendly inhibitors for corrosion of carbon steel in HCl solution

NASA Astrophysics Data System (ADS)

Golestani, Gh.; Shahidi, M.; Ghazanfari, D.

2014-07-01

The effect of penicillin G, ampicillin and amoxicillin drugs on the corrosion behavior of carbon steel (ASTM 1015) in 1.0 mol L-1 hydrochloric acid solution was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) techniques. The inhibition efficiency was found to increase with increasing inhibitor concentration. The effect of temperature on the rate of corrosion in the absence and presence of these drugs was also studied. Some thermodynamic parameters were computed from the effect of temperature on corrosion and inhibition processes. Adsorption of these inhibitors was found to obey Langmuir adsorption isotherm. There was a case of mixed mode of adsorption here but while penicillin was adsorbed mainly through chemisorption, two other drugs were adsorbed mainly through physisorption. Potentiodynamic polarization measurements indicated that the inhibitors were of mixed type. In addition, this paper suggests that the electrochemical noise (EN) technique under open circuit conditions as the truly noninvasive electrochemical method can be employed for the quantitative evaluation of corrosion inhibition. This was done by using the standard deviation of partial signal (SDPS) for calculation of the amount of noise charges at the particular interval of frequency, thereby obtaining the inhibition efficiency (IE) of an inhibitor. These IE values showed a reasonable agreement with those obtained from potentiodynamic polarization and EIS measurements.

Electrochemical Detection of Human Mesenchymal Stem Cell Differentiation on Fabricated Gold Nano-Dot Cell Chips.

PubMed

An, Jeung Hee; Kim, Seung U; Park, Mi-Kyung; Choi, Jeong Woo

2015-10-01

Human mesenchymal stem cells (MSCs) have the capacity for self-renewal and maintain pluripotency, which is defined by their ability to differentiate into cells such as osteoblasts, neurons, and glial cells. In this study, we report a method for defining the status of human MSCs based on electrochemical detection systems. Gold nano-dot structures were fabricated using a nanoporous alumina mask, and the structural formations were confirmed by scanning electron microscopy (SEM). Human MSCs were allowed to attach to RGD (Arg-Gly-Asp) peptide nanopatterned surfaces, and electrochemical tools were applied to the MSCs attached on the chip surface. The cultured MSCs were shown to differentiate into neural cell types, as indicated by immunocytochemical staining for tyrosine hydroxylase and beta tubulin III. Following treatment with basic fibroblast growth factor (bFGF) for 14 days, most of the B10 cells exhibited bipolar or multipolar morphology with branched processes, and the proportion of B10 cells expressing neuronal cell markers considerably increased. Electrophysiological recordings from MSCs treated with bFGF for 5-14 days were examined with cyclic voltammetry, and the electrochemical signals were shown to increase during differentiation from MSCs to neuronal cells. This human MSC cell line is a useful tool for studying organogenesis, specifically neurogenesis, and in addition, the cell line provides a valuable source of cells for cell therapy. The electrochemical measurement system proposed here could be utilized in electrical cell chips for numerous applications, including cell differentiation, disease diagnosis, drug detection, and on-site monitoring.

Problems analysis and new fabrication strategies of mediated electrochemical biosensors for wastewater toxicity assessment.

PubMed

Yang, Yajie; Fang, Deyu; Liu, Yanran; Liu, Runze; Wang, Xiaoshen; Yu, Yuan; Zhi, Jinfang

2018-06-15

Conventional mediated electrochemical biosensors for toxicity assessment were almost based on 'one-pot' principle, i.e., mediators and the under-test chemicals were mixed together in the same vessel. In this process, the electron mediator is assumed to be merely an electron acceptor and cannot react with under-test toxicants. Actually，some under-test pollutants (such as metal ions) could react with the electron mediators, thus affecting the detection accuracy and sensitivity of the sensors. It was also found that at least two other interference factors have been ignored in present'one-pot' mediated electrochemical biosensor systems, i.e., (1) the electrochemical sensitivity of mediators to pH; and (2) the potential reactions between under-test chemicals and buffers and the consequent pH changes. In this study, the three ignored interference factors have been investigated systematically and demonstrated by significance tests. Moreover, a solving strategy, an isolation method, is proposed for fabrication of novel mediated electrochemical biosensor to avoid the interference factors existing at present mediated electrochemical biosensor. According to the testing results obtained from the isolation method, IC 50 values of Cu 2+ , Cd 2+ , Zn 2+ , Fe 3+ , Ni 2+ and Cr 3+ were 21.3 mg/L, 3.7 mg/L, 26.7 mg/L, 4.4 mg/L and 10.7 mg/L, respectively. The detection results of four real water samples also suggested this method could be applied for the practical and complex samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Light-Regulated Electrochemical Sensor Array for Efficiently Discriminating Hazardous Gases.

PubMed

Liang, Hongqiu; Zhang, Xin; Sun, Huihui; Jin, Han; Zhang, Xiaowei; Jin, Qinghui; Zou, Jie; Haick, Hossam; Jian, Jiawen

2017-10-27

Inadequate detection limit and unsatisfactory discrimination features remain the challenging issues for the widely applied electrochemical gas sensors. Quite recently, we confirmed that light-regulated electrochemical reaction significantly enhanced the electrocatalytic activity, and thereby can potentially extend the detection limit to the parts per billion (ppb) level. Nevertheless, impact of the light-regulated electrochemical reaction on response selectivity has been discussed less. Herein, we systematically report on the effect of illumination on discrimination features via design and fabrication of a light-regulated electrochemical sensor array. Upon illumination (light on), response signal to the examined gases (C 3 H 6 , NO, and CO) is selectively enhanced, resulting in the sensor array demonstrating disparate response patterns when compared with that of the sensor array operated at light off. Through processing all the response patterns derived from both light on and light off with a pattern recognition algorithm, a satisfactory discrimination feature is observed. In contrast, apparent mutual interference between NO and CO is found when the sensor array is solely operated without illumination. The impact mechanism of the illumination is studied and it is deduced that the effect of the illumination on the discriminating features can be mainly attributed to the competition of electrocatalytic activity and gas-phase reactivity. If the enhanced electrocatalytic activity (to specific gas) dominates the whole sensing progress, enhancements in the corresponding response signal would be observed upon illumination. Otherwise, illumination gives a negligible impact. Hence, the response signal to part of the examined gases is selectively enhanced by illumination. Conclusively, light-regulated electrochemical reaction would provide an efficient approach to designing future smart sensing devices.

Membrane with internal passages to permit fluid flow and an electrochemical cell containing the same

NASA Technical Reports Server (NTRS)

Cisar, Alan J. (Inventor); Murphy, Oliver J. (Inventor); Gonzalez-Martin, Anuncia (Inventor); Hitchens, G. Duncan (Inventor)

1997-01-01

The invention provides an improved proton exchange membrane for use in electrochemical cells having internal passages parallel to the membrane surface, an apparatus and process for making the membrane, membrane and electrode assemblies fabricated using the membrane, and the application of the membrane and electrode assemblies to a variety of devices, both electrochemical and otherwise. The passages in the membrane extend from one edge of the membrane to another and allow fluid flow through the membrane and give access directly to the membrane for purposes of hydration.

Comparison study of biomimetic strontium-doped calcium phosphate coatings by electrochemical deposition and air plasma spray: morphology, composition and bioactive performance.

PubMed

Li, Ling; Lu, Xia; Meng, Yizhi; Weyant, Christopher M

2012-10-01

In this study, strontium-doped calcium phosphate coatings were deposited by electrochemical deposition and plasma spray under different process parameters to achieve various coating morphologies. The coating composition was investigated by energy dispersive X-ray spectroscopy and X-ray diffraction. The surface morphologies of the coatings were studied through scanning electron microscopy while the cytocompatibility and bioactivity of the strontium-doped calcium phosphate coatings were evaluated using bone cell culture using MC3T3-E1 osteoblast-like cells. The addition of strontium leads to enhanced proliferation suggesting the possible benefits of strontium incorporation in calcium phosphate coatings. The morphology and composition of deposited coatings showed a strong influence on the growth of cells.

Electrochemical study of pre- and post-transition corrosion of Zr alloys in PWR coolant

NASA Astrophysics Data System (ADS)

Macák, Jan; Novotný, Radek; Sajdl, Petr; Renčiuková, Veronika; Vrtílková, Věra

Corrosion properties of Zr-Sn and Zr-Nb zirconium alloys were studied under simulated PWR conditions (or, more exactly, VVER conditions — boric acid, potassium hydroxide, lithium hydroxide) at temperatures up to 340°C and 15MPa using in-situ electrochemical impedance spectroscopy (EIS) and polarization measurements. EIS spectra were obtained in a wide range of frequencies (typically 100kHz — 100μHz). It enabled to gain information of both dielectric properties of oxide layers developing on the Zr-alloys surface and of the kinetics of the corrosion process and the associated charge and mass transfer phenomena. Experiments were run for more than 380 days; thus, the study of all the corrosion stages (pre-transition, transition, post-transition) was possible.

Energy-Efficient and Environmentally Friendly Solid Oxide Membrane Electrolysis Process for Magnesium Oxide Reduction: Experiment and Modeling

NASA Astrophysics Data System (ADS)

Guan, Xiaofei; Pal, Uday B.; Powell, Adam C.

2014-06-01

This paper reports a solid oxide membrane (SOM) electrolysis experiment using an LSM(La0.8Sr0.2MnO3-δ)-Inconel inert anode current collector for production of magnesium and oxygen directly from magnesium oxide at 1423 K (1150 °C). The electrochemical performance of the SOM cell was evaluated by means of various electrochemical techniques including electrochemical impedance spectroscopy, potentiodynamic scan, and electrolysis. Electronic transference numbers of the flux were measured to assess the magnesium dissolution in the flux during SOM electrolysis. The effects of magnesium solubility in the flux on the current efficiency and the SOM stability during electrolysis are discussed. An inverse correlation between the electronic transference number of the flux and the current efficiency of the SOM electrolysis was observed. Based on the experimental results, a new equivalent circuit of the SOM electrolysis process is presented. A general electrochemical polarization model of SOM process for magnesium and oxygen gas production is developed, and the maximum allowable applied potential to avoid zirconia dissociation is calculated as well. The modeling results suggest that a high electronic resistance of the flux and a relatively low electronic resistance of SOM are required to achieve membrane stability, high current efficiency, and high production rates of magnesium and oxygen.

Electrochemical and ab initio investigations to design a new phenothiazine based organic redox polymeric material for metal-ion battery cathodes.

PubMed

Godet-Bar, T; Leprêtre, J-C; Le Bacq, O; Sanchez, J-Y; Deronzier, A; Pasturel, A

2015-10-14

Different N-substituted phenothiazines have been synthesized and their electrochemical behavior has been investigated in CH3CN in order to design the best polyphenothiazine based cathodic material candidate for lithium batteries. These compounds exhibit two successive reversible one-electron oxidation processes. Ab initio calculations demonstrate that the potential of the first process is a result of both the hybridization effects between the substituent and the phenothiazine unit as well as the change of conformation of the phenothiazine heterocycle during the oxidation process. More specifically, we show that an asymmetric molecular orbital spreading throughout an external cycle of the phenothiazine unit and the alkyl fragment is formed only if the alkyl fragment is long enough (from the methyl moiety onwards) and is at the origin of the bent conformation for N-substituted phenothiazines during oxidation. Electrochemical investigations supported by ab initio calculations allow the selection of a phenothiazinyl unit which is then polymerized by a Suzuki coupling strategy to avoid the common solubilization issue in carbonate-based liquid electrolytes of lithium cells. The first electrochemical measurements performed show that phenothiazine derivatives pave the way for a promising family of redox polymers intended to be used as organic positives for lithium batteries.

Engineering the Interfaces of Superadsorbing Graphene-Based Electrodes with Gas and Electrolyte to Boost Gas Evolution and Activation Reactions.

PubMed

Zhang, Jun-Jun; Lv, Li-Bing; Zhao, Tian-Jian; Lin, Yun-Xiao; Yu, Qiu-Ying; Su, Juan; Hirano, Shin-Ichi; Li, Xin-Hao; Chen, Jie-Sheng

2018-05-30

Electrochemical gas evolution and activation reactions are complicated processes, involving not only active electrocatalysts but also the interaction among solid electrodes, electrolyte, and gas-phase products and reactants. In this study, multiphase interfaces of superadsorbing graphene-based electrodes were controlled without changing the active centers to significantly facilitate mass diffusion kinetics for superior performance. The achieved in-depth understanding of how to regulate the interfacial properties to promote the electrochemical performance could provide valuable clues for electrode manufacture and for the design of more active electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

ECLSS Universal Waste Management System (UWMS) Metal Materials Compatibility Study- Electrochemical and Crevice Corrosion Evaluation

NASA Technical Reports Server (NTRS)

Lee, R. E.

2017-01-01

Electrochemical and crevice corrosion laboratory test results are presented for three noble metal candidates with possible application on the Universal Waste Management System (UWMS) in support of the Environmental Control and Life Support System (ECLSS) aboard the International Space Station (ISS). The three metal candidates, which included Inconel 625, Hastelloy C276 and Titanium 6Al-4V, were evaluated in two solutions representative of the acidic pretreatment formulations utilized during processing of waste liquids within the ECLSS. Final test results and data analysis indicated that the passive layer on all three metals provides excellent corrosion protection in both solutions under standard test conditions.

Voltammetric Behavior of o-Nitrophenol and Damage to DNA

PubMed Central

Zhang, Da-Peng; Wu, Wei-Li; Long, Hai-Yan; Liu, Yun-Chun; Yang, Zhou-Sheng

2008-01-01

The electrochemical behavior of o-nitrophenol was studied in detail with a glassy carbon electrode (GCE). The dependence of peak potential on pH indicated that equivalent electrons and protons were involved in the process of o-nitrophenol reduction. The interaction of o-nitrophenol with calf thymus DNA was investigated by adding DNA to the o-nitrophenol solution and by immobilizing DNA on GCE, respectively. The peak current decrement and peak potential shift in presence of DNA indicated that o-nitrophenol could interact with DNA. The result was demonstrated that the in situ DNA damage was detected by differential pulse voltammetry after the o-nitrophenol was electrochemically reduced. PMID:19325751

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

PubMed

Li, Bin; Yu, Bo; Zhou, Feng

2013-02-12

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

Understanding trends in electrochemical carbon dioxide reduction rates

DOE PAGES

Liu, Xinyan; Xiao, Jianping; Peng, Hongjie; ...

2017-05-22

Electrochemical carbon dioxide reduction to fuels presents one of the great challenges in chemistry. Herein we present an understanding of trends in electrocatalytic activity for carbon dioxide reduction over different metal catalysts that rationalize a number of experimental observations including the selectivity with respect to the competing hydrogen evolution reaction. We also identify two design criteria for more active catalysts. The understanding is based on density functional theory calculations of activation energies for electrochemical carbon monoxide reduction as a basis for an electrochemical kinetic model of the process. Furthermore, we develop scaling relations relating transition state energies to the carbonmore » monoxide adsorption energy and determine the optimal value of this descriptor to be very close to that of copper.« less

Understanding trends in electrochemical carbon dioxide reduction rates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xinyan; Xiao, Jianping; Peng, Hongjie

Electrochemical carbon dioxide reduction to fuels presents one of the great challenges in chemistry. Herein we present an understanding of trends in electrocatalytic activity for carbon dioxide reduction over different metal catalysts that rationalize a number of experimental observations including the selectivity with respect to the competing hydrogen evolution reaction. We also identify two design criteria for more active catalysts. The understanding is based on density functional theory calculations of activation energies for electrochemical carbon monoxide reduction as a basis for an electrochemical kinetic model of the process. Furthermore, we develop scaling relations relating transition state energies to the carbonmore » monoxide adsorption energy and determine the optimal value of this descriptor to be very close to that of copper.« less

Electrochemical corrosion behaviour of nickel chromium-chromium carbide coating by HVOF process

NASA Astrophysics Data System (ADS)

Amudha, A.; Nagaraja, H. S.; Shashikala, H. D.

2018-04-01

To overcome the corrosion problem in marine industry, coatings are one of the most economical solutions. In this paper, the corrosion behaviour of 25(NiCr)-75Cr3C2 cermet coating on low carbon steel substrate by HVOF process is studied. Different phases such as Cr7C3 and Cr3C2, along with Ni and chromium oxide(Cr3O2) constituents present in the coating were revealed by X-Ray Diffraction (XRD) analysis. The morphology of the coating obtained by scanning electron microscope (SEM) gave confirmation for the XRD analysis. Electrochemical corrosion techniques such as Linear Polarization Resistance (LPR) and Electrochemical Impedance Spectroscopy (EIS) were used to study the corrosion behaviour of the cermet in 3.5wt% NaCl electrolyte solution. The corrosion current density of the coated sample and substrate were found to be 6.878µA/cm-2 and 21.091µA/cm-2 respectively. The Nyquist Impedance spectra were used to derive an equivalent circuit to analyze the interaction between the coating and electrolyte. The Bode Impedance plots obtained by EIS for the coating showed a typical passive material capacitive behaviour, indicated by medium to low frequency with phase angle approaching -60o, suggesting that a stable film is formed on the tested material in the electrolyte used.

Electrochemical Behavior of Biomedical Titanium Alloys Coated with Diamond Carbon in Hanks' Solution

NASA Astrophysics Data System (ADS)

Gnanavel, S.; Ponnusamy, S.; Mohan, L.; Radhika, R.; Muthamizhchelvan, C.; Ramasubramanian, K.

2018-03-01

Biomedical implants in the knee and hip are frequent failures because of corrosion and stress on the joints. To solve this important problem, metal implants can be coated with diamond carbon, and this coating plays a critical role in providing an increased resistance to implants toward corrosion. In this study, we have employed diamond carbon coating over Ti-6Al-4V and Ti-13Nb-13Zr alloys using hot filament chemical vapor deposition method which is well-established coating process that significantly improves the resistance toward corrosion, wears and hardness. The diamond carbon-coated Ti-13Nb-13Zr alloy showed an increased microhardness in the range of 850 HV. Electrochemical impedance spectroscopy and polarization studies in SBF solution (simulated body fluid solution) were carried out to understand the in vitro behavior of uncoated as well as coated titanium alloys. The experimental results showed that the corrosion resistance of Ti-13Nb-13Zr alloy is relatively higher when compared with diamond carbon-coated Ti-6Al-4V alloys due to the presence of β phase in the Ti-13Nb-13Zr alloy. Electrochemical impedance results showed that the diamond carbon-coated alloys behave as an ideal capacitor in the body fluid solution. Moreover, the stability in mechanical properties during the corrosion process was maintained for diamond carbon-coated titanium alloys.

Excellent electrochemical performances of cabbage-like polyaniline fabricated by template synthesis

NASA Astrophysics Data System (ADS)

Hu, Chenglong; Chen, Shaoyun; Wang, Yuan; Peng, Xianghong; Zhang, Weihong; Chen, Jian

2016-07-01

In this article, we explore a novel route to fabricate cabbage-like polyaniline (PANI) by in situ polymerization of aniline using the hydroxylated poly (methyl methacrylate) nanospheres (i.e. PMMAsbnd OHsbnd NS) as a template. A maximum specific capacitance of 584 F/g (the current density is 0.1 A/g) is achieved at 10 mV s-1 as well as a high stability of over 3000 cycles (the decrease in the SC is ∼9.1%), which suggests the potential application of the cabbage-like polyaniline in supercapacitors. The predominant electrochemical performances of the cabbage-like polyaniline can be attributed to their large surface area and larger-scale π-π conjugated system present in the quinoid structure of the PANI molecular chain, which can drastically facilitate electron diffusion and improve the utilization of the electroactive PANI during the charge/discharge processes. Accordingly, the facility of charge transfer can decrease resistance along with the PANI molecular chain to improve the electrochemical stability and achieve high-capacitance response characteristics. The present study introduces a new synthesis method for the development of various morphology of other conducting polymer, which may find potential applications in a variety of high-performance electrochemical devices.

Green synthesis of cobalt (II, III) oxide nanoparticles using Moringa Oleifera natural extract as high electrochemical electrode for supercapacitors

NASA Astrophysics Data System (ADS)

Matinise, N.; Mayedwa, N.; Fuku, X. G.; Mongwaketsi, N.; Maaza, M.

2018-05-01

The research work involved the development of a better, inexpensive, reliable, easily and accurate way for the fabrication of Cobalt (II, III) oxide (Co3O4) nanoparticles through a green synthetic method using Moringa Oleifera extract. The electrochemical activity, crystalline structure, morphology, isothermal behaviour and optical properties of Co3O4 nanoparticles were studied using various characterization techniques. The X-ray diffraction (XRD) and Energy Dispersive X-ray Spectroscopy (EDS) analysis confirmed the formation of Co3O4 nanoparticles. The pseudo-capacitor behaviour of spinel Co3O4 nanoparticles on Nickel foam electrode was investigated by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) in 3M KOH solution. The CV curve revealed a pairs of redox peaks, indicating the pseudo-capacitive characteristics of the Ni/Co3O4 electrode. EIS results showed a small semicircle and Warburg impedance, indicating that the electrochemical process on the surface electrode is kinetically and diffusion controlled. The charge-discharge results indicating that the specific capacitance Ni/Co3O4 electrode is approximately 1060 F/g at a discharge current density of at 2 A/g.

Electrochemically exfoliated graphene anodes with enhanced biocurrent production in single-chamber air-breathing microbial fuel cells.

PubMed

Najafabadi, Amin Taheri; Ng, Norvin; Gyenge, Előd

2016-07-15

Microbial fuel cells (MFCs) present promising options for environmentally sustainable power generation especially in conjunction with waste water treatment. However, major challenges remain including low power density, difficult scale-up, and durability of the cell components. This study reports enhanced biocurrent production in a membrane-free MFC, using graphene microsheets (GNs) as anode and MnOx catalyzed air cathode. The GNs are produced by ionic liquid assisted simultaneous anodic and cathodic electrochemical exfoliation of iso-molded graphite electrodes. The GNs produced by anodic exfoliation increase the MFC peak power density by over 300% compared to plain carbon cloth (i.e., 2.85Wm(-2) vs 0.66Wm(-2), respectively), and by 90% compared to conventional carbon black (i.e., Vulcan XC-72) anode. These results exceed previously reported power densities for graphene-containing MFC anodes. The fuel cell polarization results are corroborated by electrochemical impedance spectroscopy indicating three times lower charge transfer resistance for the GN anode. Material characterizations suggest that the best performing GN samples were of relatively smaller size (~500nm), with higher levels of ionic liquid induced surface functionalization during the electrochemical exfoliation process. Copyright © 2016 Elsevier B.V. All rights reserved.

Application of electrochemical technology for removing petroleum hydrocarbons from produced water using lead dioxide and boron-doped diamond electrodes.

PubMed

Gargouri, Boutheina; Gargouri, Olfa Dridi; Gargouri, Bochra; Trabelsi, Souhel Kallel; Abdelhedi, Ridha; Bouaziz, Mohamed

2014-12-01

Although diverse methods exist for treating polluted water, the most promising and innovating technology is the electrochemical remediation process. This paper presents the anodic oxidation of real produced water (PW), generated by the petroleum exploration of the Petrobras plant-Tunisia. Experiments were conducted at different current densities (30, 50 and 100 mA cm(-2)) using the lead dioxide supported on tantalum (Ta/PbO2) and boron-doped diamond (BDD) anodes in an electrolytic batch cell. The electrolytic process was monitored by the chemical oxygen demand (COD) and the residual total petroleum hydrocarbon [TPH] in order to know the feasibility of electrochemical treatment. The characterization and quantification of petroleum wastewater components were performed by gas chromatography mass spectrometry. The COD removal was approximately 85% and 96% using PbO2 and BDD reached after 11 and 7h, respectively. Compared with PbO2, the BDD anode showed a better performance to remove petroleum hydrocarbons compounds from produced water. It provided a higher oxidation rate and it consumed lower energy. However, the energy consumption and process time make useless anodic oxidation for the complete elimination of pollutants from PW. Cytotoxicity has shown that electrochemical oxidation using BDD could be efficiently used to reduce more than 90% of hydrocarbons compounds. All results suggest that electrochemical oxidation could be an effective approach to treat highly concentrated organic pollutants present in the industrial petrochemical wastewater and significantly reduce the cost and time of treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electrochemical Deburring

NASA Technical Reports Server (NTRS)

Burley, R. K.

1983-01-01

Electrochemical deburring removes burrs from assembled injector tubes. Since process uses liquid anodic dissolution in liquid electrolyte to proide deburring action, smoothes surfaces and edges in otherwise inaccessible areas. Tool consists of sleeve that contains metallic ring cathode. Sleeve is placed over tube, and electrolytic solution is forced to flow between tube and sleeve. The workpiece serves an anode.

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).

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.

Electrochemical fabrication of nanoporous copper films in choline chloride-urea deep eutectic solvent.

PubMed

Zhang, Q B; Abbott, Andrew P; Yang, C

2015-06-14

Nanoporous copper films were fabricated by a facile electrochemical alloying/dealloying process without the need of a template. A deep eutectic solvent made from choline chloride (ChCl) and urea was used with zinc oxide as the metal salt. Cyclic voltammetry was used to characterise the electrochemical reduction of zinc and follow Cu-Zn alloy formation on the copper substrate at elevated temperatures from 353 to 393 K. The alloy formation was confirmed by X-ray diffraction spectra. 3D, open and bicontinuous nanoporous copper films were obtained by in situ electrochemically etching (dealloying) of the zinc component in the Cu-Zn surface alloys at an appropriate potential (-0.4 V vs. Ag). This dealloying process was found to be highly temperature dependent and surface diffusion controlled, which involved the self-assembly of copper atoms at the alloy/electrolyte interface. Additionally, the effects of the deposition parameters, including deposition temperature, current density as well as total charge density on resulting the microstructure were investigated by scanning electron microscopy, and atomic force microscope.

Recent Development of Advanced Electrode Materials by Atomic Layer Deposition for Electrochemical Energy Storage.

PubMed

Guan, Cao; Wang, John

2016-10-01

Electrode materials play a decisive role in almost all electrochemical energy storage devices, determining their overall performance. Proper selection, design and fabrication of electrode materials have thus been regarded as one of the most critical steps in achieving high electrochemical energy storage performance. As an advanced nanotechnology for thin films and surfaces with conformal interfacial features and well controllable deposition thickness, atomic layer deposition (ALD) has been successfully developed for deposition and surface modification of electrode materials, where there are considerable issues of interfacial and surface chemistry at atomic and nanometer scale. In addition, ALD has shown great potential in construction of novel nanostructured active materials that otherwise can be hardly obtained by other processing techniques, such as those solution-based processing and chemical vapor deposition (CVD) techniques. This review focuses on the recent development of ALD for the design and delivery of advanced electrode materials in electrochemical energy storage devices, where typical examples will be highlighted and analyzed, and the merits and challenges of ALD for applications in energy storage will also be discussed.

Recent Development of Advanced Electrode Materials by Atomic Layer Deposition for Electrochemical Energy Storage

PubMed Central

2016-01-01

Electrode materials play a decisive role in almost all electrochemical energy storage devices, determining their overall performance. Proper selection, design and fabrication of electrode materials have thus been regarded as one of the most critical steps in achieving high electrochemical energy storage performance. As an advanced nanotechnology for thin films and surfaces with conformal interfacial features and well controllable deposition thickness, atomic layer deposition (ALD) has been successfully developed for deposition and surface modification of electrode materials, where there are considerable issues of interfacial and surface chemistry at atomic and nanometer scale. In addition, ALD has shown great potential in construction of novel nanostructured active materials that otherwise can be hardly obtained by other processing techniques, such as those solution‐based processing and chemical vapor deposition (CVD) techniques. This review focuses on the recent development of ALD for the design and delivery of advanced electrode materials in electrochemical energy storage devices, where typical examples will be highlighted and analyzed, and the merits and challenges of ALD for applications in energy storage will also be discussed. PMID:27840793

Electrochemical writing on edible polysaccharide films for intelligent food packaging.

PubMed

Wu, Si; Wang, Wenqi; Yan, Kun; Ding, Fuyuan; Shi, Xiaowen; Deng, Hongbing; Du, Yumin

2018-04-15

Polysaccharide films used as intelligent food packaging possess the advantages of renewability, safety and biodegradability. Printing on the polysaccharidic food packaging is challenging due to the high demand for edible-ink and the need for a suitable printing technique. In this work, we propose an electrochemical method for writing on polysaccharide film. Unlike conventional printing, this electrochemical writing process relies on the pH responsive color change of anthocyanin embedded in the chitosan/agarose hydrogel. By biasing a negative potential to a stainless wire (used as a pen) contacting the surface of the chitosan/agarose/ATH hydrogel, the locally generated pH change induced the color change of ATH and wrote programmed information on the hydrogel. We demonstrate the writing can be temporary in the hydrogel but stable when the hydrogel is dried. We further demonstrate that the written film is applicable for the detection of the spoilage of crucian fish. The reported electrochemical writing process provides a novel method for printing information on polysaccharide film and great potential for intelligent food packaging. Copyright © 2018 Elsevier Ltd. All rights reserved.

Gelation Mechanisms and Characterization of Electrochemically Generated Protein Films at Metal Interfaces

NASA Astrophysics Data System (ADS)

Martin, Elizabeth J.

Although the electrochemical behavior of metals used in orthopedic implants has been studied extensively, the material interactions with proteins during corrosion processes remains poorly understood. Some studies suggest that metal-protein interactions accelerate corrosion, while others suggest that proteins protect the material from degradation. Corrosion of implant materials is a major concern due to the metal ion release that can sometimes cause adverse local tissue reactions and ultimately, failure of the implant. The initial purpose of this research was therefore to study the corrosion behavior of CoCrMo, an alloy commonly used in hip replacements, with a quartz crystal microbalance (QCM) in physiologically relevant media. The QCM enables in situ characterization of surface changes accompanying corrosion and is sensitive to viscoelastic effects at its surface. Results of QCM studies in proteinaceous media showed film deposition on the alloy surface under electrochemical conditions that otherwise produced mass loss if proteins were not present in the electrolyte. Additional studies on pure Co, Cr, and Mo demonstrated that the protein films also form on Mo surfaces after a release of molybdate ions, suggesting that these ions are essential for film formation. The electrochemically generated protein films are reminiscent of carbonaceous films that form on implant surfaces in vivo, therefore a second goal of the research was to delineate mechanisms that cause the films to form. In the second stage of this research, electrochemical QCM tests were conducted on models of the CoCrMo system consisting of Cr electrodes in proteinaceous or polymeric media containing dissolved molybdate ions. Studies indicated that films can be generated through electrochemical processes so long as both amine functional groups and molybdate ions are present in the electrolyte solution. These results suggest that the films form due to an ionic cross-linking reaction between the positively charged amine groups in the proteins and the negatively charged molybdate ions. Results also indicated that film generation is controlled by the potential at the electrode surface. Numerical analysis on the model systems suggest that a drop in the local pH at the corroding electrode surface may influence film generation, but a critical concentration of molybdate-amine cross-links must be exceeded for gels to form. A final goal of this research was to develop a technique to characterize the viscoelastic properties of polymer films in liquid media using the QCM as a high-frequency rheometer. The work showed that by measuring frequency and dissipation shifts at multiple harmonics of the QCM resonant frequency, the viscoelastic phase angle, density-modulus product, and areal mass of a film submersed in liquid can be quantified in situ. The method was successfully applied to characterize the electrochemically generated protein films. Results implied that the films are composed of a weakly cross-linked network with properties similar to concentrated albumin solutions containing 40 wt% protein. The analysis technique can be extended to characterize any polymer film in a liquid environment, with applications including adsorption, self-assembly, or cell-substrate interactions.

Performance of (in)active anodic materials for the electrooxidation of phenolic wastewaters from cashew-nut processing industry.

PubMed

Oliveira, Edna M S; Silva, Francisco R; Morais, Crislânia C O; Oliveira, Thiago Mielle B F; Martínez-Huitle, Carlos A; Motheo, Artur J; Albuquerque, Cynthia C; Castro, Suely S L

2018-06-01

This study investigated the anodic oxidation of phenolic wastewater generated by cashew-nut processing industry (CNPI) using active (Ti/RuO 2 -TiO 2 ) and inactive (boron doped diamond, BDD) anodes. During electrochemical treatment, various operating parameters were investigated, such as current density, chemical oxygen demand (COD), total phenols, O 2 production, temperature, pH, as well as current efficiency and energy consumption. After electrolysis under optimized working conditions, samples were evaluated by chromatography and toxicological tests against L. sativa. When both electrode materials were compared under the same operating conditions, higher COD removal efficiency was achieved for BDD anode; achieving lower energy requirements when compared with the values estimated for Ti/RuO 2 -TiO 2 . The presence of Cl - in the wastewater promoted the electrogeneration of strong oxidant species as chlorine, hypochlorite and mainly hypochlorous acid, increasing the efficiency of degradation process. Regarding the temperature effect, BDD showed slower performances than those achieved for Ti/RuO 2 -TiO 2 . Chromatographic and phytotoxicity studies indicated formation of some by-products after electrolytic process, regardless of the anode evaluated, and phytotoxic action of the effluent. Results encourage the applicability of the electrochemical method as wastewater treatment process for the CNPI, reducing depuration time. Copyright © 2018. Published by Elsevier Ltd.

Alternative Anodes for the Electrolytic Reduction of Uranium Dioxide

NASA Astrophysics Data System (ADS)

Merwin, Augustus

Reprocessing of spent nuclear fuel is an essential step in closing the nuclear fuel cycle. In order to consume current stockpiles, ceramic uranium dioxide spent nuclear fuel will be subjected to an electrolytic reduction process. The current reduction process employs a platinum anode and a stainless steel alloy 316 cathode in a molten salt bath consisting of LiCl-2wt% Li 2O and occurs at 700°C. A major shortcoming of the existing process is the degradation of the platinum anode under the severely oxidizing conditions encountered during electrolytic reduction. This work investigates alternative anode materials for the electrolytic reduction of uranium oxide. The high temperature and extreme oxidizing conditions encountered in these studies necessitated a unique set of design constraints on the system. Thus, a customized experimental apparatus was designed and constructed. The electrochemical experiments were performed in an electrochemical reactor placed inside a furnace. This entire setup was housed inside a glove box, in order to maintain an inert atmosphere. This study investigates alternative anode materials through accelerated corrosion testing. Surface morphology was studied using scanning electron microscopy. Surface chemistry was characterized using energy dispersive spectroscopy and Raman spectroscopy. Electrochemical behavior of candidate materials was evaluated using potentiodynamic polarization characteristics. After narrowing the number of candidate electrode materials, ferrous stainless steel alloy 316, nickel based Inconel 718 and elemental tungsten were chosen for further investigation. Of these materials only tungsten was found to be sufficiently stable at the anodic potential required for electrolysis of uranium dioxide in molten salt. The tungsten anode and stainless steel alloy 316 cathode electrode system was studied at the required reduction potential for UO2 with varying lithium oxide concentrations. Electrochemical impedance spectroscopy showed mixed (kinetic and diffusion) control and an overall low impedance due to extreme corrosion. It was observed that tungsten is sufficiently stable in LiCl - 2wt% Li 2O at 700°C at the required anodic potential for the reduction of uranium oxide. This study identifies tungsten to be a superior anode material to platinum for the electrolytic reduction of uranium oxide, both in terms of superior corrosion behavior and reduced cost, and thus recommends that tungsten be further investigated as an alternative anode for the electrolytic reduction of uranium dioxide.

Length-Scale-Dependent Phase Transformation of LiFePO4 : An In situ and Operando Study Using Micro-Raman Spectroscopy and XRD.

PubMed

Siddique, N A; Salehi, Amir; Wei, Zi; Liu, Dong; Sajjad, Syed D; Liu, Fuqiang

2015-08-03

The charge and discharge of lithium ion batteries are often accompanied by electrochemically driven phase-transformation processes. In this work, two in situ and operando methods, that is, micro-Raman spectroscopy and X-ray diffraction (XRD), have been combined to study the phase-transformation process in LiFePO4 at two distinct length scales, namely, particle-level scale (∼1 μm) and macroscopic scale (∼several cm). In situ Raman studies revealed a discrete mode of phase transformation at the particle level. Besides, the preferred electrochemical transport network, particularly the carbon content, was found to govern the sequence of phase transformation among particles. In contrast, at the macroscopic level, studies conducted at four different discharge rates showed a continuous but delayed phase transformation. These findings uncovered the intricate phase transformation in LiFePO4 and potentially offer valuable insights into optimizing the length-scale-dependent properties of battery materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microelectrode voltammetry of multi-electron transfers complicated by coupled chemical equilibria: a general theory for the extended square scheme.

PubMed

Laborda, Eduardo; Gómez-Gil, José María; Molina, Angela

2017-06-28

A very general and simple theoretical solution is presented for the current-potential-time response of reversible multi-electron transfer processes complicated by homogeneous chemical equilibria (the so-called extended square scheme). The expressions presented here are applicable regardless of the number of electrons transferred and coupled chemical processes, and they are particularized for a wide variety of microelectrode geometries. The voltammetric response of very different systems presenting multi-electron transfers is considered for the most widely-used techniques (namely, cyclic voltammetry, square wave voltammetry, differential pulse voltammetry and steady state voltammetry), studying the influence of the microelectrode geometry and the number and thermodynamics of the (electro)chemical steps. Most appropriate techniques and procedures for the determination of the 'interaction' between successive transfers are discussed. Special attention is paid to those situations where homogeneous chemical processes, such as protonation, complexation or ion association, affect the electrochemical behaviour of the system by different stabilization of the oxidation states.

Electrochemical behavior and voltammetric determination of acetaminophen based on glassy carbon electrodes modified with poly(4-aminobenzoic acid)/electrochemically reduced graphene oxide composite films.

PubMed

Zhu, Wencai; Huang, Hui; Gao, Xiaochun; Ma, Houyi

2014-12-01

Poly(4-aminobenzoic acid)/electrochemically reduced graphene oxide composite film modified glassy carbon electrodes (4-ABA/ERGO/GCEs) were fabricated by a two-step electrochemical method. The electrochemical behavior of acetaminophen at the modified electrode was investigated by means of cyclic voltammetry. The results indicated that 4-ABA/ERGO composite films possessed excellent electrocatalytic activity towards the oxidation of acetaminophen. The electrochemical reaction of acetaminophen at 4-ABA/ERGO/GCE is proved to be a surface-controlled process involving the same number of protons and electrons. The voltammetric determination of acetaminophen performed with the 4-ABA/ERGO modified electrode presents a good linearity in the range of 0.1-65 μM with a low detection limit of 0.01 μM (S/N=3). In the case of using the 4-ABA/ERGO/GCE, acetaminophen and dopamine can be simultaneously determined without mutual interference. Furthermore, the 4-ABA/ERGO/GCE has good reproducibility and stability, and can be used to determine acetaminophen in tablets. Copyright © 2014 Elsevier B.V. All rights reserved.

Enhancing the Electrochemical Behavior of Pure Copper by Cyclic Potentiodynamic Passivation: A Comparison between Coarse- and Nano-Grained Pure Copper

NASA Astrophysics Data System (ADS)

Fattah-alhosseini, Arash; Imantalab, Omid; Attarzadeh, Farid Reza

2016-10-01

Electrochemical behavior of coarse- and nano-grained pure copper were modified and improved to a large extent by the application of cyclic potentiodynamic passivation. The efficacy of this method was evaluated on the basis of grain size which is of great importance in corrosion studies. In this study, the eight passes of accumulative roll bonding process at room temperature were successfully performed to produce nano-grained pure copper. Transmission electron microscopy image indicated that the average grain size reached below 100 nm after eight passes. On the basis of cyclic voltammetry and also the electrochemical tests performed after that, it was revealed that cyclic potentiodynamic passivation had a significant improving effect on the passive behavior of both coarse- and nano-grained samples. In addition, a superior behavior of nano-grained sample in comparison to coarse-grained one was distinguished by its smaller cyclic voltammogram loops, nobler free potentials, larger capacitive arcs in the Nyquist plots, and less charge carrier densities within the passive film.

A preliminary study on the potency of nanofluids as the electro-active materials for nanoelectrofuel flow batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kristiawan, B., E-mail: budi-k@uns.ac.id; Wijayanta, A. T., E-mail: agungtw@uns.ac.id; Juwana, W. E., E-mail: wibawa.ej@gmail.com

2016-03-29

This study presents a characterization of nanofluids as electroactive materials with dispersing metal oxide nanoparticles into aqueous polyelectrolytes of 20 wt.%, in particular, their electrochemical activites. The fundamental characterizations including X-ray diffraction, transmission electron microscopy, and Fourier ttransform iinfrared measurement were performed to ensure metal oxide component used in this work. Alumina (Al{sub 2}O{sub 3}) and copper oxide (CuO) nanoparticles of 0.5 vol.% in volume fraction were dispersed into Poly(diallyldimethylammonium chloride) solution (PDADMAC) and Poly(sodium 4-styrenesulfonate) (PSS), respectively. Alumina and copper oxide nanoparticles were dispersed into ionic solution with volume fraction of 0.5 vol.% by using two-step method. The generalmore » cyclic voltammetry measurement was used to analyze electrochemical behavior within three-electrode cell setup. The results show that PSS-based nanofluids demonstrate redox process. However, unclearly redox phenomenon was depicted PDADMAC-based nanofluids. Dispersing nanoparticles could shift pure ionic solution’s cyclic profile. It is clear that a significant impact on electrochemical behavior can be provided because of the existence metal oxide nanoparticles into polyelectrolyte solution.« less

The morphological study of porous silicon formed by electrochemical anodization method

NASA Astrophysics Data System (ADS)

Suryana, R.; Sandi, D. K.; Nakatsuka, O.

2018-03-01

Due to its good physical and chemical properties, porous silicon (PSi) is very attractive to study. In this research, PSi has been fabricated on n-type Si (100) by the electrochemical anodization method. The electrolyte solution used was a mixture of HF (40%), ethanol (99%) and aquadest with volume ratio of 1:1:2, respectively. It was anodized on Si(100) surface at different current densities of 10 mA/cm2 and 20 mA/cm2 with the anodization time at each current density for 10 min, 20 min, and 30 min. The Scanning Electron Microscope (SEM) images showed that the PSi surfaces have inhomogeneous sized pores in the range of 95.00 nm–1.46 μm. The PSi layers with current density and anodization time of 10 mA/cm2 (10 min), 10mA/cm2 (20 min), and 20mA/cm2 (10 min) have spherical shaped pores while the others have some uncommon (cross sectional) shaped pores on surfaces. It is considered that the cross sectional shaped maybe caused by unstable the current during the electrochemical anodization process.

In situ electrochemical digital holographic microscopy; a study of metal electrodeposition in deep eutectic solvents.

PubMed

Abbott, Andrew P; Azam, Muhammad; Ryder, Karl S; Saleem, Saima

2013-07-16

This study has shown for the first time that digital holographic microscopy (DHM) can be used as a new analytical tool in analysis of kinetic mechanism and growth during electrolytic deposition processes. Unlike many alternative established electrochemical microscopy methods such as probe microscopy, DHM is both the noninvasive and noncontact, the unique holographic imaging allows the observations and measurement to be made remotely. DHM also provides interferometric resolution (nanometer vertical scale) with a very short acquisition time. It is a surface metrology technique that enables the retrieval of information about a 3D structure from the phase contrast of a single hologram acquired using a conventional digital camera. Here DHM has been applied to investigate directly the electro-crystallization of a metal on a substrate in real time (in situ) from two deep eutectic solvent (DES) systems based on mixture of choline chloride and either urea or ethylene glycol. We show, using electrochemical DHM that the nucleation and growth of silver deposits in these systems are quite distinct and influenced strongly by the hydrogen bond donor of the DES.

Multiplex acute leukemia cytosensing using multifunctional hybrid electrochemical nanoprobes at a hierarchically nanoarchitectured electrode interface

NASA Astrophysics Data System (ADS)

Zheng, Tingting; Tan, Tingting; Zhang, Qingfeng; Fu, Jia-Ju; Wu, Jia-Jun; Zhang, Kui; Zhu, Jun-Jie; Wang, Hui

2013-10-01

We have developed a robust, nanobiotechnology-based electrochemical cytosensing approach with high sensitivity, selectivity, and reproducibility toward the simultaneous multiplex detection and classification of both acute myeloid leukemia and acute lymphocytic leukemia cells. The construction of the electrochemical cytosensor involves the hierarchical assembly of dual aptamer-functionalized, multilayered graphene-Au nanoparticle electrode interface and the utilization of hybrid electrochemical nanoprobes co-functionalized with redox tags, horseradish peroxidase, and cell-targeting nucleic acid aptamers. The hybrid nanoprobes are multifunctional, capable of specifically targeting the cells of interest, amplifying the electrochemical signals, and generating distinguishable signals for multiplex cytosensing. The as-assembled electrode interface not only greatly facilitates the interfacial electron transfer process due to its high conductivity and surface area but also exhibits excellent biocompatibility and specificity for cell recognition and adhesion. A superstructured sandwich-type sensor geometry is adopted for electrochemical cytosensing, with the cells of interest sandwiched between the nanoprobes and the electrode interface. Such an electrochemical sensing strategy allows for ultrasensitive, multiplex acute leukemia cytosensing with a detection limit as low as ~350 cells per mL and a wide linear response range from 5 × 102 to 1 × 107 cells per mL for HL-60 and CEM cells, with minimal cross-reactivity and interference from non-targeting cells. This electrochemical cytosensing approach holds great promise as a new point-of-care diagnostic tool for early detection and classification of human acute leukemia and may be readily expanded to multiplex cytosensing of other cancer cells.We have developed a robust, nanobiotechnology-based electrochemical cytosensing approach with high sensitivity, selectivity, and reproducibility toward the simultaneous multiplex detection and classification of both acute myeloid leukemia and acute lymphocytic leukemia cells. The construction of the electrochemical cytosensor involves the hierarchical assembly of dual aptamer-functionalized, multilayered graphene-Au nanoparticle electrode interface and the utilization of hybrid electrochemical nanoprobes co-functionalized with redox tags, horseradish peroxidase, and cell-targeting nucleic acid aptamers. The hybrid nanoprobes are multifunctional, capable of specifically targeting the cells of interest, amplifying the electrochemical signals, and generating distinguishable signals for multiplex cytosensing. The as-assembled electrode interface not only greatly facilitates the interfacial electron transfer process due to its high conductivity and surface area but also exhibits excellent biocompatibility and specificity for cell recognition and adhesion. A superstructured sandwich-type sensor geometry is adopted for electrochemical cytosensing, with the cells of interest sandwiched between the nanoprobes and the electrode interface. Such an electrochemical sensing strategy allows for ultrasensitive, multiplex acute leukemia cytosensing with a detection limit as low as ~350 cells per mL and a wide linear response range from 5 × 102 to 1 × 107 cells per mL for HL-60 and CEM cells, with minimal cross-reactivity and interference from non-targeting cells. This electrochemical cytosensing approach holds great promise as a new point-of-care diagnostic tool for early detection and classification of human acute leukemia and may be readily expanded to multiplex cytosensing of other cancer cells. Electronic supplementary information (ESI) available: Additional figures as noted in the text. See DOI: 10.1039/c3nr02903d

High voltage electrophoretic deposition for electrochemical energy storage and other applications

NASA Astrophysics Data System (ADS)

Santhanagopalan, Sunand

High voltage electrophoretic deposition (HVEPD) has been developed as a novel technique to obtain vertically aligned forests of one-dimensional nanomaterials for efficient energy storage. The ability to control and manipulate nanomaterials is critical for their effective usage in a variety of applications. Oriented structures of one-dimensional nanomaterials provide a unique opportunity to take full advantage of their excellent mechanical and electrochemical properties. However, it is still a significant challenge to obtain such oriented structures with great process flexibility, ease of processing under mild conditions and the capability to scale up, especially in context of efficient device fabrication and system packaging. This work presents HVEPD as a simple, versatile and generic technique to obtain vertically aligned forests of different one-dimensional nanomaterials on flexible, transparent and scalable substrates. Improvements on material chemistry and reduction of contact resistance have enabled the fabrication of high power supercapacitor electrodes using the HVEPD method. The investigations have also paved the way for further enhancements of performance by employing hybrid material systems and AC/DC pulsed deposition. Multi-walled carbon nanotubes (MWCNTs) were used as the starting material to demonstrate the HVEPD technique. A comprehensive study of the key parameters was conducted to better understand the working mechanism of the HVEPD process. It has been confirmed that HVEPD was enabled by three key factors: high deposition voltage for alignment, low dispersion concentration to avoid aggregation and simultaneous formation of holding layer by electrodeposition for reinforcement of nanoforests. A set of suitable parameters were found to obtain vertically aligned forests of MWCNTs. Compared with their randomly oriented counterparts, the aligned MWCNT forests showed better electrochemical performance, lower electrical resistance and a capability to achieve superhydrophpbicity, indicating their potential in a broad range of applications. The versatile and generic nature of the HVEPD process has been demonstrated by achieving deposition on flexible and transparent substrates, as well as aligned forests of manganese dioxide (MnO2) nanorods. A continuous roll-printing HVEPD approach was then developed to obtain aligned MWCNT forest with low contact resistance on large, flexible substrates. Such large-scale electrodes showed no deterioration in electrochemical performance and paved the way for practical device fabrication. The effect of a holding layer on the contact resistance between aligned MWCNT forests and the substrate was studied to improve electrochemical performance of such electrodes. It was found that a suitable precursor salt like nickel chloride could be used to achieve a conductive holding layer which helped to significantly reduce the contact resistance. This in turn enhanced the electrochemical performance of the electrodes. High-power scalable redox capacitors were then prepared using HVEPD. Very high power/energy densities and excellent cyclability have been achieved by synergistically combining hydrothermally synthesized, highly crystalline α-MnO 2 nanorods, vertically aligned forests and reduced contact resistance. To further improve the performance, hybrid electrodes have been prepared in the form of vertically aligned forest of MWCNTs with branches of α-MnO 2 nanorods on them. Large- scale electrodes with such hybrid structures were manufactured using continuous HVEPD and characterized, showing further improved power and energy densities. The alignment quality and density of MWCNT forests were also improved by using an AC/DC pulsed deposition technique. In this case, AC voltage was first used to align the MWCNTs, followed by immediate DC voltage to deposit the aligned MWCNTs along with the conductive holding layer. Decoupling of alignment from deposition was proven to result in better alignment quality and higher electrochemical performance.

Effect of the size-selective silver clusters on lithium peroxide morphology in lithium–oxygen batteries

DOE PAGES

Lu, Jun; Cheng, Lei; Lau, Kah Chun; ...

2014-09-12

Lithium–oxygen batteries have the potential needed for long-range electric vehicles, but the charge and discharge chemistries are complex and not well understood. The active sites on cathode surfaces and their role in electrochemical reactions in aprotic lithium–oxygen cells are difficult to ascertain because the exact nature of the sites is unknown. In this paper, we report the deposition of subnanometre silver clusters of exact size and number of atoms on passivated carbon to study the discharge process in lithium–oxygen cells. The results reveal dramatically different morphologies of the electrochemically grown lithium peroxide dependent on the size of the clusters. Thismore » dependence is found to be due to the influence of the cluster size on the formation mechanism, which also affects the charge process. Finally, the results of this study suggest that precise control of subnanometre surface structure on cathodes can be used as a means to improve the performance of lithium–oxygen cells.« less

Synthesis and characterization of hybrid micro/nano-structured NiTi surfaces by a combination of etching and anodizing

NASA Astrophysics Data System (ADS)

Huan, Z.; Fratila-Apachitei, L. E.; Apachitei, I.; Duszczyk, J.

2014-02-01

The purpose of this study was to generate hybrid micro/nano-structures on biomedical nickel-titanium alloy (NiTi). To achieve this, NiTi surfaces were firstly electrochemically etched and then anodized in fluoride-containing electrolyte. With the etching process, the NiTi surface was micro-roughened through the formation of micropits uniformly distributed over the entire surface. Following the subsequent anodizing process, self-organized nanotube structures enriched in TiO2 could be superimposed on the etched surface under specific conditions. Furthermore, the anodizing treatment significantly reduced water contact angles and increased the surface free energy compared to the surfaces prior to anodizing. The results of this study show for the first time that it is possible to create hybrid micro/nano-structures on biomedical NiTi alloys by combining electrochemical etching and anodizing under controlled conditions. These novel structures are expected to significantly enhance the surface biofunctionality of the material when compared to conventional implant devices with either micro- or nano-structured surfaces.

Synthesis and characterization of hybrid micro/nano-structured NiTi surfaces by a combination of etching and anodizing.

PubMed

Huan, Z; Fratila-Apachitei, L E; Apachitei, I; Duszczyk, J

2014-02-07

The purpose of this study was to generate hybrid micro/nano-structures on biomedical nickel-titanium alloy (NiTi). To achieve this, NiTi surfaces were firstly electrochemically etched and then anodized in fluoride-containing electrolyte. With the etching process, the NiTi surface was micro-roughened through the formation of micropits uniformly distributed over the entire surface. Following the subsequent anodizing process, self-organized nanotube structures enriched in TiO2 could be superimposed on the etched surface under specific conditions. Furthermore, the anodizing treatment significantly reduced water contact angles and increased the surface free energy compared to the surfaces prior to anodizing. The results of this study show for the first time that it is possible to create hybrid micro/nano-structures on biomedical NiTi alloys by combining electrochemical etching and anodizing under controlled conditions. These novel structures are expected to significantly enhance the surface biofunctionality of the material when compared to conventional implant devices with either micro- or nano-structured surfaces.

Fabrication of high reflectivity nanoporous distributed Bragg reflectors by controlled electrochemical etching of GaN

NASA Astrophysics Data System (ADS)

Lee, Seung-Min; Kang, Jin-Ho; Lee, June Key; Ryu, Sang-Wan

2016-09-01

The nanoporous medium is a valuable feature of optical devices because of its variable optical refractive index with porosity. One important application is in a GaN-based vertical cavity surface emitting laser having a distributed Bragg reflector (DBR) composed of alternating nanoporous and bulk GaNs. However, optimization of the fabrication process for high reflectivity DBRs having wellcontrolled high reflection bands has not been studied yet. We used electrochemical etching to study the fabrication process of a nanoporous GaN DBR and analyzed the relationship between the morphology and optical reflectivity. Several electrolytes were examined for the formation of the optimized nanoporous structure. A highly reflective DBRs having reflectivity of ~100% were obtained over a wide wavelength range of 450-750 nm. Porosification of semiconductors into nanoporous layers could provide a high reflectivity DBR due to controlled index-contrast, which would be advantages for the construction of a high-Q optical cavity.

The graphene oxide membrane immersing in the aqueous solution studied by electrochemical impedance spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Yongjing; Chen, Zhe; Yao, Lei; Wang, Xiao; Fu, Ping; Lin, Zhidong

2018-04-01

The interlayer spacing of graphene oxide (GO) is a key property for GO membrane. To probe the variation of interlayer spacing of the GO membrane immersing in KCl aqueous solution, electrochemical impedance spectroscopy (EIS), x-ray diffraction (XRD) and computational calculation was utilized in this study. The XRD patterns show that soaking in KCl aqueous solution leads to an increase of interlayer spacing of GO membrane. And the EIS results indicate that during the immersing process, the charge transfer resistance of GO membrane decreases first and then increases. Computational calculation confirms that intercalated water molecules can result in an increase of interlayer spacing of GO membrane, while the permeation of K+ ions would lead to a decrease of interlayer spacing. All the results are in agreement with each other. It suggests that during the immersing process, the interlayer spacing of GO enlarges first and then decreases. EIS can be a promisingly online method for examining the interlayer spacing of GO in the aqueous solution.

Controlled electrochemical doping of graphene-based 3D nanoarchitecture electrodes for supercapacitors and capacitive deionisation.

PubMed

Abdelkader, A M; Fray, D J

2017-10-05

Chemically-doped graphenes are promising electrode materials for energy storage and electrosorption applications. Here, an affordable electrochemical green process is introduced to dope graphene with nitrogen. The process is based on reversing the polarity of two identical graphene oxide (GO) electrodes in molten KCl-LiCl-Li 3 N. During the cathodic step, the oxygen functional groups on the GO surface are removed through direct electro-deoxidation reactions or a reaction with the deposited lithium. In the anodic step, nitrogen is adsorbed onto the surface of graphene and subsequently reacts to form nitrogen-doped graphene. The doping process is controllable, and graphene with up to 7.4 at% nitrogen can be produced. The electrochemically treated electrodes show a specific capacitance of 320 F g -1 in an aqueous KOH electrolyte and maintain 96% of this value after 10 000 cycles. The electrodes also display excellent electrosorption performance in capacitive deionisation devices with the salt removal efficiency reaching up to 18.6 mg g -1 .

Pyroprocessing of Light Water Reactor Spent Fuels Based on an Electrochemical Reduction Technology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohta, Hirokazu; Inoue, Tadashi; Sakamura, Yoshiharu

A concept of pyroprocessing light water reactor (LWR) spent fuels based on an electrochemical reduction technology is proposed, and the material balance of the processing of mixed oxide (MOX) or high-burnup uranium oxide (UO{sub 2}) spent fuel is evaluated. Furthermore, a burnup analysis for metal fuel fast breeder reactors (FBRs) is conducted on low-decontamination materials recovered by pyroprocessing. In the case of processing MOX spent fuel (40 GWd/t), UO{sub 2} is separately collected for {approx}60 wt% of the spent fuel in advance of the electrochemical reduction step, and the product recovered through the rare earth (RE) removal step, which hasmore » the composition uranium:plutonium:minor actinides:fission products (FPs) = 76.4:18.4:1.7:3.5, can be applied as an ingredient of FBR metal fuel without a further decontamination process. On the other hand, the electroreduced alloy of high-burnup UO{sub 2} spent fuel (48 GWd/t) requires further decontamination of residual FPs by an additional process such as electrorefining even if RE FPs are removed from the alloy because the recovered plutonium (Pu) is accompanied by almost the same amount of FPs in addition to RE. However, the amount of treated materials in the electrorefining step is reduced to {approx}10 wt% of the total spent fuel owing to the prior UO{sub 2} recovery step. These results reveal that the application of electrochemical reduction technology to LWR spent oxide fuel is a promising concept for providing FBR metal fuel by a rationalized process.« less

Towards First Principles-Based Prediction of Highly Accurate Electrochemical Pourbaix Diagrams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng, Zhenhua; Chan, Maria K. Y.; Zhao, Zhi-Jian

2015-08-13

Electrochemical potential/pH (Pourbaix) diagrams underpin many aqueous electrochemical processes and are central to the identification of stable phases of metals for processes ranging from electrocatalysis to corrosion. Even though standard DFT calculations are potentially powerful tools for the prediction of such diagrams, inherent errors in the description of transition metal (hydroxy)oxides, together with neglect of van der Waals interactions, have limited the reliability of such predictions for even the simplest pure metal bulk compounds, and corresponding predictions for more complex alloy or surface structures are even more challenging. In the present work, through synergistic use of a Hubbard U correction,more » a state-of-the-art dispersion correction, and a water-based bulk reference state for the calculations, these errors are systematically corrected. The approach describes the weak binding that occurs between hydroxyl-containing functional groups in certain compounds in Pourbaix diagrams, corrects for self-interaction errors in transition metal compounds, and reduces residual errors on oxygen atoms by preserving a consistent oxidation state between the reference state, water, and the relevant bulk phases. The strong performance is illustrated on a series of bulk transition metal (Mn, Fe, Co and Ni) hydroxides, oxyhydroxides, binary, and ternary oxides, where the corresponding thermodynamics of redox and (de)hydration are described with standard errors of 0.04 eV per (reaction) formula unit. The approach further preserves accurate descriptions of the overall thermodynamics of electrochemically-relevant bulk reactions, such as water formation, which is an essential condition for facilitating accurate analysis of reaction energies for electrochemical processes on surfaces. The overall generality and transferability of the scheme suggests that it may find useful application in the construction of a broad array of electrochemical phase diagrams, including both bulk Pourbaix diagrams and surface phase diagrams of interest for corrosion and electrocatalysis.« less

Synthesis and electrochemical properties of NiO nanospindles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hai; University of Chinese Academy of Sciences, Beijing 100049; Lv, Baoliang, E-mail: lbl604@sxicc.ac.cn

2014-02-01

Graphical abstract: NiO nanospindles with a different electrochemical activity as compared to those previous reports were synthesized via an agglomeration–dissolution–recrystallization growth process without the addition of any surfactant. - Highlights: • NiO nanospindles were synthesized without the addition of any surfactant. • The agglomeration–dissolution–recrystallization growth process was used to explain the precursors’ formation process of the spindle-like NiO. • As-obtained spindle-like NiO showed a different electrochemical activity as compared to those previous reports. - Abstract: NiO nanospindles were successfully synthesized via a hydrothermal and post-treatment method. The as-synthesized nanospindles were about several hundred nanometers in width and about one micrometermore » in length. X-ray diffraction (XRD) analysis revealed that the spindle-like structure was cubic NiO phase crystalline. Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) analysis indicated that these NiO nanospindles were of single crystal nature. On the basis of time-dependent experiments, a possible agglomeration–dissolution–recrystallization growth process was proposed to explain the formation process of the spindle-like precursors. The cyclic voltammetry (CV) measurement showed that the as-prepared spindle-like NiO exhibited a pseudo-capacitance behavior.« less

Electric field effects on current–voltage relationships in microfluidic channels presenting multiple working electrodes in the weak-coupling limit

DOE PAGES

Contento, Nicholas M.; Bohn, Paul W.

2014-05-23

While electrochemical methods are well suited for lab-on-a-chip applications, reliably coupling multiple, electrode-controlled processes in a single microfluidic channel remains a considerable challenge, because the electric fields driving electrokinetic flow make it difficult to establish a precisely known potential at the working electrode(s). The challenge of coupling electrochemical detection with microchip electrophoresis is well known; however, the problem is general, arising in other multielectrode arrangements with applications in enhanced detection and chemical processing. Here, we study the effects of induced electric fields on voltammetric behavior in a microchannel containing multiple in-channel electrodes, using a Fe(CN) 6 3/4- model system. Whenmore » an electric field is induced by applying a cathodic potential at one inchannel electrode, the half-wave potential (E 1/2) for the oxidation of ferrocyanide at an adjacent electrode shifts to more negative potentials. The E 1/2 value depends linearly on the electric field current at a separate in-channel electrode. The observed shift in E 1/2 is quantitatively described by a model, which accounts for the change in solution potential caused by the iR drop along the length of the microchannel. The model, which reliably captures changes in electrode location and solution conductivity, apportions the electric field potential between iR drop and electrochemical potential components, enabling the study of microchannel electric field magnitudes at low applied potentials. In the system studied, the iR component of the electric field potential increases exponentially with applied current before reaching an asymptotic value near 80 % of the total applied potential. The methods described will aid in the development and interpretation of future microchip electrochemistry methods, particularly those that benefit from the coupling of electrokinetic and electrochemical phenomena at low voltages.« less

Peculiarities of steel and alloy electrochemical and corrosion behavior after laser processing

NASA Astrophysics Data System (ADS)

Kuzmenko, Tat'yana G.; Kosyrev, Feliks K.; Rodin, Anatoly V.; Sayapin, V. P.

1997-04-01

Different types of laser processing can significantly increase the corrosion resistance of constructive materials, secure higher levels of metal properties in comparison with standard protection from corrosion and can be successfully used for industrial application. The research carried out in TRINITI during the last 10 years allowed us to create a data base about corrosion behavior in different chemical media of various metals, alloys and steels after welding, melting, surface alloying, etc. on technological continuous-wave carbon-dioxide-laser with average power up to 5 kilowatt. The investigated materials were subdivided into two groups: (1) without changes of phases composition after laser processing (pure metals, stainless steels); and (2) exposed to structural and phase changes under laser-matter interaction (carbon steels with different carbon content). It has allowed us to investigate the peculiarities of corrosion process mechanism depending on matter surface structure and phase composition both on laser irradiation regimes. Our research was based on the high sensitive electrochemical analysis combined with other corrosion and physical methods. The essential principles of electrochemical analysis are next. There are two main processes on metal under the interaction with electrolyte solution: anodic reaction -- which means the metal oxidation or transition of metal kations into solution; cathodic reaction -- the reoxidation of the ions or molecular of the solution. They are characterizing by the values of current densities and the rates of these reactions are dependent upon the potential arising on the metal-solution frontier. The electrochemical reactions kinetic investigations gives a unique possibility for the research of metal structure and corrosion behavior even in the case of small thickness of laser processed layers.

In vitro electrochemical corrosion and cell viability studies on nickel-free stainless steel orthopedic implants.

PubMed

Salahinejad, Erfan; Hadianfard, Mohammad Jafar; Macdonald, Digby Donald; Sharifi-Asl, Samin; Mozafari, Masoud; Walker, Kenneth J; Rad, Armin Tahmasbi; Madihally, Sundararajan V; Tayebi, Lobat

2013-01-01

The corrosion and cell viability behaviors of nanostructured, nickel-free stainless steel implants were studied and compared with AISI 316L. The electrochemical studies were conducted by potentiodynamic polarization and electrochemical impedance spectroscopic measurements in a simulated body fluid. Cytocompatibility was also evaluated by the adhesion behavior of adult human stem cells on the surface of the samples. According to the results, the electrochemical behavior is affected by a compromise among the specimen's structural characteristics, comprising composition, density, and grain size. The cell viability is interpreted by considering the results of the electrochemical impedance spectroscopic experiments.

Quantum-Dot-Based Electrochemical Immunoassay for High-Throughput Screening of the Prostate-Specific Antigen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jun; Liu, Guodong; Wu, Hong

2008-01-01

In this paper, we demonstrate an electrochemical high-throughput sensing platform for simple, sensitive detection of PSA based on QD labels. This sensing platform uses a microplate for immunoreactions and disposable screen-printed electrodes (SPE) for electrochemical stripping analysis of metal ions released from QD labels. With the 96-well microplate, capturing antibodies are conveniently immobilized to the well surface, and the process of immunoreaction is easily controlled. The formed sandwich complexes on the well surface are also easily isolated from reaction solutions. In particular, a microplate-based electrochemical assay can make it feasible to conduct a parallel analysis of several samples or multiplemore » protein markers. This assay offers a number of advantages including (1) simplicity, cost-effectiveness, (2) high sensitivity, (3) capability to sense multiple samples or targets in parallel, and (4) a potentially portable device with an SPE array implanted in the microplate. This PSA assay is sensitive because it uses two amplification processes: (1) QDs as a label for enhancing electrical signal since secondary antibodies are linked to QDs that contain a large number of metal atoms and (2) there is inherent signal amplification for electrochemical stripping analysis—preconcentration of metal ion onto the electrode surface for amplifying electrical signals. Therefore, the high sensitivity of this method, stemming from dual signal amplification via QD labels and pre-concentration, allows low concentration levels to be detected while using small sample volumes. Thus, this QD-based electrochemical detection approach offers a simple, rapid, cost-effective, and high throughput assay of PSA.« less

A study on optimal pore development of modified commercial activated carbons for electrode materials of supercapacitors

NASA Astrophysics Data System (ADS)

Bang, Joon Hyuk; Lee, Hye-Min; An, Kay-Hyeok; Kim, Byung-Joo

2017-09-01

This study aimed to understand the impact of CO2 activation of commercial activated carbons (AC) on the changes in pore characteristics and the electrochemical property. The surface structure of manufactured AC was observed with a X-ray diffraction (XRD); the pore characteristics were analyzed at N2/77 K isothermal absorption using the Brunauer-Emmett-Teller (BET) and Dubinin-Radushkevich (DR) equations. In addition, the electrochemical characteristics were analyzed by means of an electrolyte of 1 M (C2H5)4NBF4/propylene carbonate, using a charge/discharge test, cyclic voltammetry (CV), and impedance. The N2/77 K isothermal absorption curve of the manufactured AC falls under Type I in the classification of the International Union of Pure and Applied Chemistry (IUPAC) and was found to largely comprise micropores. The specific surface area increased from 1690 m2/g to 2290 m2/g, and the pore volume grew from 0.80 cm3/g to 1.10 cm3/g. The analysis of electrochemical characteristics also found that the specific capacity increased from 17 F/g to 20 F/g (in a full cell condition). Based on these results, we were able to determine the pore characteristics of commercial AC through an additional activation process, which consequently allowed us to manufacture the AC with an advanced electrochemical property.

Analysis of Protein-Phenolic Compound Modifications Using Electrochemistry Coupled to Mass Spectrometry.

PubMed

Kallinich, Constanze; Schefer, Simone; Rohn, Sascha

2018-01-29

In the last decade, electrochemical oxidation coupled with mass spectrometry has been successfully used for the analysis of metabolic studies. The application focused in this study was to investigate the redox potential of different phenolic compounds such as the very prominent chlorogenic acid. Further, EC/ESI-MS was used as preparation technique for analyzing adduct formation between electrochemically oxidized phenolic compounds and food proteins, e.g., alpha-lactalbumin or peptides derived from a tryptic digestion. In the first step of this approach, two reactant solutions are combined and mixed: one contains the solution of the digested protein, and the other contains the phenolic compound of interest, which was, prior to the mixing process, electrochemically transformed to several oxidation products using a boron-doped diamond working electrode. As a result, a Michael-type addition led to covalent binding of the activated phenolic compounds to reactive protein/peptide side chains. In a follow-up approach, the reaction mix was further separated chromatographically and finally detected using ESI-HRMS. Compound-specific, electrochemical oxidation of phenolic acids was performed successfully, and various oxidation and reaction products with proteins/peptides were observed. Further optimization of the reaction (conditions) is required, as well as structural elucidation concerning the final adducts, which can be phenolic compound oligomers, but even more interestingly, quite complex mixtures of proteins and oxidation products.

Electrochemical models for the radical annihilation reactions in organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Armstrong, Neal R.; Anderson, Jeffrey D.; Lee, Paul A.; McDonald, Erin; Wightman, R. M.; Hall, Hank K.; Hopkins, Tracy; Padias, Anne; Thayumanavan, Sankaran; Barlow, Stephen; Marder, Seth R.

1998-12-01

Bilayer organic light emitting diodes (OLEDs), based upon vacuum deposited molecules, or single layer OLEDs, based upon spin-cast polymeric materials, doped with these same molecules, produce light from emissive states of the lumophores which are created through annihilation reactions of radical species, which can be modeled through solution electrochemistry. Difference seen in solution reduction and oxidation potentials of molecular components of OLEDs are a lower limit estimate to the differences in energy of these same radical species in the condensed phase environmental. The light emitted from an aluminum quinolate (Alq3)/triarylamine (TPD)-based OLED, or an Alq3/PVK single layers OLED, can be reproduce from solution cross reactions of Alq3/TPD+. The efficiency of this process increases as the oxidation potential of the TPD increases, due to added substituents. Radical cations and anions of solubilized version of quinacridone dopants (DIQA) which have been used to enhance efficiencies in these OLEDs, are shown to be electrochemically more stable than Alq3 and Alq3, and DIQA radical annihilation reactions produce the same emissive state as in the quinacridone-doped OLEDs. Electrochemical studies demonstrate the ways in which other dopants might enhance the efficiency and shift the color output of OLEDs, across the entire visible and near-IR spectrum. Chemical degradation pathways of these same molecular components, which they may undergo during OLED operation, are also revealed by these electrochemical studies.

Influence of surfactants on the microstructure and electrochemical performance of the tin oxide anode in lithium ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Yan-Hui, E-mail: sunyanhui0102@163.com; Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, South China Normal University, Guangzhou 510006; Dong, Pei-Pei

2016-02-15

Highlights: • CTAB and SDS alter the formation of SnO{sub 2} from nanosheets to nanocubes during oxalate precipitation. • The CTAB concentration affects the SnO{sub 2} crystal growth direction, morphology and size. • The SnO{sub 2} anode synthesized using CTAB exhibited superior electrochemical performance. • Proposed a mechanism of influence of surfactant on SnO{sub 2} in the precipitation and annealing process. - Abstract: Different SnO{sub 2} micro–nano structures are prepared by precipitation using a surfactant-assisted process. The surfactants, such as cetyltriethylammonium bromide (CTAB) or sodium dodecyl benzene sulfonate (SDBS), can change the crystal growth direction and microstructure of SnO{sub 2}more » primary and secondary particles. Larger SnO{sub 2} nanosheets were synthesized without surfactant, and micro-fragments composed of small nanospheres or nanocubes were synthesized using CTAB and SDBS. The CTAB-assisted process resulted in smaller primary particles and larger specific surface area and larger pore volume, as a lithium-ion-battery anode that exhibits superior electrochemical performance compared to the other two anodes. Further investigation showed that the concentration of CTAB had a substantial influence on the growth of the crystal face, morphology and size of the SnO{sub 2} secondary particles, which influenced the electrochemical performance of the anode. A simple mechanism for the influence of surfactants on SnO{sub 2} morphology and size in the precipitation and annealing process is proposed.« less

Electrochemical synthesis of elongated noble metal nanoparticles, such as nanowires and nanorods, on high-surface area carbon supports

DOEpatents

Adzic, Radoslav; Blyznakov, Stoyan; Vukmirovic, Miomir

2015-08-04

Elongated noble-metal nanoparticles and methods for their manufacture are disclosed. The method involves the formation of a plurality of elongated noble-metal nanoparticles by electrochemical deposition of the noble metal on a high surface area carbon support, such as carbon nanoparticles. Prior to electrochemical deposition, the carbon support may be functionalized by oxidation, thus making the manufacturing process simple and cost-effective. The generated elongated nanoparticles are covalently bound to the carbon support and can be used directly in electrocatalysis. The process provides elongated noble-metal nanoparticles with high catalytic activities and improved durability in combination with high catalyst utilization since the nanoparticles are deposited and covalently bound to the carbon support in their final position and will not change in forming an electrode assembly.

Effect of the Cerium Oxide (CeO2) on the Structural and Electrochemical Properties of the LaNi5Ce Metal Hydride Anode

NASA Astrophysics Data System (ADS)

Utami Hapsari, Ade; Zulfia, Anne; Raharjo, Jarot; Agustanhakri

2017-07-01

One of negative electrode, AB5-type alloy electrodes, have been extensively studied and applied in rechargeable Ni-MH batteries due to their excellent electrochemical characteristics. Some researchers have found that addition of rare earth oxides (La, Ce, Pr, Er, Tm, Yb) to AB5-type alloy (MH) electrode improves battery performance significantly. Cerium Oxide (CeO2) is a light rare earth oxide is widely obtained from the processing of tailings in mining activities. During this time, there is still little data for research applications of cerium oxide for electrode materials. In this paper, the effects of adding CeO2 on the performance metal hydride electrode were investigated. In order to study the effects of CeO2 on the performance of anode material, 1%, 2%, and 3% of weight ratio CeO2 was mixed to LaNi5 as an negative electrode. The powder mixtures were mechanically milled at a speed of rpm 240 for 2 hours using ball mill. The powder mixtures were characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscope (SEM). Electrochemical characteristics were measured using electrochemical impedance spectroscopy (EIS). The powder mixing showed the presence of Ce atom substitution into LaNi5 structures that affect the electrochemical properties of the material. The addition of cerium oxide at LaNi5 increase of the value of impedance. However, the addition of the value of impedance at 1% CeO2 is not significant when compared with the addition of 2% and 3% CeO2 that actually make the electrochemical properties of LaNi5 worst. Although the addition of 1% CeO2 also slightly increases the impedance value of LaNi5, but the addition of 1% CeO2 showed increase the corrosion resistance than without the addition of CeO2 and the addition of 2% and 3% CeO2.

Destruction of organic pollutants by cerium(IV) MEO process: a study on the influence of process conditions for EDTA mineralization.

PubMed

Balaji, Subramanian; Chung, Sang Joon; Matheswaran, Manickam; Vasilivich, Kokovkin Vasily; Moon, Il Shik

2008-02-11

The mediated electrochemical oxidation (MEO) process with cerium(IV) and nitric acid as the oxidizing medium was employed for the destruction of various model organic pollutants in continuous organic feeding mode. A near complete destruction was observed for all the organics studied. The effects of various experimental conditions were evaluated with respect to EDTA mineralization. The key parameters varied in the process were concentration of EDTA (67-268 mM), temperature (70, 80 and 95 degrees C), concentrations of Ce(IV) (0.7, 0.8 and 0.95 M), nitric acid (2, 3 and 4M) and duration of organic addition (30 and 120 min). Under the experimental conditions of 80 degrees C and 0.95 M Ce(IV) in 3 M nitric acid, nearly 90% destruction was achieved based on CO(2) production and 95% based on TOC analyses for all the organic compounds studied. The in situ regeneration of mediator ion by the electrochemical cell was found to be good during the organic destruction within the range of experimental conditions studied. In the case of long term organic feeding (120 min) the destruction was calculated after the CO(2) evolution attained the steady state and under this condition the destruction efficiency was found to be 85% based on CO(2) evolution.

Effect of nitro substituent on electrochemical oxidation of phenols at boron-doped diamond anodes.

PubMed

Jiang, Yi; Zhu, Xiuping; Li, Hongna; Ni, Jinren

2010-02-01

In order to investigate nitro-substitutent's effect on degradation of phenols at boron-doped diamond (BDD) anodes, cyclic voltammetries of three nitrophenol isomers: 2-nitrophenol (2NP), 3-nitrophenol (3NP) and 4-nitrophenol (4NP) were studied, and their bulk electrolysis results were compared with phenol's (Ph) under alkaline condition. The voltammetric study showed nitrophenols could be attacked by hydroxyl radicals and nitro-group was released from the aromatic ring. Results of bulk electrolysis showed degradation of all phenols were fit to a pseudo first-order equation and followed in this order: 2NP>4NP>3NP>Ph. Molecular structures, especially carbon atom charge, significantly influenced the electrochemical oxidation of these isomers. Intermediates were analyzed during the electrolysis process, and were mainly catechol, resorcinol, hydroquinone, and carboxylic acids, such as acetic acid and oxalic acid. A simple degradation pathway was proposed. Moreover, a linear increasing relationship between degradation rates and Hammett constants of the studied phenols was observed, which demonstrated that electrochemical oxidation of these phenols was mainly initiated by electrophilic attack of hydroxyl radicals at BDD anodes. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Fabrication and Demonstration of Mercury Disc-Well Probes for Stripping-Based Cyclic Voltammetry Scanning Electrochemical Microscopy.

PubMed

Barton, Zachary J; Rodríguez-López, Joaquín

2017-03-07

Scanning electrochemical microscopy (SECM) is a rising technique for the study of energy storage materials. Hg-based probes allow the extension of SECM investigations to ionic processes, but the risk of irreversible Hg amalgam saturation limits their operation to rapid timescales and dilute analyte solutions. Here, we report a novel fabrication protocol for Hg disc-well ultramicroelectrodes (UMEs), which retain access to stripping information but are less susceptible to amalgam saturation than traditional Hg sphere-caps or thin-films. The amalgamation and stripping behaviors of Hg disc-well UMEs are compared to those of traditional Hg sphere-cap UMEs and corroborated with data from finite element simulations. The improved protection against amalgam saturation allows Hg disc-wells to operate safely in highly concentrated environments at long timescales. The utility of the probes for bulk measurements extends also to SECM studies, where the disc geometry facilitates small tip-substrate gaps and improves both spatial and temporal resolution. Because they can carry out slow, high-resolution anodic stripping voltammetry approaches and imaging in concentrated solutions, Hg disc-well electrodes fill a new analytical niche for studies of ionic reactivity and are a valuable addition to the electrochemical toolbox.

Efficient electrochemical CO2 conversion powered by renewable energy.

PubMed

Kauffman, Douglas R; Thakkar, Jay; Siva, Rajan; Matranga, Christopher; Ohodnicki, Paul R; Zeng, Chenjie; Jin, Rongchao

2015-07-22

The catalytic conversion of CO2 into industrially relevant chemicals is one strategy for mitigating greenhouse gas emissions. Along these lines, electrochemical CO2 conversion technologies are attractive because they can operate with high reaction rates at ambient conditions. However, electrochemical systems require electricity, and CO2 conversion processes must integrate with carbon-free, renewable-energy sources to be viable on larger scales. We utilize Au25 nanoclusters as renewably powered CO2 conversion electrocatalysts with CO2 → CO reaction rates between 400 and 800 L of CO2 per gram of catalytic metal per hour and product selectivities between 80 and 95%. These performance metrics correspond to conversion rates approaching 0.8-1.6 kg of CO2 per gram of catalytic metal per hour. We also present data showing CO2 conversion rates and product selectivity strongly depend on catalyst loading. Optimized systems demonstrate stable operation and reaction turnover numbers (TONs) approaching 6 × 10(6) molCO2 molcatalyst(-1) during a multiday (36 h total hours) CO2 electrolysis experiment containing multiple start/stop cycles. TONs between 1 × 10(6) and 4 × 10(6) molCO2 molcatalyst(-1) were obtained when our system was powered by consumer-grade renewable-energy sources. Daytime photovoltaic-powered CO2 conversion was demonstrated for 12 h and we mimicked low-light or nighttime operation for 24 h with a solar-rechargeable battery. This proof-of-principle study provides some of the initial performance data necessary for assessing the scalability and technical viability of electrochemical CO2 conversion technologies. Specifically, we show the following: (1) all electrochemical CO2 conversion systems will produce a net increase in CO2 emissions if they do not integrate with renewable-energy sources, (2) catalyst loading vs activity trends can be used to tune process rates and product distributions, and (3) state-of-the-art renewable-energy technologies are sufficient to power larger-scale, tonne per day CO2 conversion systems.

Treatment of an azo dye effluent by peroxi-coagulation and its comparison to traditional electrochemical advanced processes.

PubMed

do Vale-Júnior, Edilson; da Silva, Djalma R; Fajardo, Ana S; Martínez-Huitle, Carlos A

2018-08-01

Peroxi-coagulation (PC) is an interesting new process that has not been widely studied in the literature. This work presents the application of this technology to treat an azo dye synthetic effluent, studying the effect of different parameters including initial pH, current density (j), initial dye concentration and supporting electrolyte. The two former variables significantly affected the colour removal of the wastewater, followed by the initial dye concentration and the kind of electrolyte, in a lesser extent. The optimum operating conditions achieved were initial pH of 3.0, j = 33.3 mA cm -2 , 100 mg L -1 of methyl orange (MO) and Na 2 SO 4 as supporting electrolyte. The performance of PC was also compared to other electrochemical advanced processes, under similar experimental conditions. Results indicate that the kinetic decay of the MO increases in the following order: electrocoagulation (EC) < electrochemical oxidation (EO) with electrogenerated H 2 O 2 < PC < electro-Fenton (EF). This behaviour is given to the high oxidant character of the homogenous OH radicals generated by EF and PC approaches. The EO process with production of H 2 O 2 (EO-H 2 O 2 ) is limited by mass transport and the EC, as a separation method, takes longer times to achieve similar removal results. Energy requirements about 0.06 kWh g COD -1 , 0.09 kWh g COD -1 , 0.7 kWh g COD -1 and 0.1 kWh g COD -1 were achieved for PC, EF, EO-H 2 O 2 and EC, respectively. Degradation intermediates were monitored and carboxylic acids were detected for PC and EF processes, being rapidly removed by the former technology. PC emerges as a promising and competitive alternative for wastewaters depollution, among other oxidative approaches. Copyright © 2018 Elsevier Ltd. All rights reserved.