WorldWideScience

Sample records for bifunctional redox flow

  1. Bifunctional redox flow battery

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Y.H. [Research Institute of Chemical Defense, Beijing 100083 (China)], E-mail: wen_yuehua@126.com; Cheng, J. [Research Institute of Chemical Defense, Beijing 100083 (China); Beijing Science and Technology University, Beijing 100083 (China); Xun, Y. [Research Institute of Chemical Defense, Beijing 100083 (China); Ma, P.H. [Full Cell R and D Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Yang, Y.S. [Research Institute of Chemical Defense, Beijing 100083 (China); Beijing Science and Technology University, Beijing 100083 (China)

    2008-08-20

    A new bifunctional redox flow battery (BRFB) system, V(III)/V(II)-L-cystine(O{sub 2}), was systematically investigated by using different separators. It is shown that during charge, water transfer is significantly restricted with increasing the concentration of HBr when the Nafion 115 cation exchange membrane is employed. The same result can be obtained when the gas diffusion layer (GDL) hot-pressed separator is used. The organic electro-synthesis is directly correlated with the crossover of vanadium. When employing the anion exchange membrane, the electro-synthesis efficiency is over 96% due to a minimal crossover of vanadium. When the GDL hot-pressed separator is applied, the crossover of vanadium and water transfer are noticeably prevented and the electro-synthesis efficiency of over 99% is obtained. Those impurities such as vanadium ions and bromine can be eliminated through the purification of organic electro-synthesized products. The purified product is identified to be L-cysteic acid by IR spectrum. The BRFB shows a favorable discharge performance at a current density of 20 mA cm{sup -2}. Best discharge performance is achieved by using the GDL hot-pressed separator. The coulombic efficiency of 87% and energy efficiency of about 58% can be obtained. The cause of major energy losses is mainly associated with the cross-contamination of anodic and cathodic active electrolytes.

  2. Bifunctional redox flow battery - 2. V(III)/V(II)-L-cystine(O{sub 2}) system

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Y.H.; Xun, Y. [Research Institute of Chemical Defense, Beijing 100083 (China); Cheng, J.; Yang, Y.S. [Research Institute of Chemical Defense, Beijing 100083 (China); Beijing Science and Technology University, Beijing 100083 (China); Ma, P.H. [Full Cell R and D Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China)

    2008-08-20

    A new bifunctional redox flow battery (BRFB) system, V(III)/V(II) - L-cystine(O{sub 2}), was systematically investigated by using different separators. It is shown that during charge, water transfer is significantly restricted with increasing the concentration of HBr when the Nafion 115 cation exchange membrane is employed. The same result can be obtained when the gas diffusion layer (GDL) hot-pressed separator is used. The organic electro-synthesis is directly correlated with the crossover of vanadium. When employing the anion exchange membrane, the electro-synthesis efficiency is over 96% due to a minimal crossover of vanadium. When the GDL hot-pressed separator is applied, the crossover of vanadium and water transfer are noticeably prevented and the electro-synthesis efficiency of over 99% is obtained. Those impurities such as vanadium ions and bromine can be eliminated through the purification of organic electro-synthesized products. The purified product is identified to be L-cysteic acid by IR spectrum. The BRFB shows a favorable discharge performance at a current density of 20 mA cm{sup -2}. Best discharge performance is achieved by using the GDL hot-pressed separator. The coulombic efficiency of 87% and energy efficiency of about 58% can be obtained. The cause of major energy losses is mainly associated with the cross-contamination of anodic and cathodic active electrolytes. (author)

  3. Bifunctional Crosslinking Agents Enhance Anion Exchange Membrane Efficacy for Vanadium Redox Flow Batteries.

    Science.gov (United States)

    Wang, Wenpin; Xu, Min; Wang, Shubo; Xie, Xiaofeng; Lv, Yafei; Ramani, Vijay K

    2014-06-01

    A series of cross-linked fluorinated poly (aryl ether oxadiazole) membranes (FPAEOM) derivatized with imidazolium groups were prepared. Poly (N-vinylimidazole) (PVI) was used as the bifunctional cross-linking agent to: a) lower vanadium permeability, b) enhance dimensional stability, and c) concomitantly provide added ion exchange capacity in the resultant anion exchange membranes. At a molar ratio of PVI to FPAEOM of 1.5, the resultant membrane (FPAEOM-1.5 PVI) had an ion exchange capacity of 2.2 meq g-1, a vanadium permeability of 6.8×10-7 cm2 min-1, a water uptake of 68 wt.%, and an ionic conductivity of 22.0 mS cm-1, all at 25°C. Single cells prepared with the FPAEOM-1.5 PVI membrane exhibited a higher coulombic efficiency (> 92%) and energy efficiency (> 86%) after 40 test cycles in vanadium redox flow battery. The imidazolium cation showed high chemical stability in highly acidic and oxidizing vanadium solution as opposed to poor stability in alkaline solutions. Based on our DFT studies, this was attributed to the lower HOMO energy (-7.265 eV) of the HSO4- ion (compared to the OH- ion; -5.496 eV) and the larger HOMO-LUMO energy gap (6.394 eV) of dimethylimidazolium bisulfate ([DMIM] [HSO4]) as compared to [DMIM] [OH] (5.387 eV).

  4. Redox Flow Batteries, a Review

    Energy Technology Data Exchange (ETDEWEB)

    Knoxville, U. Tennessee; U. Texas Austin; U, McGill; Weber, Adam Z.; Mench, Matthew M.; Meyers, Jeremy P.; Ross, Philip N.; Gostick, Jeffrey T.; Liu, Qinghua

    2011-07-15

    Redox flow batteries are enjoying a renaissance due to their ability to store large amounts of electrical energy relatively cheaply and efficiently. In this review, we examine the components of redox flow batteries with a focus on understanding the underlying physical processes. The various transport and kinetic phenomena are discussed along with the most common redox couples.

  5. Membranes for Redox Flow Battery Applications

    OpenAIRE

    Maria Skyllas-Kazacos; Aishwarya Parasuraman; Tuti Mariana Lim; Suminto Winardi; Helen Prifti

    2012-01-01

    The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. Th...

  6. Membranes for Redox Flow Battery Applications

    Directory of Open Access Journals (Sweden)

    Maria Skyllas-Kazacos

    2012-06-01

    Full Text Available The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention.

  7. Membranes for redox flow battery applications.

    Science.gov (United States)

    Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

    2012-06-19

    The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention.

  8. Progress of all vanadium redox flow batteries

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    @@ Aresearch team headed by Prof.ZHANG Huamin from the CAS Dalian Institute of Chemical Physics has made important progress in the research and development of a LED screen demo system powered by vanadium redox flow batteries (VRB).The system has operated continuously for over one year without any malfunction.So far,the total running time is up to 11,000 hours.

  9. Membrane development for vanadium redox flow batteries.

    Science.gov (United States)

    Schwenzer, Birgit; Zhang, Jianlu; Kim, Soowhan; Li, Liyu; Liu, Jun; Yang, Zhenguo

    2011-10-17

    Large-scale energy storage has become the main bottleneck for increasing the percentage of renewable energy in our electricity grids. Redox flow batteries are considered to be among the best options for electricity storage in the megawatt range and large demonstration systems have already been installed. Although the full technological potential of these systems has not been reached yet, currently the main problem hindering more widespread commercialization is the high cost of redox flow batteries. Nafion, as the preferred membrane material, is responsible for about 11% of the overall cost of a 1 MW/8 MWh system. Therefore, in recent years two main membrane related research threads have emerged: 1) chemical and physical modification of Nafion membranes to optimize their properties with regard to vanadium redox flow battery (VRFB) application; and 2) replacement of the Nafion membranes with different, less expensive materials. This review summarizes the underlying basic scientific issues associated with membrane use in VRFBs and presents an overview of membrane-related research approaches aimed at improving the efficiency of VRFBs and making the technology cost-competitive. Promising research strategies and materials are identified and suggestions are provided on how materials issues could be overcome.

  10. Rebalancing electrolytes in redox flow battery systems

    Science.gov (United States)

    Chang, On Kok; Pham, Ai Quoc

    2014-12-23

    Embodiments of redox flow battery rebalancing systems include a system for reacting an unbalanced flow battery electrolyte with a rebalance electrolyte in a first reaction cell. In some embodiments, the rebalance electrolyte may contain ferrous iron (Fe.sup.2+) which may be oxidized to ferric iron (Fe.sup.3+) in the first reaction cell. The reducing ability of the rebalance reactant may be restored in a second rebalance cell that is configured to reduce the ferric iron in the rebalance electrolyte back into ferrous iron through a reaction with metallic iron.

  11. Fe-V redox flow batteries

    Science.gov (United States)

    Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Xia, Guanguang

    2014-07-08

    A redox flow battery having a supporting solution that includes Cl.sup.- anions is characterized by an anolyte having V.sup.2+ and V.sup.3+ in the supporting solution, a catholyte having Fe.sup.2+ and Fe.sup.3+ in the supporting solution, and a membrane separating the anolyte and the catholyte. The anolyte and catholyte can have V cations and Fe cations, respectively, or the anolyte and catholyte can each contain both V and Fe cations in a mixture. Furthermore, the supporting solution can contain a mixture of SO.sub.4.sup.2- and Cl.sup.- anions.

  12. Iron-sulfide redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Xia, Guanguang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

    2016-06-14

    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  13. Hybrid anodes for redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Wei; Xiao, Jie; Wei, Xiaoliang; Liu, Jun; Sprenkle, Vincent L.

    2015-12-15

    RFBs having solid hybrid electrodes can address at least the problems of active material consumption, electrode passivation, and metal electrode dendrite growth that can be characteristic of traditional batteries, especially those operating at high current densities. The RFBs each have a first half cell containing a first redox couple dissolved in a solution or contained in a suspension. The solution or suspension can flow from a reservoir to the first half cell. A second half cell contains the solid hybrid electrode, which has a first electrode connected to a second electrode, thereby resulting in an equipotential between the first and second electrodes. The first and second half cells are separated by a separator or membrane.

  14. High energy density redox flow device

    Energy Technology Data Exchange (ETDEWEB)

    Carter, W. Craig; Chiang, Yet-Ming; Duduta, Mihai; Limthongkul, Pimpa

    2017-04-04

    Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % of the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.

  15. Iron-sulfide redox flow batteries

    Science.gov (United States)

    Xia, Guan-Guang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

    2013-12-17

    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  16. Economics of vanadium redox flow battery membranes

    Science.gov (United States)

    Minke, Christine; Turek, Thomas

    2015-07-01

    The membrane is a key component of the vanadium redox flow battery (VRFB) in terms of electrochemical performance as well as costs. The standard material Nafion® is cost intensive and therefore several alternative materials are in the focus of research. In this paper a substantial analytical approach is presented in order to quantify bottom price limits for different types of membranes. An in-depth analysis of material and production cost allows statements concerning cost potentials of different ion exchange membranes (IEM) and nano filtration membranes (NFM). The final result reveals that expected costs of IEM and NFM at high production volumes differ by one order of magnitude. Moreover, an analysis of the current market situation is made to provide a framework for economic considerations at present.

  17. Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

    Science.gov (United States)

    Wedege, Kristina; Dražević, Emil; Konya, Denes; Bentien, Anders

    2016-12-01

    Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V.

  18. Performance of redox flow battery systems in Japan

    Institute of Scientific and Technical Information of China (English)

    Shibata Toshikazu; Kumamoto Takahiro; Nagaoko Yoshiyuki; Kawase Kazunori; Yano Keiji

    2013-01-01

    Renewable energies, such as solar and wind power, are increasingly being introduced as alternative energy sources on a glosbal scale toward a low-carbon society. For the next generation power network, which uses a large number of these distributed power generation sources, energy storage technologies will be indispensable. Among these technologies, battery energy storage technology is considered to be most viable. Sumitomo Electric Industries, Ltd. has developed a redox flow battery system suitable for large scale energy storage, and carried out several demonstration projects on the stabilization of renewable energy output using the redox flow battery system. This paper describes the advantages of the redox flow battery and reviews the demonstration projects.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-03-29

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

  20. Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

    Science.gov (United States)

    Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

    2015-10-01

    Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites.

  1. Chloride supporting electrolytes for all-vanadium redox flow batteries.

    Science.gov (United States)

    Kim, Soowhan; Vijayakumar, M; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Chen, Feng; Hu, Jianzhi; Li, Liyu; Yang, Zhenguo

    2011-10-28

    This paper examines vanadium chloride solutions as electrolytes for an all-vanadium redox flow battery. The chloride solutions were capable of dissolving more than 2.3 M vanadium at varied valence states and remained stable at 0-50 °C. The improved stability appeared due to the formation of a vanadium dinuclear [V(2)O(3)·4H(2)O](4+) or a dinuclear-chloro complex [V(2)O(3)Cl·3H(2)O](3+) in the solutions over a wide temperature range. The all-vanadium redox flow batteries with the chloride electrolytes demonstrated excellent reversibility and fairly high efficiencies. Only negligible, if any, gas evolution was observed. The improved energy capacity and good performance, along with the ease in heat management, would lead to substantial reduction in capital cost and life-cycle cost, making the vanadium chloride redox flow battery a promising candidate for stationary applications.

  2. Pulsating electrolyte flow in a full vanadium redox battery

    Science.gov (United States)

    Ling, C. Y.; Cao, H.; Chng, M. L.; Han, M.; Birgersson, E.

    2015-10-01

    Proper management of electrolyte flow in a vanadium redox battery (VRB) is crucial to achieve high overall system efficiency. On one hand, constant flow reduces concentration polarization and by extension, energy efficiency; on the other hand, it results in higher auxiliary pumping costs, which can consume around 10% of the discharge power. This work seeks to reduce the pumping cost by adopting a novel pulsing electrolyte flow strategy while retaining high energy efficiency. The results indicate that adopting a short flow period, followed by a long flow termination period, results in high energy efficiencies of 80.5% with a pumping cost reduction of over 50%.

  3. Redox-Flow Batteries: From Metals to Organic Redox-Active Materials.

    Science.gov (United States)

    Winsberg, Jan; Hagemann, Tino; Janoschka, Tobias; Hager, Martin D; Schubert, Ulrich S

    2017-01-16

    Research on redox-flow batteries (RFBs) is currently experiencing a significant upturn, stimulated by the growing need to store increasing quantities of sustainably generated electrical energy. RFBs are promising candidates for the creation of smart grids, particularly when combined with photovoltaics and wind farms. To achieve the goal of "green", safe, and cost-efficient energy storage, research has shifted from metal-based materials to organic active materials in recent years. This Review presents an overview of various flow-battery systems. Relevant studies concerning their history are discussed as well as their development over the last few years from the classical inorganic, to organic/inorganic, to RFBs with organic redox-active cathode and anode materials. Available technologies are analyzed in terms of their technical, economic, and environmental aspects; the advantages and limitations of these systems are also discussed. Further technological challenges and prospective research possibilities are highlighted.

  4. Polyoxometalate active charge-transfer material for mediated redox flow battery

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Travis Mark; Hudak, Nicholas; Staiger, Chad; Pratt, Harry

    2017-01-17

    Redox flow batteries including a half-cell electrode chamber coupled to a current collecting electrode are disclosed herein. In a general embodiment, a separator is coupled to the half-cell electrode chamber. The half-cell electrode chamber comprises a first redox-active mediator and a second redox-active mediator. The first redox-active mediator and the second redox-active mediator are circulated through the half-cell electrode chamber into an external container. The container includes an active charge-transfer material. The active charge-transfer material has a redox potential between a redox potential of the first redox-active mediator and a redox potential of the second redox-active mediator. The active charge-transfer material is a polyoxometalate or derivative thereof. The redox flow battery may be particularly useful in energy storage solutions for renewable energy sources and for providing sustained power to an electrical grid.

  5. Numerical modeling of an all vanadium redox flow battery.

    Energy Technology Data Exchange (ETDEWEB)

    Clausen, Jonathan R.; Brunini, Victor E.; Moffat, Harry K.; Martinez, Mario J.

    2014-01-01

    We develop a capability to simulate reduction-oxidation (redox) flow batteries in the Sierra Multi-Mechanics code base. Specifically, we focus on all-vanadium redox flow batteries; however, the capability is general in implementation and could be adopted to other chemistries. The electrochemical and porous flow models follow those developed in the recent publication by [28]. We review the model implemented in this work and its assumptions, and we show several verification cases including a binary electrolyte, and a battery half-cell. Then, we compare our model implementation with the experimental results shown in [28], with good agreement seen. Next, a sensitivity study is conducted for the major model parameters, which is beneficial in targeting specific features of the redox flow cell for improvement. Lastly, we simulate a three-dimensional version of the flow cell to determine the impact of plenum channels on the performance of the cell. Such channels are frequently seen in experimental designs where the current collector plates are borrowed from fuel cell designs. These designs use a serpentine channel etched into a solid collector plate.

  6. A carbon-free lithium-ion solid dispersion redox couple with low viscosity for redox flow batteries

    Science.gov (United States)

    Qi, Zhaoxiang; Koenig, Gary M.

    2016-08-01

    A new type of non-aqueous redox couple without carbon additives for flow batteries is proposed and the target anolyte chemistry is demonstrated. The so-called "Solid Dispersion Redox Couple" incorporates solid electroactive materials dispersed in organic lithium-ion battery electrolyte as its flowing suspension. In this work, a unique and systematic characterization approach has been used to study the flow battery redox couple in half cell demonstrations relative to a lithium electrode. An electrolyte laden with Li4Ti5O12 (LTO) has been characterized in multiple specially designed lithium half cell configurations. The flow battery redox couple described in this report has relatively low viscosity, especially in comparison to other flow batteries with solid active materials. The lack of carbon additive allows characterization of the electrochemical properties of the electroactive material in flow without the complication of conductive additives and unambiguous observation of the electrorheological coupling in these dispersed particle systems.

  7. Redox flow batteries based on supporting solutions containing chloride

    Energy Technology Data Exchange (ETDEWEB)

    Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Xia, Guanguang

    2014-01-14

    Redox flow battery systems having a supporting solution that contains Cl.sup.- ions can exhibit improved performance and characteristics. Furthermore, a supporting solution having mixed SO.sub.4.sup.2- and Cl.sup.- ions can provide increased energy density and improved stability and solubility of one or more of the ionic species in the catholyte and/or anolyte. According to one example, a vanadium-based redox flow battery system is characterized by an anolyte having V.sup.2+ and V.sup.3+ in a supporting solution and a catholyte having V.sup.4+ and V.sup.5+ in a supporting solution. The supporting solution can contain Cl.sup.- ions or a mixture of SO.sub.4.sup.2- and Cl.sup.- ions.

  8. Redox flow batteries based on supporting solutions containing chloride

    Energy Technology Data Exchange (ETDEWEB)

    Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Nie, Zimin; Chen, Baowei; Zhang, Jianlu; Xia, Guanguang

    2015-07-07

    Redox flow battery systems having a supporting solution that contains Cl.sup.- ions can exhibit improved performance and characteristics. Furthermore, a supporting solution having mixed SO.sub.4.sup.2- and Cl.sup.- ions can provide increased energy density and improved stability and solubility of one or more of the ionic species in the catholyte and/or anolyte. According to one example, a vanadium-based redox flow battery system is characterized by an anolyte having V.sup.2+ and V.sup.3+ in a supporting solution and a catholyte having V.sup.4+ and V.sup.5+ in a supporting solution. The supporting solution can contain Cl.sup.- ions or a mixture of SO.sub.4.sup.2- and Cl.sup.- ions.

  9. Redox flow batteries based on supporting solutions containing chloride

    Energy Technology Data Exchange (ETDEWEB)

    Li, Liyu; Kim, Soowhan; Yang, Zhenguo; Wang, Wei; Nie, Zimin; Chen, Baowei; Zhang, Jianlu; Xia, Guanguang

    2015-09-01

    Redox flow battery systems having a supporting solution that contains Cl.sup.- ions can exhibit improved performance and characteristics. Furthermore, a supporting solution having mixed SO.sub.4.sup.2- and Cl.sup.- ions can provide increased energy density and improved stability and solubility of one or more of the ionic species in the catholyte and/or anolyte. According to one example, a vanadium-based redox flow battery system is characterized by an anolyte having V.sup.2+ and V.sup.3+ in a supporting solution and a catholyte having V.sup.4+ and V.sup.5+ in a supporting solution. The supporting solution can contain Cl.sup.- ions or a mixture of SO.sub.4.sup.2- and Cl.sup.- ions.

  10. Microporous separators for Fe/V redox flow batteries

    Science.gov (United States)

    Wei, Xiaoliang; Li, Liyu; Luo, Qingtao; Nie, Zimin; Wang, Wei; Li, Bin; Xia, Guan-Guang; Miller, Eric; Chambers, Jeff; Yang, Zhenguo

    2012-11-01

    The Fe/V redox flow battery has demonstrated promising performance with distinct advantages over other redox flow battery systems. Due to the less oxidative nature of the Fe(III) species, hydrocarbon-based ion exchange membranes or separators can be used. Daramic® microporous polyethylene separators were tested on Fe/V flow cells using sulphuric/chloric mixed acid-supporting electrolytes. Among them, separator C exhibited good flow cell cycling performance with satisfactory repeatability over a broad temperature range of 5-50 °C. Energy efficiency (EE) of C remains around 70% at current densities of 50-80 mA cm-2 in temperatures ranging from room temperature to 50 °C. The capacity decay problem could be circumvented through hydraulic pressure balancing by means of applying different pump rates to the positive and negative electrolytes. Stable capacity and energy were obtained over 20 cycles at room temperature and 40 °C. These results show that extremely low-cost separators ($1-20 m-2) are applicable in the Fe/V flow battery system with acceptable energy efficiency. This represents a remarkable breakthrough: a significant reduction of the capital cost of the Fe/V flow battery system, which could further its market penetration in grid stabilization and renewable integration.

  11. Highly efficient redox isomerisation of allylic alcohols catalysed by pyrazole-based ruthenium(IV) complexes in water: mechanisms of bifunctional catalysis in water.

    Science.gov (United States)

    Bellarosa, Luca; Díez, Josefina; Gimeno, José; Lledós, Agustí; Suárez, Francisco J; Ujaque, Gregori; Vicent, Cristian

    2012-06-18

    The catalytic activity of ruthenium(IV) ([Ru(η(3):η(3)-C(10)H(16))Cl(2)L]; C(10)H(16) = 2,7-dimethylocta-2,6-diene-1,8-diyl, L = pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, 2-(1H-pyrazol-3-yl)phenol or indazole) and ruthenium(II) complexes ([Ru(η(6)-arene)Cl(2)(3,5-dimethylpyrazole)]; arene = C(6)H(6), p-cymene or C(6)Me(6)) in the redox isomerisation of allylic alcohols into carbonyl compounds in water is reported. The former show much higher catalytic activity than ruthenium(II) complexes. In particular, a variety of allylic alcohols have been quantitatively isomerised by using [Ru(η(3):η(3)-C(10)H(16))Cl(2)(pyrazole)] as a catalyst; the reactions proceeded faster in water than in THF, and in the absence of base. The isomerisations of monosubstituted alcohols take place rapidly (10-60 min, turn-over frequency = 750-3000 h(-1)) and, in some cases, at 35 °C in 60 min. The nature of the aqueous species formed in water by this complex has been analysed by ESI-MS. To analyse how an aqueous medium can influence the mechanism of the bifunctional catalytic process, DFT calculations (B3LYP) including one or two explicit water molecules and using the polarisable continuum model have been carried out and provide a valuable insight into the role of water on the activity of the bifunctional catalyst. Several mechanisms have been considered and imply the formation of aqua complexes and their deprotonated species generated from [Ru(η(3):η(3)-C(10)H(16))Cl(2)(pyrazole)]. Different competitive pathways based on outer-sphere mechanisms, which imply hydrogen-transfer processes, have been analysed. The overall isomerisation implies two hydrogen-transfer steps from the substrate to the catalyst and subsequent transfer back to the substrate. In addition to the conventional Noyori outer-sphere mechanism, which involves the pyrazolide ligand, a new mechanism with a hydroxopyrazole complex as the active species can be at work in water. The

  12. Systems and methods for rebalancing redox flow battery electrolytes

    Science.gov (United States)

    Pham, Ai Quoc; Chang, On Kok

    2015-03-17

    Various methods of rebalancing electrolytes in a redox flow battery system include various systems using a catalyzed hydrogen rebalance cell configured to minimize the risk of dissolved catalyst negatively affecting flow battery performance. Some systems described herein reduce the chance of catalyst contamination of RFB electrolytes by employing a mediator solution to eliminate direct contact between the catalyzed membrane and the RFB electrolyte. Other methods use a rebalance cell chemistry that maintains the catalyzed electrode at a potential low enough to prevent the catalyst from dissolving.

  13. ZrO2-Nanoparticle-Modified Graphite Felt: Bifunctional Effects on Vanadium Flow Batteries.

    Science.gov (United States)

    Zhou, Haipeng; Shen, Yi; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

    2016-06-22

    To improve the electrochemical performance of graphite felt (GF) electrodes in vanadium flow batteries (VFBs), we synthesize a series of ZrO2-modified GF (ZrO2/GF) electrodes with varying ZrO2 contents via a facile immersion-precipitation approach. It is found that the uniform immobilization of ZrO2 nanoparticles on the GF not only significantly promotes the accessibility of vanadium electrolyte, but also provides more active sites for the redox reactions, thereby resulting in better electrochemical activity and reversibility toward the VO(2+)/VO2(+) and V(2+)/V(3+) redox reactions as compared with those of GF. In particular, The ZrO2/GF composite with 0.3 wt % ZrO2 displays the best electrochemical performance with voltage and energy efficiencies of 71.9% and 67.4%, respectively, which are much higher than those of 57.3% and 53.8% as obtained from the GF electrode at 200 mA cm(-2). The cycle life tests demonstrate that the ZrO2/GF electrodes exhibit outstanding stability. The ZrO2/GF-based VFB battery shows negligible activity decay after 200 cycles.

  14. Determining the Limiting Current Density of Vanadium Redox Flow Batteries

    Directory of Open Access Journals (Sweden)

    Jen-Yu Chen

    2014-09-01

    Full Text Available All-vanadium redox flow batteries (VRFBs are used as energy storage systems for intermittent renewable power sources. The performance of VRFBs depends on materials of key components and operating conditions, such as current density, electrolyte flow rate and electrolyte composition. Mass transfer overpotential is affected by the electrolyte flow rate and electrolyte composition, which is related to the limiting current density. In order to investigate the effect of operating conditions on mass transport overpotential, this study established a relationship between the limiting current density and operating conditions. First, electrolyte solutions with different states of charge were prepared and used for a single cell to obtain discharging polarization curves under various operating conditions. The experimental results were then analyzed and are discussed in this paper. Finally, this paper proposes a limiting current density as a function of operating conditions. The result helps predict the effect of operating condition on the cell performance in a mathematical model.

  15. A significantly improved membrane for vanadium redox flow battery

    Science.gov (United States)

    Jia, Chuankun; Liu, Jianguo; Yan, Chuanwei

    A novel sandwich-type sulfonated poly(ether ether ketone) (SPEEK)/tungstophosphoric acid (TPA)/polypropylene (PP) composite membrane for a vanadium redox flow battery (VRB) has been developed with improved properties: the permeability of vanadium ions is greatly reduced and the performance of the VRB cell is greatly increased. The membrane is based on a traditional SPEEK membrane embedded with TPA but PP is used to enhance the membrane for the first time. Although its voltage efficiency (VE) is a little lower than that of a Nafion 212 membrane, it is expected to have good prospects for VRB systems because of its low cost and good performance.

  16. Reduction of Europium in a Redox Flow Cell

    Science.gov (United States)

    Lu, Daluh; Horng, Jiin-Shiung; Tung, Chia-Pao

    1988-05-01

    An electrolytic cell similar to the iron I chromium redox flow cell was used to investigate the reduction of europium. The cell contains two compartments partitioned by an anion exchange membrane, which is permeable to chloride ions. The anolyte is ferrous chloride which is oxidized to ferric form at the anode. Rare-earth chloride prepared from Taiwan black monazite is fed as the catholyte. The reduction of europium was tested in two connected cells at 20 and 45°C. All of Eu3+ can be reduced at 45°C, and 72% of the europium can be recovered in sulfate form. In oxide form, purity is about 84%.

  17. Recent Development of Nanocomposite Membranes for Vanadium Redox Flow Batteries

    Directory of Open Access Journals (Sweden)

    Sang-Ho Cha

    2015-01-01

    Full Text Available The vanadium redox flow battery (VRB has received considerable attention due to its long cycle life, flexible design, fast response time, deep-discharge capability, and low pollution emissions in large-scale energy storage. The key component of VRB is an ion exchange membrane that prevents cross mixing of the positive and negative electrolytes by separating two electrolyte solutions, while allowing the conduction of ions. This review summarizes efforts in developing nanocomposite membranes with reduced vanadium ion permeability and improved proton conductivity in order to achieve high performance and long life of VRB systems. Moreover, functionalized nanocomposite membranes will be reviewed for the development of next-generation materials to further improve the performance of VRB, focusing on their properties and performance of VRB.

  18. Composite separators and redox flow batteries based on porous separators

    Science.gov (United States)

    Li, Bin; Wei, Xiaoliang; Luo, Qingtao; Nie, Zimin; Wang, Wei; Sprenkle, Vincent L.

    2016-01-12

    Composite separators having a porous structure and including acid-stable, hydrophilic, inorganic particles enmeshed in a substantially fully fluorinated polyolefin matrix can be utilized in a number of applications. The inorganic particles can provide hydrophilic characteristics. The pores of the separator result in good selectivity and electrical conductivity. The fluorinated polymeric backbone can result in high chemical stability. Accordingly, one application of the composite separators is in redox flow batteries as low cost membranes. In such applications, the composite separator can also enable additional property-enhancing features compared to ion-exchange membranes. For example, simple capacity control can be achieved through hydraulic pressure by balancing the volumes of electrolyte on each side of the separator. While a porous separator can also allow for volume and pressure regulation, in RFBs that utilize corrosive and/or oxidizing compounds, the composite separators described herein are preferable for their robustness in the presence of such compounds.

  19. Neural Network Predictive Control for Vanadium Redox Flow Battery

    Directory of Open Access Journals (Sweden)

    Hai-Feng Shen

    2013-01-01

    Full Text Available The vanadium redox flow battery (VRB is a nonlinear system with unknown dynamics and disturbances. The flowrate of the electrolyte is an important control mechanism in the operation of a VRB system. Too low or too high flowrate is unfavorable for the safety and performance of VRB. This paper presents a neural network predictive control scheme to enhance the overall performance of the battery. A radial basis function (RBF network is employed to approximate the dynamics of the VRB system. The genetic algorithm (GA is used to obtain the optimum initial values of the RBF network parameters. The gradient descent algorithm is used to optimize the objective function of the predictive controller. Compared with the constant flowrate, the simulation results show that the flowrate optimized by neural network predictive controller can increase the power delivered by the battery during the discharge and decrease the power consumed during the charge.

  20. An Aqueous Redox Flow Battery Based on Neutral Alkali Metal Ferri/ferrocyanide and Polysulfide Electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Xiaoliang; Xia, Gordon; Kirby, Brent W.; Thomsen, Edwin C.; Li, Bin; Nie, Zimin; Graff, Gordon L.; Liu, Jun; Sprenkle, Vincent L.; Wang, Wei

    2015-11-13

    Aiming to explore low-cost redox flow battery systems, a novel iron-polysulfide (Fe/S) flow battery has been demonstrated in a laboratory cell. This system employs alkali metal ferri/ferrocyanide and alkali metal polysulfides as the redox electrolytes. When proper electrodes, such as pretreated graphite felts, are used, 78% energy efficiency and 99% columbic efficiency are achieved. The remarkable advantages of this system over current state-of-the-art redox flow batteries include: 1) less corrosive and relatively environmentally benign redox solutions used; 2) excellent energy and utilization efficiencies; 3) low cost for redox electrolytes and cell components. These attributes can lead to significantly reduced capital cost and make the Fe/S flow battery system a promising low-cost energy storage technology. The major drawbacks of the present cell design are relatively low power density and possible sulfur species crossover. Further work is underway to address these concerns.

  1. Peak power prediction of a vanadium redox flow battery

    Science.gov (United States)

    Yu, V. K.; Chen, D.

    2014-12-01

    The vanadium redox flow battery (VRFB) is a promising grid-scale energy storage technology, but future widespread commercialization requires a considerable reduction in capital costs. Determining the appropriate battery size for the intended power range can help minimize the amount of materials needed, thereby reducing capital costs. A physics-based model is an essential tool for predicting the power range of large scale VRFB systems to aid in the design optimization process. This paper presents a modeling framework that accounts for the effects of flow rate on the pumping losses, local mass transfer rate, and nonuniform vanadium concentration in the cell. The resulting low-order model captures battery performance accurately even at high power densities and remains computationally practical for stack-level optimization and control purposes. We first use the model to devise an optimal control strategy that maximizes battery life during discharge. Assuming optimal control is implemented, we then determine the upper efficiency limits of a given VRFB system and compare the net power and associated overpotential and pumping losses at different operating points. We also investigate the effects of varying the electrode porosity, stack temperature, and total vanadium concentration on the peak power.

  2. Novel catalytic effects of Mn3O4 for all vanadium redox flow batteries.

    Science.gov (United States)

    Kim, Ki Jae; Park, Min-Sik; Kim, Jae-Hun; Hwang, Uk; Lee, Nam Jin; Jeong, Goojin; Kim, Young-Jun

    2012-06-01

    A new approach for enhancing the electrochemical performance of carbon felt electrodes by employing non-precious metal oxides is designed. The outstanding electro-catalytic activity and mechanical stability of Mn(3)O(4) are advantageous in facilitating the redox reaction of vanadium ions, leading to efficient operation of a vanadium redox flow battery.

  3. High-energy density nonaqueous all redox flow lithium battery enabled with a polymeric membrane.

    Science.gov (United States)

    Jia, Chuankun; Pan, Feng; Zhu, Yun Guang; Huang, Qizhao; Lu, Li; Wang, Qing

    2015-11-01

    Redox flow batteries (RFBs) are considered one of the most promising large-scale energy storage technologies. However, conventional RFBs suffer from low energy density due to the low solubility of the active materials in electrolyte. On the basis of the redox targeting reactions of battery materials, the redox flow lithium battery (RFLB) demonstrated in this report presents a disruptive approach to drastically enhancing the energy density of flow batteries. With LiFePO4 and TiO2 as the cathodic and anodic Li storage materials, respectively, the tank energy density of RFLB could reach ~500 watt-hours per liter (50% porosity), which is 10 times higher than that of a vanadium redox flow battery. The cell exhibits good electrochemical performance under a prolonged cycling test. Our prototype RFLB full cell paves the way toward the development of a new generation of flow batteries for large-scale energy storage.

  4. High–energy density nonaqueous all redox flow lithium battery enabled with a polymeric membrane

    Science.gov (United States)

    Jia, Chuankun; Pan, Feng; Zhu, Yun Guang; Huang, Qizhao; Lu, Li; Wang, Qing

    2015-01-01

    Redox flow batteries (RFBs) are considered one of the most promising large-scale energy storage technologies. However, conventional RFBs suffer from low energy density due to the low solubility of the active materials in electrolyte. On the basis of the redox targeting reactions of battery materials, the redox flow lithium battery (RFLB) demonstrated in this report presents a disruptive approach to drastically enhancing the energy density of flow batteries. With LiFePO4 and TiO2 as the cathodic and anodic Li storage materials, respectively, the tank energy density of RFLB could reach ~500 watt-hours per liter (50% porosity), which is 10 times higher than that of a vanadium redox flow battery. The cell exhibits good electrochemical performance under a prolonged cycling test. Our prototype RFLB full cell paves the way toward the development of a new generation of flow batteries for large-scale energy storage. PMID:26702440

  5. Performance enhancement of iron-chromium redox flow batteries by employing interdigitated flow fields

    Science.gov (United States)

    Zeng, Y. K.; Zhou, X. L.; Zeng, L.; Yan, X. H.; Zhao, T. S.

    2016-09-01

    The catalyst for the negative electrode of iron-chromium redox flow batteries (ICRFBs) is commonly prepared by adding a small amount of Bi3+ ions in the electrolyte and synchronously electrodepositing metallic particles onto the electrode surface at the beginning of charge process. Achieving a uniform catalyst distribution in the porous electrode, which is closely related to the flow field design, is critically important to improve the ICRFB performance. In this work, the effects of flow field designs on catalyst electrodeposition and battery performance are investigated. It is found that compared to the serpentine flow field (SFF) design, the interdigitated flow field (IFF) forces the electrolyte through the porous electrode between the neighboring channels and enhances species transport during the processes of both the catalyst electrodeposition and iron/chromium redox reactions, thus enabling a more uniform catalyst distribution and higher mass transport limitation. It is further demonstrated that the energy efficiency of the ICRFB with the IFF reaches 80.7% at a high current density (320 mA cm-2), which is 8.2% higher than that of the ICRFB with the SFF. With such a high performance and intrinsically low-cost active materials, the ICRFB with the IFF offers a great promise for large-scale energy storage.

  6. Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Xiaoliang; Xu, Wu; Huang, Jinhua; Zhang, Lu; Walter, Eric D.; Lawrence, Chad W.; Vijayakumar, M.; Henderson, Wesley A.; Liu, Tianbiao L.; Cosimbescu, Lelia; Li, Bin; Sprenkle, Vincent L.; Wang, Wei

    2015-07-20

    Nonaqueous redox flow batteries hold the promise to achieve higher energy density ascribed to the broader voltage window than their aqueous counterparts, but their current performance is limited by low redox material concentration, poor cell efficiency, and inferior cycling stability. We report a new nonaqueous total-organic flow battery based on high concentrations of 9-fluorenone as negative and 2,5-di-tert-butyl-1-methoxy-4-[2’-methoxyethoxy]benzene as positive redox materials. The supporting electrolytes are found to greatly affect the cycling stability of flow cells through varying chemical stabilities of the charged radical species, especially the 9-fluorenone radical anions, as confirmed by electron spin resonance. Such an electrolyte optimization sheds light on mechanistic understandings of capacity fading in flow batteries employing organic radical-based redox materials and demonstrates that rational design of supporting electrolyte is vital for stable cyclability.

  7. Techno-Economic Modeling and Analysis of Redox Flow Battery Systems

    Directory of Open Access Journals (Sweden)

    Jens Noack

    2016-08-01

    Full Text Available A techno-economic model was developed to investigate the influence of components on the system costs of redox flow batteries. Sensitivity analyses were carried out based on an example of a 10 kW/120 kWh vanadium redox flow battery system, and the costs of the individual components were analyzed. Particular consideration was given to the influence of the material costs and resistances of bipolar plates and energy storage media as well as voltages and electric currents. Based on the developed model, it was possible to formulate statements about the targeted optimization of a developed non-commercial vanadium redox flow battery system and general aspects for future developments of redox flow batteries.

  8. Studies on pressure losses and flow rate optimization in vanadium redox flow battery

    Science.gov (United States)

    Tang, Ao; Bao, Jie; Skyllas-Kazacos, Maria

    2014-02-01

    Premature voltage cut-off in the operation of the vanadium redox flow battery is largely associated with the rise in concentration overpotential at high state-of-charge (SOC) or state-of-discharge (SOD). The use of high constant volumetric flow rate will reduce concentration overpotential, although potentially at the cost of consuming excessive pumping energy which in turn lowers system efficiency. On the other hand, any improper reduction in flow rate will also limit the operating SOC and lead to deterioration in battery efficiency. Pressure drop losses are further exacerbated by the need to reduce shunt currents in flow battery stacks that requires the use of long, narrow channels and manifolds. In this paper, the concentration overpotential is modelled as a function of flow rate in an effort to determine an appropriate variable flow rate that can yield high system efficiency, along with the analysis of pressure losses and total pumping energy. Simulation results for a 40-cell stack under pre-set voltage cut-off limits have shown that variable flow rates are superior to constant flow rates for the given system design and the use of a flow factor of 7.5 with respect to the theoretical flow rate can reach overall high system efficiencies for different charge-discharge operations.

  9. Optimized anion exchange membranes for vanadium redox flow batteries.

    Science.gov (United States)

    Chen, Dongyang; Hickner, Michael A; Agar, Ertan; Kumbur, E Caglan

    2013-08-14

    In order to understand the properties of low vanadium permeability anion exchange membranes for vanadium redox flow batteries (VRFBs), quaternary ammonium functionalized Radel (QA-Radel) membranes with three ion exchange capacities (IECs) from 1.7 to 2.4 mequiv g(-1) were synthesized and 55-60 μm thick membrane samples were evaluated for their transport properties and in-cell battery performance. The ionic conductivity and vanadium permeability of the membranes were investigated and correlated to the battery performance through measurements of Coulombic efficiency, voltage efficiency and energy efficiency in single cell tests, and capacity fade during cycling. Increasing the IEC of the QA-Radel membranes increased both the ionic conductivity and VO(2+) permeability. The 1.7 mequiv g(-1) IEC QA-Radel had the highest Coulombic efficiency and best cycling capacity maintenance in the VRFB, while the cell's voltage efficiency was limited by the membrane's low ionic conductivity. Increasing the IEC resulted in higher voltage efficiency for the 2.0 and 2.4 mequiv g(-1) samples, but the cells with these membranes displayed reduced Coulombic efficiency and faster capacity fade. The QA-Radel with an IEC of 2.0 mequiv g(-1) had the best balance of ionic conductivity and VO(2+) permeability, achieving a maximum power density of 218 mW cm(-2) which was higher than the maximum power density of a VRFB assembled with a Nafion N212 membrane in our system. While anion exchange membranes are under study for a variety of VRFB applications, this work demonstrates that the material parameters must be optimized to obtain the maximum cell performance.

  10. Integrating a dual-silicon photoelectrochemical cell into a redox flow battery for unassisted photocharging

    DEFF Research Database (Denmark)

    Liao, Shichao; Zong, Xu; Seger, Brian

    2016-01-01

    photoelectrochemical reactions. Here we report an efficient SRFC based on a dual-silicon photoelectrochemical cell and a quinone/bromine redox flow battery for in situ solar energy conversion and storage. Using narrow bandgap silicon for efficient photon collection and fast redox couples for rapid interface charge......Solar rechargeable flow cells (SRFCs) provide an attractive approach for in situ capture and storage of intermittent solar energy via photoelectrochemical regeneration of discharged redox species for electricity generation. However, overall SFRC performance is restricted by inefficient...

  11. Advanced porous electrodes with flow channels for vanadium redox flow battery

    Science.gov (United States)

    Bhattarai, Arjun; Wai, Nyunt; Schweiss, Ruediger; Whitehead, Adam; Lim, Tuti M.; Hng, Huey Hoon

    2017-02-01

    Improving the overall energy efficiency by reducing pumping power and improving flow distribution of electrolyte, is a major challenge for developers of flow batteries. The use of suitable channels can improve flow distribution through the electrodes and reduce flow resistance, hence reducing the energy consumption of the pumps. Although several studies of vanadium redox flow battery have proposed the use of bipolar plates with flow channels, similar to fuel cell designs, this paper presents the use of flow channels in the porous electrode as an alternative approach. Four types of electrodes with channels: rectangular open channel, interdigitated open cut channel, interdigitated circular poked channel and cross poked circular channels, are studied and compared with a conventional electrode without channels. Our study shows that interdigitated open channels can improve the overall energy efficiency up to 2.7% due to improvement in flow distribution and pump power reduction while interdigitated poked channel can improve up to 2.5% due to improvement in flow distribution.

  12. Effect of flow field on the performance of an all-vanadium redox flow battery

    Science.gov (United States)

    Kumar, S.; Jayanti, S.

    2016-03-01

    A comparative study of the electrochemical energy conversion performance of a single-cell all-vanadium redox flow battery (VRFB) fitted with three flow fields has been carried out experimentally. The charge-discharge, polarization curve, Coulombic, voltage and round-trip efficiencies of a 100 cm2 active area VRFB fitted with serpentine, interdigitated and conventional flow fields have been obtained under nearly identical experimental conditions. The effect of electrolyte circulation rate has also been investigated for each flow field. Stable performance has been obtained for each flow field for at least 40 charge/discharge cycles. Ex-situ measurements of pressure drop have been carried out using water over a range of Reynolds numbers. Together, the results show that the cell fitted with the serpentine flow field gives the highest energy efficiency, primarily due to high voltaic efficiency and also the lowest pressure drop. The electrolyte flow rate is seen to have considerable effect on the performance; a high round-trip energy efficiency of about 80% has been obtained at the highest flow rate with the serpentine flow field. The data offer interesting insights into the effect of electrolyte circulation on the performance of VRFB.

  13. Cost-driven materials selection criteria for redox flow battery electrolytes

    Science.gov (United States)

    Dmello, Rylan; Milshtein, Jarrod D.; Brushett, Fikile R.; Smith, Kyle C.

    2016-10-01

    Redox flow batteries show promise for grid-scale energy storage applications but are presently too expensive for widespread adoption. Electrolyte material costs constitute a sizeable fraction of the redox flow battery price. As such, this work develops a techno-economic model for redox flow batteries that accounts for redox-active material, salt, and solvent contributions to the electrolyte cost. Benchmark values for electrolyte constituent costs guide identification of design constraints. Nonaqueous battery design is sensitive to all electrolyte component costs, cell voltage, and area-specific resistance. Design challenges for nonaqueous batteries include minimizing salt content and dropping redox-active species concentration requirements. Aqueous battery design is sensitive to only redox-active material cost and cell voltage, due to low area-specific resistance and supporting electrolyte costs. Increasing cell voltage and decreasing redox-active material cost present major materials selection challenges for aqueous batteries. This work minimizes cost-constraining variables by mapping the battery design space with the techno-economic model, through which we highlight pathways towards low price and moderate concentration. Furthermore, the techno-economic model calculates quantitative iterations of battery designs to achieve the Department of Energy battery price target of 100 per kWh and highlights cost cutting strategies to drive battery prices down further.

  14. Multicomponent transport in membranes for redox flow batteries

    Science.gov (United States)

    Monroe, Charles

    2015-03-01

    Redox flow batteries (RFBs) incorporate separator membranes, which ideally prevent mixing of electrochemically active species while permitting crossover of inactive supporting ions. Understanding crossover and membrane selectivity may require multicomponent transport models that account for solute/solute interactions within the membrane, as well as solute/membrane interactions. Application of the Onsager-Stefan-Maxwell formalism allows one to account for all the dissipative phenomena that may accompany component fluxes through RFB membranes. The magnitudes of dissipative interactions (diffusional drag forces) are quantified by matching experimentally established concentration transients with theory. Such transients can be measured non-invasively using DC conductometry, but the accuracy of this method requires precise characterization of the bulk RFB electrolytes. Aqueous solutions containing both vanadyl sulfate (VOSO4) and sulfuric acid (H2SO4) are relevant to RFB technology. One of the first precise characterizations of aqueous vanadyl sulfate has been implemented and will be reported. To assess the viability of a separator for vanadium RFB applications with cell-level simulations, it is critical to understand the tendencies of various classes of membranes to absorb (uptake) active species, and to know the relative rates of active-species and supporting-electrolyte diffusion. It is also of practical interest to investigate the simultaneous diffusion of active species and supports, because interactions between solutes may ultimately affect the charge efficiency and power efficiency of the RFB system as a whole. A novel implementation of Barnes's classical model of dialysis-cell diffusion [Physics 5:1 (1934) 4-8] is developed to measure the binary diffusion coefficients and sorption equilibria for single solutes (VOSO4 or H2SO4) in porous membranes and cation-exchange membranes. With the binary diffusion and uptake measurement in hand, a computer simulation that

  15. Maximizing flow velocities in redox-magnetohydrodynamic microfluidics using the transient faradaic current.

    Science.gov (United States)

    Weston, Melissa C; Nash, Christena K; Homesley, Jerry J; Fritsch, Ingrid

    2012-11-01

    There is a need for a microfluidic pumping technique that is simple to fabricate, yet robust, compatible with a variety of solvents, and which has easily controlled fluid flow. Redox-magnetohydrodynamics (MHD) offers these advantages. However, the presence of high concentrations of redox species, important for inducing sufficient convection at low magnetic fields for hand-held devices, can limit the use of redox-MHD pumping for analytical applications. A new method for redox-MHD pumping is investigated that takes advantage of the large amplitude of the transient portion of the faradaic current response that occurs upon stepping the potential sufficiently past the standard electrode potential, E°, of the pumping redox species at an electrode. This approach increases the velocity of the fluid for a given redox concentration. An electronic switch was implemented between the potentiostat and electrochemical cell to alternately turn on and off different electrodes along the length of the flow path to maximize this transient electronic current and, as a result, the flow speed. Velocities were determined by tracking microbeads in a solution containing electroactive potassium ferrocyanide and potassium ferricyanide, and supporting electrolyte, potassium chloride, in the presence of a magnetic field. Fluid velocities with slight pulsation were obtained with the switch that were 70% faster than the smooth velocities without the switch. This indicates that redox species concentrations can be lowered by a similar amount to achieve a given speed, thereby diminishing interference of the redox species with detection of the analyte in applications of redox-MHD microfluidics for chemical analysis.

  16. Innovative model-based flow rate optimization for vanadium redox flow batteries

    Science.gov (United States)

    König, S.; Suriyah, M. R.; Leibfried, T.

    2016-11-01

    In this paper, an innovative approach is presented to optimize the flow rate of a 6-kW vanadium redox flow battery with realistic stack dimensions. Efficiency is derived using a multi-physics battery model and a newly proposed instantaneous efficiency determination technique. An optimization algorithm is applied to identify optimal flow rates for operation points defined by state-of-charge (SoC) and current. The proposed method is evaluated against the conventional approach of applying Faraday's first law of electrolysis, scaled to the so-called flow factor. To make a fair comparison, the flow factor is also optimized by simulating cycles with different charging/discharging currents. It is shown through the obtained results that the efficiency is increased by up to 1.2% points; in addition, discharge capacity is also increased by up to 1.0 kWh or 5.4%. Detailed loss analysis is carried out for the cycles with maximum and minimum charging/discharging currents. It is shown that the proposed method minimizes the sum of losses caused by concentration over-potential, pumping and diffusion. Furthermore, for the deployed Nafion 115 membrane, it is observed that diffusion losses increase with stack SoC. Therefore, to decrease stack SoC and lower diffusion losses, a higher flow rate during charging than during discharging is reasonable.

  17. Estimating the system price of redox flow batteries for grid storage

    Science.gov (United States)

    Ha, Seungbum; Gallagher, Kevin G.

    2015-11-01

    Low-cost energy storage systems are required to support extensive deployment of intermittent renewable energy on the electricity grid. Redox flow batteries have potential advantages to meet the stringent cost target for grid applications as compared to more traditional batteries based on an enclosed architecture. However, the manufacturing process and therefore potential high-volume production price of redox flow batteries is largely unquantified. We present a comprehensive assessment of a prospective production process for aqueous all vanadium flow battery and nonaqueous lithium polysulfide flow battery. The estimated investment and variable costs are translated to fixed expenses, profit, and warranty as a function of production volume. When compared to lithium-ion batteries, redox flow batteries are estimated to exhibit lower costs of manufacture, here calculated as the unit price less materials costs, owing to their simpler reactor (cell) design, lower required area, and thus simpler manufacturing process. Redox flow batteries are also projected to achieve the majority of manufacturing scale benefits at lower production volumes as compared to lithium-ion. However, this advantage is offset due to the dramatically lower present production volume of flow batteries compared to competitive technologies such as lithium-ion.

  18. Flow distribution and maximum current density studies in redox flow batteries with a single passage of the serpentine flow channel

    Science.gov (United States)

    Ke, Xinyou; Alexander, J. Iwan D.; Prahl, Joseph M.; Savinell, Robert F.

    2014-12-01

    Flow batteries show promise for very large-scale stationary energy storage such as needed for the grid and renewable energy implementation. In recent years, researchers and developers of redox flow batteries (RFBs) have found that electrode and flow field designs of PEM fuel cell (PEMFC) technology can increase the power density and consequently push down the cost of flow battery stacks. In this paper we present a macroscopic model of a typical PEMFC-like RFB electrode-flow field design. The model is a layered system comprised of a single passage of a serpentine flow channel and a parallel underlying porous electrode (or porous layer). The effects of the inlet volumetric flow rate, permeability of the porous layer, thickness of the porous layer and thickness of the flow channel on the flow penetration into the porous layer are investigated. The maximum current density corresponding to stoichiometry is estimated to be 377 mA cm-2 and 724 mA cm-2, which compares favorably with experiments of ∼400 mA cm-2 and ∼750 mA cm-2, for a single layer and three layers of the carbon fiber paper, respectively.

  19. Verified reduction of dimensionality for an all-vanadium redox flow battery model

    Science.gov (United States)

    Sharma, A. K.; Ling, C. Y.; Birgersson, E.; Vynnycky, M.; Han, M.

    2015-04-01

    The computational cost for all-vanadium redox flow batteries (VRFB) models that seek to capture the transport phenomena usually increases with the number of spatial dimensions considered. In this context, we carry out scale analysis to derive a reduced zero-dimensional model. Two nondimensional numbers and their limits to support the model reduction are identified. We verify the reduced model by comparing its charge-discharge curve predictions with that of a full two-dimensional model. The proposed analysis leading to reduction in dimensionality is generic and can be employed for other types of redox flow batteries.

  20. Integrating a dual-silicon photoelectrochemical cell into a redox flow battery for unassisted photocharging.

    Science.gov (United States)

    Liao, Shichao; Zong, Xu; Seger, Brian; Pedersen, Thomas; Yao, Tingting; Ding, Chunmei; Shi, Jingying; Chen, Jian; Li, Can

    2016-05-04

    Solar rechargeable flow cells (SRFCs) provide an attractive approach for in situ capture and storage of intermittent solar energy via photoelectrochemical regeneration of discharged redox species for electricity generation. However, overall SFRC performance is restricted by inefficient photoelectrochemical reactions. Here we report an efficient SRFC based on a dual-silicon photoelectrochemical cell and a quinone/bromine redox flow battery for in situ solar energy conversion and storage. Using narrow bandgap silicon for efficient photon collection and fast redox couples for rapid interface charge injection, our device shows an optimal solar-to-chemical conversion efficiency of ∼5.9% and an overall photon-chemical-electricity energy conversion efficiency of ∼3.2%, which, to our knowledge, outperforms previously reported SRFCs. The proposed SRFC can be self-photocharged to 0.8 V and delivers a discharge capacity of 730 mAh l(-1). Our work may guide future designs for highly efficient solar rechargeable devices.

  1. Development and testing of mechanically stable Vanadium redox flow battery

    OpenAIRE

    Molchanov, Bogdan

    2016-01-01

    This thesis work is concerned with electrochemical energy storage and conversion technology based on vanadium chemistry. This thesis is continuation of a work done at Arcada in summer 2015 and is expected to become a foundation for future research in the flow battery area. The major objective of this study was to build a prototype of vanadium flow battery that is robust enough to be analyzed and compared against flow batteries of other research groups. The work is broken down into four smalle...

  2. A Step-by-Step Design Methodology for a Base Case Vanadium Redox-Flow Battery

    Science.gov (United States)

    Moore, Mark; Counce, Robert M.; Watson, Jack S.; Zawodzinski, Thomas A.; Kamath, Haresh

    2012-01-01

    The purpose of this work is to develop an evolutionary procedure to be used by Chemical Engineering students for the base-case design of a Vanadium Redox-Flow Battery. The design methodology is based on the work of Douglas (1985) and provides a profitability analysis at each decision level so that more profitable alternatives and directions can be…

  3. A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage.

    Science.gov (United States)

    Zhao, Yu; Ding, Yu; Li, Yutao; Peng, Lele; Byon, Hye Ryung; Goodenough, John B; Yu, Guihua

    2015-11-21

    Electrical energy storage system such as secondary batteries is the principle power source for portable electronics, electric vehicles and stationary energy storage. As an emerging battery technology, Li-redox flow batteries inherit the advantageous features of modular design of conventional redox flow batteries and high voltage and energy efficiency of Li-ion batteries, showing great promise as efficient electrical energy storage system in transportation, commercial, and residential applications. The chemistry of lithium redox flow batteries with aqueous or non-aqueous electrolyte enables widened electrochemical potential window thus may provide much greater energy density and efficiency than conventional redox flow batteries based on proton chemistry. This Review summarizes the design rationale, fundamentals and characterization of Li-redox flow batteries from a chemistry and material perspective, with particular emphasis on the new chemistries and materials. The latest advances and associated challenges/opportunities are comprehensively discussed.

  4. Ferrocene and cobaltocene derivatives for non-aqueous redox flow batteries.

    Science.gov (United States)

    Hwang, Byunghyun; Park, Min-Sik; Kim, Ketack

    2015-01-01

    Ferrocene and cobaltocene and their derivatives are studied as new redox materials for redox flow cells. Their high reaction rates and moderate solubility are attractive properties for their use as active materials. The cyclability experiments are carried out in a static cell; the results showed that these materials exhibit stable capacity retention and predictable discharge potentials, which agree with the potential values from the cyclic voltammograms. The diffusion coefficients of these materials are 2 to 7 times higher than those of other non-aqueous materials such as vanadium acetylacetonate, iron tris(2,2'-bipyridine) complexes, and an organic benzene derivative.

  5. A Coupled Dynamical Model of Redox Flow Battery Based on Chemical Reaction, Fluid Flow, and Electrical Circuit

    OpenAIRE

    Li, Minghua; Hikihara, Takashi

    2008-01-01

    The redox (Reduction-Oxidation) flow battery is one of the most promising rechargeable batteries due to its ability to average loads and output of power sources. The transient characteristics are well known as the remarkable feature of the battery. Then it can also compensate for a sudden voltage drop. The dynamics are governed by the chemical reactions, fluid flow, and electrical circuit of its structure. This causes the difficulty of the analysis at transient state. This paper discusses the...

  6. Graphite felt modified with bismuth nanoparticles as negative electrode in a vanadium redox flow battery.

    Science.gov (United States)

    Suárez, David J; González, Zoraida; Blanco, Clara; Granda, Marcos; Menéndez, Rosa; Santamaría, Ricardo

    2014-03-01

    A graphite felt decorated with bismuth nanoparticles was studied as negative electrode in a vanadium redox flow battery (VRFB). The results confirm the excellent electrochemical performance of the bismuth modified electrode in terms of the reversibility of the V(3+) /V(2+) redox reactions and its long-term cycling performance. Moreover a mechanism that explains the role that Bi nanoparticles play in the redox reactions in this negative half-cell is proposed. Bi nanoparticles favor the formation of BiHx , an intermediate that reduces V(3+) to V(2+) and, therefore, inhibits the competitive irreversible reaction of hydrogen formation (responsible for the commonly observed loss of Coulombic efficiency of VRFBs). Thus, the total charge consumed during the cathodic sweep in this electrode is used to reduce V(3+) to V(2+) , resulting in a highly reversible and efficient process.

  7. Investigation of the electrospun carbon web as the catalyst layer for vanadium redox flow battery

    Science.gov (United States)

    Wei, Guanjie; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei

    2014-12-01

    Polyacrylonitrile (PAN) carbon nonwoven web consisting of 100-200 nm ultrafine fibers has been developed by electrospinning and subsequent carbonization process at 1000 °C for different times. The surface morphology, composition, structure, and electrical conductivity of the electrospun carbon webs (ECWs) as well as their electrochemical properties toward vanadium redox couples have been characterized. With the increasing of carbonization time, the electrochemical reversibility of the vanadium redox couples on the ECW is enhanced greatly. As the carbonization time increases up to 120 min, the hydrogen evolution is facilitated while the reversibility is promoted a little bit further. The excellent performance of ECW may be attributed to the conversion of fibers carbon structure and improvement of electrical conductivity. Due to the good electrochemical activity and freestanding 3-dimensional structure, the ECW carbonized for 90 min is used as catalyst layer in vanadium redox flow battery (VRFB) and enhances the cell performance.

  8. A redox-flow battery with an alloxazine-based organic electrolyte

    Science.gov (United States)

    Lin, Kaixiang; Gómez-Bombarelli, Rafael; Beh, Eugene S.; Tong, Liuchuan; Chen, Qing; Valle, Alvaro; Aspuru-Guzik, Alán; Aziz, Michael J.; Gordon, Roy G.

    2016-09-01

    Redox-flow batteries (RFBs) can store large amounts of electrical energy from variable sources, such as solar and wind. Recently, redox-active organic molecules in aqueous RFBs have drawn substantial attention due to their rapid kinetics and low membrane crossover rates. Drawing inspiration from nature, here we report a high-performance aqueous RFB utilizing an organic redox compound, alloxazine, which is a tautomer of the isoalloxazine backbone of vitamin B2. It can be synthesized in high yield at room temperature by single-step coupling of inexpensive o-phenylenediamine derivatives and alloxan. The highly alkaline-soluble alloxazine 7/8-carboxylic acid produces a RFB exhibiting open-circuit voltage approaching 1.2 V and current efficiency and capacity retention exceeding 99.7% and 99.98% per cycle, respectively. Theoretical studies indicate that structural modification of alloxazine with electron-donating groups should allow further increases in battery voltage. As an aza-aromatic molecule that undergoes reversible redox cycling in aqueous electrolyte, alloxazine represents a class of radical-free redox-active organics for use in large-scale energy storage.

  9. Cerium-zinc redox flow battery: Positive half-cell electrolyte studies

    Institute of Scientific and Technical Information of China (English)

    XIE Zhipeng; ZHOU Debi; XIONG Fengjiao; ZHANG Shimin; HUANG Kelong

    2011-01-01

    Experimental work was performed to evaluate the Ce3+/Ce4+ redox couple in methane sulfonic acid (MSA) electrolyte for use in redox flow battery (RFB) technology. The electrochemical behaviour of the Ce3+/Ce4+ in MSA media was investigated using cyclic voltammetry, linear sweep voltammetry, chronoamperometry and rotating disc electrode. The standard rate constant of the Ce3+/Ce4+ redox reaction on graphite electrode in MSA was 4.06x10-4 cm/s. The diffusion coefficient of Ce3+ in MSA was 5.87-6.15x10-6 cm2/s, and was 2.56-2.68x 10-6 cm2/s for Ce4+. The energy efficiency of a cerium-zinc test cell was 74.8%. The high stability of cerium salts in MSA media and relatively fast redox kinetics of the Ce3+/Ce4+ redox reaction at graphite ectrode indicated that the Ce3+/Ce4+ might be well suited for use in RFB technology.

  10. Comparative analysis for various redox flow batteries chemistries using a cost performance model

    Energy Technology Data Exchange (ETDEWEB)

    Crawford, Aladsair J.; Viswanathan, Vilayanur V.; Stephenson, David E.; Wang, Wei; Thomsen, Edwin C.; Reed, David M.; Li, Bin; Balducci, Patrick J.; Kintner-Meyer, Michael CW; Sprenkle, Vincent L.

    2015-10-20

    A robust performance-based cost model is developed for all-vanadium, iron-vanadium and iron chromium redox flow batteries. Systems aspects such as shunt current losses, pumping losses and thermal management are accounted for. The objective function, set to minimize system cost, allows determination of stack design and operating parameters such as current density, flow rate and depth of discharge (DOD). Component costs obtained from vendors are used to calculate system costs for various time frames. A 2 kW stack data was used to estimate unit energy costs and compared with model estimates for the same size electrodes. The tool has been shared with the redox flow battery community to both validate their stack data and guide future direction.

  11. Operating a redox flow battery with a negative electrolyte imbalance

    Science.gov (United States)

    Pham, Quoc; Chang, On; Durairaj, Sumitha

    2015-03-31

    Loss of flow battery electrode catalyst layers during self-discharge or charge reversal may be prevented by establishing and maintaining a negative electrolyte imbalance during at least parts of a flow battery's operation. Negative imbalance may be established and/or maintained actively, passively or both. Actively establishing a negative imbalance may involve detecting an imbalance that is less negative than a desired threshold, and processing one or both electrolytes until the imbalance reaches a desired negative level. Negative imbalance may be effectively established and maintained passively within a cell by constructing a cell with a negative electrode chamber that is larger than the cell's positive electrode chamber, thereby providing a larger quantity of negative electrolyte for reaction with positive electrolyte.

  12. Influence of architecture and material properties on vanadium redox flow battery performance

    Science.gov (United States)

    Houser, Jacob; Clement, Jason; Pezeshki, Alan; Mench, Matthew M.

    2016-01-01

    This publication reports a design optimization study of all-vanadium redox flow batteries (VRBs), including performance testing, distributed current measurements, and flow visualization. Additionally, a computational flow simulation is used to support the conclusions made from the experimental results. This study demonstrates that optimal flow field design is not simply related to the best architecture, but is instead a more complex interplay between architecture, electrode properties, electrolyte properties, and operating conditions which combine to affect electrode convective transport. For example, an interdigitated design outperforms a serpentine design at low flow rates and with a thin electrode, accessing up to an additional 30% of discharge capacity; but a serpentine design can match the available discharge capacity of the interdigitated design by increasing the flow rate or the electrode thickness due to differing responses between the two flow fields. The results of this study should be useful to design engineers seeking to optimize VRB systems through enhanced performance and reduced pressure drop.

  13. Microwave-treated graphite felt as the positive electrode for all-vanadium redox flow battery

    Science.gov (United States)

    Wu, Xiaoxin; Xu, Hongfeng; Xu, Pengcheng; Shen, Yang; Lu, Lu; Shi, Jicheng; Fu, Jie; Zhao, Hong

    2014-10-01

    An environmental, economic, and highly effective method based on microwave treatment was firstly used to improve the electrochemical activity of graphite felt as the positive electrode in all vanadium redox flow battery (VRFB). The graphite felt was treated by microwave and characterized by Fourier transform infrared and scanning electron microscopy. The electrochemical performance of the prepared electrode was evaluated with cyclic voltammetry and electrochemical impedance spectroscopy. Results show that graphite felt treated by microwave for 15 min at 400 °C exhibits excellent electro-catalytic activity and reactive velocity to vanadium redox couples. The coulombic, voltage, and energy efficiency of the VRFB with as-prepared electrodes at 50 mA cm-2 are 96.9%, 75.5%, and 73.2%, respectively; these values are much higher than those of cell-assembled conventionally and thermally treated graphite felt electrodes. The microwave-treated graphite felt will carry more hydrophilic groups, such as -OH, on its defects, and rough degree of the surface which should be advantageous in facilitating the redox reaction of vanadium ions, leading to the efficient operation of a vanadium redox flow battery. Moreover, microwave treatment can be easily scaled up to treat graphite felt for VRFB in large quantities.

  14. Critical transport issues for improving the performance of aqueous redox flow batteries

    Science.gov (United States)

    Zhou, X. L.; Zhao, T. S.; An, L.; Zeng, Y. K.; Wei, L.

    2017-01-01

    As the fraction of electricity generated from intermittent renewable sources (such as solar and wind) grows, developing reliable energy storage technologies to store electrical energy in large scale is of increasing importance. Redox flow batteries are now enjoying a renaissance and regarded as a leading technology in providing a well-balanced solution for current daunting challenges. In this article, state-of-the-art studies of the complex multicomponent transport phenomena in aqueous redox flow batteries, with a special emphasis on all-vanadium redox flow batteries, are reviewed and summarized. Rather than elaborating on the details of previous experimental and numerical investigations, this article highlights: i) the key transport issues in each battery's component that need to be tackled so that the rate capability and cycling stability of flow batteries can be significantly improved, ii) the basic mechanisms that control the active species/ion/electron transport behaviors in each battery's component, and iii) the key experimental and numerical findings regarding the correlations between the multicomponent transport processes and battery performance.

  15. Nanostructured Electrocatalysts for PEM Fuel Cells and Redox Flow Batteries: A Selected Review

    Energy Technology Data Exchange (ETDEWEB)

    Shao, Yuyan; Cheng, Yingwen; Duan, Wentao; Wang, Wei; Lin, Yuehe; Wang, Yong; Liu, Jun

    2015-12-04

    PEM fuel cells and redox flow batteries are two very similar technologies which share common component materials and device design. Electrocatalysts are the key components in these two devices. In this Review, we discuss recent progress of electrocatalytic materials for these two technologies with a focus on our research activities at Pacific Northwest National Laboratory (PNNL) in the past years. This includes (1) nondestructive functionalization of graphitic carbon as Pt support to improve its electrocatalytic performance, (2) triple-junction of metal–carbon–metal oxides to promote Pt performance, (3) nitrogen-doped carbon and metal-doped carbon (i.e., metal oxides) to improve redox reactions in flow batteries. A perspective on future research and the synergy between the two technologies are also discussed.

  16. Thermodynamic derivation of open circuit voltage in vanadium redox flow batteries

    Science.gov (United States)

    Pavelka, Michal; Wandschneider, Frank; Mazur, Petr

    2015-10-01

    Open circuit voltage of vanadium redox flow batteries is carefully calculated using equilibrium thermodynamics. This analysis reveals some terms in the Nernst relation which are usually omitted in literature. Due to the careful thermodynamic treatment, all uncertainties about the form of Nernst relation are removed except for uncertainties in activity coefficients of particular species. Moreover, it is shown (based again on equilibrium thermodynamics) that batteries with anion-exchange membranes follow different Nernst relation than batteries with cation-exchange membranes. The difference is calculated, and it is verified experimentally that the formula for anion-exchange membranes describes experiments with anion-exchange membranes better than the corresponding formula for cation-exchange membranes. In summary, careful thermodynamic calculation of open circuit voltage of vanadium redox flow batteries is presented, and the difference between voltage for anion-exchange and cation-exchange membranes is revealed.

  17. Description and performance of a novel aqueous all-copper redox flow battery

    Science.gov (United States)

    Sanz, Laura; Lloyd, David; Magdalena, Eva; Palma, Jesús; Kontturi, Kyösti

    2014-12-01

    In this paper we present a novel aqueous redox flow battery chemistry based on copper chloro complexes. The energy density (20 Wh L-1) achieved is comparable to traditional vanadium redox flow batteries. This is due to the high solubility of copper (3 M), which offsets the relatively low cell potential (0.6 V). The electrolyte is cheap, simple to prepare and easy to recycle since no additives or catalysts are used. The stack used is based on plain graphite electrode materials and a low-cost microporous separator. The system can be operated at 60 °C eliminating the need for a heat exchanger and delivers an energy efficiency of 93, 86 and 74% at 5, 10 and 20 mA cm-2 respectively.

  18. Membrane Separator for Redox Flow Batteries that Utilize Anion Radical Mediators.

    Energy Technology Data Exchange (ETDEWEB)

    Delnick, Frank M.

    2014-10-01

    A Na + ion conducting polyethylene oxide membrane is developed for an organic electrolyte redox flow battery that utilizes anion radical mediators. To achieve high specific ionic conductivity, tetraethyleneglycol dimethylether (TEGDME) is used as a plasticizer to reduce crystallinity and increase the free volume of the gel film. This membrane is physically and chemically stable in TEGDME electrolyte that contains highly reactive biphenyl anion radical mediators.

  19. Assessment of the development of a battery charging infrastructure for a redox flow battery based electromobility concept; Bewertung des Aufbaus einer Ladeinfrastruktur fuer eine Redox-Flow-Batteriebasierte Elektromobilitaet

    Energy Technology Data Exchange (ETDEWEB)

    Arpad Funke, Simon; Wietschel, Martin [Fraunhofer-Institut fuer System- und Innovationsforschung (ISI), Karlsruhe (Germany). Competence Center Energietechnologien und Energiesysteme

    2012-07-01

    Apart from the high acquisition cost, the major obstacles to widespread use of electric-powered vehicles today are long battery charging times and limited mileage. Rechargeable batteries might be a solution. The publication investigates a potential infrastructure for electric-powered vehicles based on so-called redox flow batteries. Redox flow batteries are characterized in that active materials are dissolved in liquid electrolyte and are stored outside the cell. Batteries are recharged by exchanging charged electrolyte for discharged electrolyte, which can be done in fuel stations. Redox flow batteries have the drawback of low energy and power density and were hardly ever considered for mobile applications so far. A technical analysis of RFB technology identified the vanadium oxygen redox flow fuel cell (VOFC) as a promising version. It provides higher energy density than conventional redox flow batteries, but development is still in an early stage. Assuming a 'best case' scenario, a refuelling infrastructure for VOFC vehicles was developed and compared with battery-powered vehicles (BEV) and fuel cell vehicles (FVEV). It was found that electromobility based on VOFC may be a promising alternative to current electromobility concepts. (orig./AKB) [German] Neben den Anschaffungsausgaben stehen lange Ladezeiten und eine beschraenkte Reichweite dem heutigen Einsatz von Elektrofahrzeugen oft entgegen. Eine moegliche Abhilfe koennten betankbare Batterien leisten. In der vorliegenden Arbeit soll ein moeglicher Infrastrukturaufbau fuer Elektrofahrzeuge mit sogenannten Redox-Flow-Batterien untersucht werden. Redox-Flow-Batterien besitzen die Eigenschaft, dass aktive Materialien geloest in Fluessigelektrolyten ausserhalb der Zelle gespeichert werden. Dieser Aufbau ermoeglicht das Aufladen der Batterie, indem der entladene Elektrolyt durch geladenen ausgetauscht wird. Dieser Tausch kann an einer Tankstelle durchgefuehrt werden. Ein wesentlicher Nachteil von Redox-Flow

  20. A highly permeable and enhanced surface area carbon-cloth electrode for vanadium redox flow batteries

    Science.gov (United States)

    Zhou, X. L.; Zhao, T. S.; Zeng, Y. K.; An, L.; Wei, L.

    2016-10-01

    In this work, a high-performance porous electrode, made of KOH-activated carbon-cloth, is developed for vanadium redox flow batteries (VRFBs). The macro-scale porous structure in the carbon cloth formed by weaving the carbon fibers in an ordered manner offers a low tortuosity (∼1.1) and a broad pore distribution from 5 μm to 100 μm, rendering the electrode a high hydraulic permeability and high effective ionic conductivity, which are beneficial for the electrolyte flow and ion transport through the porous electrode. The use of KOH activation method to create nano-scale pores on the carbon-fiber surfaces leads to a significant increase in the surface area for redox reactions from 2.39 m2 g-1 to 15.4 m2 g-1. The battery assembled with the present electrode delivers an energy efficiency of 80.1% and an electrolyte utilization of 74.6% at a current density of 400 mA cm-2, as opposed to an electrolyte utilization of 61.1% achieved by using a conventional carbon-paper electrode. Such a high performance is mainly attributed to the combination of the excellent mass/ion transport properties and the high surface area rendered by the present electrode. It is suggested that the KOH-activated carbon-cloth electrode is a promising candidate in redox flow batteries.

  1. Redox-magnetohydrodynamics, flat flow profile-guided enzyme assay detection: toward multiple, parallel analyses.

    Science.gov (United States)

    Sahore, Vishal; Fritsch, Ingrid

    2014-10-07

    A proof-of-concept superparamagnetic microbead-enzyme complex was integrated with microfluidics pumped by redox-magneto-hydrodynamics (MHD) to take advantage of the magnet (0.56 T) beneath the chip and the uniform flat flow profile, as a first step toward developing multiple, parallel chemical analyses on a chip without the need for independent channels. The superparamagnetic beads were derivatized with alkaline phosphatase (a common enzyme label for biochemical assays) and magnetically immobilized at three different locations on the chip with one directly on the path to the detector and the other two locations adjacent to, but off the path, by a distance >5 times the detector diameter. Electroactive p-aminophenol, enzymatically generated at the bead-enzyme complex from its electroinactive precursor p-aminophenyl phosphate in a solution containing a redox species [Ru(NH3)6](3+/2+) for pumping and Tris buffer, was transported by redox-MHD and detected with square wave voltammetry at a 312 μm diameter gold microdisk stationed 2 mm downstream from the bead-complex on the flow path. Oppositely biased pumping electrodes, consisting of 2.5 cm long gold bands and separated by 5.6 mm, flanked the active flow region containing the bead-enzyme complex and detection site. The signal from adjacent paths was only 20% of that for the direct path and ≤8% when pumping electrodes were inactive.

  2. Effect of mesocelluar carbon foam electrode material on performance of vanadium redox flow battery

    Science.gov (United States)

    Jeong, Sanghyun; An, Sunhyung; Jeong, Jooyoung; Lee, Jinwoo; Kwon, Yongchai

    2015-03-01

    Languid reaction rate of VO2+/VO2+ redox couple is a problem to solve for improving performance of vanadium redox flow battery (VRFB). To facilitate the slow reaction materials including large pore sized mesocellular carbon foam (MSU-F-C and Pt/MSU-F-C) are used as new catalyst. Their catalytic activity and reaction reversibility are estimated and compared with other catalysts, while cycle tests of charge-discharge and polarization curve tests are implemented to evaluate energy efficiency (EE) and maximum power density (MPD). Their crystal structure, specific surface area and catalyst morphology are measured by XRD, BET and TEM. The new catalysts indicate high peak current ratio, small peak potential difference and high electron transfer rate constant, proving that their catalytic activity and reaction reversibility are superior. Regarding the charge-discharge and polarization curve tests, the VRFB single cells including new catalysts show high EE as well as low overpotential and internal resistance and high MPD. Such excellent results are due to mostly unique characteristics of MSU-F-C having large interconnected mesopores, high surface area and large contents of hydroxyl groups that serve as active sites for VO2+/VO2+ redox reaction and platinums (Pts) supporting the MSU-F-C. Indeed, employment of the catalysts including MSU-F-C leads to enhancement in performance of VRFB by facilitating the slow VO2+/VO2+ redox reaction.

  3. Electrospun carbon nanofibers/electrocatalyst hybrids as asymmetric electrodes for vanadium redox flow battery

    Science.gov (United States)

    Wei, Guanjie; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei

    2015-05-01

    To improve the electrochemical activity of polyacrylonitrile (PAN)-based electrospun carbon nanofibers (ECNFs) toward vanadium redox couples, the multi-wall carbon nanotubes (CNTs) and Bi-based compound as electrocatalyst have been embedded in the ECNFs to make composite electrode, respectively. The morphology and electrochemical properties of pristine ECNFs, CNTs/ECNFs and Bi/ECNFs have been characterized. Among the three kinds of electrodes, the CNTs/ECNFs show best electrochemical activity toward VO2+/VO2+ redox couple, while the Bi/ECNFs present the best electrochemical activity toward V2+/V3+ redox couple. Furthermore, the high overpotential of hydrogen evolution on Bi/ECNFs makes the side-reaction suppressed. Because of the large property difference between the two composite electrodes, the CNTs/ECNFs and Bi/ECNFs are designed to act as positive and negative electrode for vanadium redox flow battery (VRFB), respectively. It not only does improve the kinetics of two electrode reactions at the same time, but also reduce the kinetics difference between them. Due to the application of asymmetric electrodes, performance of the cell is improved greatly.

  4. Measurement of local current density of all-vanadium redox flow batteries

    Science.gov (United States)

    Hsieh, Wen-Yen; Leu, Chih-Hsing; Wu, Chun-Hsing; Chen, Yong-Song

    2014-12-01

    This article presents a preliminary study of the measurement of local current density in all-vanadium redox flow batteries. Two batteries are designed and manufactured in this study, and the experimental results are compared. In the first cell, the current collector is divided into 25 segments, and the flow field plate is not segmented, whereas in the other cell, the flow field plate is segmented. The effects of the electrolyte flow rate on the battery efficiencies and the local current density variation are investigated. The experimental results show that the current density near the outlet significantly decreases when the discharge capacity approaches zero. In addition, the battery has a larger discharge depth at a higher electrolyte flow rate.

  5. Polyvinyl Chloride/Silica Nanoporous Composite Separator for All-Vanadium Redox Flow Battery Applications

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Xiaoliang; Nie, Zimin; Luo, Qingtao; Li, Bin; Sprenkle, Vincent L.; Wang, Wei

    2013-04-22

    Redox flow batteries (RFBs) are capable of reversible conversion between electricity and chemical energy. Potential RFB applications resolve around mitigating the discrepancy between electricity production and consumption to improve the stability and utilization of the power infrastructure and tackling the intermittency of renewables such as photovoltaics or wind turbines to enable their reliable integration [1, 2]. Because the energy is stored in externally contained liquid electrolytes and the energy conversion reactions take place at the electrodes, RFBs hold a unique capability to separate energy and power and thus possess considerable design flexibility to meet either energy management driven or power rating oriented grid applications, which is considered to be a unparalleled advantage over conventional solid-state secondary batteries [3]. Other advantages of RFBs include fast response to load changes, high round-trip efficiency, long calender and cycle lives, safe operations, tolerance to deep discharge, etc. [4]. Among various flow battery chemistries, all-vanadium redox flow battery (VRB) was invented by Maria Skyllas-Kazacos at the University of New South Wales in the 1980s [5, 6] and have attracted substantial attention in both research and industrial communities today [7, 8]. A well-recognized advantage that makes VRB stands out among other redox chemistries is the reduced crossover contamination ascribed to employing four different oxidation states of the same vanadium element as the two redox couples. Recently, great progress has led to remarkably improved energy density of VRB by using sulfuric-chloric mixed acid supporting electrolytes that were stable at 2.5M vanadium and had wider operational temperature window of -5~50oC [9], compared with the traditional sulfuric acid VRB system [10].

  6. Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery.

    Science.gov (United States)

    Li, Bin; Nie, Zimin; Vijayakumar, M; Li, Guosheng; Liu, Jun; Sprenkle, Vincent; Wang, Wei

    2015-02-24

    Redox flow batteries are receiving wide attention for electrochemical energy storage due to their unique architecture and advantages, but progress has so far been limited by their low energy density (~25 Wh l(-1)). Here we report a high-energy density aqueous zinc-polyiodide flow battery. Using the highly soluble iodide/triiodide redox couple, a discharge energy density of 167 Wh l(-1) is demonstrated with a near-neutral 5.0 M ZnI2 electrolyte. Nuclear magnetic resonance study and density functional theory-based simulation along with flow test data indicate that the addition of an alcohol (ethanol) induces ligand formation between oxygen on the hydroxyl group and the zinc ions, which expands the stable electrolyte temperature window to from -20 to 50 °C, while ameliorating the zinc dendrite. With the high-energy density and its benign nature free from strong acids and corrosive components, zinc-polyiodide flow battery is a promising candidate for various energy storage applications.

  7. Performance of a low cost interdigitated flow design on a 1 kW class all vanadium mixed acid redox flow battery

    Energy Technology Data Exchange (ETDEWEB)

    Reed, David; Thomsen, Edwin; Li, Bin; Wang, Wei; Nie, Zimin; Koeppel, Brian; Sprenkle, Vincent

    2016-02-01

    Three flow designs were operated in a 3-cell 1 kW class all vanadium mixed acid redox flow battery. The influence of electrode surface area and flow rate on the coulombic, voltage, and energy efficiency and the pressure drop in the flow circuit will be discussed and correlated to the flow design. Material cost associated with each flow design will also be discussed.

  8. Performance of a low cost interdigitated flow design on a 1 kW class all vanadium mixed acid redox flow battery

    Science.gov (United States)

    Reed, David; Thomsen, Edwin; Li, Bin; Wang, Wei; Nie, Zimin; Koeppel, Brian; Sprenkle, Vincent

    2016-02-01

    Three flow designs were operated in a 3-cell 1 kW class all vanadium mixed acid redox flow battery. The influence of electrode surface area and flow rate on the coulombic, voltage, and energy efficiency and the pressure drop in the flow circuit will be discussed and correlated to the flow design. Material cost associated with each flow design will also be discussed.

  9. A new electrocatalyst and its application method for vanadium redox flow battery

    Science.gov (United States)

    Wei, Guanjie; Jing, Minghua; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei

    2015-08-01

    The edge plane in carbon structure has good electrocatalytic activity toward vanadium redox reaction. To apply it in vanadium redox flow battery (VRFB) practically, the graphite nanopowders (GNPs) containing amounts of edge planes are used as electrocatalyst and embedded in the electrospun carbon nanofibers (ECNFs) by different mass ratios to make composite electrodes. The morphology and electrochemical activity of the GNPs and the composite electrodes containing them are characterized. Compared with the pristine ECNFs, the composite electrodes show much higher electrochemical activity. With the increase of GNPs content in composite electrodes, the electrochemical reversibility of the vanadium redox couples also increases. It proves the addition of GNPs can surely improve the electrochemical activity of ECNFs. Among the composite electrodes, the ECNFs containing 30 nm GNP by mass ratio of 1:50 show the best electrochemical activity, largest active surface area and excellent stability. Due to the high performance of GNP/ECNFs composite electrode and its relatively low cost preparation process, the GNPs are expected to be used as electrocatalyst in VRFB on a large scale to improve the cell performance.

  10. Investigation of local environments in Nafion-SiO(2) composite membranes used in vanadium redox flow batteries.

    Science.gov (United States)

    Vijayakumar, M; Schwenzer, Birgit; Kim, Soowhan; Yang, Zhenguo; Thevuthasan, S; Liu, Jun; Graff, Gordon L; Hu, Jianzhi

    2012-04-01

    Proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, polymer composite membranes, such as SiO(2) incorporated Nafion membranes, are recently reported as highly promising for the use in redox flow batteries. However, there is conflicting reports regarding the performance of this type of Nafion-SiO(2) composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO(2) composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transform Infra Red (FTIR) spectroscopy, and ultraviolet-visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the (19)F and (29)Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The (29)Si NMR shows that the silica particles interact via hydrogen bonds with the sulfonic groups of Nafion and the diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO(2) composite membrane materials in vanadium redox flow batteries.

  11. Modelling and simulation of thermal behaviour of vanadium redox flow battery

    Science.gov (United States)

    Yan, Yitao; Li, Yifeng; Skyllas-Kazacos, Maria; Bao, Jie

    2016-08-01

    This paper extends previous thermal models of the vanadium redox flow battery to predict temperature profiles within multi-cell stacks. This involves modelling the thermal characteristics of the stack as a whole to modelling each individual cell. The study investigates the thermal behaviour for two different scenarios: during standby periods when the pumps are turned off, and in a residential power arbitrage scenario for two types of membranes. It was found that the temperature gradient across the cells is most significant during the standby case, with the simulation results showing completely different thermal behaviours between the two systems.

  12. A Quaternized Polysulfone Membrane for Zinc-Bromine Redox Flow Battery

    OpenAIRE

    Mingqiang Li; Hang Su; Qinggang Qiu; Guang Zhao; Yu Sun; Wenjun Song

    2014-01-01

    A quaternized polysulfone (QNPSU) composite membrane is fabricated for zinc-bromine redox flow battery. The structure of the membrane is examined by FT-IR spectra and SEM. The conductivity of the membrane is tested by electrochemical analyzer. After a zinc-bromine battery with this composite membrane is operated at different voltage while charging and at different current while discharging to examine the performance of the membrane, it is found that the discharge voltage was 0.9672 V and the ...

  13. Experimental Testing Procedures and Dynamic Model Validation for Vanadium Redox Flow Battery Storage System

    DEFF Research Database (Denmark)

    Baccino, Francesco; Marinelli, Mattia; Nørgård, Per Bromand;

    2013-01-01

    The paper aims at characterizing the electrochemical and thermal parameters of a 15 kW/320 kWh vanadium redox flow battery (VRB) installed in the SYSLAB test facility of the DTU Risø Campus and experimentally validating the proposed dynamic model realized in Matlab-Simulink. The adopted testing...... efficiency of the battery system. The test procedure has general validity and could also be used for other storage technologies. The storage model proposed and described is suitable for electrical studies and can represent a general model in terms of validity. Finally, the model simulation outputs...

  14. Nuclear Magnetic resonance studies of the solvation of a high-performance nonaqueous redox flow electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Xuchu; Hu, Mary Y.; Wei, Xiaoliang; Wang, Wei; Mueller, Karl T.; Chen, Zhong; Hu, Jian Z.

    2016-03-15

    Understanding the solvation structures of electrolytes is important for developing nonaqueous redox flow batteries that hold considerable potential for future large scale energy storage systems. The utilization of an emerging ionic-derivative ferrocene compounds, ferrocenylmethyl dimethyl ethyl ammonium bis (triflyoromethanesulfonyl)imide (Fc1N112-TFSI), has recently overcome the issue of solubility in the supporting electrolyte. In this work, 13C1H and 17O NMR investigations were carried out using solvent. It was observed that the spectra of 13C experience changes of chemical shifts while those of 17O undergo line width broadening, indicating interactions between solute and solvent molecules

  15. Reversible chemical delithiation/lithiation of LiFePO4: towards a redox flow lithium-ion battery.

    Science.gov (United States)

    Huang, Qizhao; Li, Hong; Grätzel, Michael; Wang, Qing

    2013-02-14

    Reversible chemical delithiation/lithiation of LiFePO(4) was successfully demonstrated using ferrocene derivatives, based on which a novel energy storage system--the redox flow lithium-ion battery (RFLB), was devised by integrating the operation flexibility of a redox flow battery and high energy density of a lithium-ion battery. Distinct from the recent semi-solid lithium rechargeable flow battery, the energy storage materials of RFLB stored in separate energy tanks remain stationary upon operation, giving us a fresh perspective on building large-scale energy storage systems with higher energy density and improved safety.

  16. Critical rate of electrolyte circulation for preventing zinc dendrite formation in a zinc-bromine redox flow battery

    Science.gov (United States)

    Yang, Hyeon Sun; Park, Jong Ho; Ra, Ho Won; Jin, Chang-Soo; Yang, Jung Hoon

    2016-09-01

    In a zinc-bromine redox flow battery, a nonaqueous and dense polybromide phase formed because of bromide oxidation in the positive electrolyte during charging. This formation led to complicated two-phase flow on the electrode surface. The polybromide and aqueous phases led to different kinetics of the Br/Br- redox reaction; poor mixing of the two phases caused uneven redox kinetics on the electrode surface. As the Br/Br- redox reaction was coupled with the zinc deposition reaction, the uneven redox reaction on the positive electrode was accompanied by nonuniform zinc deposition and zinc dendrite formation, which degraded battery stability. A single-flow cell was operated at varying electrolyte circulation rates and current densities. Zinc dendrite formation was observed after cell disassembly following charge-discharge testing. In addition, the flow behavior in the positive compartment was observed by using a transparent version of the cell. At low rate of electrolyte circulation, the polybromide phase clearly separated from the aqueous phase and accumulated at the bottom of the flow frame. In the corresponding area on the negative electrode, a large amount of zinc dendrites was observed after charge-discharge testing. Therefore, a minimum circulation rate should be considered to avoid poor mixing of the positive electrolyte.

  17. Balancing Osmotic Pressure of Electrolytes for Nanoporous Membrane Vanadium Redox Flow Battery with a Draw Solute.

    Science.gov (United States)

    Yan, Ligen; Li, Dan; Li, Shuaiqiang; Xu, Zhi; Dong, Junhang; Jing, Wenheng; Xing, Weihong

    2016-12-28

    Vanadium redox flow batteries with nanoporous membranes (VRFBNM) have been demonstrated to be good energy storage devices. Yet the capacity decay due to permeation of vanadium and water makes their commercialization very difficult. Inspired by the forward osmosis (FO) mechanism, the VRFBNM battery capacity decrease was alleviated by adding a soluble draw solute (e.g., 2-methylimidazole) into the catholyte, which can counterbalance the osmotic pressure between the positive and negative half-cell. No change of the electrolyte volume has been observed after VRFBNM being operated for 55 h, revealing that the permeation of water and vanadium ions was effectively limited. Consequently, the Coulombic efficiency (CE) of nanoporous TiO2 vanadium redox flow battery (VRFB) was enhanced from 93.5% to 95.3%, meanwhile, its capacity decay was significantly suppressed from 60.7% to 27.5% upon the addition of soluble draw solute. Moreover, the energy capacity of the VRFBNM was noticeably improved from 297.0 to 406.4 mAh remarkably. These results indicate balancing the osmotic pressure via the addition of draw solute can restrict pressure-dependent vanadium permeation and it can be established as a promising method for up-scaling VRFBNM application.

  18. Porous poly(benzimidazole) membrane for all vanadium redox flow battery

    Science.gov (United States)

    Luo, Tao; David, Oana; Gendel, Youri; Wessling, Matthias

    2016-04-01

    Porous poly(benzimidazole) (PBI) membranes of low vanadium ions permeability are described for an all vanadium redox flow battery (VRFB). The PBI membrane was prepared by a water vapour induced phase inversion process of a PBI polymer solution. The membrane has a symmetrical cross-sectional morphology. A low water permeability of 16.5 L (m2 h bar)-1 indicates the high hydraulic resistance stemming from a closed cell morphology with nanoporous characteristics. The PBI membrane doped with 2.5 M H2SO4 shows a proton conductivity of 16.6 mS cm-1 and VO2+ permeability as low as 4.5 × 10-8 cm2 min-1. The stability test of dense PBI membrane in VO2+ solution indicates good chemical stability. An all vanadium redox flow battery (VRFB) operated with the porous PBI membrane shows 98% coulombic efficiency and more than 10% higher energy efficiency compared to VRFB operated with Nafion 112 at applied current densities of 20-40 mA cm-2. High in situ stability of the porous PBI membrane was confirmed by about 50 cycles of continuous charge and discharge operation of the battery.

  19. Composite Nafion 117-TMSP membrane for Fe-Cr redox flow battery applications

    Science.gov (United States)

    Haryadi, Gunawan, Y. B.; Mursid, S. P.; Harjogi, D.

    2016-04-01

    The modification of Nafion 117 - TMSP (trimethoxysylilprophanthiol) composite membrane has been conducted by in-situ sol-gel method followed by characterization of structural and properties of material using spectroscopic techniques. The performance of composite membrane has then been examined in the single stack module of Fe-Cr Redox Flow Battery. It was found that the introduction of silica from TMSP through sol-gel process within the Nafion 117 membrane produced composite membrane that has slightly higher proton conductivity values as compared to the pristine of Nafion 117 membrane observed by electrochemical impedance spectroscopy. The degree of swelling of water in the composite membrane demonstrated greatly reduced than a pristine Nafion 117 signifying low water cross over. The SEM-EDX measurements indicated that there was no phase separation occurred suggesting that silica nanoparticles are distributed homogeneously within the composite membrane. The composite membrane used as separator in the system of Fe-Cr Redox Flow Battery revealed no cross mixing (crossover) occurred between anolyte and catholyte in the system as observed from the total voltage measurements that closed to the theoretical value. The battery efficiency generally increased as the volume of the electrolytes enlarged.

  20. Redox conditions effect on flow accelerated corrosion: Influence of hydrazine and oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Bouvier, O. de [EDF, R and D Div., Moret sur Loing (France); Bouchacourt, M. [EDF, Engineering and Service Div., Villeurbanne (France); Fruzzetti, K. [EPRI, Science and Technology Div., Palo Alto, CA (United States)

    2002-07-01

    Flow accelerated corrosion (FAC) of carbon steels has been studied world-wide for more than twenty years and is now fairly well understood. The influence of several parameters like water chemistry (i.e. pH and oxygen content), temperature, hydrodynamic or mass transfer conditions (i.e. flow velocity, geometry, steam quality..) and steel composition on the corrosion kinetics has been demonstrated both theoretically and experimentally. However, the effect of a reducing environment and variable redox conditions have not yet been fully explored. It's well known that a reducing environment is effective in increasing the resistance of steam generator tubing to intergranular attack / stress corrosion cracking (IGA/SCC) and pitting. In that way, secondary water chemistry specifications have been modified from low hydrazine to high hydrazine chemistry in the steam-water circuit. Nevertheless, increasing hydrazine levels up to 200 {mu}g/kg could have a detrimental effect by potentially enhancing the FAC process. Moreover, in order to have a complete understanding of the possible impact of the water chemistry environment it is also important to consider the impact of redox conditions during shutdowns (cold and/or hot shutdowns) and start up periods when aerated water injections are made to maintain a constant water level in the Steam Generators from the auxiliary feedwater circuit. Therefore, a common EDF and EPRI R and D effort has been recently carried out to study the effects of hydrazine and oxygen on FAC. The results are presented as follows. (authors)

  1. A low-cost iron-cadmium redox flow battery for large-scale energy storage

    Science.gov (United States)

    Zeng, Y. K.; Zhao, T. S.; Zhou, X. L.; Wei, L.; Jiang, H. R.

    2016-10-01

    The redox flow battery (RFB) is one of the most promising large-scale energy storage technologies that offer a potential solution to the intermittency of renewable sources such as wind and solar. The prerequisite for widespread utilization of RFBs is low capital cost. In this work, an iron-cadmium redox flow battery (Fe/Cd RFB) with a premixed iron and cadmium solution is developed and tested. It is demonstrated that the coulombic efficiency and energy efficiency of the Fe/Cd RFB reach 98.7% and 80.2% at 120 mA cm-2, respectively. The Fe/Cd RFB exhibits stable efficiencies with capacity retention of 99.87% per cycle during the cycle test. Moreover, the Fe/Cd RFB is estimated to have a low capital cost of 108 kWh-1 for 8-h energy storage. Intrinsically low-cost active materials, high cell performance and excellent capacity retention equip the Fe/Cd RFB to be a promising solution for large-scale energy storage systems.

  2. Nanorod niobium oxide as powerful catalysts for an all vanadium redox flow battery.

    Science.gov (United States)

    Li, Bin; Gu, Meng; Nie, Zimin; Wei, Xiaoliang; Wang, Chongmin; Sprenkle, Vincent; Wang, Wei

    2014-01-01

    A powerful low-cost electrocatalyst, nanorod Nb2O5, is synthesized using the hydrothermal method with monoclinic phases and simultaneously deposited on the surface of a graphite felt (GF) electrode in an all vanadium flow battery (VRB). Cyclic voltammetry (CV) study confirmed that Nb2O5 has catalytic effects toward redox couples of V(II)/V(III) at the negative side and V(IV)/V(V) at the positive side to facilitate the electrochemical kinetics of the vanadium redox reactions. Because of poor conductivity of Nb2O5, the performance of the Nb2O5 loaded electrodes is strongly dependent on the nanosize and uniform distribution of catalysts on GF surfaces. Accordingly, an optimal amount of W-doped Nb2O5 nanorods with minimum agglomeration and improved distribution on GF surfaces are established by adding water-soluble compounds containing tungsten (W) into the precursor solutions. The corresponding energy efficiency is enhanced by ∼10.7% at high current density (150 mA·cm(-2)) as compared with one without catalysts. Flow battery cyclic performance also demonstrates the excellent stability of the as prepared Nb2O5 catalyst enhanced electrode. These results suggest that Nb2O5-based nanorods, replacing expensive noble metals, uniformly decorating GFs holds great promise as high-performance electrodes for VRB applications.

  3. Concentration Dependence of VO2+ Crossover of Nafion for Vanadium Redox Flow Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Lawton, Jamie [University of Tennessee, Knoxville (UTK); Jones, Amanda [University of Tennessee, Knoxville (UTK); Zawodzinski, Thomas A [ORNL

    2013-01-01

    The VO2+ crossover, or permeability, through Nafion in a vanadium redox flow battery (VRFB) was monitored as a function of sulfuric acid concentration and VO2+ concentration. A vanadium rich solution was flowed on one side of the membrane through a flow field while symmetrically on the other side a blank or vanadium deficit solution was flowed. The blank solution was flowed through an electron paramagnetic resonance (EPR) cavity and the VO2+ concentration was determined from the intensity of the EPR signal. Concentration values were fit using a solution of Fick s law that allows for the effect of concentration change on the vanadium rich side. The fits resulted in permeability values of VO2+ ions across the membrane. Viscosity measurements of many VO2+ and H2SO4 solutions were made at 30 60 C. These viscosity values were then used to determine the effect of the viscosity of the flowing solution on the permeability of the ion. 2013 The Electrochemical Society. [DOI: 10.1149/2.004306jes] All rights reserved.

  4. A Quaternized Polysulfone Membrane for Zinc-Bromine Redox Flow Battery

    Directory of Open Access Journals (Sweden)

    Mingqiang Li

    2014-01-01

    Full Text Available A quaternized polysulfone (QNPSU composite membrane is fabricated for zinc-bromine redox flow battery. The structure of the membrane is examined by FT-IR spectra and SEM. The conductivity of the membrane is tested by electrochemical analyzer. After a zinc-bromine battery with this composite membrane is operated at different voltage while charging and at different current while discharging to examine the performance of the membrane, it is found that the discharge voltage was 0.9672 V and the power density was 6 mW/cm2 at a current of 0.1 A, which indicated that the novel composite membrane is a promising material for the flow battery.

  5. A high-performance dual-scale porous electrode for vanadium redox flow batteries

    Science.gov (United States)

    Zhou, X. L.; Zeng, Y. K.; Zhu, X. B.; Wei, L.; Zhao, T. S.

    2016-09-01

    In this work, we present a simple and cost-effective method to form a dual-scale porous electrode by KOH activation of the fibers of carbon papers. The large pores (∼10 μm), formed between carbon fibers, serve as the macroscopic pathways for high electrolyte flow rates, while the small pores (∼5 nm), formed on carbon fiber surfaces, act as active sites for rapid electrochemical reactions. It is shown that the Brunauer-Emmett-Teller specific surface area of the carbon paper is increased by a factor of 16 while maintaining the same hydraulic permeability as that of the original carbon paper electrode. We then apply the dual-scale electrode to a vanadium redox flow battery (VRFB) and demonstrate an energy efficiency ranging from 82% to 88% at current densities of 200-400 mA cm-2, which is record breaking as the highest performance of VRFB in the open literature.

  6. All-vanadium redox flow batteries with graphite felt electrodes treated by atmospheric pressure plasma jets

    Science.gov (United States)

    Chen, Jian-Zhang; Liao, Wei-Yang; Hsieh, Wen-Yen; Hsu, Cheng-Che; Chen, Yong-Song

    2015-01-01

    Graphite felts modified with atmospheric pressure plasma jets (APPJs) are applied as electrodes in an all-vanadium redox flow battery (VRFB). APPJ flow penetrates deeply into the graphite felt, improving significantly the wettability of the graphite felt inside out and, thereby, enhancing graphite fiber-electrolyte contact during battery operation. The energy efficiency of a VRFB was improved from 62% (untreated) to 76% (APPJ-treated with the scan mode) at a current density of 80 mA cm-2, an improvement of 22%. The efficiency improvement is attributed to the oxygen-containing groups and nitrogen doping introduced by N2 APPJs on the fiber surfaces of graphite felt, both of which enhance electrochemical reactivity.

  7. Nanorod Niobium Oxide as Powerful Catalysts for an All Vanadium Redox Flow Battery

    Energy Technology Data Exchange (ETDEWEB)

    Li, Bin; Gu, Meng; Nie, Zimin; Wei, Xiaoliang; Wang, Chong M.; Sprenkle, Vincent L.; Wang, Wei

    2014-01-01

    Graphite felts (GFs), as typical electrode materials for all vanadium redox flow batteries (VRBs), limit the cell operation to low current density because of their poor kinetic reversibility and electrochemical activity. Here, in order to address this issue we report an electrocatalyst, Nb2O5, decorating the surface of GFs to reduce the activation barrier for redox conversion. Nb2O5 nanofibers with monoclinic phases are synthesized by hydrothermal method and deposited on GFs, which is confirmed to have catalytic effects towards redox couples of V(II)/V(III) at the negative side and V(IV)/V(V) at the positive side, and thus applied in both electrodes of VRB cells. Due to the low conductivity of Nb2O5, the performance of electrodes heavily depends on the nano size and uniform distribution of catalysts on GFs surfaces. The addition of the water-soluble compounds containing W element into the precursor solutions facilitates the precipitation of nanofibers on the GFs. Accordingly, an optimal amount of W-doped Nb2O5 nanofibers with weaker agglomeration and better distribution on GFs surfaces are obtained, leading to significant improvement of the electrochemical performances of VRB cells particularly under the high power operation. The corresponding energy efficiency is enhanced by 10.7 % under the operation of high charge/discharge current density (150 mA•cm-2) owing to faster charge transfer as compared with that without catalysts. These results suggest that Nb2O5 based nanofibers-decorating GFs hold great promise as high-performance electrodes for VRB applications.

  8. PbO2-modified graphite felt as the positive electrode for an all-vanadium redox flow battery

    Science.gov (United States)

    Wu, Xiaoxin; Xu, Hongfeng; Lu, Lu; Zhao, Hong; Fu, Jie; Shen, Yang; Xu, Pengcheng; Dong, Yiming

    2014-03-01

    A novel approach for enhancing the electrochemical performance of graphite felt electrodes by employing non-precious metal oxides is designed for an all-vanadium redox flow battery (VRFB). Lead dioxide (PbO2) is prepared through pulse electrodeposition method and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical performance of the prepared electrode is evaluated through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Results show that PbO2 exhibits excellent electro-catalytic activity and reactive velocity to vanadium redox couples. The coulombic efficiency (CE), voltage efficiency (VE), and energy efficiency (EE) of the vanadium redox flow battery with as-prepared electrodes at 70 mA cm-2 are 99.5%, 82.4%, and 82.0%, respectively; these values are much higher than those of a cell assembled with bare graphite felt electrodes. The outstanding electro-catalytic activity and mechanical stability of PbO2 are advantageous in facilitating the redox reaction of vanadium ions, leading to the efficient operation of a vanadium redox flow battery.

  9. Outstanding electrochemical performance of a graphene-modified graphite felt for vanadium redox flow battery application

    Science.gov (United States)

    González, Zoraida; Flox, Cristina; Blanco, Clara; Granda, Marcos; Morante, Juan R.; Menéndez, Rosa; Santamaría, Ricardo

    2017-01-01

    The development of more efficient electrode materials is essential to obtain vanadium redox flow batteries (VRFBs) with enhanced energy densities and to make these electrochemical energy storage devices more competitive. A graphene-modified graphite felt synthesized from a raw graphite felt and a graphene oxide water suspension by means of electrophoretic deposition (EPD) is investigated as a suitable electrode material in the positive side of a VRFB cell by means of cyclic voltammetry, impedance spectroscopy and charge/discharge experiments. The remarkably enhanced performance of the resultant hybrid material, in terms of electrochemical activity and kinetic reversibility towards the VO2+/VO2+, and mainly the markedly high energy efficiency of the VRFB cell (c.a. 95.8% at 25 mA cm-2) can be ascribed to the exceptional morphological and chemical characteristics of this tailored material. The 3D-architecture consisting of fibers interconnected by graphene-like sheets positively contributes to the proper development of the vanadium redox reactions and so represents a significant advance in the design of effective electrode materials.

  10. An all-organic non-aqueous lithium-ion redox flow battery

    Energy Technology Data Exchange (ETDEWEB)

    Brushett, Fikile R.; Vaughey, John T.; Jansen, Andrew N. [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439 (United States)

    2012-11-15

    A non-aqueous lithium-ion redox flow battery employing organic molecules is proposed and investigated. 2,5-Di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene and a variety of molecules derived from quinoxaline are employed as initial high-potential and low-potential active materials, respectively. Electrochemical measurements highlight that the choice of electrolyte and of substituent groups can have a significant impact on redox species performance. The charge-discharge characteristics are investigated in a modified coin-cell configuration. After an initial break-in period, coulombic and energy efficiencies for this unoptimized system are {proportional_to}70% and {proportional_to}37%, respectively, with major charge and discharge plateaus between 1.8-2.4 V and 1.7-1.3 V, respectively, for 30 cycles. Performance enhancements are expected with improvements in cell design and materials processing. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Water-activated graphite felt as a high-performance electrode for vanadium redox flow batteries

    Science.gov (United States)

    Kabtamu, Daniel Manaye; Chen, Jian-Yu; Chang, Yu-Chung; Wang, Chen-Hao

    2017-02-01

    A simple, green, novel, time-efficient, and potentially cost-effective water activation method was employed to enhance the electrochemical activity of graphite felt (GF) electrodes for vanadium redox flow batteries (VRFBs). The GF electrode prepared with a water vapor injection time of 5 min at 700 °C exhibits the highest electrochemical activity for the VO2+/VO2+ couple among all the tested electrodes. This is attributed to the small, controlled amount of water vapor that was introduced producing high contents of oxygen-containing functional groups, such as sbnd OH groups, on the surface of the GF fibers, which are known to be electrochemically active sites for vanadium redox reactions. Charge-discharge tests further confirm that only 5 min of GF water activation is required to improve the efficiency of the VRFB cell. The average coulombic efficiency, voltage efficiency, and energy efficiency are 95.06%, 87.42%, and 83.10%, respectively, at a current density of 50 mA cm-2. These voltage and energy efficiencies are determined to be considerably higher than those of VRFB cells assembled using heat-treated GF electrodes without water activation and pristine GF electrodes.

  12. An Aqueous Redox-Flow Battery with High Capacity and Power: The TEMPTMA/MV System.

    Science.gov (United States)

    Janoschka, Tobias; Martin, Norbert; Hager, Martin D; Schubert, Ulrich S

    2016-11-07

    Redox-flow batteries (RFB) can easily store large amounts of electric energy and thereby mitigate the fluctuating output of renewable power plants. They are widely discussed as energy-storage solutions for wind and solar farms to improve the stability of the electrical grid. Most common RFB concepts are based on strongly acidic metal-salt solutions or poorly performing organics. Herein we present a battery which employs the highly soluble N,N,N-2,2,6,6-heptamethylpiperidinyl oxy-4-ammonium chloride (TEMPTMA) and the viologen derivative N,N'-dimethyl-4,4-bipyridinium dichloride (MV) in a simple and safe aqueous solution as redox-active materials. The resulting battery using these electrolyte solutions has capacities of 54 Ah L(-1) , giving a total energy density of 38 Wh L(-1) at a cell voltage of 1.4 V. With peak current densities of up to 200 mA cm(-2) the TEMPTMA/MV system is a suitable candidate for compact high-capacity and high-power applications.

  13. Comparative analysis for various redox flow batteries chemistries using a cost performance model

    Science.gov (United States)

    Crawford, Alasdair; Viswanathan, Vilayanur; Stephenson, David; Wang, Wei; Thomsen, Edwin; Reed, David; Li, Bin; Balducci, Patrick; Kintner-Meyer, Michael; Sprenkle, Vincent

    2015-10-01

    The total energy storage system cost is determined by means of a robust performance-based cost model for multiple flow battery chemistries. Systems aspects such as shunt current losses, pumping losses and various flow patterns through electrodes are accounted for. The system cost minimizing objective function determines stack design by optimizing the state of charge operating range, along with current density and current-normalized flow. The model cost estimates are validated using 2-kW stack performance data for the same size electrodes and operating conditions. Using our validated tool, it has been demonstrated that an optimized all-vanadium system has an estimated system cost of costs facilitated by economies of scale from larger production volumes, coupled with performance improvements enabled by technology development, the system cost is expected to decrease to 160 kWh-1 for a 4-h application, and to 100 kWh-1 for a 10-h application. This tool has been shared with the redox flow battery community to enable cost estimation using their stack data and guide future direction.

  14. Experimental testing procedures and dynamic model validation for vanadium redox flow battery storage system

    Science.gov (United States)

    Baccino, Francesco; Marinelli, Mattia; Nørgård, Per; Silvestro, Federico

    2014-05-01

    The paper aims at characterizing the electrochemical and thermal parameters of a 15 kW/320 kWh vanadium redox flow battery (VRB) installed in the SYSLAB test facility of the DTU Risø Campus and experimentally validating the proposed dynamic model realized in Matlab-Simulink. The adopted testing procedure consists of analyzing the voltage and current values during a power reference step-response and evaluating the relevant electrochemical parameters such as the internal resistance. The results of different tests are presented and used to define the electrical characteristics and the overall efficiency of the battery system. The test procedure has general validity and could also be used for other storage technologies. The storage model proposed and described is suitable for electrical studies and can represent a general model in terms of validity. Finally, the model simulation outputs are compared with experimental measurements during a discharge-charge sequence.

  15. Tuning the Perfluorosulfonic Acid Membrane Morphology for Vanadium Redox-Flow Batteries.

    Science.gov (United States)

    Vijayakumar, M; Luo, Qingtao; Lloyd, Ralph; Nie, Zimin; Wei, Xiaoliang; Li, Bin; Sprenkle, Vincent; Londono, J-David; Unlu, Murat; Wang, Wei

    2016-12-21

    The microstructure of perfluorinated sulfonic acid proton-exchange membranes such as Nafion significantly affects their transport properties and performance in a vanadium redox-flow battery (VRB). In this work, Nafion membranes with various equivalent weights ranging from 1000 to 1500 are prepared and the morphology-property-performance relationship is investigated. NMR and small-angle X-ray scattering studies revealed their composition and morphology variances, which lead to major differences in key transport properties related to proton conduction and vanadium-ion permeation. Their performances are further characterized as VRB membranes. On the basis of this understanding, a new perfluorosulfonic acid membrane is designed with optimal pore geometry and thickness, leading to higher ion selectivity and lower cost compared with the widely used Nafion 115. Excellent VRB single-cell performance (89.3% energy efficiency at 50 mA·cm(-2)) was achieved along with a stable cyclical capacity over prolonged cycling.

  16. Integrated Photoelectrochemical Solar Energy Conversion and Organic Redox Flow Battery Devices

    KAUST Repository

    Li, Wenjie

    2016-09-21

    Building on regenerative photoelectrochemical solar cells and emerging electrochemical redox flow batteries (RFBs), more efficient, scalable, compact, and cost-effective hybrid energy conversion and storage devices could be realized. An integrated photoelectrochemical solar energy conversion and electrochemical storage device is developed by integrating regenerative silicon solar cells and 9,10-anthraquinone-2,7-disulfonic acid (AQDS)/1,2-benzoquinone-3,5-disulfonic acid (BQDS) RFBs. The device can be directly charged by solar light without external bias, and discharged like normal RFBs with an energy storage density of 1.15 Wh L−1 and a solar-to-output electricity efficiency (SOEE) of 1.7 % over many cycles. The concept exploits a previously undeveloped design connecting two major energy technologies and promises a general approach for storing solar energy electrochemically with high theoretical storage capacity and efficiency.

  17. Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application

    Science.gov (United States)

    Mai, Zhensheng; Zhang, Huamin; Li, Xianfeng; Bi, Cheng; Dai, Hua

    Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test.

  18. Integrated Photoelectrochemical Solar Energy Conversion and Organic Redox Flow Battery Devices.

    Science.gov (United States)

    Li, Wenjie; Fu, Hui-Chun; Li, Linsen; Cabán-Acevedo, Miguel; He, Jr-Hau; Jin, Song

    2016-10-10

    Building on regenerative photoelectrochemical solar cells and emerging electrochemical redox flow batteries (RFBs), more efficient, scalable, compact, and cost-effective hybrid energy conversion and storage devices could be realized. An integrated photoelectrochemical solar energy conversion and electrochemical storage device is developed by integrating regenerative silicon solar cells and 9,10-anthraquinone-2,7-disulfonic acid (AQDS)/1,2-benzoquinone-3,5-disulfonic acid (BQDS) RFBs. The device can be directly charged by solar light without external bias, and discharged like normal RFBs with an energy storage density of 1.15 Wh L(-1) and a solar-to-output electricity efficiency (SOEE) of 1.7 % over many cycles. The concept exploits a previously undeveloped design connecting two major energy technologies and promises a general approach for storing solar energy electrochemically with high theoretical storage capacity and efficiency.

  19. Highly accurate apparatus for electrochemical characterization of the felt electrodes used in redox flow batteries

    Science.gov (United States)

    Park, Jong Ho; Park, Jung Jin; Park, O. Ok; Jin, Chang-Soo; Yang, Jung Hoon

    2016-04-01

    Because of the rise in renewable energy use, the redox flow battery (RFB) has attracted extensive attention as an energy storage system. Thus, many studies have focused on improving the performance of the felt electrodes used in RFBs. However, existing analysis cells are unsuitable for characterizing felt electrodes because of their complex 3-dimensional structure. Analysis is also greatly affected by the measurement conditions, viz. compression ratio, contact area, and contact strength between the felt and current collector. To address the growing need for practical analytical apparatus, we report a new analysis cell for accurate electrochemical characterization of felt electrodes under various conditions, and compare it with previous ones. In this cell, the measurement conditions can be exhaustively controlled with a compression supporter. The cell showed excellent reproducibility in cyclic voltammetry analysis and the results agreed well with actual RFB charge-discharge performance.

  20. Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application

    Energy Technology Data Exchange (ETDEWEB)

    Mai, Zhensheng; Bi, Cheng; Dai, Hua [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100039 (China); Zhang, Huamin; Li, Xianfeng [PEMFC Key Materials and Technology Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023 (China)

    2011-01-01

    Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test. (author)

  1. High performance electrodes in vanadium redox flow batteries through oxygen-enriched thermal activation

    Science.gov (United States)

    Pezeshki, Alan M.; Clement, Jason T.; Veith, Gabriel M.; Zawodzinski, Thomas A.; Mench, Matthew M.

    2015-10-01

    The roundtrip electrochemical energy efficiency is improved from 63% to 76% at a current density of 200 mA cm-2 in an all-vanadium redox flow battery (VRFB) by utilizing modified carbon paper electrodes in the high-performance no-gap design. Heat treatment of the carbon paper electrodes in a 42% oxygen/58% nitrogen atmosphere increases the electrochemically wetted surface area from 0.24 to 51.22 m2 g-1, resulting in a 100-140 mV decrease in activation overpotential at operationally relevant current densities. An enriched oxygen environment decreases the amount of treatment time required to achieve high surface area. The increased efficiency and greater depth of discharge doubles the total usable energy stored in a fixed amount of electrolyte during operation at 200 mA cm-2.

  2. Hydrogen evolution at the negative electrode of the all-vanadium redox flow batteries

    Science.gov (United States)

    Sun, Che-Nan; Delnick, Frank M.; Baggetto, Loïc; Veith, Gabriel M.; Zawodzinski, Thomas A.

    2014-02-01

    This work demonstrates a quantitative method to determine the hydrogen evolution rate occurring at the negative carbon electrode of the all vanadium redox flow battery (VRFB). Two carbon papers examined by buoyancy measurements yield distinct hydrogen formation rates (0.170 and 0.005 μmol min-1 g-1). The carbon papers have been characterized using electron microscopy, nitrogen gas adsorption, capacitance measurement by electrochemical impedance spectroscopy (EIS), and X-ray photoelectron spectroscopy (XPS). We find that the specific electrochemical surface area (ECSA) of the carbon material has a strong influence on the hydrogen generation rate. This is discussed in light of the use of high surface area material to obtain high reaction rates in the VRFB.

  3. "Unexpected" behaviour of the internal resistance of a vanadium redox flow battery

    Science.gov (United States)

    Rudolph, S.; Schröder, U.; Bayanov, I. M.; Hage-Packhäuser, S.

    2016-02-01

    This article presents the results of experimental and theoretical studies of energy losses owing to the internal resistance of vanadium redox flow batteries (VRFBs). A dependence of the internal cell resistance (ICR) on the electric current was measured and calculated. During the cyclic operation of a test battery, the internal resistance was halved by increasing the electric current from 3 A to 9 A. This is due to a strongly non-linear dependence of an over-potential of the electrochemical reactions on the current density. However, the energy efficiency does not increase due to a squared dependence of the energy losses on the increasing electric current. The energy efficiency of the test battery versus the electric current was measured and simulated. The deviation between the simulation results and experimental data is less than ±3.5%.

  4. Analysis and measurement of the electrolyte imbalance in a vanadium redox flow battery

    Science.gov (United States)

    Ngamsai, Kittima; Arpornwichanop, Amornchai

    2015-05-01

    Electrolyte imbalance in vanadium redox flow batteries is an important problem for its long-term operation as it leads to loss of energy. To address this problem, a modified open circuit voltage (OCV) cell is developed by adding a middle half cell between the negative and positive half cells of a conventional OCV cell and used to predict the oxidation state of vanadium in the electrolyte solution from the measured voltage in each side of the electrolyte (positive and negative). The correlation between the oxidation state of vanadium and cell voltage is explained by a basic electrochemical principle and the Nernst equation. The experimental results show that at different oxidation states of vanadium, the predicted OCV agrees reasonably with the experimental data. In addition, the effect of the state of charge (SOC) and electrolyte imbalance on the energy capacity of a cell is discussed.

  5. A multi-stack simulation of shunt currents in vanadium redox flow batteries

    Science.gov (United States)

    Wandschneider, F. T.; Röhm, S.; Fischer, P.; Pinkwart, K.; Tübke, J.; Nirschl, H.

    2014-09-01

    A model for the shunt currents in an all-vanadium redox flow battery consisting of 3 stacks which are electrically connected in series. It is based on an equivalent circuit which treats the shunt current pathways as Ohmic resistors. The conductivity of the vanadium electrolyte has been measured for different state-of-charges in order to implement a dependency of the resistances on the state-of-charge of the system. Published results are used to validate the simulation data of a single stack. Three setups of pipe networks are evaluated using the model. The pipe connections between the stacks give rise to external shunt currents, which also increase the amount of shunt currents within the stacks. These connections also lead to a nonuniform distribution of the shunt currents. The effects of the shunt currents on the Coulombic efficiency and the energy efficiency of the system are studied by the means of the model.

  6. Tuning the Perfluorosulfonic Acid Membrane Morphology for Vanadium Redox-Flow Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Vijayakumar, M.; Luo, Qingtao; Lloyd, Ralph; Nie, Zimin; Wei, Xiaoliang; Li, Bin; Sprenkle, Vincent; Londono, J-David; Unlu, Murat; Wang, Wei

    2016-12-23

    The microstructure of the perfluorinated sulfonic acid proton exchange membranes such as Nafion significantly affects their transport properties and performance in a vanadium redox flow battery (VRB). In this work, Nafion membranes with various equivalent weights (EW) ranging from 1000 to 1500 are prepared and the structure-property-performance relationship is investigated. Nuclear magnetic resonance (NMR) and small-angle X-ray scattering (SAXS) studies revealed their composition and morphology variances, which lead to major differences in key transport properties related to proton conduction and vanadium ion permeation. Their performances are further characterized as VRB membranes. Based on those understanding, a new perfluorosulfonic acid membrane is designed with optimal pore geometry and thickness, leading to higher ion selectivity and lower cost compared with the widely used Nafion® 115. Excellent VRB single-cell performance (89.3% energy efficiency at 50mA∙cm-2) was achieved along with a stable cyclical capacity over prolonged cycling.

  7. Long-Cycling Aqueous Organic Redox Flow Battery (AORFB) toward Sustainable and Safe Energy Storage.

    Science.gov (United States)

    Hu, Bo; DeBruler, Camden; Rhodes, Zayn; Liu, T Leo

    2017-01-25

    Redox flow batteries (RFBs) are a viable technology to store renewable energy in the form of electricity that can be supplied to electricity grids. However, widespread implementation of traditional RFBs, such as vanadium and Zn-Br2 RFBs, is limited due to a number of challenges related to materials, including low abundance and high costs of redox-active metals, expensive separators, active material crossover, and corrosive and hazardous electrolytes. To address these challenges, we demonstrate a neutral aqueous organic redox flow battery (AORFB) technology utilizing a newly designed cathode electrolyte containing a highly water-soluble ferrocene molecule. Specifically, water-soluble (ferrocenylmethyl)trimethylammonium chloride (FcNCl, 4.0 M in H2O, 107.2 Ah/L, and 3.0 M in 2.0 NaCl, 80.4 Ah/L) and N(1)-ferrocenylmethyl-N(1),N(1),N(2),N(2),N(2)-pentamethylpropane-1,2-diaminium dibromide, (FcN2Br2, 3.1 M in H2O, 83.1 Ah/L, and 2.0 M in 2.0 M NaCl, 53.5 Ah/L) were synthesized through structural decoration of hydrophobic ferrocene with synergetic hydrophilic functionalities including an ammonium cation group and a halide anion. When paired with methyl viologen (MV) as an anolyte, resulting FcNCl/MV and FcN2Br2/MV AORFBs were operated in noncorrosive neutral NaCl supporting electrolytes using a low-cost anion-exchange membrane. These ferrocene/MV AORFBs are characterized as having high theoretical energy density (45.5 Wh/L) and excellent cycling performance from 40 to 100 mA/cm(2). Notably, the FcNCl/MV AORFBs (demonstrated at 7.0 and 9.9 Wh/L) exhibited unprecedented long cycling performance, 700 cycles at 60 mA/cm(2) with 99.99% capacity retention per cycle, and delivered power density up to 125 mW/cm(2). These AORFBs are built from earth-abundant elements and are environmentally benign, thus representing a promising choice for sustainable and safe energy storage.

  8. Evaluation of heart tissue viability under redox-magnetohydrodynamics conditions: toward fine-tuning flow in biological microfluidics applications.

    Science.gov (United States)

    Cheah, Lih Tyng; Fritsch, Ingrid; Haswell, Stephen J; Greenman, John

    2012-07-01

    A microfluidic system containing a chamber for heart tissue biopsies, perfused with Krebs-Henseleit buffer containing glucose and antibiotic (KHGB) using peristaltic pumps and continuously stimulated, was used to evaluate tissue viability under redox-magnetohydrodynamics (redox-MHD) conditions. Redox-MHD possesses unique capabilities to control fluid flow using ionic current from oxidation and reduction processes at electrodes in a magnetic field, making it attractive to fine-tune fluid flow around tissues for "tissue-on-a-chip" applications. The manuscript describes a parallel setup to study two tissue samples simultaneously, and 6-min static incubation with Triton X100. Tissue viability was subsequently determined by assaying perfusate for lactate dehydrogenase (LDH) activity, where LDH serves as an injury marker. Incubation with KHGB containing 5 mM hexaammineruthenium(III) (ruhex) redox species with and without a pair of NdFeB magnets (∼ 0.39 T, placed parallel to the chamber) exhibited no additional tissue insult. MHD fluid flow, viewed by tracking microbeads with microscopy, occurred only when the magnet was present and stimulating electrodes were activated. Pulsating MHD flow with a frequency similar to the stimulating waveform was superimposed over thermal convection (from a hotplate) for Triton-KHGB, but fluid speed was up to twice as fast for ruhex-Triton-KHGB. A large transient ionic current, achieved when switching on the stimulating electrodes, generates MHD perturbations visible over varying peristaltic flow. The well-controlled flow methodology of redox-MHD is applicable to any tissue type, being useful in various drug uptake and toxicity studies, and can be combined equally with on- or off-device analysis modalities.

  9. A comprehensive equivalent circuit model of all-vanadium redox flow battery for power system analysis

    Science.gov (United States)

    Zhang, Yu; Zhao, Jiyun; Wang, Peng; Skyllas-Kazacos, Maria; Xiong, Binyu; Badrinarayanan, Rajagopalan

    2015-09-01

    Electrical equivalent circuit models demonstrate excellent adaptability and simplicity in predicting the electrical dynamic response of the all-vanadium redox flow battery (VRB) system. However, only a few publications that focus on this topic are available. The paper presents a comprehensive equivalent circuit model of VRB for system level analysis. The least square method is used to identify both steady-state and dynamic characteristics of VRB. The inherent features of the flow battery such as shunt current, ion diffusion and pumping energy consumption are also considered. The proposed model consists of an open-circuit voltage source, two parasitic shunt bypass circuits, a 1st order resistor-capacitor network and a hydraulic circuit model. Validated with experimental data, the proposed model demonstrates excellent accuracy. The mean-error of terminal voltage and pump consumption are 0.09 V and 0.49 W respectively. Based on the proposed model, self-discharge and system efficiency are studied. An optimal flow rate which maximizes the system efficiency is identified. Finally, the dynamic responses of the proposed VRB model under step current profiles are presented. Variables such as SOC and stack terminal voltage can be provided.

  10. Modeling biogeochemical processes in subterranean estuaries : Effect of flow dynamics and redox conditions on submarine groundwater discharge of nutrients

    NARCIS (Netherlands)

    Spiteri, C.; Slomp, C.P.; Tuncay, K.; Meile, C.

    2008-01-01

    A two-dimensional density-dependent reactive transport model, which couples groundwater flow and biogeochemical reactions, is used to investigate the fate of nutrients (NO3 −, NH4 +, and PO4) in idealized subterranean estuaries representing four end-members of oxic/anoxic aquifer and seawater redox

  11. A dynamic plug flow reactor model for a vanadium redox flow battery cell

    Science.gov (United States)

    Li, Yifeng; Skyllas-Kazacos, Maria; Bao, Jie

    2016-04-01

    A dynamic plug flow reactor model for a single cell VRB system is developed based on material balance, and the Nernst equation is employed to calculate cell voltage with consideration of activation and concentration overpotentials. Simulation studies were conducted under various conditions to investigate the effects of several key operation variables including electrolyte flow rate, upper SOC limit and input current magnitude on the cell charging performance. The results show that all three variables have a great impact on performance, particularly on the possibility of gassing during charging at high SOCs or inadequate flow rates. Simulations were also carried out to study the effects of electrolyte imbalance during long term charging and discharging cycling. The results show the minimum electrolyte flow rate needed for operation within a particular SOC range in order to avoid gassing side reactions during charging. The model also allows scheduling of partial electrolyte remixing operations to restore capacity and also avoid possible gassing side reactions during charging. Simulation results also suggest the proper placement for cell voltage monitoring and highlight potential problems associated with setting the upper charging cut-off limit based on the inlet SOC calculated from the open-circuit cell voltage measurement.

  12. Bio-mass derived mesoporous carbon as superior electrode in all vanadium redox flow battery with multicouple reactions

    Science.gov (United States)

    Ulaganathan, Mani; Jain, Akshay; Aravindan, Vanchiappan; Jayaraman, Sundaramurthy; Ling, Wong Chui; Lim, Tuti Mariana; Srinivasan, Madapusi P.; Yan, Qingyu; Madhavi, Srinivasan

    2015-01-01

    We first report the multi-couple reaction in all vanadium redox flow batteries (VRFB) while using bio-mass (coconut shell) derived mesoporous carbon as electrode. The presence of V3+/V4+ redox couple certainly supplies the additional electrons for the electrochemical reaction and subsequently provides improved electrochemical performance of VRFB system. The efficient electro-catalytic activity of such coconut shell derived high surface area mesoporous carbon is believed for the improved cell performance. Extensive power and electrochemical studies are performed for VRFB application point of view and described in detail.

  13. A comparative study of all-vanadium and iron-chromium redox flow batteries for large-scale energy storage

    Science.gov (United States)

    Zeng, Y. K.; Zhao, T. S.; An, L.; Zhou, X. L.; Wei, L.

    2015-12-01

    The promise of redox flow batteries (RFBs) utilizing soluble redox couples, such as all vanadium ions as well as iron and chromium ions, is becoming increasingly recognized for large-scale energy storage of renewables such as wind and solar, owing to their unique advantages including scalability, intrinsic safety, and long cycle life. An ongoing question associated with these two RFBs is determining whether the vanadium redox flow battery (VRFB) or iron-chromium redox flow battery (ICRFB) is more suitable and competitive for large-scale energy storage. To address this concern, a comparative study has been conducted for the two types of battery based on their charge-discharge performance, cycle performance, and capital cost. It is found that: i) the two batteries have similar energy efficiencies at high current densities; ii) the ICRFB exhibits a higher capacity decay rate than does the VRFB; and iii) the ICRFB is much less expensive in capital costs when operated at high power densities or at large capacities.

  14. Development of Integrally Molded Bipolar Plates for All-Vanadium Redox Flow Batteries

    Directory of Open Access Journals (Sweden)

    Chih-Hsun Chang

    2016-05-01

    Full Text Available All-vanadium redox flow batteries (VRBs are potential energy storage systems for renewable power sources because of their flexible design, deep discharge capacity, quick response time, and long cycle life. To minimize the energy loss due to the shunt current, in a traditional design, a flow field is machined on two electrically insulated frames with a graphite plate in between. A traditional bipolar plate (BP of a VRB consists of many components, and thus, the assembly process is time consuming. In this study, an integrally molded BP is designed and fabricated to minimize the manufacturing cost. First, the effects of the mold design and injection parameters on frame formability were analyzed by simulation. Second, a new graphite plate design for integral molding was proposed, and finally, two integrally molded BPs were fabricated and compared. Results show that gate position significantly affects air traps and the maximum volume shrinkage occurs at the corners of a BP. The volume shrinkage can be reduced using a large graphite plate embedded within the frame.

  15. Bismuth nanoparticle decorating graphite felt as a high-performance electrode for an all-vanadium redox flow battery.

    Science.gov (United States)

    Li, Bin; Gu, Meng; Nie, Zimin; Shao, Yuyan; Luo, Qingtao; Wei, Xiaoliang; Li, Xiaolin; Xiao, Jie; Wang, Chongmin; Sprenkle, Vincent; Wang, Wei

    2013-03-13

    Employing electrolytes containing Bi(3+), bismuth nanoparticles are synchronously electrodeposited onto the surface of a graphite felt electrode during operation of an all-vanadium redox flow battery (VRFB). The influence of the Bi nanoparticles on the electrochemical performance of the VRFB is thoroughly investigated. It is confirmed that Bi is only present at the negative electrode and facilitates the redox reaction between V(II) and V(III). However, the Bi nanoparticles significantly improve the electrochemical performance of VRFB cells by enhancing the kinetics of the sluggish V(II)/V(III) redox reaction, especially under high power operation. The energy efficiency is increased by 11% at high current density (150 mA·cm(-2)) owing to faster charge transfer as compared with one without Bi. The results suggest that using Bi nanoparticles in place of noble metals offers great promise as high-performance electrodes for VRFB application.

  16. Control of fermentation types in continuous-flow acidogenic reactors: effects of pH and redox potential

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The experiments were carried out in continuous-flow acidogenic reactors with molasses used as sub strate to study the effects of pH and redox potential on fermentation types. The conditions for each fermentation type were investigated at different experimental stages of start-up, pH-regulating and redox potential-regulating.The experiments confirmed that butyric acid-type fermentation would occur at pH > 6, the propionic acid-type fermentation at pH about 5.5 with Eh > - 278 mV, and the ethanol-type fermentation at pH < 4.5. A higher redox potential will lead to propionic acid-type fermentation because propionogens are facultative anaerobic bacteria.

  17. AGC of a multi-area power system under deregulated environment using redox flow batteries and interline power flow controller

    Directory of Open Access Journals (Sweden)

    Tulasichandra Sekhar Gorripotu

    2015-12-01

    Full Text Available In this paper, Proportional Integral Derivative with Filter (PIDF is proposed for Automatic Generation Control (AGC of a multi-area power system in deregulated environment. Initially, a two area four units thermal system without any physical constraints is considered and the gains of the PIDF controller are optimized employing Differential Evolution (DE algorithm using ITAE criterion. The superiority of proposed DE optimized PIDF controller over Fuzzy Logic controller is demonstrated. Then, to further improve the system performance, an Interline Power Flow Controller (IPFC is placed in the tie-line and Redox Flow Batteries (RFB is considered in the first area and the controller parameters are tuned. Additionally, to get an accurate insight of the AGC problem, important physical constraints such as Time Delay (TD and Generation Rate Constraints (GRC are considered and the controller parameters are retuned. The performance of proposed controller is evaluated under different operating conditions that take place in a deregulated power market. Further, the proposed approach is extended to a two area six units hydro thermal system. Finally, sensitivity analysis is performed by varying the system parameters and operating load conditions from their nominal values.

  18. Model of a vanadium redox flow battery with an anion exchange membrane and a Larminie-correction

    Science.gov (United States)

    Wandschneider, F. T.; Finke, D.; Grosjean, S.; Fischer, P.; Pinkwart, K.; Tübke, J.; Nirschl, H.

    2014-12-01

    Membranes are an important part of vanadium redox flow battery cells. Most cell designs use Nafion®-type membranes which are cation exchange membranes. Anion exchange membranes are reported to improve cell performance. A model for a vanadium redox flow battery with an anion exchange membrane is developed. The model is then used to calculate terminal voltages for open circuit and charge-discharge conditions. The results are compared to measured data from a laboratory test cell with 40 cm2 active membrane area. For higher charge and discharge currents, an empirical correction for the terminal voltage is proposed. The model geometry comprises the porous electrodes and the connected pipes, allowing a study of the flow in the entrance region for different state-of-charges.

  19. Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries.

    Science.gov (United States)

    Doris, Sean E; Ward, Ashleigh L; Baskin, Artem; Frischmann, Peter D; Gavvalapalli, Nagarjuna; Chénard, Etienne; Sevov, Christo S; Prendergast, David; Moore, Jeffrey S; Helms, Brett A

    2017-02-01

    Intermittent energy sources, including solar and wind, require scalable, low-cost, multi-hour energy storage solutions in order to be effectively incorporated into the grid. All-Organic non-aqueous redox-flow batteries offer a solution, but suffer from rapid capacity fade and low Coulombic efficiency due to the high permeability of redox-active species across the battery's membrane. Here we show that active-species crossover is arrested by scaling the membrane's pore size to molecular dimensions and in turn increasing the size of the active material above the membrane's pore-size exclusion limit. When oligomeric redox-active organics (RAOs) were paired with microporous polymer membranes, the rate of active-material crossover was reduced more than 9000-fold compared to traditional separators at minimal cost to ionic conductivity. This corresponds to an absolute rate of RAO crossover of less than 3 μmol cm(-2)  day(-1) (for a 1.0 m concentration gradient), which exceeds performance targets recently set forth by the battery industry. This strategy was generalizable to both high and low-potential RAOs in a variety of non-aqueous electrolytes, highlighting the versatility of macromolecular design in implementing next-generation redox-flow batteries.

  20. A mixed acid based vanadium-cerium redox flow battery with a zero-gap serpentine architecture

    Science.gov (United States)

    Leung, P. K.; Mohamed, M. R.; Shah, A. A.; Xu, Q.; Conde-Duran, M. B.

    2015-01-01

    This paper presents the performance of a vanadium-cerium redox flow battery using conventional and zero-gap serpentine architectures. Mixed-acid solutions based on methanesulfonate-sulfate anions (molar ratio 3:1) are used to enhance the solubilities of the vanadium (>2.0 mol dm-3) and cerium species (>0.8 mol dm-3), thus achieving an energy density (c.a. 28 Wh dm-3) comparable to that of conventional all-vanadium redox flow batteries (20-30 Wh dm-3). Electrochemical studies, including cyclic voltammetry and galvanostatic cycling, show that both vanadium and cerium active species are suitable for energy storage applications in these electrolytes. To take advantage of the high open-circuit voltage (1.78 V), improved mass transport and reduced internal resistance are facilitated by the use of zero-gap flow field architecture, which yields a power density output of the battery of up to 370 mW cm-2 at a state-of-charge of 50%. In a charge-discharge cycle at 200 mA cm-2, the vanadium-cerium redox flow battery with the zero-gap architecture is observed to discharge at a cell voltage of c.a. 1.35 V with a coulombic efficiency of up to 78%.

  1. 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl as a model organic redox active compound for nonaqueous flow batteries

    Science.gov (United States)

    Milshtein, Jarrod D.; Barton, John L.; Darling, Robert M.; Brushett, Fikile R.

    2016-09-01

    Nonaqueous redox flow batteries (NAqRFBs) that utilize redox active organic molecules are an emerging energy storage concept with the possibility of meeting grid storage requirements. Sporadic and uneven advances in molecular discovery and development, however, have stymied efforts to quantify the performance characteristics of nonaqueous redox electrolytes and flow cells. A need exists for archetypal redox couples, with well-defined electrochemical properties, high solubility in relevant electrolytes, and broad availability, to serve as probe molecules. This work investigates the 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl (AcNH-TEMPO) redox pair for such an application. We report the physicochemical and electrochemical properties of the reduced and oxidized compounds at dilute concentrations for electroanalysis, as well as moderate-to-high concentrations for RFB applications. Changes in conductivity, viscosity, and UV-vis absorbance as a function of state-of-charge are quantified. Cyclic voltammetry investigates the redox potential, reversibility, and diffusion coefficients of dilute solutions, while symmetric flow cell cycling determines the stability of the AcNH-TEMPO redox pair over long experiment times. Finally, single electrolyte flow cell studies demonstrate the utility of this redox couple as a platform chemistry for benchmarking NAqRFB performance.

  2. All-Iron Redox Flow Battery Tailored for Off-Grid Portable Applications.

    Science.gov (United States)

    Tucker, Michael C; Phillips, Adam; Weber, Adam Z

    2015-12-01

    An all-iron redox flow battery is proposed and developed for end users without access to an electricity grid. The concept is a low-cost battery which the user assembles, discharges, and then disposes of the active materials. The design goals are: (1) minimize upfront cost, (2) maximize discharge energy, and (3) utilize non-toxic and environmentally benign materials. These are different goals than typically considered for electrochemical battery technology, which provides the opportunity for a novel solution. The selected materials are: low-carbon-steel negative electrode, paper separator, porous-carbon-paper positive electrode, and electrolyte solution containing 0.5 m Fe2 (SO4 )3 active material and 1.2 m NaCl supporting electrolyte. With these materials, an average power density around 20 mW cm(-2) and a maximum energy density of 11.5 Wh L(-1) are achieved. A simple cost model indicates the consumable materials cost US$6.45 per kWh(-1) , or only US$0.034 per mobile phone charge.

  3. Sulfonated graphene oxide/nafion composite membrane for vanadium redox flow battery.

    Science.gov (United States)

    Kim, Byung Guk; Han, Tae Hee; Cho, Chang Gi

    2014-12-01

    Nafion is the most frequently used as the membrane material due to its good proton conductivity, and excellent chemical and mechanical stabilities. But it is known to have poor barrier property due to its well-developed water channels. In order to overcome this drawback, graphene oxide (GO) derivatives were introduced for Nafion composite membranes. Sulfonated graphene oxide (sGO) was prepared from GO. Both sGO and GO were treated each with phenyl isocyanate and transformed into corresponding isGO and iGO in order to promote miscibility with Nafion. Then composite membranes were obtained, and the adaptability as a membrane for vanadium redox flow battery (VRFB) was investigated in terms of proton conductivity and vanadium permeability. Compared to a pristine Nafion, proton conductivities of both isGO/Nafion and iGO/Nafion membranes showed less temperature sensitivity. Both membranes also showed quite lower vanadium permeability at room temperature. Selectivity of the membrane was the highest for isGO/Nafion and the lowest for the pristine Nafion.

  4. SPEEK/PVDF/PES Composite as Alternative Proton Exchange Membrane for Vanadium Redox Flow Batteries

    Science.gov (United States)

    Fu, Zhimin; Liu, Jinying; Liu, Qifeng

    2016-01-01

    A membrane consisting of a blend of sulfonated poly(ether ether ketone) (SPEEK), poly(vinylidene fluoride) (PVDF), and poly(ether sulfone) (PES) has been fabricated and used as an ion exchange membrane for application in vanadium redox flow batteries (VRBs). The vanadium ion permeability of the SPEEK/PVDF/PES membrane was one order of magnitude lower than that of Nafion 117 membrane. The low-cost composite membrane exhibited better performance than Nafion 117 membrane at the same operating condition. A VRB single cell with SPEEK/PVDF/PES membrane showed significantly lower capacity loss, higher coulombic efficiency (>95%), and higher energy efficiency (>82%) compared with Nafion 117 membrane. In the self-discharge test, the duration of the cell with the SPEEK/PVDF/PES membrane was nearly two times longer than that with Nafion 117 membrane. Considering these good properties and its low cost, SPEEK/PVDF/PES membrane is expected to have excellent commercial prospects as an ion exchange membrane for VRB systems.

  5. Poly(phenyl sulfone) anion exchange membranes with pyridinium groups for vanadium redox flow battery applications

    Science.gov (United States)

    Zhang, Bengui; Zhang, Enlei; Wang, Guosheng; Yu, Ping; Zhao, Qiuxia; Yao, Fangbo

    2015-05-01

    To develop high performance and cost-effective membranes with low permeability of vanadium ions for vanadium redox flow battery (VRFB) application, poly(phenyl sulfone) anion exchange membranes with pyridinium groups (PyPPSU) are prepared and first investigated for VRFB application. PyPPSU membranes show much lower vanadium ions permeability (0.07 × 10-7-0.15 × 10-7 cm2 min-1) than that of Nafion 117 membrane (31.3 × 10-7 cm2 min-1). As a result, the self-discharge duration of the VRFB cell with PyPPSU membrane (418 h) is about four times longer than that of VRFB cell with Nafion 117 membrane (110 h). Furthermore, the VRFB cell with PyPPSU membrane exhibits higher battery efficiency (coulombic efficiency of 97.8% and energy efficiency of 80.2%) compare with that of VRFB cell with Nafion 117 membrane (coulombic efficiency of 96.1% and energy efficiency of 77.2%) at a high current density of 100 mA cm-2. In addition, PyPPSU membrane exhibits stable performance in 100-cycle test. The results indicate that PyPPSU membrane is high performance and low-cost alternative membrane for VRFB application.

  6. An alternative low-loss stack topology for vanadium redox flow battery: Comparative assessment

    Science.gov (United States)

    Moro, Federico; Trovò, Andrea; Bortolin, Stefano; Del, Davide, , Col; Guarnieri, Massimo

    2017-02-01

    Two vanadium redox flow battery topologies have been compared. In the conventional series stack, bipolar plates connect cells electrically in series and hydraulically in parallel. The alternative topology consists of cells connected in parallel inside stacks by means of monopolar plates in order to reduce shunt currents along channels and manifolds. Channelled and flat current collectors interposed between cells were considered in both topologies. In order to compute the stack losses, an equivalent circuit model of a VRFB cell was built from a 2D FEM multiphysics numerical model based on Comsol®, accounting for coupled electrical, electrochemical, and charge and mass transport phenomena. Shunt currents were computed inside the cells with 3D FEM models and in the piping and manifolds by means of equivalent circuits solved with Matlab®. Hydraulic losses were computed with analytical models in piping and manifolds and with 3D numerical analyses based on ANSYS Fluent® in the cell porous electrodes. Total losses in the alternative topology resulted one order of magnitude lower than in an equivalent conventional battery. The alternative topology with channelled current collectors exhibits the lowest shunt currents and hydraulic losses, with round-trip efficiency higher by about 10%, as compared to the conventional topology.

  7. Optimal AGC with redox flow batteries in multi-area restructured power systems

    Directory of Open Access Journals (Sweden)

    Yogendra Arya

    2016-09-01

    Full Text Available This paper attempts to investigate the effect of Redox flow batteries (RFB in Automatic Generation Control (AGC of multi-area restructured power systems. Initially, a two-area restructured thermal power system is investigated. For the analysis, optimal AGC regulators (OARs are designed employing performance index minimization criterion. The advantages of the OARs are shown by comparing the results with Genetic Algorithm (GA based integral controllers for the same restructured system. MATLAB simulation results further demonstrate significant improvements in the dynamic performance of the system with RFB. System stability enhancement with OARs/RFB is outlined by conducting the system modes study. The study is additionally extended to a more realistic two-area multi-source thermal–hydro–gas restructured system with/without RFB. To add nonlinearities, appropriate generation rate constraints (GRCs are considered for the thermal, hydro and gas plants. Results verify that OARs are able to satisfy the AGC requirement under varied power transactions taking place in an open power market. The robustness of OARs is demonstrated by sensitivity analysis, which is carried out with wide variation in initial loading, system parameters and magnitude/position of the uncontracted power demands. Finally, the study is extended to a two-area multi-source thermal–hydro power system with/without considering RFB.

  8. Zirconium oxide nanotube-Nafion composite as high performance membrane for all vanadium redox flow battery

    Science.gov (United States)

    Aziz, Md. Abdul; Shanmugam, Sangaraju

    2017-01-01

    A high-performance composite membrane for vanadium redox flow battery (VRB) consisting of ZrO2 nanotubes (ZrNT) and perfluorosulfonic acid (Nafion) was fabricated. The VRB operated with a composite (Nafion-ZrNT) membrane showed the improved ion-selectivity (ratio of proton conductivity to permeability), low self-discharge rate, high discharge capacity and high energy efficiency in comparison with a pristine commercial Nafion-117 membrane. The incorporation of zirconium oxide nanotubes in the Nafion matrix exhibits high proton conductivity (95.2 mS cm-1) and high oxidative stability (99.9%). The Nafion-ZrNT composite membrane exhibited low vanadium ion permeability (3.2 × 10-9 cm2 min-1) and superior ion selectivity (2.95 × 107 S min cm-3). The VRB constructed with a Nafion-ZrNT composite membrane has lower self-discharge rate maintaining an open-circuit voltage of 1.3 V for 330 h relative to a pristine Nafion membrane (29 h). The discharge capacity of Nafion-ZrNT membrane (987 mAh) was 3.5-times higher than Nafion-117 membrane (280 mAh) after 100 charge-discharge cycles. These superior properties resulted in higher coulombic and voltage efficiencies with Nafion-ZrNT membranes compared to VRB with Nafion-117 membrane at a 40 mA cm-2 current density.

  9. Hierarchical porous carbon toward effective cathode in advanced zinc-cerium redox flow battery

    Institute of Scientific and Technical Information of China (English)

    谢志鹏; 杨斌; 蔡定建; 杨亮

    2014-01-01

    Advanced zinc-cerium redox flow battery (ZCRFB) is a large-scale energy storage system which plays a significant role in the application of new energy sources. The requirement of superior cathode with high acitivity and fast ion diffusion is a hierarchical porous structure, which was synthesized in this work by a method in which both hard template and soft template were used. The structure and the performance of the cathode prepared here were characterized and evaluated by a variety of techniques such as scan-ning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), cyclic voltam-metry (CV), linear sweep voltammetry (LSV), and chronoamperometry (CA). There were mainly three types of pore size within the hierarchical porous carbon:2μm, 80 nm, and 10 nm. The charge capacity of the cell using hierarchical porous carbon (HPC) as posi-tive electrode was obviously larger than that using carbon felt;the former was 665.5 mAh with a coulombic efficiency of 89.0%and an energy efficiency of 79.0%, whereas the latter was 611.1 mAh with a coulombic efficiency of 81.5%and an energy efficiency of 68.6%. In addition, performance of the ZCRFB using HPC as positive electrode showed a good stability over 50 cycles. These results showed that the hierarchical porous carbon was superior over the carbon felt for application in ZCRFB.

  10. A transient electrochemical model incorporating the Donnan effect for all-vanadium redox flow batteries

    Science.gov (United States)

    Lei, Y.; Zhang, B. W.; Bai, B. F.; Zhao, T. S.

    2015-12-01

    In a typical all-vanadium redox flow battery (VRFB), the ion exchange membrane is directly exposed in the bulk electrolyte. Consequently, the Donnan effect occurs at the membrane/electrolyte (M/E) interfaces, which is critical for modeling of ion transport through the membrane and the prediction of cell performance. However, unrealistic assumptions in previous VRFB models, such as electroneutrality and discontinuities of ionic potential and ion concentrations at the M/E interfaces, lead to simulated results inconsistent with the theoretical analysis of ion adsorption in the membrane. To address this issue, this work proposes a continuous-Donnan effect-model using the Poisson equation coupled with the Nernst-Planck equation to describe variable distributions at the M/E interfaces. A one-dimensional transient VRFB model incorporating the Donnan effect is developed. It is demonstrated that the present model enables (i) a more realistic simulation of continuous distributions of ion concentrations and ionic potential throughout the membrane and (ii) a more comprehensive estimation for the effect of the fixed charge concentration on species crossover across the membrane and cell performance.

  11. Electrochemical Properties of Current Collector in the All-vanadium Redox Flow Battery

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Gan-Jin; Oh, Yong-Hwan; Ryu, Cheol-Hwi [Hoseo University, Asan (Korea, Republic of); Choi, Ho-Sang [Kyungil University, Gyeongsan, (Korea, Republic of)

    2014-04-15

    Two commercial carbon plates were evaluated as a current collector (bipolar plate) in the all vanadium redox-flow battery (V-RFB). The performance properties of V-RFB were test in the current density of 60 mA/cm{sup 2}. The electromotive forces (OCV at SOC 100%) of V-RFB using A and B current collector were 1.47 V and 1.54 V. The cell resistance of V-RFB using A current collector was 4.44-5.00 Ω·cm{sup 2} and 3.28-3.75 Ω·cm{sup 2} for charge and discharge, respectively. The cell resistance of V-RFB using B current collector was 4.19-4.42Ω·cm{sup 2} and 4.71-5.49Ω·cm{sup 2} for charge and discharge, respectively. The performance of V-RFB using each current collector was evaluated. The performance of V-RFB using A current collector was 93.1%, 76.8% and 71.4% for average current efficiency, average voltage efficiency and average energy efficiency, respectively. The performance of V-RFB using B current collector was 96.4%, 73.6% and 71.0% for average current efficiency, average voltage efficiency and average energy efficiency, respectively.

  12. Investigation of crossover processes in a unitized bidirectional vanadium/air redox flow battery

    Science.gov (United States)

    grosse Austing, Jan; Nunes Kirchner, Carolina; Komsiyska, Lidiya; Wittstock, Gunther

    2016-02-01

    In this paper the losses in coulombic efficiency are investigated for a vanadium/air redox flow battery (VARFB) comprising a two-layered positive electrode. Ultraviolet/visible (UV/Vis) spectroscopy is used to monitor the concentrations cV2+ and cV3+ during operation. The most likely cause for the largest part of the coulombic losses is the permeation of oxygen from the positive to the negative electrode followed by an oxidation of V2+ to V3+. The total vanadium crossover is followed by inductively coupled plasma mass spectroscopy (ICP-MS) analysis of the positive electrolyte after one VARFB cycle. During one cycle 6% of the vanadium species initially present in the negative electrolyte are transferred to the positive electrolyte, which can account at most for 20% of the coulombic losses. The diffusion coefficients of V2+ and V3+ through Nafion® 117 are determined as DV2+ ,N 117 = 9.05 ·10-6 cm2 min-1 and DV3+ ,N 117 = 4.35 ·10-6 cm2 min-1 and are used to calculate vanadium crossover due to diffusion which allows differentiation between vanadium crossover due to diffusion and migration/electroosmotic convection. In order to optimize coulombic efficiency of VARFB, membranes need to be designed with reduced oxygen permeation and vanadium crossover.

  13. Investigating the air oxidation of V(II) ions in a vanadium redox flow battery

    Science.gov (United States)

    Ngamsai, Kittima; Arpornwichanop, Amornchai

    2015-11-01

    The air oxidation of vanadium (V(II)) ions in a negative electrolyte reservoir is a major side reaction in a vanadium redox flow battery (VRB), which leads to electrolyte imbalance and self-discharge of the system during long-term operation. In this study, an 80% charged negative electrolyte solution is employed to investigate the mechanism and influential factors of the reaction in a negative-electrolyte reservoir. The results show that the air oxidation of V(II) ions occurs at the air-electrolyte solution interface area and leads to a concentration gradient of vanadium ions in the electrolyte solution and to the diffusion of V(II) and V(III) ions. The effect of the ratio of the electrolyte volume to the air-electrolyte solution interface area and the concentrations of vanadium and sulfuric acid in an electrolyte solution is investigated. A higher ratio of electrolyte volume to the air-electrolyte solution interface area results in a slower oxidation reaction rate. The high concentrations of vanadium and sulfuric acid solution also retard the air oxidation of V(II) ions. This information can be utilized to design an appropriate electrolyte reservoir for the VRB system and to prepare suitable ingredients for the electrolyte solution.

  14. Composite blend polymer membranes with increased proton selectivity and lifetime for vanadium redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Dongyang; Kim, Soowhan; Sprenkle, Vincent L.; Hickner, Michael A.

    2013-06-01

    Composite membranes based on sulfonated fluorinated poly(arylene ether) (SFPAE) and poly(vinylidene fluoride-co-hexafluoropropene) (P(VDF-co-HFP)) were prepared with various contents of P(VDF-co-HFP) for vanadium redox flow battery (VRFB) applications. The compatibility and interaction of SFPAE and P(VDF-co-HFP) were characterized by atomic force microscopy, differential scanning calorimetry, and Fourier transform infrared spectroscopy. The water uptake, mechanical properties, thermal property, proton conductivity, VO2+ permeability and cell performance of the composite membranes were investigated in detail and compared to the pristine SFPAE membrane. It was found that SFPAE had good compatibility with P(VDF-co-HFP) and the incorporation of P(VDF-co-HFP) increased the mechanical properties, thermal property, and proton selectivity of the materials effectively. An SFPAE composite membrane with 10 wt.% P(VDF-co-HFP) exhibited a 44% increase in VRFB cell lifetime as compared to a cell with a pure SFPAE membrane. Therefore, the P(VDF-co-HFP) blending approach is a facile method for producing low-cost, high-performance VRFB membranes.

  15. Flat flow profiles achieved with microfluidics generated by redox-magnetohydrodynamics.

    Science.gov (United States)

    Sahore, V; Fritsch, I

    2013-12-17

    Horizontal flow profiles having uniform velocities (3-13% RSD) at fixed heights across 0.5, 2.0, and 5.6 mm widths, with magnitudes of ≤124 μm/s, can be sustained along a ∼25.0 mm path using redox-magnetohydrodynamics (MHD) microfluidic pumping in a small volume (14.3 mm wide × 27.0 mm long × 620 μm high) on a chip. Uniform velocity profiles are important in moving volume elements without shape distortion for assays and separations for lab-on-a-chip applications. Fluid movement resulting from the MHD force (FB = j × B) was monitored with video microscopy by tracking 10 μm, polystyrene latex beads mixed into the solution. The ionic current density, j, was generated in 0.095 M K3Fe(CN)6, 0.095 M K4Fe(CN)6, and 0.095 M KCl by applying a constant current across a 0.5, 2.0, or 5.6 mm gap between an anode-cathode pair of electrodes, consisting of one to four shorted parallel, coplanar gold microbands [each 25.0 mm × 98 μm × ∼100 nm (thickness), and separated by 102 μm] fabricated on an insulated silicon substrate. By shorting the increasing numbers of microbands together, increasing currents (118, 180, 246, and 307 μA) could be applied without electrode damage, and the impact of ionic current density gradients on velocity profiles over the anodes and cathodes could also be investigated. The magnetic field, B, was produced with a 0.36 T NdFeB permanent magnet beneath the chip. Data analysis was performed using particle image velocimetry software. A vertical flow profile was also obtained in the middle of the 5.6 mm gap.

  16. 全钒液流电池研究进展%Research Progress of Vanadium Redox Flow Battery

    Institute of Scientific and Technical Information of China (English)

    朱厚军; 郎俊山

    2012-01-01

    The principle and characteristics of vanadium redox flow battery (VRB) are introduced. The R&D status in China and abroad and research hotspot of VRB are reviewed, and the development expectation is pointed out in this paper.%介绍了全钒液流电池的原理和特点,综述了国内外研究发展现状和研究热点,展望了发展前景。

  17. Nanoporous Polytetrafluoroethylene/Silica Composite Separator as a High-Performance All-Vanadium Redox Flow Battery Membrane

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Xiaoliang; Nie, Zimin; Luo, Qingtao; Li, Bin; Chen, Baowei; Simmons, Kevin L.; Sprenkle, Vincent L.; Wang, Wei

    2013-09-02

    Driven by the motivation of searching for low-cost membrane alternatives, a novel nanoporous polytetrafluoroethylene/silica composite separator has been prepared and evaluated for its use in all-vanadium mixed-acid redox flow battery. This separator consisting of silica particles enmeshed in a polytetrafluoroethylene fibril matrix has no ion exchange capacity and is featured with unique nanoporous structures, which function as the ion transport channels in redox flow battery operation, with an average pore size of 38nm and a porosity of 48%. This separator has produced excellent electrochemical performance in the all-vanadium mixed-acid system with energy efficiency delivery comparable to Nafion membrane and superior rate capability and temperature tolerance. The separator also demonstrates an exceptional capacity retention capability over extended cycling, offering additional operational latitude towards conveniently mitigating the capacity decay that is inevitable for Nafion. Because of the inexpensive raw materials and simple preparation protocol, the separator is particularly low-cost, estimated to be at least an order of magnitude more inexpensive than Nafion. Plus the proven chemical stability due to the same backbone material as Nafion, this separator possesses a good combination of critical membrane requirements and shows great potential to promote market penetration of the all-vanadium redox flow battery by enabling significant reduction of capital and cycle costs.

  18. 3D imaging of flow patterns in an internally-pumped microfluidic device: redox magnetohydrodynamics and electrochemically-generated density gradients.

    Science.gov (United States)

    Gao, Feng; Kreidermacher, Adam; Fritsch, Ingrid; Heyes, Colin D

    2013-05-07

    Redox magnetohydrodynamics (MHD) is a promising technique for developing new electrochemical-based microfluidic flow devices with unique capabilities, such as easily switching flow direction and adjusting flow speeds and flow patterns as well as avoiding bubble formation. However, a detailed description of all the forces involved and predicting flow patterns in confined geometries is lacking. In addition to redox-MHD, density gradients caused by the redox reactions also play important roles. Flow in these devices with small fluid volumes has mainly been characterized by following microbead motion by optical microscopy either by particle tracking velocimetry (PTV) or by processing the microbead images by particle image velocimetry (PIV) software. This approach has limitations in spatial resolution and dimensionality. Here we use fluorescence correlation spectroscopy (FCS) to quantitatively and accurately measure flow speeds and patterns in the ~5-50 μm/s range in redox-MHD-based microfluidic devices, from which 3D flow maps are obtained with a spatial resolution down to 2 μm. The 2 μm spatial resolution flow speeds map revealed detailed flow profiles during redox-MHD in which the velocity increases linearly from above the electrode and reaches a plateau across the center of the cell. By combining FCS and video-microscopy (with PTV and PIV processing approaches), we are able to quantify a vertical flow of ~10 μm/s above the electrodes as a result of density gradients caused by the redox reactions and follow convection flow patterns. Overall, combining FCS, PIV, and PTV analysis of redox-MHD is a powerful combination to more thoroughly characterize the underlying forces in these promising microfluidic devices.

  19. 全钒液流电池流场模拟与优化%Simulation and optimization of flow field of all vanadium redox flow battery

    Institute of Scientific and Technical Information of China (English)

    马相坤; 张华民; 邢枫; 孙晨曦

    2012-01-01

    The structure of flow field is one of the key factors that affect the performance of all vanadium redox flow battery. A two-dimensional model for the flow field of all vanadium redox flow battery was proposed based on CFD technology. The distribution of electrolyte in electrode in the specified structure of flow field could be obtained by the proposed model. The flow field was optimized to enhance the distributional uniformity of electrolyte in electrode. The conclusion indicates that the distributional uniformity can be improved by increasing the number of distributional ports and extending the length of inlet vertical channel. Meanwhile, the effects of width of distributional channel and flow rate on distributional uniformity of electrolyte were considered. The conclusion has great guidance for the design of flow field of all vanadium redox flow battery.%流场结构是影响全钒液流电池性能的关键问题之一.基于CFD技术建立全钒液流电池流场的二维数学模型,通过模拟获得在给定流场结构下电解液在石墨毡电极内的分布规律,优化流场结构提高电解液在石墨毡电极内分布的均匀性.研究结果表明,增加分配口个数和延长入口竖直主流道的长度能够有效提高电解液的分配均匀性;同时考察了分配流道宽度和流量对电解液分配均匀性的影响;所得结论对全钒液流电池流场结构设计具有重要的指导意义.

  20. Influence of bulk fibre properties of PAN-based carbon felts on their performance in vanadium redox flow batteries

    Science.gov (United States)

    Schweiss, Rüdiger

    2015-03-01

    Polyacrylonitrile (PAN)-based carbon felts with different fibre properties were studied in terms of their suitability as porous flow-through electrode materials in all vanadium redox flow batteries. The crystallinity and their bulk hetero element content (in particular nitrogen) of the carbon fibres was shown to produce a significant effect on the electrocatalytical properties of the electrodes towards vanadium species. Similar effects were seen on the capacity losses associated with concomitant hydrogen evolution. Adjustments of fibre properties offer the potential of manufacturing improved electrode materials, potentially without additional steps such as surface activation or decoration with catalytically active species.

  1. Investigating redox processes under diffusive and advective flow conditions using a coupled omics and synchrotron approach

    Science.gov (United States)

    Kemner, K. M.; Boyanov, M.; Flynn, T. M.; O'Loughlin, E. J.; Antonopoulos, D. A.; Kelly, S.; Skinner, K.; Mishra, B.; Brooks, S. C.; Watson, D. B.; Wu, W. M.

    2015-12-01

    FeIII- and SO42--reducing microorganisms and the mineral phases they produce have profound implications for many processes in aquatic and terrestrial systems. In addition, many of these microbially-catalysed geochemical transformations are highly dependent upon introduction of reactants via advective and diffusive hydrological transport. We have characterized microbial communities from a set of static microcosms to test the effect of ethanol diffusion and sulfate concentration on UVI-contaminated sediment. The spatial distribution, valence states, and speciation of both U and Fe were monitored in situ throughout the experiment by synchrotron x-ray absorption spectroscopy, in parallel with solution measurements of pH and the concentrations of sulfate, ethanol, and organic acids. After reaction initiation, a ~1-cm thick layer of sediment near the sediment-water (S-W) interface became visibly dark. Fe XANES spectra of the layer were consistent with the formation of FeS. Over the 4 year duration of the experiment, U LIII-edge XANES indicated reduction of U, first in the dark layer and then throughout the sediment. Next, the microcosms were disassembled and samples were taken from the overlying water and different sediment regions. We extracted DNA and characterized the microbial community by sequencing 16S rRNA gene amplicons with the Illumina MiSeq platform and found that the community evolved from its originally homogeneous composition, becoming significantly spatially heterogeneous. We have also developed an x-ray accessible column to probe elemental transformations as they occur along the flow path in a porous medium with the purpose of refining reactive transport models (RTMs) that describe coupled physical and biogeochemical processes in environmental systems. The elemental distribution dynamics and the RTMs of the redox driven processes within them will be presented.

  2. Species Transport Mechanisms Governing Crossover and Capacity Loss in Vanadium Redox Flow Batteries

    Science.gov (United States)

    Agar, Ertan

    Vanadium redox flow batteries (VRFBs) are an emerging energy storage technology that offers unique advantages for grid-scale energy storage due to their flexible design and decoupled power/energy feature. Despite their popularity, a series of technical challenges hinder their widespread implementation. Among these, capacity loss (i.e., loss of energy storage capability) due to the undesired species crossover across the membrane has been identified as the key issue limiting the longevity of these systems. This issue is primarily governed by the properties of the membrane and can be mitigated by using proper membrane architectures with desired features. Presently, identifying proper membrane architectures for VRFB systems is hampered by the lack of a fundamental understanding of the nature of species transport mechanisms and how they are related to the membrane properties and key operating conditions. This Ph.D. study seeks to address this critical challenge by exploring the fundamental mechanisms responsible for species transport within the membrane. The overall objective of this dissertation study is to establish a fundamental understanding of the multi-ionic transport in VRFB membranes by investigating the ionic transport mechanisms responsible for crossover, and utilize this understanding to reveal the role of membrane properties and operating conditions on the capacity loss. To achieve these goals, a combined experimental and computational study was designed. An experimentally validated, 2-D, transient VRFB model that can track the vanadium crossover and capture the related capacity loss was developed. In addition to the model, several electrochemical techniques were used to characterize different types of membrane and study the effects of various operating conditions on the species crossover. Using these computational and experimental tools, an in-depth understanding of the species transport mechanisms within the membrane and how they are related to membrane

  3. Amino-silica modified Nafion membrane for vanadium redox flow battery

    Science.gov (United States)

    Lin, Chien-Hong; Yang, Ming-Chien; Wei, Hwa-Jou

    2015-05-01

    A hybrid membrane of Nafion/amino-silica (amino-SiO2) for vanadium redox flow battery (VRB) systems is prepared via the sol-gel method to improve the selectivity of the Nafion membrane, to reduce the crossover of vanadium ions, and to decrease water transfer across the membranes. The sulfonated pores of the pristine Nafion membrane are filled with amino-SiO2 nanoparticles localized by electrostatic interaction. The permeability of vanadium ions through the Nafion/amino-SiO2 hybrid membrane is determined by electrometric titration. The results indicate the crossover of vanadium ions through the hybrid membrane is 26.8% of the pristine Nafion membrane. The presence of amino-SiO2 in the hybrid membrane is verified by X-ray photoelectron spectroscopy (XPS). Nafion/amino-SiO2 hybrid membrane exhibits through plane conductivity about the same as the pristine Nafion membrane. The ion exchange capacity (IEC) of the hybrid membrane is 9.4% higher than that of the pristine Nafion membrane. In addition, Nafion/amino-SiO2 hybrid membrane exhibits a higher coulombic efficiency (CE), voltage efficiency (VE), and energy efficiency (EE) over a range of current densities from 20 to 80 mA cm-2. The performance of VRB with Nafion/amino-SiO2 hybrid membrane varies little around a charge-discharge current density of 80 mA cm-2 for 150 cycles. Thus, the Nafion/amino-SiO2 hybrid membrane can suppress the vanadium ions crossover in VRB.

  4. Understanding Aqueous Electrolyte Stability through Combined Computational and Magnetic Resonance Spectroscopy: A Case Study on Vanadium Redox Flow Battery Electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Vijayakumar, M.; Nie, Zimin; Walter, Eric D.; Hu, Jian Z.; Liu, Jun; Sprenkle, Vincent L.; Wang, Wei

    2015-02-01

    Redox flow battery (RFB) is a promising candidate for energy storage component in designing resilient grid scale power supply due to the advantage of the separation of power and energy. However, poorly understood chemical and thermal stability issues of electrolytes currently limit the performance of RFB. Designing of high performance stable electrolytes requires comprehensive knowledge about the molecular level solvation structure and dynamics of their redox active species. The molecular level understanding of detrimental V2O5 precipitation process led to successful designing of mixed acid based electrolytes for vanadium redox flow batteries (VRFB). The higher stability of mixed acid based electrolytes is attributed to the choice of hydrochloric acid as optimal co-solvent, which provides chloride anions for ligand exchange process in vanadium solvation structure. The role of chloride counter anion on solvation structure and dynamics of vanadium species were studied using combined magnetic resonance spectroscopy and DFT based theoretical methods. Finally, the solvation phenomenon of multiple vanadium species and their impact on VRFB electrolyte chemical stability were discussed.

  5. Study and characterization of positive electrolytes for application in the aqueous all-copper redox flow battery

    Science.gov (United States)

    Sanz, Laura; Lloyd, David; Magdalena, Eva; Palma, Jesús; Anderson, Marc; Kontturi, Kyösti

    2015-03-01

    In recent studies, the employment of the aqueous solution system comprised of Cu(II)-Cu(I)-Cl system was addressed for massive energy storage in Redox Flow Batteries (RFBs) [5,6], providing important practical advantages compared to the widespread all-vanadium or Zn/Br systems [5]. The substitution of vanadium electrolytes by copper-chloride electrolytes allows the simplification of the process and notably reduces the cost, allowing for a better commercialization of RFBs. Here, a complete physico-chemical characterization of positive copper electrolytes and their electrochemical performance using different supporting electrolytes, HCl and CaCl2, is presented. Once the physical properties and the electrochemical performance of each one of the supporting electrolytes were determined, the final composition of supporting electrolyte for this Cu(II)/Cu(I) redox couple could be optimized by mixing different sources of chloride, regarding its practical application in the all-copper RFB.

  6. Polarization curve measurements combined with potential probe sensing for determining current density distribution in vanadium redox-flow batteries

    Science.gov (United States)

    Becker, Maik; Bredemeyer, Niels; Tenhumberg, Nils; Turek, Thomas

    2016-03-01

    Potential probes are applied to vanadium redox-flow batteries for determination of effective felt resistance and current density distribution. During the measurement of polarization curves in 100 cm2 cells with different carbon felt compression rates, alternating potential steps at cell voltages between 0.6 V and 2.0 V are applied. Polarization curves are recorded at different flow rates and states of charge of the battery. Increasing compression rates lead to lower effective felt resistances and a more uniform resistance distribution. Low flow rates at high or low state of charge result in non-linear current density distribution with high gradients, while high flow rates give rise to a nearly linear behavior.

  7. Direct Conversion of Wheat Straw into Electricity with a Biomass Flow Fuel Cell Mediated by Two Redox Ion Pairs.

    Science.gov (United States)

    Gong, Jian; Liu, Wei; Du, Xu; Liu, Congmin; Zhang, Zhe; Sun, Feifei; Yang, Le; Xu, Dong; Guo, Hua; Deng, Yulin

    2017-02-08

    In this paper, a biomass flow fuel cell to directly convert wheat straw to electricity at low temperature (80-90 °C) and atmospheric pressure is presented. Two redox ion pairs, Fe(3+) /Fe(2+) and VO2(+) /VO(2+) , acting as redox catalysts and charge carriers, were used in the anode and cathode flow tanks, respectively. The wheat straw was first oxidized by Fe(3+) in the anode tank at approximately 100 °C. The reduced Fe(2+) in the anode was used to construct a fuel cell with VO2(+) in the cathode. The VO2(+) ions were reduced to VO(2+) and regenerated to VO2(+) by oxygen oxidation. The wheat straw flow fuel cell showed a power output of 100 mW cm(-2) . Mediated with liquid Fe(3+) carriers, the solid powder of wheat straw could be gradually degraded into low-molecular-weight organic molecules and even oxidized to CO2 at the anode without using noble-metal catalysts. The overpotential for the electrodes of the flow fuel cell was examined and the energy cost was estimated.

  8. Performance and cost characteristics of multi-electron transfer, common ion exchange non-aqueous redox flow batteries

    Science.gov (United States)

    Laramie, Sydney M.; Milshtein, Jarrod D.; Breault, Tanya M.; Brushett, Fikile R.; Thompson, Levi T.

    2016-09-01

    Non-aqueous redox flow batteries (NAqRFBs) have recently received considerable attention as promising high energy density, low cost grid-level energy storage technologies. Despite these attractive features, NAqRFBs are still at an early stage of development and innovative design techniques are necessary to improve performance and decrease costs. In this work, we investigate multi-electron transfer, common ion exchange NAqRFBs. Common ion systems decrease the supporting electrolyte requirement, which subsequently improves active material solubility and decreases electrolyte cost. Voltammetric and electrolytic techniques are used to study the electrochemical performance and chemical compatibility of model redox active materials, iron (II) tris(2,2‧-bipyridine) tetrafluoroborate (Fe(bpy)3(BF4)2) and ferrocenylmethyl dimethyl ethyl ammonium tetrafluoroborate (Fc1N112-BF4). These results help disentangle complex cycling behavior observed in flow cell experiments. Further, a simple techno-economic model demonstrates the cost benefits of employing common ion exchange NAqRFBs, afforded by decreasing the salt and solvent contributions to total chemical cost. This study highlights two new concepts, common ion exchange and multi-electron transfer, for NAqRFBs through a demonstration flow cell employing model active species. In addition, the compatibility analysis developed for asymmetric chemistries can apply to other promising species, including organics, metal coordination complexes (MCCs) and mixed MCC/organic systems, enabling the design of low cost NAqRFBs.

  9. Resolving Losses at the Negative Electrode in All-Vanadium Redox Flow Batteries Using Electrochemical Impedance Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Che Nan [ORNL; Delnick, Frank M [ORNL; Aaron, D [University of Tennessee, Knoxville (UTK); Mench, Matthew M [ORNL; Zawodzinski, Thomas A [ORNL

    2014-01-01

    We present an in situ electrochemical technique for the quantitative measurement and resolution of the ohmic, charge transfer and diffusion overvoltages at the negative electrode of an all-vanadium redox flow battery (VRFB) using electrochemical impedance spectroscopy (EIS). The mathematics describing the complex impedance of the V+2/V+3 redox reaction is derived and matches the experimental data. The voltage losses contributed by each process have been resolved and quantified at various flow rates and electrode thicknesses as a function of current density during anodic and cathodic polarization. The diffusion overvoltage was affected strongly by flow rate while the charge transfer and ohmic losses were invariant. On the other hand, adopting a thicker electrode significantly changed both the charge transfer and diffusion losses due to increased surface area. Furthermore, the Tafel plot obtained from the impedance resolved charge transfer overvoltage yielded the geometric exchange current density, anodic and cathodic Tafel slopes (135 5 and 121 5 mV/decade respectively) and corresponding transfer coefficients = 0.45 0.02 and = 0.50 0.02 in an operating cell.

  10. A zinc–iron redox-flow battery under $100 per kW h of system capital cost

    OpenAIRE

    Gong, Ke; Ma, Xiaoya; Kuttler, Kevin J.; Grunewald, Jonathan B.; Yeager, Kelsey L.; Bazant, Martin Z.; Gu, Shuang; Yan, Yushan; Conforti, Kameron Michael

    2015-01-01

    Redox flow batteries (RFBs) are one of the most promising scalable electricity-storage systems to address the intermittency issues of renewable energy sources such as wind and solar. The prerequisite for RFBs to be economically viable and widely employed is their low cost. Here we present a new zinc–iron (Zn–Fe) RFB based on double-membrane triple-electrolyte design that is estimated to have under $100 per kW h system capital cost. Such a low cost is achieved by a combination of inexpensive r...

  11. Carbon felt and carbon fiber - A techno-economic assessment of felt electrodes for redox flow battery applications

    Science.gov (United States)

    Minke, Christine; Kunz, Ulrich; Turek, Thomas

    2017-02-01

    Carbon felt electrodes belong to the key components of redox flow batteries. The purpose of this techno-economic assessment is to uncover the production costs of PAN- and rayon-based carbon felt electrodes. Raw material costs, energy demand and the impact of processability of fiber and felt are considered. This innovative, interdisciplinary approach combines deep insights into technical, ecologic and economic aspects of carbon felt and carbon fiber production. Main results of the calculation model are mass balances, cumulative energy demands (CED) and the production costs of conventional and biogenic carbon felts supplemented by market assessments considering textile and carbon fibers.

  12. Friedel-Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery.

    Science.gov (United States)

    Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

    2013-12-30

    Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel-Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

  13. Highly stable pyridinium-functionalized cross-linked anion exchange membranes for all vanadium redox flow batteries

    Science.gov (United States)

    Zeng, L.; Zhao, T. S.; Wei, L.; Zeng, Y. K.; Zhang, Z. H.

    2016-11-01

    It has recently been demonstrated that the use of anion exchange membranes (AEMs) in vanadium redox flow batteries (VRFBs) can reduce the migration of vanadium ions through the membrane due to the Donnan exclusion effect among the positively charged functional groups and vanadium ions. However, AEMs are plagued by low chemical stability in harsh chemical environments. Here we propose and fabricate a pyridinium-functionalized cross-linked AEM for VRFBs. The pyridinium-functionalized bromomethylated poly (2,6-dimethyl-1,4-phenylene oxide) exhibits a superior chemical stability as a result of the strengthened internal cross-linking networks and the chemical inertness of the polymer backbone. Therefore, the membrane exhibits littler decay in a harsh environment for 20 days during the course of an ex situ immersion test. A cycling test also demonstrates that the VRFB assembled with the membrane enable to retain 80% of the initial discharge capacity over 537 cycles with a capacity decay rate of 0.037% cycle-1. Meanwhile, the membrane also shows a low vanadium permeability and a reasonably high conductivity in supporting electrolytes. Hence, all the measurements and performance tests reported in this work suggest that the membrane is a promising AEM for redox flow batteries to achieve excellent cycling stability and superior cell performance.

  14. Friedel–Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK Membranes for a Vanadium/Air Redox Flow Battery

    Directory of Open Access Journals (Sweden)

    Géraldine Merle

    2013-12-01

    Full Text Available Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone (cSPEEK membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel–Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a crosslinking on the sulfonic acid groups; and (b crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

  15. Bismuth Nanoparticle Decorating Graphite Felt as a High-Performance Electrode for an All-Vanadium Redox Flow Battery

    Energy Technology Data Exchange (ETDEWEB)

    Li, Bin; Gu, Meng; Nie, Zimin; Shao, Yuyan; Luo, Qingtao; Wei, Xiaoliang; Li, Xiaolin; Xiao, Jie; Wang, Chong M.; Sprenkle, Vincent L.; Wang, Wei

    2013-02-04

    The selection of electrode materials plays a great role in improving performances of all vanadium redox flow batteries (VRBs). Low-cost graphite felt (GF) as traditional electrode material has to be modified to address its issue of low electrocatalytic activity. In our paper, low-cost and highly conductive bismuth nanoparticles, as a powerful alternative electrocatalyst to noble metal, are proposed and synchronously electro-deposited onto the surface of GF while running flow cells employing the electrolytes containing suitable Bi3+. Although bismuth is proved to only take effect on the redox reaction of V(II)/V(III) and present at negative half-cell side, the whole cell electrochemical performances are significantly improved. In particular, the energy efficiency is increased by 11% owing to faster charge transfer as compared with one without Bi at high charge/discharge rate of 150 mA/cm2, which is prone to reduce stack size, thus dramatically reducing the cost. The excellent results show great promise of Bi nano-catalysts in the commercialization of VRBs in terms of product cost as well as electrochemical properties.

  16. Impact of membrane characteristics on the performance and cycling of the Br-2-H-2 redox flow cell

    Energy Technology Data Exchange (ETDEWEB)

    Tucker, MC; Cho, KT; Spingler, FB; Weber, AZ; Lin, GY

    2015-06-15

    The Br-2/H-2 redox flow cell shows promise as a high-power, low-cost energy storage device. In this paper, the effect of various aspects of material selection and processing of proton exchange membranes on the operation of the Br-2/H-2 redox flow cell is determined. Membrane properties have a significant impact on the performance and efficiency of the system. In particular, there is a tradeoff between conductivity and crossover, where conductivity limits system efficiency at high current density and crossover limits efficiency at low current density. The impact of thickness, pretreatment procedure, swelling state during cell assembly, equivalent weight, membrane reinforcement, and addition of a microporous separator layer on this tradeoff is assessed. NR212 (50 mu m) pretreated by soaking in 70 degrees C water is found to be optimal for the studied operating conditions. For this case, an energy efficiency of greater than 75% is achieved for current density up to 400 mA cm(-2), with a maximum obtainable energy efficiency of 88%. A cell with this membrane was cycled continuously for 3164 h. Membrane transport properties, including conductivity and bromine and water crossover, were found to decrease moderately upon cycling but remained higher than those for the as-received membrane. (C) 2015 Elsevier B.V. All rights reserved.

  17. Friedel–Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery

    Science.gov (United States)

    Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

    2014-01-01

    Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel–Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion. PMID:24957118

  18. Redox zone II. Coupled modeling of groundwater flow, solute transport, chemical reactions and microbial processes in the Aespoe island

    Energy Technology Data Exchange (ETDEWEB)

    Samper, Javier; Molinero, Jorge; Changbing Yang; Guoxiang Zhang [Univ. Da Coruna (Spain)

    2003-12-01

    The Redox Zone Experiment was carried out at the Aespoe HRL in order to study the redox behaviour and the hydrochemistry of an isolated vertical fracture zone disturbed by the excavation of an access tunnel. Overall results and interpretation of the Redox Zone Project were reported by Banwart et al. Later, Banwart presented a summary of the hydrochemistry of the Redox Zone Experiment. Coupled groundwater flow and reactive transport models of this experiment were carried out by Molinero who proposed a revised conceptual model for the hydrogeology of the Redox Zone Experiment which could explain simultaneously measured drawdown and salinity data. The numerical model was found useful to understand the natural system. Several conclusions were drawn about the redox conditions of recharge waters, cation exchange capacity of the fracture zone and the role of mineral phases such as pyrite, calcite, hematite and goethite. This model could reproduce the measured trends of dissolved species, except for bicarbonate and sulphate which are affected by microbially-mediated processes. In order to explore the role of microbial processes, a coupled numerical model has been constructed which accounts for water flow, reactive transport and microbial processes. The results of this model is presented in this report. This model accounts for groundwater flow and reactive transport in a manner similar to that of Molinero and extends the preliminary microbial model of Zhang by accounting for microbially-driven organic matter fermentation and organic matter oxidation. This updated microbial model considers simultaneously the fermentation of particulate organic matter by yeast and the oxidation of dissolved organic matter, a product of fermentation. Dissolved organic matter is produced by yeast and serves also as a substrate for iron-reducing bacteria. Model results reproduce the observed increase in bicarbonate and sulfaphe concentration, thus adding additional evidence for the possibility

  19. Increasing the energy density of the non-aqueous vanadium redox flow battery with new electrolytes; Neue Elektrolyte zur Steigerung der Energiedichte einer nicht-waessrigen Vanadium-Acetylacetonat-Redox-Flow-Batterie

    Energy Technology Data Exchange (ETDEWEB)

    Herr, Tatjana

    2015-07-01

    Redox flow battery (RFB) is a promising energy storage technology which is similar to a polymer electrolyte membrane fuel cell. Currently, this electrochemical energy conversion device is used as a storage system for renewable energies or as uninterruptable power source. All-Vanadium-RFB (VRFB) and Zinc-Bromine-RFB are most well-known types of the aqueous RFB for these applications. But also the non-aqueous RFB is becoming more and more famous, because non-aqueous electrolytes offer wider operating temperature ranges, wider stable potential windows and a potentially higher energy density. However, current research studies show that the solubility of the most used redox active species is not sufficient. Therefore, present study aims to show concepts in order to solve this problem. Vanadium(III)acetylacetonate (V(acac){sub 3}) is used as active species, supported by tetrabutylammonium hexafluorophosphate. In acetonitrile it shows two quasi-reversible redox couples and a cell potential ∝2.2 V. The maximum solubility is ∝0.6 M. In this work other solvents and solvent mixtures were examined with the objective of increasing the solubility of V(acac){sub 3}. In 1,3-dioxolane the solubility was e.g. 0.8 M, dimethyl sulfoxide showed good battery performance with the highest energy efficiency ∝44 %. Acetylacetone is able to regenerate V(acac){sub 3} from the side product that is formed by reaction with water. The new electrolyte solution consisting of acetonitrile, 1,3-dioxolane and dimethyl sulfoxide nearly doubled the solubility of V(acac){sub 3}. In galvanostatic charge-discharge tests, single cell V(acac){sub 3} RFB exhibited energy efficiency between 25-50 % depending an test conditions. Also, the influence of water and oxygen addition an electrolyte was investigated. Finally, experiments with different ambient temperatures show that V(acac){sub 3} RFB is able to operate at temperatures such as 0 C and -25 C.

  20. 液流储能电池技术研究进展%Redox Flow Battery Technology

    Institute of Scientific and Technical Information of China (English)

    张华民; 张宇; 刘宗浩; 王晓丽

    2009-01-01

    Redox flow battery technology is a new electrical energy storage technology with virtues of high efficiency and large scale. It can meet the great demands of promoting the wide application of the renewable resources, pushing the construction of smart grid and achieving the target for energy saving and emission reduction. In this paper, we focus on the introduction to the working principles, characteristics, R&D progress and development trend of the all-vanadium, sodium polysulfide/bromine and zinc/bromine redox flow batteries. Also we discuss other types of flow batteries. Finally, the key problems limiting the technology development are pointed out and the suggestions for future research are given.%液流储能电池技术是一种高效、大规模电化学储能技术,在风能、太阳能等可再生能源发电、智能电网建设等方面有着广阔的应用前景.本文重点对全钒、多硫化钠-溴和锌-溴液流储能电池的工作原理、特点、国内外研究现状及发展趋势进行了综述,并对其他探索性液流储能电池体系进行了介绍.最后,提出了制约液流储能电池技术发展瓶颈问题,展望了液流储能电池未来发展趋势.

  1. Use of Bifunctional Immunotherapeutic Agents to Target Breast Cancer

    Science.gov (United States)

    2007-07-01

    Selective Tumor Cell Targeting Using Low-Affinity, Multivalent Interactions Coby B. Carlson†,‡, Patricia Mowery‡, Robert M. Owen†, Emily C. Dykhuizen†, and...washed cells and immediately analyzed for fluorescence using a FACSCalibur flow cytometer (Becton Dickinson ). Data were ana- lyzed using CellQuest...software (Becton Dickinson ). An identical assay omitting the bifunctional conjugate assessed background fluorescence. The relative fluorescence is

  2. The lightest organic radical cation for charge storage in redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Jinhua; Pan, Baofei; Duan, Wentao; Wei, Xiaoliang; Assary, Rajeev S.; Su, Liang; Brushett, Fikile; Cheng, Lei; Liao, Chen; Ferrandon, Magali S.; Wang, Wei; Zhang, Zhengcheng; Burrell, Anthony K.; Curtiss, Larry A.; Shkrob, Ilya A.; Moore, Jeffrey S.; Zhang, Lu

    2016-08-25

    Electrochemically reversible fluids of high energy density are promising materials for capturing the electrical energy generated from intermittent sources like solar and wind. To meet this technological challenge there is a need to understand the fundamental limits and interplay of electrochemical potential, stability and solubility in “lean” derivatives of redox-active molecules. Here we describe the process of molecular pruning, illustrated for 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene, a molecule known to produce a persistently stable, high-potential radical cation. By systematically shedding molecular fragments considered important for radical cation steric stabilization, we discovered a minimalistic structure that retains long-term stability in its oxidized form. Interestingly, we find the tert-butyl groups are unnecessary; high stability of the radical cation and high solubility are both realized in derivatives having appropriately positioned arene methyl groups. These stability trends are rationalized by mechanistic considerations of the postulated decomposition pathways. We suggest that the molecular pruning approach will uncover lean redox active derivatives for electrochemical energy storage leading to materials with long-term stability and high intrinsic capacity.

  3. Improvement of the Performance of Graphite Felt Electrodes for Vanadium-Redox-Flow-Batteries by Plasma Treatment

    Directory of Open Access Journals (Sweden)

    Eva-Maria Hammer

    2014-02-01

    Full Text Available In the frame of the present contribution oxidizing plasma pretreatment is used for the improvement of the electrocatalytic activity of graphite felt electrodes for Vanadium-Redox-Flow-Batteries (VRB. The influence of the working gas media on the catalytic activity and the surface morphology is demonstrated. The electrocatalytical properties of the graphite felt electrodes were examined by cyclic voltammetry and electrochemical impedance spectroscopy. The obtained results show that a significant improvement of the redox reaction kinetics can be achieved for all plasma modified samples using different working gasses (Ar, N2 and compressed air in an oxidizing environment. Nitrogen plasma treatment leads to the highest catalytical activities at the same operational conditions. Through a variation of the nitrogen plasma treatment duration a maximum performance at about 14 min cm-2 was observed, which is also represented by a minimum of 90 Ω in the charge transfer resistance obtained by EIS measurements. The morphology changes of the graphitized surface were followed using SEM.

  4. The impact of pH on side reactions for aqueous redox flow batteries based on nitroxyl radical compounds

    Science.gov (United States)

    Orita, A.; Verde, M. G.; Sakai, M.; Meng, Y. S.

    2016-07-01

    Electrochemical and UV-VIS measurements demonstrate that the pH value of a 4-hydroxy-2,2,6,6-tetramethyl-1-pipperidinyloxyl (TEMPOL) electrolyte significantly impacts its redox reversibility. The diffusion coefficient and kinetic rate constant of TEMPOL in neutral aqueous solution are determined and shown to be comparable to those of vanadium ions used for industrially utilized redox flow batteries (RFBs). RFBs that incorporate a TEMPOL catholyte and Zn-based anolyte have an average voltage of 1.46 V and an energy efficiency of 80.4% during the initial cycle, when subject to a constant current of 10 mA cm-2. We demonstrate several factors that significantly influence the concentration and capacity retention of TEMPOL upon cycling; namely, pH and atmospheric gases dissolved in electrolyte. We expand upon the known reactions of TEMPOL in aqueous electrolyte and propose several concepts to improve its electrochemical performance in a RFB. Controlling these factors will be the key to enable the successful implementation of this relatively inexpensive and environmentally friendly battery.

  5. A new strategy for integrating abundant oxygen functional groups into carbon felt electrode for vanadium redox flow batteries

    Science.gov (United States)

    Kim, Ki Jae; Lee, Seung-Wook; Yim, Taeeun; Kim, Jae-Geun; Choi, Jang Wook; Kim, Jung Ho; Park, Min-Sik; Kim, Young-Jun

    2014-11-01

    The effects of surface treatment combining corona discharge and hydrogen peroxide (H2O2) on the electrochemical performance of carbon felt electrodes for vanadium redox flow batteries (VRFBs) have been thoroughly investigated. A high concentration of oxygen functional groups has been successfully introduced onto the surface of the carbon felt electrodes by a specially designed surface treatment, which is mainly responsible for improving the energy efficiency of VRFBs. In addition, the wettability of the carbon felt electrodes also can be significantly improved. The energy efficiency of the VRFB cell employing the surface modified carbon felt electrodes is improved by 7% at high current density (148 mA cm-2). Such improvement is attributed to the faster charge transfer and better wettability allowed by surface-active oxygen functional groups. Moreover, this method is much more competitive than other surface treatments in terms of processing time, production costs, and electrochemical performance.

  6. Detection of capacity imbalance in vanadium electrolyte and its electrochemical regeneration for all-vanadium redox-flow batteries

    Science.gov (United States)

    Roznyatovskaya, Nataliya; Herr, Tatjana; Küttinger, Michael; Fühl, Matthias; Noack, Jens; Pinkwart, Karsten; Tübke, Jens

    2016-01-01

    A vanadium electrolyte for redox-flow batteries (VRFB) with different VIII and VIV mole fractions has been studied by UV-vis spectroscopy. Spectrophotometric detection enables a rough estimate of the VIV and VIII content, which can be used to detect an electrolyte capacity imbalance, i.e. a deviation in the mole fraction of VIV or VIII away from 50%. The isosbestic point at 600 nm can be used as a reference point in the analysis of common VRFB electrolyte batches. The VRFB electrolyte is observed to have an imbalance after prolonged storage (a couple of years) in a tank under ambient conditions. A regeneration procedure, which involves pre-charging the unbalanced electrolyte and mixing part of it with a portion of initial unbalanced electrolyte, has been tested. The resulting rebalanced electrolyte has been compared with a common electrolyte in a charge-discharge cell test and is shown to be suitable for cell operation.

  7. Structure and stability of hexa-aqua V(III) cations in vanadium redox flow battery electrolytes.

    Science.gov (United States)

    Vijayakumar, M; Li, Liyu; Nie, Zimin; Yang, Zhenguo; Hu, JianZhi

    2012-08-01

    The vanadium(III) cation structure in mixed acid based electrolyte solution from vanadium redox flow batteries is studied by (17)O and (35/37)Cl nuclear magnetic resonance (NMR) spectroscopy, electronic spectroscopy and density functional theory (DFT) based computational modelling. Both computational and experimental results reveal that the V(III) species can complex with counter anions (sulfate/chlorine) depending on the composition of its solvation sphere. By analyzing the powder precipitate it was found that the formation of sulfate complexed V(III) species is the crucial process in the precipitation reaction. The precipitation occurs through nucleation of neutral species formed through deprotonation and ion-pair formation process. However, the powder precipitate shows a multiphase nature which warrants multiple reaction pathways for precipitation reaction.

  8. Nitrogen-Doped Carbon Nanotube/Graphite Felts as Advanced Electrode Materials for Vanadium Redox Flow Batteries.

    Science.gov (United States)

    Wang, Shuangyin; Zhao, Xinsheng; Cochell, Thomas; Manthiram, Arumugam

    2012-08-16

    Nitrogen-doped carbon nanotubes have been grown, for the first time, on graphite felt (N-CNT/GF) by a chemical vapor deposition approach and examined as an advanced electrode for vanadium redox flow batteries (VRFBs). The unique porous structure and nitrogen doping of N-CNT/GF with increased surface area enhances the battery performance significantly. The enriched porous structure of N-CNTs on graphite felt could potentially facilitate the diffusion of electrolyte, while the N-doping could significantly contribute to the enhanced electrode performance. Specifically, the N-doping (i) modifies the electronic properties of CNT and thereby alters the chemisorption characteristics of the vanadium ions, (ii) generates defect sites that are electrochemically more active, (iii) increases the oxygen species on CNT surface, which is a key factor influencing the VRFB performance, and (iv) makes the N-CNT electrochemically more accessible than the CNT.

  9. Metabolic engineering of carbon and redox flow in the production of small organic acids.

    Science.gov (United States)

    Thakker, Chandresh; Martínez, Irene; Li, Wei; San, Ka-Yiu; Bennett, George N

    2015-03-01

    The review describes efforts toward metabolic engineering of production of organic acids. One aspect of the strategy involves the generation of an appropriate amount and type of reduced cofactor needed for the designed pathway. The ability to capture reducing power in the proper form, NADH or NADPH for the biosynthetic reactions leading to the organic acid, requires specific attention in designing the host and also depends on the feedstock used and cell energetic requirements for efficient metabolism during production. Recent work on the formation and commercial uses of a number of small mono- and diacids is discussed with redox differences, major biosynthetic precursors and engineering strategies outlined. Specific attention is given to those acids that are used in balancing cell redox or providing reduction equivalents for the cell, such as formate, which can be used in conjunction with metabolic engineering of other products to improve yields. Since a number of widely studied acids derived from oxaloacetate as an important precursor, several of these acids are covered with the general strategies and particular components summarized, including succinate, fumarate and malate. Since malate and fumarate are less reduced than succinate, the availability of reduction equivalents and level of aerobiosis are important parameters in optimizing production of these compounds in various hosts. Several other more oxidized acids are also discussed as in some cases, they may be desired products or their formation is minimized to afford higher yields of more reduced products. The placement and connections among acids in the typical central metabolic network are presented along with the use of a number of specific non-native enzymes to enhance routes to high production, where available alternative pathways and strategies are discussed. While many organic acids are derived from a few precursors within central metabolism, each organic acid has its own special requirements for high

  10. Dynamic thermal-hydraulic modeling and stack flow pattern analysis for all-vanadium redox flow battery

    Science.gov (United States)

    Wei, Zhongbao; Zhao, Jiyun; Skyllas-Kazacos, Maria; Xiong, Binyu

    2014-08-01

    The present study focuses on dynamic thermal-hydraulic modeling for the all-vanadium flow battery and investigations on the impact of stack flow patterns on battery performance. The inhomogeneity of flow rate distribution and reversible entropic heat are included in the thermal-hydraulic model. The electrolyte temperature in tanks is modeled with the finite element modeling (FEM) technique considering the possible non-uniform distribution of electrolyte temperature. Results show that the established model predicts electrolyte temperature accurately under various ambient temperatures and current densities. Significant temperature gradients exist in the battery system at extremely low flow rates, while the electrolyte temperature tends to be the same in different components under relatively high flow rates. Three stack flow patterns including flow without distribution channels and two cases of flow with distribution channels are compared to investigate their effects on battery performance. It is found that the flow rates are not uniformly distributed in cells especially when the stack is not well designed, while adding distribution channels alleviates the inhomogeneous phenomenon. By comparing the three flow patterns, it is found that the serpentine-parallel pattern is preferable and effectively controls the uniformity of flow rates, pressure drop and electrolyte temperature all at expected levels.

  11. Development of carbon nanotube and graphite filled polyphenylene sulfide based bipolar plates for all-vanadium redox flow batteries

    Science.gov (United States)

    Caglar, Burak; Fischer, Peter; Kauranen, Pertti; Karttunen, Mikko; Elsner, Peter

    2014-06-01

    In this study, synthetic graphite and carbon nanotube (CNT) filled polyphenylene sulfide (PPS) based bipolar plates are produced by using co-rotating twin-screw extruder and injection molding. Graphite is the main conductive filler and CNTs are used as bridging filler between graphite particles. To improve the dispersion of the fillers and the flow behavior of the composite, titanate coupling agent (KR-TTS) is used. The concentration effect of CNTs and coupling agent on the properties of bipolar plates are examined. At 72.5 wt.% total conductive filler concentration, by addition of 2.5 wt.% CNT and 3 wt.% KR-TTS; through-plane and in-plane electrical conductivities increase from 1.42 S cm-1 to 20 S cm-1 and 6.4 S cm-1 to 57.3 S cm-1 respectively compared to sample without CNTs and additive. Extruder torque value and apparent viscosity of samples decrease significantly with coupling agent and as a result; the flow behavior is positively affected. Flexural strength is improved 15% by addition of 1.25 wt.% CNT. Differential scanning calorimeter (DSC) analysis shows nucleating effect of conductive fillers on PPS matrix. Corrosion measurements, cyclic voltammetry and galvanostatic charge-discharge tests are performed to examine the electrochemical stability and the performance of produced bipolar plates in all-vanadium redox flow battery.

  12. An adaptive model for vanadium redox flow battery and its application for online peak power estimation

    Science.gov (United States)

    Wei, Zhongbao; Meng, Shujuan; Tseng, King Jet; Lim, Tuti Mariana; Soong, Boon Hee; Skyllas-Kazacos, Maria

    2017-03-01

    An accurate battery model is the prerequisite for reliable state estimate of vanadium redox battery (VRB). As the battery model parameters are time varying with operating condition variation and battery aging, the common methods where model parameters are empirical or prescribed offline lacks accuracy and robustness. To address this issue, this paper proposes to use an online adaptive battery model to reproduce the VRB dynamics accurately. The model parameters are online identified with both the recursive least squares (RLS) and the extended Kalman filter (EKF). Performance comparison shows that the RLS is superior with respect to the modeling accuracy, convergence property, and computational complexity. Based on the online identified battery model, an adaptive peak power estimator which incorporates the constraints of voltage limit, SOC limit and design limit of current is proposed to fully exploit the potential of the VRB. Experiments are conducted on a lab-scale VRB system and the proposed peak power estimator is verified with a specifically designed "two-step verification" method. It is shown that different constraints dominate the allowable peak power at different stages of cycling. The influence of prediction time horizon selection on the peak power is also analyzed.

  13. The dynamic response of hyporheic zone redox zonation after surface flow perturbation

    Science.gov (United States)

    Kaufman, M.; Zheng, L.; Cardenas, M. B.

    2015-12-01

    As water in a stream or river flows over ripples and other bedforms, differential surface pressures create bedform-induced hyporheic exchange. The oxygen, carbon, and nutrients carried into the bed by the surface water as well as those already existing in the bed material form the basis for microbial communities in the sediment.The resulting dissolved oxygen conditions are a critical control on the ecological function of the hyporheic zone (HZ), from both micro- and macro-biological habitat perspectives. Because hyporheic exchange rates are controlled by surface flow velocity, variations in surface flow have significant impact on the subsurface oxygen conditions. Most rivers are subject to flow velocity variations due to natural forcing including precipitation and variations in evapotranspiration as well as anthropogenic forces like dam releases. We use a large (10m x 0.7m x 0.3m) programmable flume instrumented with a bedform-scale high-resolution planar optode dissolved oxygen imaging system to observe the distribution of oxygenated sediment within the HZ over time. Using this system we characterize the rate at which hyporheic oxygen conditions reconfigure in response to changes in the surface flow velocity, particularly the time it takes for conditions to recover after a pulse of increased flow velocity. In addition, we make use of numerical models to further identify critical response time drivers. With these tools, we develop equations to describe the post-disturbance recovery time as a function of relative pulse magnitude and duration. Using these equations we can predict the time scale over which the hyporheic zone will recover following both natural and anthropogenic flow regime disturbances. Being able to predict the magnitude and duration of dissolved oxygen changes in the wake of flow perturbing events allows us to better understand the impact these disturbances have on the ecology of the hyporheic zone.

  14. Numerical investigation and thermodynamic analysis of the effect of electrolyte flow rate on performance of all vanadium redox flow batteries

    Science.gov (United States)

    Khazaeli, Ali; Vatani, Ali; Tahouni, Nassim; Panjeshahi, Mohammad Hassan

    2015-10-01

    In flow batteries, electrolyte flow rate plays a crucial role on the minimizing mass transfer polarization which is at the compensation of higher pressure drop. In this work, a two-dimensional numerical method is applied to investigate the effect of electrolyte flow rate on cell voltage, maximum depth of discharge and pressure drop a six-cell stack of VRFB. The results show that during the discharge process, increasing electrolyte flow rate can raise the voltage of each cell up to 50 mV on average. Moreover, the maximum depth of discharge dramatically increases with electrolyte flow rate. On the other hand, the pressure drop also positively correlates with electrolyte flow rate. In order to investigate all these effects simultaneously, average energy and exergy efficiencies are introduced in this study for the transient process of VRFB. These efficiencies give insight into choosing an appropriate strategy for the electrolyte flow rate. Finally, the energy efficiency of electricity storage using VRFB is investigated and compared with other energy storage systems. The results illustrate that this kind of battery has at least 61% storage efficiency based on the second law of thermodynamics, which is considerably higher than that of their counterparts.

  15. An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials

    Science.gov (United States)

    Janoschka, Tobias; Martin, Norbert; Martin, Udo; Friebe, Christian; Morgenstern, Sabine; Hiller, Hannes; Hager, Martin D.; Schubert, Ulrich S.

    2015-11-01

    For renewable energy sources such as solar, wind, and hydroelectric to be effectively used in the grid of the future, flexible and scalable energy-storage solutions are necessary to mitigate output fluctuations. Redox-flow batteries (RFBs) were first built in the 1940s and are considered a promising large-scale energy-storage technology. A limited number of redox-active materials--mainly metal salts, corrosive halogens, and low-molar-mass organic compounds--have been investigated as active materials, and only a few membrane materials, such as Nafion, have been considered for RFBs. However, for systems that are intended for both domestic and large-scale use, safety and cost must be taken into account as well as energy density and capacity, particularly regarding long-term access to metal resources, which places limits on the lithium-ion-based and vanadium-based RFB development. Here we describe an affordable, safe, and scalable battery system, which uses organic polymers as the charge-storage material in combination with inexpensive dialysis membranes, which separate the anode and the cathode by the retention of the non-metallic, active (macro-molecular) species, and an aqueous sodium chloride solution as the electrolyte. This water- and polymer-based RFB has an energy density of 10 watt hours per litre, current densities of up to 100 milliamperes per square centimetre, and stable long-term cycling capability. The polymer-based RFB we present uses an environmentally benign sodium chloride solution and cheap, commercially available filter membranes instead of highly corrosive acid electrolytes and expensive membrane materials.

  16. Mixed-Metal, Structural, and Substitution Effects of Polyoxometalates on Electrochemical Behavior in a Redox Flow Battery

    Energy Technology Data Exchange (ETDEWEB)

    Pratt, Harry D [Sandia National Laboratories; Pratt, William R [Sandia National Laboratories; Fang, Xikui [Ames Laboratory; Hudak, Nicholas S [Sandia National Laboratories; Anderson, Travis M [Sandia National Laboratories

    2014-08-01

    A pair of redox flow batteries containing polyoxometalates was tested as part of an ongoing program in stationary energy storage. The iron-containing dimer, (SiFe3W9(OH)3O34)2(OH)311-, cycled between (SiFe3W9(OH)3O34)2(OH)311-/(SiFe3W9(OH)3O34)2(OH)314-and (SiFe3W9(OH)3O34)2(OH)317-/(SiFe3W9(OH)3O34)2(OH)314- for the positive and negative electrode, respectively. This compound demonstrated a coulombic efficiency of 83% after 20 cycles with an electrochemical yield (measured discharge capacity as a percentage of theoretical capacity) of 55%. Cyclic voltammetry on the Lindqvist ion, cis-V2W4O194-, showed quasi-reversible vanadium electrochemistry, but tungsten reduction was mostly irreversible. In a flow cell configuration, cis-V2W4O194-had a coulombic efficiency of 45% (for a two-electron process) and an electrochemical yield of 16% after 20 cycles. The poor performance of cis-V2W4O194-was attributed primarily to its higher charge density. Collectively, the results showed that both polyoxometalate size and charge density are both important parameters to consider in battery material performance.

  17. Laser-perforated carbon paper electrodes for improved mass-transport in high power density vanadium redox flow batteries

    Science.gov (United States)

    Mayrhuber, I.; Dennison, C. R.; Kalra, V.; Kumbur, E. C.

    2014-08-01

    In this study, we demonstrate up to 30% increase in power density of carbon paper electrodes for vanadium redox flow batteries (VRFB) by introducing perforations into the structure of electrodes. A CO2 laser was used to generate holes ranging from 171 to 421 μm diameter, and hole densities from 96.8 to 649.8 holes cm-2. Perforation of the carbon paper electrodes was observed to improve cell performance in the activation region due to thermal treatment of the area around the perforations. Results also demonstrate improved mass transport, resulting in enhanced peak power and limiting current density. However, excessive perforation of the electrode yielded a decrease in performance due to reduced available surface area. A 30% increase in peak power density (478 mW cm-2) was observed for the laser perforated electrode with 234 μm diameter holes and 352.8 holes cm-2 (1764 holes per 5 cm2 electrode), despite a 15% decrease in total surface area compared to the raw un-perforated electrode. Additionally, the effect of perforation on VRFB performance was studied at different flow rates (up to 120 mL min-1) for the optimized electrode architecture. A maximum power density of 543 mW cm-2 was achieved at 120 mL min-1.

  18. Pt{sub X}Ru{sub Y}Ir{sub Z} as a bifunctional electrocatalyst for oxygen reduction reaction in a PEM fuel cell; Pt{sub X}Ru{sub Y}Ir{sub Z} como electrocatalizador bifuncional para la reaccion redox del oxigeno en una celda tipo PEM

    Energy Technology Data Exchange (ETDEWEB)

    Morales, L.; Fernandez, A.M. [Centro de Investigacion en Energia, Universidad Nacional Autonoma de Mexico, Temixco, Morelos (Mexico)]. E-mail: limos@cie.unam.mx; Cano, U. [Instituto de Investigaciones Electricas, Cuernavaca, Morelos (Mexico)

    2009-09-15

    This work presents the synthesis and characterization of the ternary material Pt{sub X}Ru{sub Y}Ir{sub Z}, obtained by chemical reduction with NaBH{sub 4}. Two different atomic compositions were developed (sample A and B) in order to observe the kinetic effect, as suggested by the combinatorial libraries. The main objective of this synthesis is to study the oxygen reduction reaction (ORR and OER) and its potential use in the construction of a bifunctional catalyst. In addition, each of the metals are synthesized separately using the same technique in order to make the corresponding comparison. The compounds obtained were characterized by sweep electron microscopy, x-ray diffraction and composition using fluorescence and energy-dispersive x-ray spectroscopy. The results showed a displacement of the x-ray diffraction peaks for Ir and Pt in sample A, and displacement in sample B for Ru and Ir peaks. These changes suggest the possible formation of a solid solution substitution. Separate cyclic and linear voltamperometry studies were performed for the oxygen reduction and release reactions. The electrochemical analysis showed improved kinetic behavior when combining the three metals according to the composition of sample B. [Spanish] En este trabajo se presenta la sintesis y caracterizacion del material ternario Pt{sub X}Ru{sub Y}Ir{sub Z}, elaborado por la tecnica de Reduccion Quimica utilizando al NaBH{sub 4}. Se elaboraron dos composiciones atomicas diferentes (Muestra A y B) con el fin de observar el efecto cinetico, como lo sugieren las librerias combinatorias. El objetivo principal de esta sintesis es para el estudio de la Reaccion Redox del Oxigeno (RRO y REO) y su potencial uso para la construccion de un catalizador bifuncional. Asi mismo, se realiza la sintesis de cada uno de los metales por separado empleando la misma tecnica, con el proposito de realizar la comparacion correspondiente. Los compuestos obtenidos se caracterizaron por Microscopia Electronica de

  19. Design of a miniature flow cell for in situ x-ray imaging of redox flow batteries

    Science.gov (United States)

    Jervis, Rhodri; Brown, Leon D.; Neville, Tobias P.; Millichamp, Jason; Finegan, Donal P.; Heenan, Thomas M. M.; Brett, Dan J. L.; Shearing, Paul R.

    2016-11-01

    Flow batteries represent a possible grid-scale energy storage solution, having many advantages such as scalability, separation of power and energy capabilities, and simple operation. However, they can suffer from degradation during operation and the characteristics of the felt electrodes are little understood in terms of wetting, compression and pressure drops. Presented here is the design of a miniature flow cell that allows the use of x-ray computed tomography (CT) to study carbon felt materials in situ and operando, in both lab-based and synchrotron CT. Through application of the bespoke cell it is possible to observe felt fibres, electrolyte and pore phases and therefore enables non-destructive characterisation of an array of microstructural parameters during the operation of flow batteries. Furthermore, we expect this design can be readily adapted to the study of other electrochemical systems.

  20. Cost and performance prospects for composite bipolar plates in fuel cells and redox flow batteries

    Science.gov (United States)

    Minke, Christine; Hickmann, Thorsten; dos Santos, Antonio R.; Kunz, Ulrich; Turek, Thomas

    2016-02-01

    Carbon-polymer-composite bipolar plates (BPP) are suitable for fuel cell and flow battery applications. The advantages of both components are combined in a product with high electrical conductivity and good processability in convenient polymer forming processes. In a comprehensive techno-economic analysis of materials and production processes cost factors are quantified. For the first time a technical cost model for BPP is set up with tight integration of material characterization measurements.

  1. Sulfonated poly (fluorenyl ether ketone) membrane with embedded silica rich layer and enhanced proton selectivity for vanadium redox flow battery

    Science.gov (United States)

    Chen, Dongyang; Wang, Shuanjin; Xiao, Min; Han, Dongmei; Meng, Yuezhong

    A series of novel organic-inorganic hybrid membranes with special microstructure, based on sulfonated poly (fluorenyl ether ketone) ionomer (SFPEK, IEC = 1.92 mequiv. g -1) and SiO 2 or sulfonic acid group containing SiO 2 (SiO 2-SO 3H), has been successfully designed and prepared for vanadium redox flow battery (VRB) application. The SiO 2-SO 3H is synthesized by co-condensation of tetraethoxysilane and γ-propyl mercaptotrimethoxysilane via sol-gel process to control the same IEC with neat SPFEK. The hybrid membranes are prepared by simply adding the inorganic particles into the SPFEK solution in N, N‧-dimethylacetamide, followed by ultrasonic dispersion, casting and profiled temperature drying process. The morphology is examined by SEM-EDX which is applied to the top surface, bottom surface and cross-section of the hybrid membranes. The water uptake, oxidative stability, thermal property, mechanical property, proton conductivity, VO 2+ permeability and single cell performance are investigated in detail in order to understand the relationship between morphology and property of the membranes. All the hybrid membranes show dramatically improved proton selectivity at 20 °C and 40 °C when compared with Nafion117. The VRB assembled with the SPFEK/3%SiO 2 and SPFEK/9%SiO 2 membranes exhibit higher coulombic efficiency and average discharge voltage than the VRB assembled with the SPFEK membrane at all the tested current densities.

  2. Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes for vanadium redox flow battery applications

    Science.gov (United States)

    Zhang, Bengui; Zhang, Shouhai; Weng, Zhihuan; Wang, Guosheng; Zhang, Enlei; Yu, Ping; Chen, Xiaomeng; Wang, Xinwei

    2016-09-01

    Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes (QADMPEK) are prepared and investigated for vanadium redox flow batteries (VRFB) application. The bulky, rigid and highly hydrophobic adamantane segment incorporated into the backbone of membrane material makes QADMPEK membranes have low water uptake and swelling ratio, and the as-prepared membranes display significantly lower permeability of vanadium ions than that of Nafion117 membrane. As a consequence, the VRFB cell with QADMPEK-3 membrane shows higher coulombic efficiency (99.4%) and energy efficiency (84.0%) than those for Nafion117 membrane (95.2% and 80.5%, respectively) at the current density of 80 mA cm-2. Furthermore, at a much higher current density of 140 mA cm-2, QADMPEK membrane still exhibits better coulombic efficiency and energy efficiency than Nafion117 membrane (coulombic efficiency 99.2% vs 96.5% and energy efficiency 76.0% vs 74.0%). Moreover, QADMPEK membranes show high stability in in-situ VRFB cycle test and ex-situ oxidation stability test. These results indicate that QADMPEK membranes are good candidates for VRFB applications.

  3. Study on stabilities and electrochemical behavior of V(V) electrolyte with acid additives for vanadium redox flow battery

    Institute of Scientific and Technical Information of China (English)

    Gang; Wang; Jinwei; Chen; Xueqin; Wang; Jing; Tian; Hong; Kang; Xuejing; Zhu; Yu; Zhang; Xiaojiang; Liu; Ruilin; Wang

    2014-01-01

    Several acid compounds have been employed as additives of the V(V) electrolyte for vanadium redox flow battery(VRB) to improve its stability and electrochemical activity. Stability of the V(V) electrolyte with and without additives was investigated with ex-situ heating/cooling treatment at a wide temperature range of-5 ?C to 60 ?C. It was observed that methanesulfonic acid, boric acid, hydrochloric acid, trifluoroacetic acid,polyacrylic acid, oxalic acid, methacrylic acid and phosphotungstic acid could improve the stability of the V(V) electrolyte at a certain range of temperature. Their electrochemical behaviors in the V(V) electrolyte were further studied by cyclic voltammetry(CV), steady state polarization and electrochemical impedance spectroscopy(EIS). The results showed that the electrochemical activity, including the reversibility of electrode reaction, the diffusivity of V(V) species, the polarization resistance and the flexibility of charge transfer for the V(V) electrolyte with these additives were all improved compared with the pristine solution.

  4. Novel sulfonated polyimide/zwitterionic polymer-functionalized graphene oxide hybrid membranes for vanadium redox flow battery

    Science.gov (United States)

    Cao, Li; Kong, Lei; Kong, Lingqian; Zhang, Xingxiang; Shi, Haifeng

    2015-12-01

    Hybrid membranes (SPI/ZGO) composed of sulfonated polyimide (SPI) and zwitterionic polymer-functionalized graphene oxide (ZGO) are fabricated via a solution-casting method for vanadium redox flow battery (VRB). Successful preparation of ZGO fillers and SPI/ZGO hybrid membranes are demonstrated by FT-IR, XPS and SEM, indicating that ZGO fillers is homogeneously dispersed into SPI matrix. Through controlling the interfacial interaction between SPI matrix and ZGO fillers, the physicochemical properties, e.g., vanadium ion barrier and proton transport pathway, of hybrid membranes are tuned via the zwitterionic acid-base interaction in the hybrid membrane, showing a high ion selectivity and good stability with the incorporated ZGO fillers. SPI/ZGO-4 hybrid membrane proves a higher cell efficiencies (CE: 92-98%, EE: 65-79%) than commercial Nafion 117 membrane (CE: 89-94%, EE: 59-70%) for VRB application at 30-80 mA cm-2. The assembled VRB with SPI/ZGO-4 membrane presents a stable cycling charge-discharge performance over 280 times, which demonstrates its excellent chemical stability under the strong acidic and oxidizing conditions. SPI/ZGO hybrid membranes show a brilliant perspective for VRB application.

  5. Preparation and properties of sulfonated poly(fluorenyl ether ketone) membrane for vanadium redox flow battery application

    Science.gov (United States)

    Chen, Dongyang; Wang, Shuanjin; Xiao, Min; Meng, Yuezhong

    In order to develop novel membranes for vanadium redox flow battery (VRB) with low self-discharge rate and low cost, sulfonated poly(fluorenyl ether ketone) (SPFEK) was synthesized directly via aromatic nucleophilic polycondensation of bisphenol fluorene with 60% sulfonated difluorobenzophenone and 40% difluorobenzophenone. The SPFEK membrane shows the lower permeability of vanadium ions. The open circuit voltage evaluation demonstrates that the SPFEK membrane is superior to Nafion 117 membrane in self-discharge test. Both energy efficiencies (EE) and power densities of the VRB single cell based on the SPFEK membrane are higher than those of the VRB with Nafion 117 membrane at the same current densities. The highest coulombic efficiency (CE) of VRB with SPFEK membrane is 80.3% while the highest CE of the VRB with Nafion 117 membrane is 77.0%. The SPFEK membrane shows the comparative stability to Nafion 117 membrane in VO 2 + electrolyte. The experimental results suggest that SPFEK membrane is a promising ion exchange membrane for VRB.

  6. Indirect fuel cell based on a redox-flow battery with a new design to avoid crossover

    Science.gov (United States)

    Siroma, Zyun; Yamazaki, Shin-ichi; Fujiwara, Naoko; Asahi, Masafumi; Nagai, Tsukasa; Ioroi, Tsutomu

    2013-11-01

    A new design of a redox flow battery (RFB), which is composed of two subcells separated by a gas phase of hydrogen, is proposed to eliminate the crossover of ionic species between the anolyte and catholyte. This idea not only increases the possible combinations of the two electrolytes, but also opens up the prospect of a revival of the old idea of an indirect fuel cell, which is composed of an RFB and two chemical reactors to regenerate the electrolytes using a fuel and oxygen. This paper describes the operation of a subcell as a component of an indirect fuel cell system. In the cycling test, oxidation/reduction of the electroactive species in each electrolyte were repeated with a hydrogen electrode as the counter electrode. This result demonstrates the possibility of this newly proposed RFB without crossover. In the operation of the subcell with a chemical reactor, a molecular catalyst (a rhodium porphyrin) was dissolved in the anolyte, and then a fuel was bubbled in the anolyte reservoir. As the electroactive species was reduced by the fuel, a steady-state oxidation current was observed at the cell. This demonstrates the negative half of the newly proposed indirect fuel cell.

  7. Nuclear magnetic resonance studies of the solvation structures of a high-performance nonaqueous redox flow electrolyte

    Science.gov (United States)

    Deng, Xuchu; Hu, Mary; Wei, Xiaoliang; Wang, Wei; Mueller, Karl T.; Chen, Zhong; Hu, Jian Zhi

    2016-03-01

    Understanding the solvation structures of electrolytes is important for developing nonaqueous redox flow batteries that hold considerable potential for future large scale energy storage systems. The utilization of an emerging ionic-derivatived ferrocene compound, ferrocenylmethyl dimethyl ethyl ammonium bis(trifluoromethanesulfonyl)imide (Fc1N112-TFSI), has recently overcome the issue of solubility in the supporting electrolyte. In this work, 13C, 1H and 17O NMR investigations were carried out using electrolyte solutions consisting of Fc1N112-TFSI as the solute and the mixed alkyl carbonate as the solvent. It was observed that the spectra of 13C experience changes of chemical shifts while those of 17O undergo linewidth broadening, indicating interactions between solute and solvent molecules. Quantum chemistry calculations of both molecular structures and chemical shifts (13C, 1H and 17O) are performed for interpreting experimental results and for understanding the detailed solvation structures. The results indicate that Fc1N112-TFSI is dissociated at varying degrees in mixed solvent depending on concentrations. At dilute solute concentrations, most Fc1N112+ and TFSI- are fully disassociated with their own solvation shells formed by solvent molecules. At saturated concentration, Fc1N112+-TFSI- contact ion pairs are formed and the solvent molecules are preferentially interacting with the Fc rings rather than interacting with the ionic pendant arm of Fc1N112-TFSI.

  8. Influence of aminosilane precursor concentration on physicochemical properties of composite Nafion membranes for vanadium redox flow battery applications

    Science.gov (United States)

    Kondratenko, Mikhail S.; Karpushkin, Evgeny A.; Gvozdik, Nataliya A.; Gallyamov, Marat O.; Stevenson, Keith J.; Sergeyev, Vladimir G.

    2017-02-01

    A series of composite proton-exchange membranes have been prepared via sol-gel modification of commercial Nafion membranes with [N-(2-aminoethyl)-3-aminopropyl]trimethoxysilane. The structure and physico-chemical properties (water uptake, ion-exchange capacity, vanadyl ion permeability, and proton conductivity) of the prepared composite membranes have been studied as a function of the precursor loading (degree of the membrane modification). If the amount of the precursor is below 0.4/1 M ratio of the amino groups of the precursor to the sulfonic groups of Nafion, the composite membranes exhibit decreased vanadium ion permeability while having relatively high proton conductivity. With respect to the use of a non-modified Nafion membrane, the performance of the composite membrane with an optimum precursor loading in a single-cell vanadium redox flow battery demonstrates enhanced energy efficiency in 20-80 mA cm-2 current density range. The maximum efficiency increase of 8% is observed at low current densities.

  9. Electrochemical modification of a pyrolytic graphite sheet for improved negative electrode performance in the vanadium redox flow battery

    Science.gov (United States)

    Kabir, Humayun; Gyan, Isaiah O.; Francis Cheng, I.

    2017-02-01

    The vanadium redox flow battery is a promising technology for buffering renewable energies. It is recognized that negative electrode is the limitation in this device where there are problems of slow heterogeneous electron transfer (HET) of V3+/2+ and parasitic H2 evolution. Any methods aimed at addressing one of these barriers must assess the effects on the other. We examine electrochemical enhancement of a common commercially available material. Treatment of Panasonic pyrolytic graphite sheets is through oxidation at 2.1 V vs. Ag/AgCl for 1 min in 1 M H2SO4. This increases the standard HET rate for V3+/2+ from 3.2 × 10-7 to 1 × 10-3 cm/s, one of the highest in literature and shifts voltammetric reductive peak potential from -1.0 V to -0.65 V in 50 mM V3+ in 1 M H2SO4. Infrared analysis of the surfaces indicates formation of Csbnd OH, Cdbnd O, and Csbnd O functionalities. These groups catalyze HET with V3+/2+ as hypothesized by Skyllas-Kasacos. Also of significance is that electrode modification decreases the fraction of the current directed towards H2 evolution. This proportion decreases by two orders of a magnitude from 12% to 0.1% as measured at the respective voltammetric peak potentials of -1.0 V (pristine) and -0.65 V (modified).

  10. Neuronal differentiation is associated with a redox-regulated increase of copper flow to the secretory pathway.

    Science.gov (United States)

    Hatori, Yuta; Yan, Ye; Schmidt, Katharina; Furukawa, Eri; Hasan, Nesrin M; Yang, Nan; Liu, Chin-Nung; Sockanathan, Shanthini; Lutsenko, Svetlana

    2016-01-01

    Brain development requires a fine-tuned copper homoeostasis. Copper deficiency or excess results in severe neuro-pathologies. We demonstrate that upon neuronal differentiation, cellular demand for copper increases, especially within the secretory pathway. Copper flow to this compartment is facilitated through transcriptional and metabolic regulation. Quantitative real-time imaging revealed a gradual change in the oxidation state of cytosolic glutathione upon neuronal differentiation. Transition from a broad range of redox states to a uniformly reducing cytosol facilitates reduction of the copper chaperone Atox1, liberating its metal-binding site. Concomitantly, expression of Atox1 and its partner, a copper transporter ATP7A, is upregulated. These events produce a higher flux of copper through the secretory pathway that balances copper in the cytosol and increases supply of the cofactor to copper-dependent enzymes, expression of which is elevated in differentiated neurons. Direct link between glutathione oxidation and copper compartmentalization allows for rapid metabolic adjustments essential for normal neuronal function.

  11. Adaptive estimation of state of charge and capacity with online identified battery model for vanadium redox flow battery

    Science.gov (United States)

    Wei, Zhongbao; Tseng, King Jet; Wai, Nyunt; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

    2016-11-01

    Reliable state estimate depends largely on an accurate battery model. However, the parameters of battery model are time varying with operating condition variation and battery aging. The existing co-estimation methods address the model uncertainty by integrating the online model identification with state estimate and have shown improved accuracy. However, the cross interference may arise from the integrated framework to compromise numerical stability and accuracy. Thus this paper proposes the decoupling of model identification and state estimate to eliminate the possibility of cross interference. The model parameters are online adapted with the recursive least squares (RLS) method, based on which a novel joint estimator based on extended Kalman Filter (EKF) is formulated to estimate the state of charge (SOC) and capacity concurrently. The proposed joint estimator effectively compresses the filter order which leads to substantial improvement in the computational efficiency and numerical stability. Lab scale experiment on vanadium redox flow battery shows that the proposed method is highly authentic with good robustness to varying operating conditions and battery aging. The proposed method is further compared with some existing methods and shown to be superior in terms of accuracy, convergence speed, and computational cost.

  12. Investigations on transfer of water and vanadium ions across Nafion membrane in an operating vanadium redox flow battery

    Science.gov (United States)

    Sun, Chenxi; Chen, Jian; Zhang, Huamin; Han, Xi; Luo, Qingtao

    Diffusion coefficients of the vanadium ions across Nafion 115 (Dupont) in a vanadium redox flow battery (VRFB) are measured and found to be in the order of V 2+ > VO 2+ > VO 2 + > V 3+. It is found that both in self-discharge process and charge-discharge cycles, the concentration difference of vanadium ions between the positive electrolyte (+ve) and negative electrolyte (-ve) is the main reason causing the transfer of vanadium ions across the membrane. In self-discharge process, the transfer of water includes the transfer of vanadium ions with the bound water and the corresponding transfer of protons with the dragged water to balance the charges, and the transfer of water driven by osmosis. In this case, about 75% of the net transfer of water is caused by osmosis. In charge-discharge cycles, except those as mentioned in the case of self-discharge, the transfer of protons with the dragged water across the membrane during the electrode reaction for the formation of internal electric circuit plays the key role in the water transfer. But in the long-term cycles of charge-discharge, the net transfer of water towards +ve is caused by the transfer of vanadium ions with the bound water and the transfer of water driven by osmosis.

  13. Highly branched sulfonated poly(fluorenyl ether ketone sulfone)s membrane for energy efficient vanadium redox flow battery

    Science.gov (United States)

    Yin, Bibo; Li, Zhaohua; Dai, Wenjing; Wang, Lei; Yu, Lihong; Xi, Jingyu

    2015-07-01

    A series of highly branched sulfonated poly (fluorenyl ether ketone sulfone)s (HSPAEK) are synthesized by direct polycondensation reactions. The HSPAEK with 8% degree of branching is further investigated as membrane for vanadium redox flow battery (VRFB). The HSPAEK membrane prepared by solution casting method exhibits smooth, dense and tough morphology. It possesses very low VO2+ permeability and high ion selectivity compared to those of Nafion 117 membrane. When applied to VRFB, this novel membrane shows higher coulombic efficiency (CE, 99%) and energy efficiency (EE, 84%) than Nafion 117 membrane (CE, 92% and EE, 78%) at current density of 80 mA cm-2. Besides, the HSPAEK membrane shows super stable CE and EE as well as excellent discharge capacity retention (83%) during 100 cycles life test. After being soaked in 1.5 mol L-1 VO2+ solution for 21 days, the weight loss of HSPAEK membrane and the amount of VO2+ reduced from VO2+ are only 0.26% and 0.7%, respectively, indicating the superior chemical stability of the membrane.

  14. Ultra-thin polytetrafluoroethene/Nafion/silica composite membrane with high performance for vanadium redox flow battery

    Science.gov (United States)

    Teng, Xiangguo; Dai, Jicui; Bi, Fangyuan; Yin, Geping

    2014-12-01

    Ultra-thin and high performance polytetrafluoroethene (PTFE)/Nafion/silica composite membrane has been successfully prepared by solution casting and sol-gel method for all vanadium redox flow battery (VRB). Thickness of ∼25 μm polytetrafluoroethene/Nafion (P/N) membrane is first prepared by impregnating porous PTFE membrane with Nafion solution, and then the P/N membrane is immersed in tetraethoxysilane (TEOS) solution to prepare PTFE/Nafion/silica (P/N/S) composite membranes. The chemical structures of membranes are investigated by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR), which prove that the Nafion resin and silica are well impregnated in PTFE membrane. The water uptake, proton conductivity, vanadium permeability and VRB single cell tests of the composite membrane are also investigated in detail. At 80 mA cm-2, coulombic efficiency, voltage efficiency and energy efficiency of the VRB with P/N/S-7 (7 wt.% SiO2 in P/N/S) membrane are 93.9%, 87.2% and 81.9%, respectively. Furthermore, the self-discharge rate of the VRB with P/N/S membrane is much slower than that of the VRB with P/N membrane, which indicates that the membrane has good vanadium block ability. Fifty cycles charge-discharge test proves that the P/N/S membrane is very stable and possesses high chemical stability under the strong acid solutions.

  15. Ultra-low vanadium ion diffusion amphoteric ion-exchange membranes for all-vanadium redox flow batteries

    Science.gov (United States)

    Liao, J. B.; Lu, M. Z.; Chu, Y. Q.; Wang, J. L.

    2015-05-01

    An amphoteric ion-exchange membrane (AIEM) from fluoro-methyl sulfonated poly(arylene ether ketone) bearing content-controlled benzimidazole moiety, was firstly fabricated for vanadium redox flow battery (VRB). The AIEM and its covalently cross-linked membrane (AIEM-c) behave the highly suppressed vanadium-ion crossover and their tested VO2+ permeability are about 638 and 1117 times lower than that of Nafion117, respectively. This is further typically verified by the lower VO2+ concentration inside AIEM that is less than half of that inside Nafion117 detected by energy dispersive X-ray spectrometry, in addition of the nearly 3 times longer battery self-discharge time. The ultra-low vanadium ion diffusion could be ascribed to the narrower ion transporting channel originated from the acid-base interactions and the rebelling effect between the positively-charged benzimidazole structure and VO2+ ions. It is found that, VRB assembled with AIEM exhibits the equal or higher Coulombic efficiency (99.0% vs. 96.4%), voltage efficiency (90.7% vs. 90.7%) and energy efficiency (89.8% vs. 87.4%) than that with Nafion117 and keeps continuous 220 charge-discharge cycles for over 25 days, confirming that the AIEM of this type is a potentially suitable separator for VRB application.

  16. Study of an unitised bidirectional vanadium/air redox flow battery comprising a two-layered cathode

    Science.gov (United States)

    grosse Austing, Jan; Nunes Kirchner, Carolina; Hammer, Eva-Maria; Komsiyska, Lidiya; Wittstock, Gunther

    2015-01-01

    The performance of a unitised bidirectional vanadium/air redox flow battery (VARFB) is described. It contains a two-layered cathode consisting of a gas diffusion electrode (GDE) with Pt/C catalyst for discharging and of an IrO2 modified graphite felt for charging. A simple routine is shown for the modification of a graphite felt with IrO2. A maximum energy efficiency of 41.7% at a current density of 20 mA cm-2 as well as an average discharge power density of 34.6 mW cm-2 at 40 mA cm-2 were obtained for VARFB operation at room temperature with the novel cathode setup. A dynamic hydrogen electrode was used to monitor half cell potentials during operation allowing to quantify the contribution of the cathode to the overall performance of the VARFB. Four consecutive cycles revealed that crossover of vanadium ions took place and irreversible degradation processes within the reaction unit lead to a performance decrease.

  17. Sulfonated poly(ether ether ketone)/mesoporous silica hybrid membrane for high performance vanadium redox flow battery

    Science.gov (United States)

    Li, Zhaohua; Dai, Wenjing; Yu, Lihong; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

    2014-07-01

    Hybrid membranes of sulfonated poly(ether ether ketone) (SPEEK) and mesoporous silica SBA-15 are prepared with various mass ratios for vanadium redox flow battery (VRB) application and investigated in detail. The hybrid membranes are dense and homogeneous with no visible hole as the SEM and EDX images shown. With the increasing of SBA-15 mass ratio, the physicochemical property, VO2+ permeability, mechanical property and thermal stability of hybrid membranes exhibit good trends, which can be attributed to the interaction between SPEEK and SBA-15. The hybrid membrane with 20 wt.% SBA-15 (termed as S/SBA-15 20) shows the VRB single cell performance of CE 96.3% and EE 88.1% at 60 mA cm-2 due to its good balance of proton conductivity and VO2+ permeability, while Nafion 117 membrane shows the cell performance of CE 92.2% and EE 81.0%. Besides, the S/SBA-15 20 membrane shows stable cell performance of highly stable efficiency and slower discharge capacity decline during 120 cycles at 60 mA cm-2. Therefore, the SPEEK/SBA-15 hybrid membranes with optimized mass ratio and excellent VRB performance can be achieved, exhibiting good potential usage in VRB systems.

  18. Implementation and Validation of a Self-Consumption Maximization Energy Management Strategy in a Vanadium Redox Flow BIPV Demonstrator

    Directory of Open Access Journals (Sweden)

    Luis Fialho

    2016-06-01

    Full Text Available This paper presents the results of the implementation of a self-consumption maximization strategy tested in a real-scale Vanadium Redox Flow Battery (VRFB (5 kW, 60 kWh and Building Integrated Photovoltaics (BIPV demonstrator (6.74 kWp. The tested energy management strategy aims to maximize the consumption of energy generated by a BIPV system through the usage of a battery. Whenever possible, the residual load is either stored in the battery to be used later or is supplied by the energy stored previously. The strategy was tested over seven days in a real-scale VRF battery to assess the validity of this battery to implement BIPV-focused energy management strategies. The results show that it was possible to obtain a self-consumption ratio of 100.0%, and that 75.6% of the energy consumed was provided by PV power. The VRFB was able to perform the strategy, although it was noticed that the available power (either to charge or discharge varied with the state of charge.

  19. Mutants, Overexpressors, and Interactors of Arabidopsis Plastocyanin Isoforms: Revised Roles of Plastocyanin in Photosynthetic Electron Flow and Thylakoid Redox State

    Institute of Scientific and Technical Information of China (English)

    Paolo Pesaresi; Michael Scharfenberg; Martin Weigel; Irene Granlund; Wolfgang P. Schr(o)der; Giovanni Finazzi; Fabrice Rappaport; Simona Masiero; Antonella Furini; Peter Jahns; Dario Leister

    2009-01-01

    Two homologous plastocyanin isoforms are encoded by the genes PETE1 and PETE2 in the nuclear genome of Arabidopsis thaliana. The PETE2 transcript is expressed at considerably higher levels and the PETE2 protein is the more abundant isoform. Null mutations in the PETE genes resulted in plants, designated pete1 and pete2, with decreased plas-tocyanin contents. However, despite reducing plastocyanin levels by over~90%, a pete2 null mutation on its own affects rates of photosynthesis and growth only slightly, whereas pete1 knockout plants, with about 60-80% of the wild-type plastocyanin level, did not show any alteration. Hence, plastocyanin concentration is not limiting for photosynthetic elec-tron flow under optimal growth conditions, perhaps implying other possible physiological roles for the protein. Indeed, plastocyanin has been proposed previously to cooperate with cytochrome C6A (Cyt C6A) in thylakoid redox reactions, but we find no evidence for a physical interaction between the two proteins, using interaction assays in yeast. We observed homodimerization of Cyt C6A in yeast interaction assays, but also Cyt C6A homodimers failed to interact with plastocyanin. Moreover, phenotypic analysis of atc6-1 pete1 and atc6-1 pete2 double mutants, each lacking Cyt C6A and one of the two plastocyanin-encoding genes, failed to reveal any genetic interaction. Overexpression of either PETE1 or PETE2 in the pete1 pete2 double knockout mutant background results in essentially wild-type photosynthetic performance, excluding the possibility that the two plastocyanin isoforms could have distinct functions in thylakoid electron flow.

  20. 液流储能电池模拟研究的进展%Advance in simulation research of redox flow battery

    Institute of Scientific and Technical Information of China (English)

    邢枫; 张华民; 马相坤; 王晓丽

    2011-01-01

    The state of simulation research of redox flow battery was introduced. The characteristics, research progress and limitations of mathematic models of zero dimension, one dimension, two dimension and leakage current were reviewed. The commercialized simulation softwares for redox flow battery were outlined, the development direction of simulating was discussed.%介绍了液流储能电池模拟研究的现状,综述了零维、一维、二维及漏电电流等数学模型的特点、研究进展及局限性,论述了液流储能电池用的商业化模拟软件,并展望了模拟的发展方向.

  1. Modeling of ion transport through a porous separator in vanadium redox flow batteries

    Science.gov (United States)

    Zhou, X. L.; Zhao, T. S.; An, L.; Zeng, Y. K.; Wei, L.

    2016-09-01

    In this work, we develop a two-dimensional, transient model to investigate the mechanisms of ion-transport through a porous separator in VRFBs and their effects on battery performance. Commercial-available separators with pore sizes of around 45 nm are particularly investigated and effects of key separator design parameters and operation modes are explored. We reveal that: i) the transport mechanism of vanadium-ion crossover through available separators is predominated by convection; ii) reducing the pore size below 15 nm effectively minimizes the convection-driven vanadium-ion crossover, while further reduction in migration- and diffusion-driven vanadium-ion crossover can be achieved only when the pore size is reduced to the level close to the sizes of vanadium ions; and iii) operation modes that can affect the pressure at the separator/electrode interface, such as the electrolyte flow rate, exert a significant influence on the vanadium-ion crossover rate through the available separators, indicating that it is critically important to equalize the pressure on each half-cell of a power pack in practical applications.

  2. Microwave-assisted preparation of carbon nanofiber-functionalized graphite felts as electrodes for polymer-based redox-flow batteries

    Science.gov (United States)

    Schwenke, A. M.; Janoschka, T.; Stolze, C.; Martin, N.; Hoeppener, S.; Schubert, U. S.

    2016-12-01

    A simple and fast microwave-assisted protocol to functionalize commercially available graphite felts (GFs) with carbon nanofibers (CNFs) for the application as electrode materials in redox-flow batteries (RFB) is demonstrated. As catalyst for the CNF synthesis nickel acetate is applied and ethanol serves as the carbon source. By the in-situ growth of CNFs, the active surface of the electrodes is increased by a factor of 50, which is determined by the electrochemical double layer capacities of the obtained materials. Furthermore, the morphology of the CNF-coating is investigated by scanning electron microscopy. Subsequently, the functionalized electrodes are applied in a polymer-based redox-flow battery (pRFB) using a TEMPO- and a viologen polymer as active materials. Due to the increased surface area as compared to an untreated graphite felt electrode, the current rating is improved by about 45% at 80 mA cm-2 and, furthermore, a decrease in overpotentials is observed. Thus, using this microwave-assisted synthesis approach, CNF-functionalized composite electrodes are prepared with a very simple protocol suitable for real life applications and an improvement of the overall performance of the polymer-based redox-flow battery is demonstrated.

  3. Research and development of peripheral technology for photovoltaic power systems. Research and development of redox flow battery for photovoltaic power generation; Shuhen gijutsu no kenkyu kaihatsu. Taiyoko hatsuden`yo redox denchi no kenkyu kaihatsu

    Energy Technology Data Exchange (ETDEWEB)

    Tatsuta, M. [New Energy and Industrial Technology Development Organization, Tokyo (Japan)

    1994-12-01

    This paper reports the study results on R and D of redox flow battery for photovoltaic power generation in fiscal 1994. (1) On the production method of electrolyte, silica reduction treatment was attempted to use ammonium metavanadate recovered from boiler as electrolyte of redox flow battery. Silica removal rates more than 90% were achieved by crystallizing V as polyvanadate while keeping molten silica. It was ascertained in minicell experiment that trivalent and quadrivalent V electrolytes produced from recovered V are applicable to continuous charge/discharge operation for one week. (2) On development of battery systems, the relation between battery characteristics and physicochemical properties of carbon fiber electrodes was studied to improve carbon fiber electrodes. The efficiency of 80% was achieved at current density of 160mA/cm{sup 2} by use of layered electrodes, resulting in considerable cost reduction. Performance evaluation operation of the 2kW battery prepared in the last fiscal year was also carried out. 4 figs.

  4. Numerical simulation of vanadium redox flow battery flow field%全钒液流电池管道内流场模拟分析

    Institute of Scientific and Technical Information of China (English)

    邱泽晶

    2012-01-01

    Vanadium redox flow battery (VRB) has been widely applied in various fields attributed to its excellent properties, however, its electrical performance is greatly influenced by its fluid behavior. Therefore, the flow field of VRB was investigated based on Fluent 6.3.26. The influence of branch tube diameter on electrolyte distribution was specifically discussed, and the deviation between theoretical velocity and simulated velocity was comparatively analyzed. The results show that the branch tube diameter impacts the electrolyte distribution significantly, and the simulated velocity fits quite well with theoretical velocity, indicating that the proposed simulation strategy is suitable for flow field modeling of VRB.%全钒液流电池凭借其性能优点在各方面都得到了大量应用,但其在应用过程中的流场特性对其性能存在很大影响.因此提出用Fluent 6.3.26对全钒液流电池管道内流场进行分析,讨论了不同支管管径对支管电解液流量分配的影响,比较了主管入口速度、支管出口速度的理论值和模拟值的差异.结果表明,支管管径对支管电解液流量分配有着明显的影响,速度理论值和模拟值的差异较小,提出模拟方法适合用于全钒液流电池管道内流场的模拟分析.

  5. A Total Organic Aqueous Redox Flow Battery Employing Low Cost and Sustainable Methyl Viologen Anolyte and 4-HO-TEMPO Catholyte

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Tianbiao L.; Wei, Xiaoliang; Nie, Zimin; Sprenkle, Vincent L.; Wang, Wei

    2016-02-04

    The worldwide increasing energy demands and rising CO2 emissions motivate a search of new technologies to take advantage of renewable energy such as solar and wind. Rechargeable redox flow batteries (RFBs) with their high power density, high energy efficiency, scalability (up to MW and MWh), and safety features are one suitable option for integrating such energy sources and overcoming their intermittency. Source limitation and forbidden high system costs of current RFBs technologies impede wide implementation. Here we report a total organic aqueous redox flow battery (OARFB), using low cost and sustainable MV (anolyte) and 4-HO-TEMPO (catholyte), and benign NaCl supporting electrolyte. The electrochemical properties of the organic redox active materials were studied using cyclic voltammetry and rotating disk electrode voltammetry. The MV/4-HO-TEMPO ARFB has an exceptionally high cell voltage, 1.25 V. Prototypes of the organic ARFB can be operated at high current densities ranging from 20 to 100 mA/cm2, and deliver stable capacity for 100 cycles with nearly 100% coulombic efficiency. The overall technical characters of the MV/4-HO-TEMPO ARFB are very attractive for continuous technic development.

  6. PI2 controller based coordinated control with Redox Flow Battery and Unified Power Flow Controller for improved Restoration Indices in a deregulated power system

    Directory of Open Access Journals (Sweden)

    R. Thirunavukarasu

    2016-12-01

    Full Text Available The nature of power system restoration problem involves status assessment, optimization of generation capability and load pickup. This paper proposes the evaluation of Power System Restoration Indices (PSRI based on the Automatic Generation Control (AGC assessment of interconnected power system in a deregulated environment. The PSRI are useful for system planners to prepare the power system restoration plans and to improve the efficiency of the physical operation of the power system with the increased transmission capacity in the network. The stabilization of frequency and tie-line power oscillations in an interconnected power system becomes challenging when implemented in the future competitive environment. This paper also deals with the concept of AGC in two-area reheat power system having coordinated control action with Redox Flow Battery (RFB and Unified Power Flow Controller (UPFC are capable of controlling the network performance in a very fast manner and improve power transfer limits in order to have a better restoration. In addition to that a new Proportional–Double Integral (PI2 controller is designed and implemented in AGC loop and controller parameters are optimized through Bacterial Foraging Optimization (BFO algorithm. Simulation results reveal that the proposed PI2 controller is that it has good stability during load variations, excellent transient and dynamic responses when compared with the system comprising PI controller. Moreover the AGC loop with RFB coordinated with UPFC has greatly improved the dynamic response and it reduces the control input requirements, to ensure improved PSRI in order to provide the reduced restoration time, thereby improving the system reliability.

  7. Synergistic effect of carbon nanofiber/nanotube composite catalyst on carbon felt electrode for high-performance all-vanadium redox flow battery.

    Science.gov (United States)

    Park, Minjoon; Jung, Yang-jae; Kim, Jungyun; Lee, Ho il; Cho, Jeaphil

    2013-10-01

    Carbon nanofiber/nanotube (CNF/CNT) composite catalysts grown on carbon felt (CF), prepared from a simple way involving the thermal decomposition of acetylene gas over Ni catalysts, are studied as electrode materials in a vanadium redox flow battery. The electrode with the composite catalyst prepared at 700 °C (denoted as CNF/CNT-700) demonstrates the best electrocatalytic properties toward the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples among the samples prepared at 500, 600, 700, and 800 °C. Moreover, this composite electrode in the full cell exhibits substantially improved discharge capacity and energy efficiency by ~64% and by ~25% at 40 mA·cm(-2) and 100 mA·cm(-2), respectively, compared to untreated CF electrode. This outstanding performance is due to the enhanced surface defect sites of exposed edge plane in CNF and a fast electron transfer rate of in-plane side wall of the CNT.

  8. A Simple Analytical Model of Coupled Single Flow Channel over Porous Electrode in Vanadium Redox Flow Battery with Serpentine Flow Channel

    CERN Document Server

    Ke, Xinyou; Prahl, Joseph M; Savinell, Robert F

    2016-01-01

    A simple analytical model of a layered system comprised of a single passage of a serpentine flow channel and a parallel underlying porous electrode (or porous layer) is proposed. This analytical model is derived from Navier-Stokes motion in the flow channel and Darcy-Brinkman model in the porous layer. The continuities of flow velocity and normal stress are applied at the interface between the flow channel and the porous layer. The effects of the inlet volumetric flow rate, thickness of the flow channel and thickness of a typical carbon fiber paper porous layer on the volumetric flow rate within this porous layer are studied. The maximum current density based on the electrolyte volumetric flow rate is predicted, and found to be consistent with reported numerical simulation. It is found that, for a mean inlet flow velocity of 33.3 cm s-1, the analytical maximum current density is estimated to be 377 mA cm-2, which compares favorably with experimental result reported by others of ~400 mA cm-2.

  9. A simple analytical model of coupled single flow channel over porous electrode in vanadium redox flow battery with serpentine flow channel

    Science.gov (United States)

    Ke, Xinyou; Alexander, J. Iwan D.; Prahl, Joseph M.; Savinell, Robert F.

    2015-08-01

    A simple analytical model of a layered system comprised of a single passage of a serpentine flow channel and a parallel underlying porous electrode (or porous layer) is proposed. This analytical model is derived from Navier-Stokes motion in the flow channel and Darcy-Brinkman model in the porous layer. The continuities of flow velocity and normal stress are applied at the interface between the flow channel and the porous layer. The effects of the inlet volumetric flow rate, thickness of the flow channel and thickness of a typical carbon fiber paper porous layer on the volumetric flow rate within this porous layer are studied. The maximum current density based on the electrolyte volumetric flow rate is predicted, and found to be consistent with reported numerical simulation. It is found that, for a mean inlet flow velocity of 33.3 cm s-1, the analytical maximum current density is estimated to be 377 mA cm-2, which compares favorably with experimental result reported by others of ∼400 mA cm-2.

  10. Bifunctional activation of a direct methanol fuel cell

    Science.gov (United States)

    Kulikovsky, A. A.; Schmitz, H.; Wippermann, K.; Mergel, J.; Fricke, B.; Sanders, T.; Sauer, D. U.

    We report a novel method for performance recovery of direct methanol fuel cells. Lowering of air flow rate below a critical value turns the cell into bifunctional regime, when the oxygen-rich part of the cell generates current while the rest part works in electrolysis mode (electrolytic domain). Upon restoring the normal (super-critical) air flow rate, the galvanic performance of the electrolytic domain increases. This recovery effect is presumably attributed to Pt surface cleaning on the cathode with the simultaneous increase in catalyst utilization on the anode.

  11. 全钒氧化还原液流电池研究进展%Research progress of all-vanadium redox flow battery

    Institute of Scientific and Technical Information of China (English)

    刘明义; 韩临武; 郑建涛; 徐海卫; 曹传钊

    2016-01-01

    全钒氧化还原液流电池(Vanadium Redox Flow Battery,VRFB)以其灵活、环保等特性,在储能领域备受关注.作为VRFB的重要性能指标,能量效率和能量密度一直是研究热点.介绍了用于提高能量效率的优化液流电池系统结构和用于提高能量密度的盐酸体系支持电解质,并分析了其影响机理.

  12. Studies on Molecular and Ion Transport in Silicalite Membranes and Applications as Ion Separator for Redox Flow Battery

    Science.gov (United States)

    Yang, Ruidong

    Microporous zeolite membranes have been widely studied for molecular separations based on size exclusion or preferential adsorption-diffusion mechanisms. The MFI-type zeolite membranes were also demonstrated for brine water desalination by molecular sieving effect. In this research, the pure silica MFI-type zeolite (i.e. silicalite) membrane has been for the first time demonstrated for selective permeation of hydrated proton (i.e. H3O+) in acidic electrolyte solutions. The silicalite membrane allows for permeation of H 3O+ ions, but is inaccessible to the large hydrated multivalent vanadium ions due to steric effect. The silicalite membrane has been further demonstrated as an effective ion separator in the all-vanadium redox flow battery (RFB).The silicalite is nonionic and its proton conductivity relies on the electric field-driven H3O+ transport through the sub nanometer-sized pores under the RFB operation conditions. The silicalite membrane displayed a significantly reduced self-discharge rate because of its high proton-to-vanadium ion transport selectivity. However, the nonionic nature of the silicalite membrane and very small diffusion channel size render low proton conductivity and is therefore inefficient as ion exchange membranes (IEMs) for practical applications. The proton transport efficiency may be improved by reducing the membrane thickness. However, the zeolite thin films are extremely fragile and must be supported on mechanically strong and rigid porous substrates. In this work, silicalite-Nafion composite membranes were synthesized to achieve a colloidal silicalite skin on the Nafion thin film base. The "colloidal zeolite-ionic polymer" layered composite membrane combines the advantages of high proton-selectivity of the zeolite layer and the mechanical flexibility and low proton transport resistance of the ionic polymer membrane. The composite membrane exhibited higher proton/vanadium ion separation selectivity and lower electrical resistance than

  13. Polyvinylpyrrolidone-based semi-interpenetrating polymer networks as highly selective and chemically stable membranes for all vanadium redox flow batteries

    Science.gov (United States)

    Zeng, L.; Zhao, T. S.; Wei, L.; Zeng, Y. K.; Zhang, Z. H.

    2016-09-01

    Vanadium redox flow batteries (VRFBs) with their high flexibility in configuration and operation, as well as long cycle life are competent for the requirement of future energy storage systems. Nevertheless, due to the application of perfluorinated membranes, VRFBs are plagued by not only the severe migration issue of vanadium ions, but also their high cost. Herein, we fabricate semi-interpenetrating polymer networks (SIPNs), consisting of cross-linked polyvinylpyrrolidone (PVP) and polysulfone (PSF), as alternative membranes for VRFBs. It is demonstrated that the PVP-based SIPNs exhibit extremely low vanadium permeabilities, which contribute to the well-established hydrophilic/hydrophobic microstructures and the Donnan exclusion effect. As a result, the coulombic efficiencies of VRFBs with PVP-based SIPNs reach almost 100% at 40 mA cm-2 to 100 mA cm-2; the energy efficiencies are more than 3% higher than those of VRFBs with Nafion 212. More importantly, the PVP-based SIPNs exhibit a superior chemical stability, as demonstrated both by an ex situ immersion test and continuously cycling test. Hence, all the characterizations and performance tests reported here suggest that PVP-based SIPNs are a promising alternative membrane for redox flow batteries to achieve superior cell performance and excellent cycling stability at the fraction of the cost of perfluorinated membranes.

  14. Increasing the energy density of the non-aqueous vanadium redox flow battery with the acetonitrile-1,3-dioxolane-dimethyl sulfoxide solvent mixture

    Science.gov (United States)

    Herr, T.; Fischer, P.; Tübke, J.; Pinkwart, K.; Elsner, P.

    2014-11-01

    Different solvent mixtures were investigated for non-aqueous vanadium acetylacetonate (V(acac)3) redox flow batteries with tetrabutylammonium hexafluorophosphate as the supporting electrolyte. The aim of this study was to increase the energy density of the non-aqueous redox flow battery. A mixture of acetonitrile, dimethyl sulfoxide and 1-3-dioxolane nearly doubles the solubility of the active species. The proposed electrolyte system was characterized by Raman and FT-IR spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy and charge-discharge set-up. Spectroscopic methods were applied to understand the interactions between the solvents used and their impact on the solubility. The potential difference between oxidation and reduction of V(acac)3 measured by cyclic voltammetry was about 2.2 V. Impedance spectroscopy showed an electrolyte resistance of about 2400 Ω cm2. Experiments in a charge-discharge test cell achieved coulombic and energy efficiencies of ∼95% and ∼27% respectively. The highest discharge power density was 0.25 mW cm-2.

  15. Extended dynamic model for ion diffusion in all-vanadium redox flow battery including the effects of temperature and bulk electrolyte transfer

    Science.gov (United States)

    Badrinarayanan, Rajagopalan; Zhao, Jiyun; Tseng, K. J.; Skyllas-Kazacos, Maria

    2014-12-01

    As with all redox flow batteries, the Vanadium Redox flow Battery (VRB) can suffer from capacity loss as the vanadium ions diffuse at different rates leading to a build-up on one half-cell and dilution on the other. In this paper an extended dynamic model of the vanadium ion transfer is developed including the effect of temperature and bulk electrolyte transfer. The model is used to simulate capacity decay for a range of different ion exchange membranes that are being used in the VRB. The simulations show that Selemion CMV and Nafion 115 membranes have similar behavior where the impact of temperature on capacity loss is highest within the first 100 cycles. The results for Selemion AMV membrane however are seen to be very different where the capacity loss at different temperatures observed to increase linearly with increasing charging/discharging cycles. The model is made more comprehensive by including the effect of bulk electrolyte transfer. A volume change of 19% is observed in each half-cell for Nafion 115 membrane based on the simulation parameters. The effect of this change in volume directly affects concentration, and the characteristics are analyzed for each vanadium species as well as the overall concentration in the half-cells.

  16. 全钒液流电池发展现状%Current development status of all-vanadiunl redox flow battery

    Institute of Scientific and Technical Information of China (English)

    代广涛

    2013-01-01

      全钒液流电池是一种新型的高效化学储能电池,在太阳能和风能发电储能系统及其他储能系统和供电领域具有良好的应用前景。简要介绍了全钒液流电池的工作原理和特点,并对钒电池的组成、分类和关键材料进行了简明叙述,分析了国内外钒电池的发展过程和研究现状。%  All-vanadium redox flow battery (VRB) was a new type of high efficient chemical energy storage battery, applied to solar energy and wind energy storage system as much as power supply and other energy storage system with a good application prospect. Working principle and features of all-vanadium redox flow battery were briefly introduced, in addition, the composition, classification and key materials of vanadium battery are also provided. A brief analysis on domestic and foreign development process and research situation of VRB was made.

  17. Graphene-Nanowall-Decorated Carbon Felt with Excellent Electrochemical Activity Toward VO2(+)/VO(2+) Couple for All Vanadium Redox Flow Battery.

    Science.gov (United States)

    Li, Wenyue; Zhang, Zhenyu; Tang, Yongbing; Bian, Haidong; Ng, Tsz-Wai; Zhang, Wenjun; Lee, Chun-Sing

    2016-04-01

    3D graphene-nanowall-decorated carbon felts (CF) are synthesized via an in situ microwave plasma enhanced chemical vapor deposition method and used as positive electrode for vanadium redox flow battery (VRFB). The carbon fibers in CF are successfully wrapped by vertically grown graphene nanowalls, which not only increase the electrode specific area, but also expose a high density of sharp graphene edges with good catalytic activities to the vanadium ions. As a result, the VRFB with this novel electrode shows three times higher reaction rate toward VO2(+)/VO(2+) redox couple and 11% increased energy efficiency over VRFB with an unmodified CF electrode. Moreover, this designed architecture shows excellent stability in the battery operation. After 100 charging-discharging cycles, the electrode not only shows no observable morphology change, it can also be reused in another battery and practical with the same performance. It is believed that this novel structure including the synthesis procedure will provide a new developing direction for the VRFB electrode.

  18. Novel composite membrane coated with a poly(diallyldimethylammonium chloride)/urushi semi-interpenetrating polymer network for non-aqueous redox flow battery application

    Science.gov (United States)

    Cho, Eunhae; Won, Jongok

    2016-12-01

    Novel composite membranes of a semi-interpenetrating network (semi-IPN) coated on the surfaces of a porous Celgard 2400 support are prepared and investigate for application in a non-aqueous redox flow battery (RFB). A natural polymer, urushi, is used for the matrix because of its high mechanical robustness, and poly(diallyldimethylammonium chloride) (PDDA) provides anionic exchange sites. The PDDA/urushi (P/U) semi-IPN film is prepared by the photo polymerization of urushiol in the presence of PDDA. The thin layer composed of the P/U semi-IPN on the porous support provides selectivity while maintaining the ion conductivity. The coulombic and energy efficiencies increase with increasing amounts of PDDA in the P/U semi-IPN layer, and the values reach 69.5% and 42.5%, respectively, for the one containing 40 wt% of PDDA. These values are substantially higher than those of the Neosepta AHA membrane and the Celgard membrane, indicating that the selective layer reduces the crossover of the redox active species through the membrane. This result implies that the formation of composite membranes using semi-IPN selective layers on the dimensionally stable porous membrane enable the successful use of a non-aqueous RFB for future energy storage systems.

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

    Science.gov (United States)

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

    2017-02-01

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

  20. Electrochemical Switching of Conductance with Diarylethene-Based Redox-Active Polymers

    DEFF Research Database (Denmark)

    Logtenberg, Hella; van der Velde, Jasper H. M.; de Mendoza, Paula;

    2012-01-01

    Reversible switching of conductance using redox triggered switching of a polymer-modified electrode is demonstrated. A bifunctional monomer comprising a central electroswitchable core and two bithiophene units enables formation of a film through anodic electropolymerization. The conductivity...... of the polymer can be switched electrochemically in a reversible manner by redox triggered opening and closing of the diarylethene unit. In the closed state, the conductivity of the modified electrode is higher than in the open state....

  1. Microfluidic redox battery.

    Science.gov (United States)

    Lee, Jin Wook; Goulet, Marc-Antoni; Kjeang, Erik

    2013-07-01

    A miniaturized microfluidic battery is proposed, which is the first membraneless redox battery demonstrated to date. This unique concept capitalizes on dual-pass flow-through porous electrodes combined with stratified, co-laminar flow to generate electrical power on-chip. The fluidic design is symmetric to allow for both charging and discharging operations in forward, reverse, and recirculation modes. The proof-of-concept device fabricated using low-cost materials integrated in a microfluidic chip is shown to produce competitive power levels when operated on a vanadium redox electrolyte. A complete charge/discharge cycle is performed to demonstrate its operation as a rechargeable battery, which is an important step towards providing sustainable power to lab-on-a-chip and microelectronic applications.

  2. Electron Flow in Multiheme Bacterial Cytochromes is a Balancing Act Between Heme Electronic Interaction and Redox Potentials

    Energy Technology Data Exchange (ETDEWEB)

    Breuer, Marian; Rosso, Kevin M.; Blumberger, Jochen

    2014-01-14

    The naturally widespread process of electron transfer from metal reducing bacteria to extracellular solid metal oxides entails unique biomolecular machinery optimized for long-range electron transport. To perform this function efficiently microorganisms have adapted multi-heme c-type cytochromes to arrange heme cofactors into wires that cooperatively span the cellular envelope, transmitting electrons along distances greater than 100 Angstroms. Implications and opportunities for bionanotechnological device design are self-evident. However, at the molecular level how these proteins shuttle electrons along their heme wires, navigating intraprotein intersections and interprotein interfaces effciently, remains a mystery so far inaccessible to experiment. To shed light on this critical topic, we carried out extensive computer simulations to calculate Marcus theory quantities for electron transfer along the ten heme cofactors in the recently crystallized outer membrane cytochrome MtrF. The combination of electronic coupling matrix elements with free energy calculations of heme redox potentials and reorganization energies for heme-to-heme electron transfer allows the step-wise and overall electron transfer rate to be estimated and understood in terms of structural and dynamical characteristics of the protein. By solving a master equation for electron hopping, we estimate an intrinsic, maximum possible electron flux through solvated MtrF of 104-105 s-1, consistent with recently measured rates for the related MtrCAB protein complex. Intriguingly, this flux must navigate thermodynamically uphill steps past low potential hemes. Our calculations show that the rapid electron transport through MtrF is the result of a clear correlation between heme redox potential and the strength of electronic coupling along the wire: Thermodynamically uphill steps occur only between electronically well connected stacked heme pairs. This suggests that the protein evolved to harbor low potential

  3. Synthesis of bifunctional antibodies for immunoassays.

    Science.gov (United States)

    DeSilva, B S; Wilson, G S

    2000-09-01

    The synthesis of bifunctional antibodies using the principle of solid-phase synthesis is described. Two Fab' fragments were chemically linked together via a bismaleimide crosslinking reagent. The F(ab')(2) fragments from intact immunoglobulin G (IgG) were prepared using an immobilized pepsin column. Goat, mouse, and human antibodies were digested completely within 4 h. The F(ab')(2) fragments thus produced did not contain any IgG impurities. Fab' fragments were produced by reducing the heavy interchain disulfide bonds using 2-mercaptoethylamine. Use of the solid-phase reactor in the preparation of the bifunctional antibodies eliminated many of the time-consuming separation steps between the fragmentation and conjugation steps. This procedure facilitates the automation of bifunctional antibody preparation and the rapid optimization of reaction conditions.

  4. Solid phase synthesis of bifunctional antibodies.

    Science.gov (United States)

    DeSilva, B S; Wilson, G S

    1995-12-15

    Bifunctional antibodies were prepared using the principle of solid-phase synthesis. The two Fab' fragments were chemically linked together via a bismaleimide crosslinking reagent. The F(ab')2 fragments from intact IgG were prepared using an immobilized pepsin column. Goat, mouse and human antibodies were digested completely within 4 h. The F(ab')2 fragments thus produced did not contain any IgG impurities. The Fab' fragments were produced by reducing the inter-heavy chain disulfide bonds using 2-mercaptoethylamine. The use of the solid-phase reactor in the preparation of the bifunctional antibodies eliminated many of the time-consuming separation steps between the fragmentation and conjugation steps. This procedure facilitates the automation of the bifunctional antibody preparation and the rapid optimization of reaction conditions.

  5. Performance of Nafion® N115, Nafion® NR-212, and Nafion® NR-211 in a 1 kW Class All Vanadium Mixed Acid Redox Flow Battery

    Energy Technology Data Exchange (ETDEWEB)

    Reed, David M.; Thomsen, Edwin C.; Wang, Wei; Nie, Zimin; Li, Bin; Wei, Xiaoliang; Koeppel, Brian J.; Sprenkle, Vincent L.

    2015-07-01

    Three Nafion membranes of similar composition but different thicknesses were operated in a 3-cell 1kW class all vanadium mixed acid redox flow battery. The influence of current density on the charge/discharge characteristics, coulombic and energy efficiency, capacity fade, operating temperature and pressure drop in the flow circuit will be discussed and correlated to the Nafion membrane thickness. Material costs associated with the Nafion membranes, ease of handling the membranes, and performance impacts will also be discussed.

  6. Photorespiration provides the chance of cyclic electron flow to operate for the redox-regulation of P700 in photosynthetic electron transport system of sunflower leaves.

    Science.gov (United States)

    Takagi, Daisuke; Hashiguchi, Masaki; Sejima, Takehiro; Makino, Amane; Miyake, Chikahiro

    2016-09-01

    To elucidate the molecular mechanism to oxidize the reaction center chlorophyll, P700, in PSI, we researched the effects of partial pressure of O2 (pO2) on photosynthetic characteristic parameters in sunflower (Helianthus annuus L.) leaves. Under low CO2 conditions, the oxidation of P700 was stimulated; however the decrease in pO2 suppressed its oxidation. Electron fluxes in PSII [Y(II)] and PSI [Y(I)] showed pO2-dependence at low CO2 conditions. H(+)-consumption rate, estimated from Y(II) and CO2-fixation/photorespiration rates (JgH(+)), showed the positive curvature relationship with the dissipation rate of electrochromic shift signal (V H (+) ), which indicates H(+)-efflux rate from lumen to stroma in chloroplasts. Therefore, these electron fluxes contained, besides CO2-fixation/photorespiration-dependent electron fluxes, non-H(+)-consumption electron fluxes including Mehler-ascorbate peroxidase (MAP)-pathway. Y(I) that was larger than Y(II) surely implies the functioning of cyclic electron flow (CEF). Both MAP-pathway and CEF were suppressed at lower pO2, with plastoquinone-pool reduced. That is, photorespiration prepares the redox-poise of photosynthetic electron transport system for CEF activity as an electron sink. Excess Y(II), [ΔY(II)] giving the curvature relationship with V H (+) , and excess Y(I) [ΔCEF] giving the difference between Y(I) and Y(II) were used as an indicator of MAP-pathway and CEF activity, respectively. Although ΔY(II) was negligible and did not show positive relationship to the oxidation-state of P700, ΔCEF showed positive linear relationship to the oxidation-state of P700. These facts indicate that CEF cooperatively with photorespiration regulates the redox-state of P700 to suppress the over-reduction in PSI under environmental stress conditions.

  7. Systemic Inflammatory Response Syndrome in End-Stage Heart Failure Patients Following Continuous-Flow Left Ventricular Assist Device Implantation: Differences in Plasma Redox Status and Leukocyte Activation.

    Science.gov (United States)

    Mondal, Nandan K; Sorensen, Erik N; Pham, Si M; Koenig, Steven C; Griffith, Bartley P; Slaughter, Mark S; Wu, Zhongjun J

    2016-05-01

    The role of oxidative stress and leukocyte activation has not been elucidated in developing systemic inflammatory response syndrome (SIRS) in heart failure (HF) patients after continuous-flow left ventricular assist device (CF-LVAD) implantation. The objective of this study was to investigate the change of plasma redox status and leukocyte activation in CF-LVAD implanted HF patients with or without SIRS. We recruited 31 CF-LVAD implanted HF patients (16 SIRS and 15 non-SIRS) and 11 healthy volunteers as the control. Pre- and postimplant blood samples were collected from the HF patients. Plasma levels of oxidized low-density lipoprotein (oxLDL), malondialdehyde (MDA), total antioxidant capacity (TAC), superoxide dismutase (SOD) in erythrocyte, myeloperoxidase (MPO), and polymorphonuclear elastase (PMN-elastase) were measured. The HF patients had a preexisting condition of oxidative stress than healthy controls as evident from the higher oxLDL and MDA levels as well as depleted SOD and TAC. Leukocyte activation in terms of higher plasma MPO and PMN-elastase was also prominent in HF patients than controls. Persistent oxidative stress and reduced antioxidant status were found to be more belligerent in HF patients with SIRS after the implantation of CF-LVAD when compared with non-SIRS patients. Similar to oxidative stress, the activation of blood leukocyte was significantly highlighted in SIRS patients after implantation compared with non-SIRS. We identified that the plasma redox status and leukocyte activation became more prominent in CF-LVAD implanted HF patients who developed SIRS. Our findings suggest that plasma biomarkers of oxidative stress and leukocyte activation may be associated with the development of SIRS after CF-LVAD implant surgery.

  8. Degradation of all-vanadium redox flow batteries (VRFB) investigated by electrochemical impedance and X-ray photoelectron spectroscopy: Part 2 electrochemical degradation

    Science.gov (United States)

    Derr, Igor; Bruns, Michael; Langner, Joachim; Fetyan, Abdulmonem; Melke, Julia; Roth, Christina

    2016-09-01

    Electrochemical degradation (ED) of carbon felt electrodes was investigated by cycling of a flow through all-vanadium redox flow battery (VRFB) and conducting half-cell measurements with two reference electrodes inside the test bench. ED was detected using half-cell and full-cell electrochemical impedance spectroscopy (EIS) at different states of charge (SOC). Reversing the polarity of the battery to recover cell performance was performed with little success. Renewing the electrolyte after a certain amount of cycles restored the capacity of the battery. X-ray photoelectron spectroscopy (XPS) reveals that the amount of surface functional increases by more than a factor of 3 for the negative side as well as for the positive side. Scanning electron microscope (SEM) images show a peeling of the fiber surface after cycling the felts, which leads to a loss of electrochemically active surface area (ECSA). Long term cycling shows that ED has a stronger impact on the negative half-cell [V(II)/V(III)] than the positive half-cell [V(IV)/V(V)] and that the negative half-cell is the rate-determining half-cell for the VRFB.

  9. Effects of temperature on the performance of vanadium redox flow battery%温度对全钒液流电池性能的影响

    Institute of Scientific and Technical Information of China (English)

    唐重樾; 严敢; 高存博; 赵振生; 吕玉祥

    2015-01-01

    全钒电池的传热参数优化和电堆温度分布的研究,对提高全钒电池的性能和可靠性起着重要的推进作用。基于对流传热的原理,提出了一个关于全钒液流电池系统的热模型,通过对不同流量和传热系数下全钒液流电池温度分布的研究,得到全钒电池电解液罐温度和电堆温度之间的关系。利用Fluent模拟仿真不同流量下电堆中电解液的温度分布。仿真结果表明,系统的对流换热参数和电解液流量是影响温度分布的重要因素,在该电池配置下电解液流量为90 cm3·s–1时,电堆的温度分布均匀,此时的电池性能较好。%Study of the optimization of heat transfer coefficient and the electrolyte temperature distribution in stack plays an important role to improve the efficiency and reliability of the vanadium battery. Based on the knowledge of the convection heat transfer, a thermal model about the system of vanadium redox flow battery was proposed. After investigation of the temperature distribution of vanadium flow battery with different flow rates and heat transfer coefficient, the temperature relationship between the tank electrolyte and stack electrolyte in the system was obtained. Fluent software was used to simulate the temperature distribution of stack electrolyte under different flow rates. Results of simulation show that the heat transfer coefficient and the electrolyte flow rate are the important factors those affect the temperature distribution. In this battery configuration, the temperature distribution of stack electrolyte is uniform and the battery performance is better when the flow rate of electrolyte is 90 cm3·s–1.

  10. Extended Kalman filter method for state of charge estimation of vanadium redox flow battery using thermal-dependent electrical model

    Science.gov (United States)

    Xiong, Binyu; Zhao, Jiyun; Wei, Zhongbao; Skyllas-Kazacos, Maria

    2014-09-01

    State of charge (SOC) estimation is a key issue for battery management since an accurate estimation method can ensure safe operation and prevent the over-charge/discharge of a battery. Traditionally, open circuit voltage (OCV) method is utilized to estimate the stack SOC and one open flow cell is needed in each battery stack [1,2]. In this paper, an alternative method, extended Kalman filter (EKF) method, is proposed for SOC estimation for VRBs. By measuring the stack terminal voltages and applied currents, SOC can be predicted with a state estimator instead of an additional open circuit flow cell. To implement EKF estimator, an electrical model is required for battery analysis. A thermal-dependent electrical circuit model is proposed to describe the charge/discharge characteristics of the VRB. Two scenarios are tested for the robustness of the EKF. For the lab testing scenarios, the filtered stack voltage tracks the experimental data despite the model errors. For the online operation, the simulated temperature rise is observed and the maximum SOC error is within 5.5%. It is concluded that EKF method is capable of accurately predicting SOC using stack terminal voltages and applied currents in the absence of an open flow cell for OCV measurement.

  11. 全钒液流电池隔膜材料进展%Ion Exchange Membranes for Vanadium Redox Flow Battery Applications

    Institute of Scientific and Technical Information of China (English)

    刘红丽; 高艳; 谢光有

    2015-01-01

    全钒液流电池是一种新型的高效储能电池, 离子交换膜作为其核心功能部件之一, 得到广泛研究. 本文综述了商业化和改性阳离子交换膜、 阴离子交换膜、 两性离子交换膜的制备方法、 结构特点、 电池效率, 并从钒电池电堆和系统性能及寿命出发, 讨论了上述膜材料的优缺点.%Vanadium Redox Flow Battery ( VRB) is receiving more attention due to its technical advantages for large scale energy storage applications. As the key component of VRB, Ion Exchange Membrane ( IEM ) is responsible for transferring ions and preventing electrolyte from crossing over between positive and negative electrodes during the charge and discharge process of VRB. In this paper, the recent R&D progress of three types of IEM, including cation, anion and amphoteric membranes, are reviewed in terms of their fabrication method, composition and performance. Also, the pros and cons of the membranes are discussed regarding their VRB stack and system performance and lifetime.

  12. Properties investigation of sulfonated poly(ether ether ketone)/polyacrylonitrile acid-base blend membrane for vanadium redox flow battery application.

    Science.gov (United States)

    Li, Zhaohua; Dai, Wenjing; Yu, Lihong; Liu, Le; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

    2014-11-12

    Acid-base blend membrane prepared from sulfonated poly(ether ether ketone) (SPEEK) and polyacrylonitrile (PAN) was detailedly evaluated for vanadium redox flow battery (VRFB) application. SPEEK/PAN blend membrane exhibited dense and homogeneous cross-section morphology as scanning electron microscopy and energy-dispersive X-ray spectroscopy images show. The acid-base interaction of ionic cross-linking and hydrogen bonding between SPEEK and PAN could effectively reduce water uptake, swelling ratio, and vanadium ion permeability, and improve the performance and stability of blend membrane. Because of the good balance of proton conductivity and vanadium ion permeability, blend membrane with 20 wt % PAN (S/PAN-20%) showed higher Coulombic efficiency (96.2% vs 91.1%) and energy efficiency (83.5% vs 78.4%) than Nafion 117 membrane at current density of 80 mA cm(-2) when they were used in VRFB single cell. Besides, S/PAN-20% membrane kept a stable performance during 150 cycles at current density of 80 mA cm(-2) in the cycle life test. Hence the SPEEK/PAN acid-base blend membrane could be used as promising candidate for VRFB application.

  13. Influence of solvents on species crossover and capacity decay in non-aqueous vanadium redox flow batteries: Characterization of acetonitrile and 1, 3 dioxolane solvent mixture

    Science.gov (United States)

    Bamgbopa, Musbaudeen O.; Almheiri, Saif

    2017-02-01

    The importance of the choice of solvent in a non-aqueous redox flow battery (NARFB) cannot be overemphasized. Several studies demonstrated the influence of the solvent on electrolyte performance in terms of reaction rates, energy/power densities, and efficiencies. In this work, we investigate capacity decay as a direct consequence of varying reactant crossover rates through membranes in different solvent environments. Specifically, we demonstrate the superiority of an 84/16 vol% acetonitrile/1,3 dioxolane solvent mixture over pure acetonitrile in terms of energy efficiency (up to 89%) and capacity retention for vanadium NARFBs - while incorporating a Nafion 115 membrane. The permeability of Nafion to the vanadium acetylacetonate active species is an order of magnitude lower when pure acetonitrile is replaced by the solvent mixture. A method to estimate relative membrane permeability is formulated from numerical analysis of self-discharge experimental data. Furthermore, tests on a modified Nafion/SiO2 membrane, which generally offered low species permeability, also show that different solvents alter membrane permeability. Elemental and morphological analyses of cycled Nafion and NafionSi membranes in different solvent environments indicate that different crossover rates induced by the choice of solvent during cycling are due to changes in the membrane microstructure, intrinsic permeability, swelling rates, and chemical stability.

  14. Characterization of sulfonated poly(ether ether ketone)/poly(vinylidene fluoride-co-hexafluoropropylene) composite membrane for vanadium redox flow battery application

    Science.gov (United States)

    Li, Zhaohua; Liu, Le; Yu, Lihong; Wang, Lei; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

    2014-12-01

    Sulfonated poly(ether ether ketone) (SPEEK) and poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-co-HFP)) composite membranes are prepared and investigated in detail for vanadium redox flow battery (VRFB) application. With the high hydrophobicity and stability of P(VDF-co-HFP), the properties of composite membranes such as mechanical property and vanadium ion permeability are effectively improved, showing good trends with the increasing of P(VDF-co-HFP) mass ratio. The VRFB single cell assembled with the composite membrane of 15 wt.% P(VDF-co-HFP) (SPEEK-15% membrane) exhibits higher coulombic efficiency (CE, 95.4%) and energy efficiency (EE, 83.8%) than that assembled with Nafion 117 membrane (CE 91.1% and EE 78.4%) at the current density of 80 mA cm-2. Furthermore, the SPEEK-15% membrane maintains a stable performance during 100 cycles at the current density of 80 mA cm-2. Therefore the SPEEK/P(VDF-co-HFP) composite membrane could be used as low-cost and high-performance membrane for VRFB application.

  15. Measuring the state of charge of the electrolyte solution in a vanadium redox flow battery using a four-pole cell device

    Science.gov (United States)

    Ngamsai, Kittima; Arpornwichanop, Amornchai

    2015-12-01

    The decrease in the efficiency and capacity of a vanadium redox flow battery (VRB) caused by an electrolyte imbalance is an important impediment to its long-term operation. Knowing the state of charge (SOC) of an electrolyte solution can quantify the level of the electrolyte imbalance in the VRB. In this study, a four-pole cell device is devised and employed to predict the SOC. The proposed method directly measures the ionic resistance of the electrolyte solution and is sufficiently precise to be applied in real-time mode. Experimental studies on the effects of the operating current on the four-pole cell and the concentrations of vanadium and sulfuric acid in the electrolyte solution are carried out. The results show that the four-pole cell method can be utilized to measure the electrolyte SOC. The concentrations of vanadium and sulfuric acid in the electrolyte solution affect the ionic resistance of the solution. Regarding the capacity and efficiency of the VRB system, the results indicate that the electrical charge is determined from the concentration of vanadium and that the cell voltage depends on the concentration of sulfuric acid in the electrolyte solution. The decreased vanadium concentration and increased sulfuric acid concentration improves the cell voltage efficiency.

  16. Anion exchange membrane prepared from simultaneous polymerization and quaternization of 4-vinyl pyridine for non-aqueous vanadium redox flow battery applications

    Science.gov (United States)

    Maurya, Sandip; Shin, Sung-Hee; Sung, Ki-Won; Moon, Seung-Hyeon

    2014-06-01

    A simple, single step and environmentally friendly process is developed for the synthesis of anion exchange membrane (AEM) by simultaneous polymerization and quaternization, unlike the conventional membrane synthesis which consists of separate polymerization and quaternization step. The membrane synthesis is carried out by dissolving polyvinyl chloride (PVC) in cyclohexanone along with 4-vinyl pyridine (4VP) and 1,4-dibromobutane (DBB) in the presence of thermal initiator benzoyl peroxide, followed by film casting to get thin and flexible AEMs. The membrane properties such as ion exchange capacity, ionic conductivity and swelling behaviour are tuned by varying the degree of crosslinking. These AEMs exhibit low vanadium permeability, while retaining good dimensional and chemical stability in an electrolyte solution, making them appropriate candidates for non-aqueous vanadium acetylacetonate redox flow battery (VRFB) applications. The optimized membrane displays ion exchange capacity and ionic conductivity of 2.0 mequiv g-1 and 0.105 mS cm-1, respectively, whereas the efficiency of 91.7%, 95.7% and 87.7% for coulombic, voltage and energy parameter in non-aqueous VRFB, respectively. This study reveals that the non-aqueous VRFB performance is greatly influenced by membrane properties; therefore the optimal control over the membrane properties is advantageous for the improved performance.

  17. In situ X-ray near-edge absorption spectroscopy investigation of the state of charge of all-vanadium redox flow batteries.

    Science.gov (United States)

    Jia, Chuankun; Liu, Qi; Sun, Cheng-Jun; Yang, Fan; Ren, Yang; Heald, Steve M; Liu, Yadong; Li, Zhe-Fei; Lu, Wenquan; Xie, Jian

    2014-10-22

    Synchrotron-based in situ X-ray near-edge absorption spectroscopy (XANES) has been used to study the valence state evolution of the vanadium ion for both the catholyte and anolyte in all-vanadium redox flow batteries (VRB) under realistic cycling conditions. The results indicate that, when using the widely used charge-discharge profile during the first charge process (charging the VRB cell to 1.65 V under a constant current mode), the vanadium ion valence did not reach V(V) in the catholyte and did not reach V(II) in the anolyte. Consequently, the state of charge (SOC) for the VRB cell was only 82%, far below the desired 100% SOC. Thus, such incompletely charged mix electrolytes results in not only wasting the electrolytes but also decreasing the cell performance in the following cycles. On the basis of our study, we proposed a new charge-discharge profile (first charged at a constant current mode up to 1.65 V and then continuously charged at a constant voltage mode until the capacity was close to the theoretical value) for the first charge process that achieved 100% SOC after the initial charge process. Utilizing this new charge-discharge profile, the theoretical charge capacity and the full utilization of electrolytes has been achieved, thus having a significant impact on the cost reduction of the electrolytes in VRB.

  18. Effect of degree of sulfonation and casting solvent on sulfonated poly(ether ether ketone) membrane for vanadium redox flow battery

    Science.gov (United States)

    Xi, Jingyu; Li, Zhaohua; Yu, Lihong; Yin, Bibo; Wang, Lei; Liu, Le; Qiu, Xinping; Chen, Liquan

    2015-07-01

    The properties of sulfonated poly(ether ether ketone) (SPEEK) membranes with various degree of sulfonation (DS) and casting solvent are investigated for vanadium redox flow battery (VRFB). The optimum DS of SPEEK membrane is firstly confirmed by various characterizations such as physicochemical properties, ion selectivity, and VRFB single-cell performance. Subsequently the optimum casting solvent is selected for the optimum DS SPEEK membrane within N,N‧-dimethylformamide (DMF), N,N‧-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and dimethylsulfoxide (DMSO). The different performance of SPEEK membranes prepared with various casting solvents can be attributed to the different interaction between solvent and -SO3H group of SPEEK. In the VRFB single-cell test, the optimum SPEEK membrane with DS of 67% and casting solvent of DMF (S67-DMF membrane) exhibits higher VRFB efficiencies and better cycle-life performance at 80 mA cm-2. The investigation of various DS and casting solvent will be effective guidance on the selection and modification of SPEEK membrane towards VRFB application.

  19. Model based examination on influence of stack series connection and pipe diameters on efficiency of vanadium redox flow batteries under consideration of shunt currents

    Science.gov (United States)

    König, S.; Suriyah, M. R.; Leibfried, T.

    2015-05-01

    Model based design and optimization of large scale vanadium redox flow batteries can help to decrease system costs and to increase system efficiency. System complexity, e.g. the combination of hydraulic and electric circuits requires a multi-physic modeling approach to cover all dependencies between subsystems. A Matlab/Simulink model is introduced, which covers a variable number of stacks and their hydraulic circuit, as well as the impact of shunt currents. Using analytic approaches that are afterward crosschecked with the developed model, a six-stack, 54 kW/216 kWh system is designed. With the simulation results it is demonstrated how combining stacks to strings and varying pipe diameters affects system efficiency. As cell voltage is comparatively low, connecting stacks in series to strings seems reasonable to facilitate grid connection. It is shown that this significantly lowers system efficiency. Hydraulic circuit design is varied to lower efficiency drop. In total, four different electric designs are equipped with 21 hydraulic design variations to quantify dependencies between electric and hydraulic subsystems. Furthermore, it is examined whether additional shunt current losses through stack series connection can be compensated by more efficient energy conversion systems.

  20. Surface properties and graphitization of polyacrylonitrile based fiber electrodes affecting the negative half-cell reaction in vanadium redox flow batteries

    Science.gov (United States)

    Langner, J.; Bruns, M.; Dixon, D.; Nefedov, A.; Wöll, Ch.; Scheiba, F.; Ehrenberg, H.; Roth, C.; Melke, J.

    2016-07-01

    Carbon felt electrodes for vanadium redox flow batteries are obtained by the graphitization of polyacrylonitrile based felts at different temperatures. Subsequently, the surface of the felts is modified via thermal oxidation at various temperatures. A single-cell experiment shows that the voltage efficiency is increased by this treatment. Electrode potentials measured with reference electrode setup show that this voltage efficiency increase is caused mainly by a reduction of the overpotential of the negative half-cell reaction. Consequently, this reaction is investigated further by cyclic voltammetry and the electrode activity is correlated with structural and surface chemical properties of the carbon fibers. By Raman, X-ray photoelectron and near edge X-ray absorption fine structure spectroscopy the role of edge sites and oxygen containing functional groups (OCFs) for the electrochemical activity are elucidated. A significant activity increase is observed in correlation with these two characteristics. The amount of OCFs is correlated with structural defects (e.g. edge sites) of the carbon fibers and therefore decreases with an increasing graphitization degree. Thus, for the same thermal oxidation temperature carbon fibers graphitized at a lower temperature show higher activities than those graphitized at a higher temperature.

  1. A soluble-lead redox flow battery with corrugated graphite sheet and reticulated vitreous carbon as positive and negative current collectors

    Indian Academy of Sciences (India)

    A Banerjee; D Saha; T N Guru Row; A K Shukla

    2013-02-01

    A soluble-lead redox flow battery with corrugated-graphite sheet and reticulated-vitreous carbon as positive and negative current collectors is assembled and performance tested. In the cell, electrolyte comprising of 1.5M lead (II) methanesulfonate and 0.9 M methanesulfonic acid with sodium salt of lignosulfonic acid as additive is circulated through the reaction chamber at a flow rate of 50 ml min-1. During the charge cycle, pure lead (Pb) and lead dioxide (PbO2) from the soluble lead (II) species are electrodeposited onto the surface of the negative and positive current collectors, respectively. Both the electrodeposited materials are characterized by XRD, XPS and SEM. Phase purity of synthesized lead (II) methanesulfonate is unequivocally established by single crystal X-ray diffraction followed by profile refinements using high resolution powder data. During the discharge cycle, electrodeposited Pb and PbO2 are dissolved back into the electrolyte. Since lead ions are produced during oxidation and reduction at the negative and positive plates, respectively there is no risk of crossover during discharge cycle, preventing the possibility of lowering the overall efficiency of the cell. As the cell employs a common electrolyte, the need of employing a membrane is averted. It has been possible to achieve a capacity value of 114 mAh g−1 at a load current-density of 20 mA cm-2 with the cell at a faradaic efficiency of 95%. The cell is tested for 200 cycles with little loss in its capacity and efficiency.

  2. Analysis of Pump Loss on the Performance and Effect of all Vanadium Redox Flow Battery%全钒液流电池泵损耗对电池的性能和效率影响分析

    Institute of Scientific and Technical Information of China (English)

    李伟; 吕玉祥; 王启银; 赵锐

    2014-01-01

    建立一个全钒液流电池系统模型,通过对全钒液流电池系统模型在不同管径和流速下的泵损耗进行理论分析和研究,得出全钒电池泵损耗的规律。运用Fluent模拟仿真半电池在不同流速下的电解液分布,不同充电电流和流速下对全钒液流电池性能的影响。结果表明:根据钒电池结构优化控制泵的损耗和电解液流速,对于提高钒电池储能系统的效率和改善电池系统稳定性至关重要。在大规模应用储能技术时,泵损和流速的影响将更为明显。%A vanadium redox flow batteries system was modelling. Through theoretical analysis and research on the all vanadium redox flow batteries system under different pipe diameter and velocity of pump loss,the pump depletion of the law is concluded. Using the Fluent software simulate half cell electrolyte distribution under different flow rate,the performances of all vanadium redox flow batteries are affected by different charging current and velocity. Results show that according to the loss of vanadium battery structure optimization control pump and the electrolyte flow rate,it is very important to improve the efficiency of vanadium battery energy storage system and the battery system stability. In the large scale energy storage technology,the pump damage and the influence of flow rate are more apparent.

  3. Performance of Nafion® N115, Nafion® NR-212, and Nafion® NR-211 in a 1 kW class all vanadium mixed acid redox flow battery

    Science.gov (United States)

    Reed, David; Thomsen, Edwin; Wang, Wei; Nie, Zimin; Li, Bin; Wei, Xiaoliang; Koeppel, Brian; Sprenkle, Vincent

    2015-07-01

    Three Nafion® membranes of similar composition but different thicknesses were operated in a 3-cell 1 kW class all vanadium mixed acid redox flow battery. The influence of current density on the charge/discharge characteristics, coulombic and energy efficiency, capacity fade, operating temperature and pressure drop in the flow circuit will be discussed and correlated to the Nafion® membrane thickness. Material costs associated with the Nafion® membranes, ease of handling the membranes, and performance impacts will also be discussed.

  4. Tuning the Stability of Organic Active Materials for Nonaqueous Redox Flow Batteries via Reversible, Electrochemically Mediated Li + Coordination

    Energy Technology Data Exchange (ETDEWEB)

    Carino, Emily V.; Staszak-Jirkovsky, Jakub; Assary, Rajeev S.; Curtiss, Larry A.; Markovic, Nenad M.; Brushett, Fikile R.

    2016-03-24

    We describe an electrochemically mediated interaction between Li+ and a promising active material for nonaqueous redox flow batteries (RFBs), 1,2,3,4-tetrahydro-6,7-dimethoxy-1,1,4,4-tetramethylnaphthalene (TDT), and the impact of this structural interaction on material stability during voltammetric cycling. TDT could be an advantageous organic positive electrolyte material for nonaqueous RFBs due to its high oxidation potential, 4.21 V vs Li/Li+, and solubility of at least 1.0 M in select electrolytes. Although results from voltammetry suggest TDT displays Nernstian reversibility in many nonaqueous electrolyte solutions, bulk electrolysis reveals significant degradation in all electrolytes studied, the extent of which depends on the electrolyte solution composition. Results of subtractively normalized in situ Fourier transform infrared spectroscopy (SNIFTIRS) confirm that TDT undergoes reversible structural changes during cyclic voltammetry in propylene carbonate and 1,2-dimethoxyethane solutions containing Li+ electrolytes, but irreversible degradation occurs when tetrabutylammonium (TBA+) replaces Li+ as the electrolyte cation in these solutions. By combining the results from SNIFTIRS experiments with calculations from density functional theory, solution-phase active species structure and potential-dependent interactions can be determined. We find that Li+ coordinates to the Lewis basic methoxy groups of neutral TDT and, upon electrochemical oxidation, this complex dissociates into the radical cation TDT•+ and Li+. The improved cycling stability in the presence of Li+ relative to TBA+ suggests that the structural interaction reported herein may be advantageous to the design of energy storage materials based on organic molecules.

  5. A novel branched side-chain-type sulfonated polyimide membrane with flexible sulfoalkyl pendants and trifluoromethyl groups for vanadium redox flow batteries

    Science.gov (United States)

    Li, Jinchao; Liu, Suqin; He, Zhen; Zhou, Zhi

    2017-04-01

    A novel branched side-chain-type sulfonated polyimide (6F-s-bSPI) membrane with accessible branching agents of melamine, hydrophobic trifluoromethyl groups (sbnd CF3), and flexible sulfoalkyl pendants is prepared by a high-temperature polycondensation and post-sulfonation method for use in vanadium redox flow batteries (VRFBs). The chemical structure of the 6F-s-bSPI membrane is confirmed by ATR-FTIR and 1H NMR spectra. The physico-chemical properties of the as-prepared 6F-s-bSPI membrane are systematically investigated and found to be strongly related to the specially designed structure. The 6F-s-bSPI membrane offers a reduced cost and possesses a significantly lowered vanadium ion permeability (1.18 × 10-7 cm2 min-1) compared to the linear SPI (2.25 × 10-7 cm2 min-1) and commercial Nafion 115 (1.36 × 10-6 cm2 min-1) membranes, prolonging the self-discharge duration of the VRFBs. In addition, the VRFB assembled with a 6F-s-bSPI membrane shows higher coulombic (98.3%-99.7%) and energy efficiencies (88.4%-66.12%) than that with a SPI or Nafion 115 membrane under current densities ranging from 20 to 100 mA cm-2. Moreover, the VRFB with a 6F-s-bSPI membrane delivers a stable cycling performance over 100 cycles with no decline in coulombic and energy efficiencies. These results show that the branched side-chain-type structure is a promising design to prepare excellent proton conductive membranes.

  6. 钒电池电解液体积变化规律研究%Electrolyte Volume Change Study in All Vanadium Redox Flow Battery

    Institute of Scientific and Technical Information of China (English)

    赵永涛; 席靖宇; 滕祥国; 武增华; 邱新平

    2011-01-01

    Rule of electrolyte volume change was studied when the all vanadium redox flow battery was running stably with a cation exchange membrane. Electric transfer of ions will make the volume change linearly with the changing of charge-discharge capacity, that is, the positive electrolyte will be less and the negative electrolyte will be more during the charge process, which will be reversed in the discharge process.The direction of net infiltration of vanadium ions is from the negtive electrolyte to the positive electrolyte,which will make the volume of positive electrolyte larger in a couple of cycles. The direction of net water transfer is the same as the vanadium ions.%研究了钒电池在使用阳离子交换膜稳定运行过程中电解液体积的变化情况,分析了影响因素,并总结了变化规律.离子的电迁移使电解液体积随充放电容量的变化线性改变,充电过程正极电解液体积线性减小,负极电解液体积线性增大;放电过程反之.多次充放电循环过程中,钒离子的净渗透方向是由负极到正极,水的净变化方向与钒离子相同,最终使得多次循环过程正极电解液的体积逐渐增加.

  7. Investigation of Polarization Loss of Vanadium Redox Flow Battery%全钒液流电池极化损失研究

    Institute of Scientific and Technical Information of China (English)

    高艳; 周正; 刘佳燚

    2016-01-01

    Based on the charge-discharge analysis of vanadium redox flow battery ( VRB) , an in situ electrochemical technique is developed for the quantitative measurement of its activation, ohmic and concentration polarization using electrochemical impedance spectroscopy. It shows that activation and ohmic polarization are the main causes of VRB voltage loss when the current density is small. As the current density increases, the VRB voltage loss caused by ohmic polarization increases rapidly while concentration polarization becomes perceptible. The solutions are proposed for the development of high-efficiency and high-power VRB stack.%在全钒液流电池充放电性能研究基础上,采用原位电化学交流阻抗测试方法开展了全钒液流电池活化极化、欧姆极化和浓差极化的定量分析。结果表明,钒电池在较小充放电电流密度下,活化极化和欧姆极化是导致电压损失的主要原因。随着电流密度进一步增大,活化极化趋于平缓,而欧姆极化迅速增大,同时浓差极化也开始变得显著。在此基础上,针对充放电过程中的各类极化提出了系列解决方案,为高效率大功率全钒液流电池堆的开发奠定了基础。

  8. 钒液流电池建模及充放电效率分析%Vanadium redox flow battery modeling and charge-discharge efficiency analysis

    Institute of Scientific and Technical Information of China (English)

    沈洁; 李广凯; 侯耀飞; 滕松; 贾超

    2013-01-01

    The energy storage plays an important role in wind power systems and solar photovoltaic power generation system.As a new energy storage battery,the vanadium redox flow battery (VRB)'s advantages and successful example demonstrate its broad prospects in storage marker.The operating principle of VRB was introduced.Through studying stack voltage,state of charge,intemal loss and dynamic response,VRB simulation model was set up.The constant current mode for VRB was studied in detail.At the end,the factors which influenced the charging and discharging efficiency of battery energy storage were analyzed qualitatively and quantitatively.What's more,the optimal charging-discharging current was obtained.%储能系统是风力发电系统和太阳能光伏发电系统的重要组成部分,钒液流电池(VRB)作为一种新型储能电池,其优势及成功范例充分展示了它在储能市场的广阔前景.介绍了钒液流电池的工作原理,通过研究VRB的堆栈电压、荷电状态SOC、内部损耗和动态响应,构建了VRB仿真系统模型.详细研究了VRB恒电流充放电模式,定性、定量地分析了影响钒液流电池储能充放电效率的因素,并得出了最优充电电流.

  9. 全钒离子氧化还原液流电池电极活性物质的研究%Study on Electrode Active Materials for all Vanadium Redox Flow Battery

    Institute of Scientific and Technical Information of China (English)

    张环华; 肖楚民; 张平民

    2000-01-01

    介绍了以VOSO4为原料,电解制备全钒离子氧化还原液流电池的正极活性物质V(Ⅴ)盐和负极活性物V(Ⅱ)盐,并用循环伏安法研究了它们在石墨电极上的电化学性质。结果表明,在硫酸溶液中,作为全钒电池的正极和负极V(Ⅴ)/V(Ⅳ)和V(Ⅲ)/V(Ⅱ)电对在石墨电极上的氧化还原反应均为单电子准可逆过程.%Electrolytic method to prepare positive and negative active materials from VOSO4 sulphuric acid solution for all vanadium redox flow battery is described. V(Ⅴ)salt is obtained in anode area and V(Ⅱ) salt is in cathode area. The electrochemical behaviour of the two series salt on graphite electrode have also been studied by cyclic voltammetry. The results showed that the redox reactions of V(Ⅴ)/V(Ⅳ) and V(Ⅲ)/V(Ⅱ) couples in sulfuric adid,which are used for anolyte and catholyte in a redox flow battery,is qusi-reversible.

  10. Investigation on a-C:H:Me coated substrates as an alternative bipolar plate material in all-vanadium redox-flow batteries; Untersuchungen an a-C:H:Me beschichteten Substraten zur Eignung als alternatives Bipolarplattenmaterial fuer waessrige Vanadium Redox-Flow Batterien

    Energy Technology Data Exchange (ETDEWEB)

    Richards, Justin Frederick

    2015-07-01

    A crucial aspect of advancing in renewable energies is the development of affordable decentralized storage systems for the local or regional distribution grid. A technology with great potential is the all-vanadium redox-flow battery (VRFB) with the distinct feature of individual scalable power and capacity. The present work focusses on one of the essential parts in the redox-flow cell; the bipolar plates. By the application of metallic substrates instead of state-of-the-arte graphite composite plates, the design of the cell isn't limited anymore to the mechanical properties or fabrication process of the material. Although metals possess high ductility, which eases the production of such plates, they are prone to corrosion in the high acidic environment of the battery electrolyte. Therefore in this study amorphous carbon coatings (a-C:H) are investigated for corrosion protection. To attain the need of high electrical conductivity the carbon matrices is doped with a metallic element. Preferably refractory metals such as titanium, vanadium, chromium and tungsten were investigated as possible dopants. The electrochemical tests of the samples revealed less degradation the higher the coating thickness was. This can be found on all metallic substrates (material number: 1.4301, 3.7165 and 3.3535). Regarding the hydrogen overpotential, which is an essential value for the suppression of side reactions on the anode, the dominating factor was found to be the sort of doping material as well as the composition of the metallic adhesive layer between coating and substrate. Pores in the coating originate from defects in the substrates as well as from contaminations during the coating process. To understand the degradation mechanism an in-situ-corrosion cell was developed. By the means of these results, delamination could be found to be the predominant factor concerning degradation mechanisms at cathodic potentials. The degradation is initialized at the defects or at the edges

  11. 全钒液流电池电解液流场结构优化设计%Optimal design of electrolyte flow fields for all Vanadium redox flow battery

    Institute of Scientific and Technical Information of China (English)

    陈金庆; 王保国; 吕宏凌

    2011-01-01

    An excellent flow field structure of electrolyte in all vanadium redox flow battery (VRB) can bring about the uniform distribution of current density and electrolyte species for decreased polarization and improved performance. Three kinds of flow field structure are designed to evaluate the influence of the inner structure on battery polarization, current and voltage during charging and discharging,output power density and energy efficiency in this paper. The results show that the parallel-serpentine field with simple structure and easy machining leads to the uniform distribution of electrolyte species and intensifies the convection transfer of the species. The flow field enhances the electrolyte availability in storage capacity with the maximum output power density of 31. 6 mW/cm2. Compared with the conventional parallel flow field,the current efficiency, voltage efficiency and energy efficiency of the battery with the serpentine flow field are improved by 13. 9% ,6. 3% ,and 14. 8% .respectively. The discharge capacity is increased by 35. 3%.%全钒液流电池电解液流场结构合理可使电流密度、钒电解液分布均匀,降低极化,提高电池性能.设计3种不同的电解液流场,研究流场结构对电池极化、充放电电流电压、功率密度和能量效率的影响.结果表明蛇形流场结构简单且易于加工,可使钒电解液均匀分布,增强电解液对流传质能力,能较充分利用钒电解液储能容量,电池的输出功率密度最高可达31.6 mW/cm2,与传统平行流场相比,电池电流效率提高13.9%,电压效率提高6.3%,能量效率提高14.8%,放电容量提高了35.3%.

  12. Astaxanthin diferulate as a bifunctional antioxidant

    DEFF Research Database (Denmark)

    Papa, T.B.R.; Pinho, V.D.; Nascimento, E.P. do;

    2015-01-01

    Abstract Astaxanthin when esterified with ferulic acid is better singlet oxygen quencher with k2 = (1.58 ± 0.1) 10(10) L mol(- 1)s(- 1) in ethanol at 25°C compared with astaxanthin with k2 = (1.12 ± 0.01) 10(9) L mol(- 1)s(- 1). The ferulate moiety in the astaxanthin diester is a better radical s....... The mutual enhancement of antioxidant activity for the newly synthetized astaxanthin diferulate becoming a bifunctional antioxidant is rationalized according to a two-dimensional classification plot for electron donation and electron acceptance capability....

  13. 全钒液流电池隔膜的制备与性能%Preparation and Properties of Separation Membranes for Vanadium Redox Flow Battery

    Institute of Scientific and Technical Information of China (English)

    汪南方; 刘素琴

    2013-01-01

    All vanadium redox flow battery ( VRB) is accepted as a electrochemical energy storage device for the load levelling and peak shaving of the grid, the power supply for remote area, the charging power source for the electric vehicles, and the uninterruptible power supply. As one of the key components in VRB system, the membrane, in the terms of its structures and properties, is responsible for the efficiencies of the VRB. The ion conductivity and vanadium ions permeation of the membrane affect the voltage efficiency and coulombic efficiency of the battery, respectively. The chemical stability of the membrane determines the long-term performance and lifetime of the battery. This review mainly summarizes the preparation and properties of the fluorinated ionic exchange membranes, the non-fluorinated ionic exchange membranes, and the pore membranes. The promising research strategies are outlook.%全钒液流电池作为一种电化学储能装置在电网调峰、山区供电、电动车充电电源、应急电源等方面具有很广阔的应用前景.隔膜是全钒液流电池的关键组件之一,其结构和性能决定电池的效能.隔膜的离子传导率和钒离子的渗透率分别影响电池的电压效率和电流效率.隔膜的化学稳定性决定电池的长期运行的稳定性和使用寿命.本文根据隔膜的类别不同,分别阐述了含氟离子膜、非氟离子膜及多孔膜的制备与上述性能的关系,并展望了隔膜的发展方向.

  14. Research Progress of Separate Membrane for Vanadium Redox Flow Battery%钒液流电池用隔离膜研究进展

    Institute of Scientific and Technical Information of China (English)

    胡冰; 徐睿杰; 雷彩红; 石文强; 蔡启

    2013-01-01

    钒液流电池是近年来发展最为迅猛的储能电池之一.隔膜作为钒电池的重要组成部分直接关系到钒电池的转化储能效率和使用寿命.本文综述了近年来钒电池用隔离膜的发展现状.全氟磺酸质子交换膜(Nafion膜)作为当前使用最为广泛的隔膜,从传导机理、交换机理和表面涂覆、交联、复合等表面改性技术方面入手做了深入的研究,并对比分析了各种改性方法的优缺点.对磺化的特种工程塑料为主的非氟耐热型质子交换膜和功能化的聚烯烃隔膜在钒电池中的当前进展做了全面总结,并对钒液流电池用电池隔膜的发展方向做了展望.%Vanadium Redox Flow Batteries (VRB) is one of the most rapidly developed accumulation energy in recent years.Regard as the most important component,the separate membrane in VRB is directly related to the efficiency of transformation of energy storage and service life.In this paper,we give a brief introduction of the present situation of the VRB separate membrane.Nafion membrane as the most widely used membrane is discussed on the conduction mechanism,the exchange mechanism and the modification technologies,such as surface coating,crosslinking,surface recombination and so on.Then the advantages and disadvantages of various modification methods were analyzed by compared with each other.In addition,recent progresses about the non perfluorinated heat-resistant proton exchange membrane of sulfonated special engineering plastic membrane and the functionalization of polyolefin membrane are made a comprehensive summary.At last,we give the development trend of VRB in the future.

  15. 全钒液流电池的质子传导膜研究%Study on proton conductive membranes for all-vanadium redox flow battery

    Institute of Scientific and Technical Information of China (English)

    陈晓; 宋士强; 范永生; 刘平; 王保国

    2012-01-01

    研究质子传导膜对全钒液流电池性能的影响,包括膜面电阻、阻钒性以及质子传导膜厚度,为研究开发适用于全钒液流电池的质子传导膜提供依据.通过测定钒电池循环充电/放电过程的效率、暂态极化曲线、静态交叉放电曲线,建立选择与优化膜材料的评价方法;在考察膜电导率、膜厚、阻钒性和机械强度的综合性能指标后,认为膜面电阻在0.3~0.5 Ω·cm2范围,具备优良阻钒性能条件下,膜厚约150 μm比较合适.使用符合该性能的聚偏氟乙烯质子传导膜时,钒电池能量效率超过70%,有望满足发展大容量蓄电储能装备的需要.%Proton conductive membrane used in the all-vanadium redox flow battery was discussed in this paper, including the effect of membrane s area resistance, vanadium permeability, and thickness on the battery. It contributes a basis for proton conductive membrane s research. By using the methods of transient polarization curves, cross-discharging curves, and battery efficiency test, the results showed that: considering the membrane conductivity,thickness, vanadium permeability, and mechanical strength, the membrane s area resistance should be 0. 3~0. 5Ω·cm2, and with good vanadium permeability and thickness should be about 150μm. The energy efficiency of the battery used PVDF-based membranes could up to 70%, which met the needs of developing the large-scale energy storage devices.

  16. Effects of temperature on the performance of vanadium redox flow battery%温度对钒电池性能的影响

    Institute of Scientific and Technical Information of China (English)

    滕祥国; 赵永涛; 武增华; 席靖宇; 邱新平; 陈立泉

    2009-01-01

    Average coulombic efficiency, average energy efficiency, self-discharge and charge-discharge process of single vanadium redox flow cell was assembled and tested under temperature from 25-45 ℃. The mechanism of how temperature affecting the performance of VRB was investigated and discussed. Results showed that the average coulombic efficiency (CE) and average energy efficiency (EE) were reduced from 90.7% (25 ℃) to 87.4% (45 ℃) and from 81.6% (25 ℃) to 78.8% (45 ℃), respectively. At 25 ℃,open circuit voltage (OCV) of the cell during self-discharge process can keep 27 h beyond 0.8 V, while OCV can only keep 16 h beyond 0.8 V at 45 ℃%利用自行组装的实验室用钒氧化还原液流单电池,考察了25~45℃范围内温度对钒电池充放电电压、库仑效率、能量效率和自放电性能的影响,并对其影响机理进行了初步研究和讨论.结果表明:随着温度的升高,钒电池的平均库仑效率从25℃时的90.7%降到了45℃的87.4%;而电池的能量效率从25℃的81.6%降到了45℃的78.8%.研究表明:温度对电池自放电性能的影响尤为明显,在25℃时,电池的开路电压保持在0.8 V以上的时间为27 h,而在45℃则只能保持16 h.

  17. Dyes as bifunctional markers of DNA hybridization on surfaces and mutation detection.

    Science.gov (United States)

    García-Mendiola, Tania; Cerro, María Ramos; López-Moreno, José María; Pariente, Félix; Lorenzo, Encarnación

    2016-10-01

    The interaction of small molecules with DNA has found diagnostic and therapeutic applications. In this work, we propose the use of two different dyes, in particular Azure A and Safranine, as bifunctional markers of on-surface DNA hybridization and potent tools for screening of specific gene mutations directly in real DNA PCR amplicons extracted from blood cells. By combining spectroscopic and electrochemical methods we demonstrate that both dyes can interact with single and double stranded DNA to a different extent, allowing reliable hybridization detection. From these data, we have also elucidated the nature of the interaction. We conclude that the binding mode is fundamentally intercalative with an electrostatic component. The dye fluorescence allows their use as nucleic acid stains for the detection of on-surfaces DNA hybridization. Its redox activity is exploited in the development of selective electrochemical DNA biosensors.

  18. "Click" chemistry mildly stabilizes bifunctional gold nanoparticles for sensing and catalysis.

    Science.gov (United States)

    Li, Na; Zhao, Pengxiang; Liu, Na; Echeverria, María; Moya, Sergio; Salmon, Lionel; Ruiz, Jaime; Astruc, Didier

    2014-07-01

    A large family of bifunctional 1,2,3-triazole derivatives that contain both a polyethylene glycol (PEG) chain and another functional fragment (e.g., a polymer, dendron, alcohol, carboxylic acid, allyl, fluorescence dye, redox-robust metal complex, or a β-cyclodextrin unit) has been synthesized by facile "click" chemistry and mildly coordinated to nanogold particles, thus providing stable water-soluble gold nanoparticles (AuNPs) in the size range 3.0-11.2 nm with various properties and applications. In particular, the sensing properties of these AuNPs are illustrated through the detection of an analogue of a warfare agent (i.e., sulfur mustard) by means of a fluorescence "turn-on" assay, and the catalytic activity of the smallest triazole-AuNPs (core of 3.0 nm) is excellent for the reduction of 4-nitrophenol in water.

  19. Design of an integrated flow sensor device with application for monitoring in-situ pH and redox of hydrothermal diffuse flow fluids at mid-ocean ridges

    Science.gov (United States)

    Ding, K.; Seyfried, W. E.; Tan, C.; Jin, B.; Chen, Y.

    2009-05-01

    In-situ measurement of fluid chemistry with chemical sensors at deep sea conditions is always affected by drifting phenomena, which can be especially serious for long-term monitoring studies. Although fundamental changes in sensor design can be used to lessen the effect of this, in-situ calibration is still an unusually effective means to ensure measurement accuracy. With recent development of more reliable valves and pumps applicable for deep sea operation, together with results of laboratory studies showing the viability of solid state chemical sensors, it now possible to achieve in-situ calibration for sensor measurements under challenging chemical and physical conditions. Thus, a new flow device has been designed to facilitate chemical sensor measurements (e.g., pH and redox) in diffuse flow hydrothermal systems at mid-ocean ridges. The integrated calibration and measurement system was developed with a notion of promoting in-situ data acquisition at deep-sea vents for extended periods of time. Accordingly, it enables integration of multiple thermal and chemical sensors, while allowing automated in-situ calibration during deployment. Laboratory tests have successfully demonstrated the effectiveness of this in-situ calibration. For instance in the case of pH measurement with Ir/IrOx pH sensor in NaCl-bearing fluid at 220 bars, the device not only insured reliable measurement in seawater-type fluids, but also revealed effectiveness during measurement of fluids having dissolved CO2 up to 0.52 mol/kg, which is relevant to conditions likely in volcanically active back- arc settings, fluids issuing from cold seeps, as well as monitoring studies in connection with different carbon sequestration scenarios. The sea-going device consists of a sensor cell with limited internal volume of ~ 1 ml for more effectively enhancing interaction between incoming sample fluid and integrated temperature/chemical sensors. The instrument also contains a computer-controlled process

  20. Optimal Load Distribution of Microgrid With Energy Storage System Composed of Vanadium Redox Flow Battery%含钒电池储能的微电网负荷优化分配

    Institute of Scientific and Technical Information of China (English)

    陈光堂; 邱晓燕; 林伟

    2012-01-01

    储能系统是微电网的重要组成部分,其对微电网的稳定性、经济性与安全性有着非常重要的影响.以含钒液流储能电池(vanadium redox flow battery,VRB)系统的微电网为研究对象,建立了含钒电池储能微电网多目标负荷优化分配模型.以某微电网为例,分析讨论了钒电池对微电网带来的经济效益,同时研究了运行模式、控制策略和优化目标中权重等诸多因素对微电网负荷优化分配结果的影响,验证了所建立模型的有效性.%Energy storage system is an important component of microgrid and it greatly impacts the stability, security and economic operation of microgrid. Taking a microgrid containing energy storage system composed of vanadium redox flow battery (VRB) as research object, a multi-objective load distribution optimization model of microgrid with energy storage system composed of vanadium redox flow battery (VRB) is built. The economic benefit bought to microgrid by VRB is analyzed and researched, meanwhile the influences of the factors such as operating modes, control strategy and the weights of optimization objectives on load distribution optimization of microgrid are researched too, thus the effectiveness of the built model is verified.

  1. 基于全钒液流储能系统的微电网控制策略研究%Micro-grid Control Strategy Based on All-vanadium Redox Flow Battery Energy Storage System

    Institute of Scientific and Technical Information of China (English)

    张钊; 王城钢; 孙峰; 禹加

    2014-01-01

    In order to improve the security, stability and the economic operation of micro-grid, the all-vanadium redox flow energy storage system in recent years attracts much attention. It has many advantages, such as large capacity, high energy efficiency and fast response, etc. It can be used as the main power in micro-grid, playing the role of stabilizing voltage and frequency, and maintaining the balance of active and reactive power. This paper presents a control strategy for a micro-grid AC all-vanadium redox flow energy storage system, and analyzes the main circuit and the control method for the bidirectional DC/AC converter of all-vanadium redox flow battery. A model of all-vanadium redox flow battery for energy storage is established through using the RTDS platform. And based on this platform, a simulation platform of wind/PV/storage hybrid micro-grid is built. The simulation and experimental results show that the proposed control strategy is able to realize stable and reliable operation of micro-grid under all operation modes.%为提高微电网运行的安全稳定及经济性,近年来全钒液流储能系统备受关注,它具有容量大、能量效率高、反应速度快等优点,能够作为微电网中的主电源,起到稳定电压频率及维持微电网的有功、无功功率平衡的作用。提出一种交流微电网全钒液流储能系统控制策略,分析全钒液流电池双向DC/AC变流器主电路及控制方法。利用RTDS仿真平台,建立全钒液流储能电池模型,并搭建含有风、光、储的微电网仿真平台。仿真与实验结果表明,提出的微电网控制策略可保证微电网在各种运行模式下均能安全稳定运行。

  2. Acid-base bifunctional catalytic surfaces for nucleophilic addition reactions.

    Science.gov (United States)

    Motokura, Ken; Tada, Mizuki; Iwasawa, Yasuhiro

    2008-09-01

    This article illustrates the modification of oxide surfaces with organic amine functional groups to create acid-base bifunctional catalysts, summarizing our previous reports and also presenting new data. Immobilization of organic amines as bases on inorganic solid-acid surfaces afforded highly active acid-base bifunctional catalysts, which enabled various organic transformations including C--C coupling reactions, though these reactions did not proceed with either the homogeneous amine precursors or the acidic supports alone. Spectroscopic characterization, such as by solid-state MAS NMR and FTIR, revealed not only the interactions between acidic and basic sites but also bifunctional catalytic reaction mechanisms.

  3. Plant redox proteomics

    DEFF Research Database (Denmark)

    Navrot, Nicolas; Finnie, Christine; Svensson, Birte

    2011-01-01

    In common with other aerobic organisms, plants are exposed to reactive oxygen species resulting in formation of post-translational modifications related to protein oxidoreduction (redox PTMs) that may inflict oxidative protein damage. Accumulating evidence also underscores the importance of redox...... PTMs in regulating enzymatic activities and controlling biological processes in plants. Notably, proteins controlling the cellular redox state, e.g. thioredoxin and glutaredoxin, appear to play dual roles to maintain oxidative stress resistance and regulate signal transduction pathways via redox PTMs....... To get a comprehensive overview of these types of redox-regulated pathways there is therefore an emerging interest to monitor changes in redox PTMs on a proteome scale. Compared to some other PTMs, e.g. protein phosphorylation, redox PTMs have received less attention in plant proteome analysis, possibly...

  4. A geochemical transport model for redox-controlled movement of mineral fronts in groundwater flow systems: A case of nitrate removal by oxidation of pyrite

    Science.gov (United States)

    Engesgaard, Peter; Kipp, Kenneth L.

    1992-01-01

    A one-dimensional prototype geochemical transport model was developed in order to handle simultaneous precipitation-dissolution and oxidation-reduction reactions governed by chemical equilibria. Total aqueous component concentrations are the primary dependent variables, and a sequential iterative approach is used for the calculation. The model was verified by analytical and numerical comparisons and is able to simulate sharp mineral fronts. At a site in Denmark, denitrification has been observed by oxidation of pyrite. Simulation of nitrate movement at this site showed a redox front movement rate of 0.58 m yr−1, which agreed with calculations of others. It appears that the sequential iterative approach is the most practical for extension to multidimensional simulation and for handling large numbers of components and reactions. However, slow convergence may limit the size of redox systems that can be handled.

  5. Research advances of proton conductive membranes for vanadium redox flow battery%全钒液流电池用质子传导膜研究进展

    Institute of Scientific and Technical Information of China (English)

    青格乐图; 郭伟男; 范永生; 王保国

    2013-01-01

    全钒液流电池(VRB)作为一种大规模蓄电储能装备,在可再生能源发电和节能技术领域将发挥重要作用.质子传导膜是VRB中的关键材料之一,其作用主要有两方面:传导质子连通电堆内电路;阻止正负极电解液间不同价态钒离子的相互渗透,避免能量损失.质子传导膜性能对电池效率和成本有重要影响.在分析VRB基本原理基础上,阐明质子传导膜需同时满足优良的导电性、阻钒性、稳定性和合理成本等要求.以高分子膜的化学组成与物理结构的演化过程为线索,分别论述三类膜材料,包括Nafion系列膜、非全氟型质子传导膜、纳米尺度孔径的多孔膜.在归纳现有膜材料化学结构、物理性质与电学性能的基础上,阐述高性能质子传导膜的重点研究方向与发展前景.%Vanadium redox flow battery (VRB), which is regarded as one of the most promising devices for massive electricity storage in renewable energy and energy-saving processes, has attracted much attention, because of its long life-time, simple configuration and independent power and capacity ratings. Proton conductive membrane, one of key materials in VRB, performs the role of conducting protons during charge/discharge recycle, and prevents vanadium ions from direct contact between the positive and negative electrolytes. To achieve high energy efficiency, long life and low cost of VRB stack, the membrane should meet the requirements of high conductivity, chemical and mechanical resistance, low permeability of vanadium ions and acceptable cost. So far, Nafion membranes are generally employed in VRB due to their both high conductivity and chemical stability, however, their extremely high cost and poor ion selectivity have become the main barrier of commercialization of VRB. In this review, a detailed introduction about recent progress in the field of proton conductive membranes for VRB is given, including three aspects: (i) post

  6. 全钒液流电池复合材料双极板研究%Research of Composite Bipolar Plate Used for Vanadium Redox Flow Battery

    Institute of Scientific and Technical Information of China (English)

    徐冬清; 范永生; 刘平; 王保国

    2011-01-01

    Development of a bipolar plate with high conductivity and good antioxidant ability is significant for the vanadium redox flow battery (VRB) and other mass electricity storage equipments. Conductive plastic plate can be made by adding conductive fillers, such as carbon black (CB), graphite (GP), and expandable graphite (EG), into polymer matrixes. This study investigated the influences of different conductive fillers and their compositions, size, distribution method on the conductivity of the prepared bipolar plate, besides, the XRD and SEM were used to characterize the fillers and their morphologies in polymer matrixes. The filler patieles with smaller size is benefit for its distribution to improve conductivity, and the mixing method of mixing the filler with polymer in solvent or suspended solution provided an approximate result, and however, dispersion in a suspended solution is more suitable for process scaling-up. Bipolar plate with 50% (wt) and 400 mesh EG has conductivity of 92 S·cm-1, bending strength of 52 MPa. Since the bipolar plate also shows excellent properties in rejecting the permeation of vanadium ions and resisting erosion in strong oxidant, it is promising for application in VRB.%研究导电性高、耐腐蚀性强的双极板对发展全钒液流电池等大规模蓄电储能装备具有重要意义.在聚偏氟乙烯(PVDF)高分子基体中加入炭黑(CB)、鳞片石墨(GP)、膨胀石墨(EG)等导电填料,均匀分散后制备导电双极板,考察了导电填料种类、含量、粒度大小、分散方式对双极板导电性能的影响规律,利用x射线衍射(XRD)和扫描电子显微镜(SEM)表征导电填料本体和微观分散形态.结果表明使用粒径较小的可膨胀石墨有利于提高导电率,溶解法和悬浮液法均能保证导电填料的良好分散,所制备的双极板具有相近的导电性能,但后者易于进行大规模工业化生产.使用400目可膨胀石墨为导电填料制作双

  7. Iron Group Hydrides in Noyori Bifunctional Catalysis.

    Science.gov (United States)

    Morris, Robert H

    2016-12-01

    This is an overview of the hydride-containing catalysts prepared in the Morris group for the efficient hydrogenation of simple ketones, imines, nitriles and esters and the asymmetric hydrogenation and transfer hydrogenation of prochiral ketones and imines. The work was inspired by and makes use of Noyori metal-ligand bifunctional concepts involving the hydride-ruthenium amine-hydrogen HRuNH design. It describes the synthesis and some catalytic properties of hydridochloro, dihydride and amide complexes of ruthenium and in one case, osmium, with monodentate, bidentate and tetradentate phosphorus and nitrogen donor ligands. The iron hydride that has been identified in a very effective asymmetric transfer hydrogenation process is also mentioned. The link between the HMNH structure and the sense of enantioinduction is demonstrated by use of simple transition state models.

  8. Bifunctional xylanases and their potential use in biotechnology

    Digital Repository Service at National Institute of Oceanography (India)

    Khandeparker, R.; Numan, M.Th.

    is half as sweet as sucrose, can be applicable to foods as a sweetener that is capable of improving diabetic symptoms [37]. Concluding remarks This review provides the information on most of the aspects of bifunctional enzyme with special reference... of the bifunctional xylanases it is necessary in future to utilize such hybrid protein as an alternative to expensive and polluting chemical treatments or to improve already existing enzymatic processes for utilization of veg- etal by-products in the agro...

  9. Targeting Prostate Cancer with Bifunctional Modulators of the Androgen Receptor

    Science.gov (United States)

    2013-10-01

    element of immunosuppressive regimens for organ transplantation (1). Despite these 24 Bifunctional Ligand Control of Nuclear Receptors 3 well...Gerez J, Paez-Pereda M, Rein T, Iniguez-Lluhi JA, Holsboer F, Arzt E 2013 RSUME enhances glucocorticoid receptor SUMOylation and transcriptional... transplant recipients. Transpl Immunol 27:12-18 42. Marinec PS, Lancia JK, Gestwicki JE 2008 Bifunctional molecules evade cytochrome P(450) metabolism

  10. 1-N-aminoindol derivatives synthesis in no aqueous means from the 1, 4-dihydrocinnoline obtained by electrolysis in continuous flow redox cell; Sintesis de derivados del 1-N-aminoindol en medios no acuosos a partir de la 1, 4-dihidrocinolina obtenida por electrolisis en celda redox de flujo continuo

    Energy Technology Data Exchange (ETDEWEB)

    Frontana-Uribe, Bernardo A. [Universidad Nacional Autonoma de Mexico, Mexico, D.F. (Mexico); Moinet, Claude [Laboratoire d' Electrochimie et Organometalliques UMR, Paris (France)

    1999-08-01

    This work describes the synthesis of 1-N-aminoindol derivatives in organic anhydrous media from 1, 4-dihydrocinnoline. 1, 4-dihydrocinnoline 4 is obtained by electrolysis of 2-(orto-notropheny)-ethylamine 1a in a continuous flow redox cell. The cinnoline ring contraction products are obtained in low yield, but they show the possibility to carry out the reaction in organic media without water addition, as it was noted in previous works. [Spanish] En este trabajo se describe la sintesis de derivados del 1-N-aminoindol en medios anhidros a partir de la 1, 4-dihidrocinolina 4. Esta se obtiene mediante la electrolisis de la 2-(orto-notrofenil)-etilamina 1a en celda redox de flujo continuo. Los productos de contraccion del ciclo de la cinolina en 1-N-aminoindol se obtiene en rendimiento bajo, pero demuestran la posibilidad de llevar a cabo esta reaccion en medios totalmente organicos, sin la necesidad de la adicion de agua en el medio de reaccion, como esta descrito en trabajos precedentes.

  11. Effect of oxygen plasma treatment on the electrochemical performance of the rayon and polyacrylonitrile based carbon felt for the vanadium redox flow battery application

    Science.gov (United States)

    Dixon, D.; Babu, D. J.; Langner, J.; Bruns, M.; Pfaffmann, L.; Bhaskar, A.; Schneider, J. J.; Scheiba, F.; Ehrenberg, H.

    2016-11-01

    Oxygen plasma treatment was applied on commercially available graphite felt electrodes based on rayon (GFA) and polyacrylonitrile (GFD). The formation of functional groups on the surface of the felt was confirmed by X-ray photoelectron spectroscopy measurements. The BET studies of the plasma treated electrodes showed no significant increase in surface area for both the rayon as well as the PAN based felts. Both plasma treated electrodes showed significantly enhanced V3+/V2+ redox activity compared to the pristine electrodes. Since an increase of the surface area has been ruled out for plasma treated electrode the enhanced activity could be attributed to surface functional groups. Interestingly, plasma treated GFD felts showed less electrochemical activity towards V5+/V4+ compared to the pristine electrode. Nevertheless, an overall increase of the single cell performance was still observed as the negative electrode is known to be the performance limiting electrode. Thus, to a great extent the present work helps to preferentially understand the importance of functional groups on the electrochemical activity of negative and positive redox reaction. The study emphasizes the need of highly active electrodes especially at the negative electrode side as inactive electrodes can still facilitate hydrogen evolution and degrade the electrolyte in VRFBs.

  12. 全钒液流电池电化学建模与充放电分析%Electrochemical model of all vanadium redox flow battery and its charge/discharge analysis

    Institute of Scientific and Technical Information of China (English)

    周文源; 袁越; 傅质馨; 惠东; 杨凯

    2013-01-01

    全钒氧化还原液流电池凭借它的诸多优势,在电力系统中的应用潜力巨大,前景广阔,然而目前尚未有较为统一的仿真模型.以钒电池的电化学原理为基础,推导了以钒电池荷电容量和初始离子浓度为参量的电压方程,通过三组实际系统对仿真模型进行了验证.在此模型基础上,仿真分析对比了钒电池常见的恒功率和恒电流的充放电方法的各项效率指标.%With various advantages,all vanadium redox flow battery is a promising technology in power system.However,the simulation model of vanadium redox battery has not yet been united.Based on the electrochemical principal,the voltage function with the initial ion concentrations and the state of charge as parameters was deduced.The proposed model was then verified by comparing the simulations results with measured data taking from three different actual systems.Moreover,simulations of the constant power charging and constant current charging methods were taking out and their efficiencies were analyzed.

  13. 炭材料在全钒氧化还原液流电池中的电化学活性%A review of the electrochemical activity of carbon materials in vanadium redox flow batteries

    Institute of Scientific and Technical Information of China (English)

    魏冠杰; 范新庄; 刘建国; 严川伟

    2014-01-01

    Carbon materials mainly act as the electrode in a vanadium redox flow battery (VRFB). Due to the poor electrochemi-cal activity of traditional carbon materials for vanadium redox reactions, a comprehensive study of the electrochemical activity of car-bon materials, especially graphite felt (GF), is greatly needed and has become an important feature of electrode research. This pa-per presents research progress on carbon materials for use in a VRFB, focusing on modifying the GF and new carbons as catalysts for vanadium redox reactions. The electrocatalytic influence of surface oxygen and nitrogen functional groups on vanadium redox reac-tions is introduced. The use of carbon nanotubes and graphene in a VRFB is discussed and future trends to improve the electrochemi-cal activity of carbon materials are highlighted.%炭材料在全钒氧化还原液流电池(钒电池)中主要用作电极。由于传统炭材料对钒电对氧化还原反应的电化学活性较差,因此,对以石墨毡为代表的炭材料电化学活性研究成为钒电池电极研究的重要组成部分。研究从石墨毡电极改性和炭材料作为催化剂应用两方面详述炭材料在钒电池中的电化学活性研究现状,先介绍含氧官能团和含氮官能团对钒电对氧化还原反应的电催化作用,回顾碳纳米管和石墨烯两类新型炭材料在钒电池中的应用。对炭材料电化学活性的今后研究工作进行展望,通过对炭材料性构关系的全面了解和对碳电极上的钒电对电化学反应过程动力学的深入研究,才能为炭材料在钒电池中的实际应用奠定扎实的理论和应用基础。

  14. Chloroplast Redox Poise

    DEFF Research Database (Denmark)

    Steccanella, Verdiana

    the redox status of the plastoquinone pool and chlorophyll biosynthesis. Furthermore, in the plant cell, the equilibrium between redox reactions and ROS signals is also maintained by various balancing mechanisms among which the thioredoxin reductase-thioredoxin system (TR-Trx) stands out as a mediator......The redox state of the chloroplast is maintained by a delicate balance between energy production and consumption and is affected by the need to avoid increased production of reactive oxygen species (ROS). Redox power and ROS generated in the chloroplast are essential for maintaining physiological...... metabolic pathways and for optimizing chloroplast functions. The redox poise of photosynthetic electron transport components like plastoquinone is crucial to initiate signaling cascades and might also be involved in key biosynthetic pathways such as chlorophyll biosynthesis. We, therefore, explored...

  15. Research progress in improving the energy efficiency of vanadium redox flow batteries%提高全钒液流电池能量效率的研究进展

    Institute of Scientific and Technical Information of China (English)

    马军; 李爱魁; 董波; 刘飞; 黄岷江

    2013-01-01

    介绍提高全钒液流电池能量效率的研究进展,系统总结了影响全钒液流电池能量效率的内、外部关键因素,包括电堆关键材料、漏电电流及流体分配等,分析了上述关键因素的影响机制,同时提出了提高电池能量效率的改进方向.%The effects of the critical material,shunt current,fluid distribution and operating mode on the energy efficiency of vanadium redox flow battery were investigated.In addition,the mechanism of the influence of these factors was analyzed; the related measures were proposed to improve the energy efficiency of the energy storage system.

  16. 全钒液流电池10kW单元电堆性能研究%Performance of 10kW cell stack of vanadium redox flow battery

    Institute of Scientific and Technical Information of China (English)

    陈伟; 孟凡明; 李晓兵; 刘效疆; 马海波

    2013-01-01

    详细研究了全钒液流电池10kW单元电堆的功率输出特性和单体电压一致性及不同充放电电流密度与库仑效率和能量效率的关系.研究了电堆长期运行时,库仑效率、能量效率及电压平台的变化.%The power output characteristics and single voltage consistency of 10 kW cell stack of vanadium redox flow battery,as well as the coulombic efficiency and energy efficiency for different charge and discharge current density were studied.The variety of coulombic and energy efficiency and voltage platform of the stack was researched in a long-term operation.

  17. Astaxanthin diferulate as a bifunctional antioxidant.

    Science.gov (United States)

    Papa, T B R; Pinho, V D; do Nascimento, E S P; Santos, W G; Burtoloso, A C B; Skibsted, L H; Cardoso, D R

    2015-01-01

    Astaxanthin when esterified with ferulic acid is better singlet oxygen quencher with k2 = (1.58 ± 0.1) 10(10) L mol(-1)s(-1) in ethanol at 25°C compared with astaxanthin with k2 = (1.12 ± 0.01) 10(9) L mol(-1)s(-1). The ferulate moiety in the astaxanthin diester is a better radical scavenger than free ferulic acid as seen from the rate constant of scavenging of 1-hydroxyethyl radicals in ethanol at 25°C with a second-order rate constant of (1.68 ± 0.1) 10(8) L mol(-1)s(-1) compared with (1.60 ± 0.03) 10(7) L mol(-1)s(-1) for the astaxanthin:ferulic acid mixture, 1:2 equivalents. The mutual enhancement of antioxidant activity for the newly synthetized astaxanthin diferulate becoming a bifunctional antioxidant is rationalized according to a two-dimensional classification plot for electron donation and electron acceptance capability.

  18. 全钒液流电池用离子交换膜的研究进展%Development of ion exchange membrane for all-vanadium redox flow battery

    Institute of Scientific and Technical Information of China (English)

    李彦; 徐铜文

    2015-01-01

    The all-vanadium redox flow battery (VRB) has received wide attention due to its excellent features for large-scale energy storage and stable power generation. As a key component in VRB, the ion exchange membranes (IEMs) not only separate the electrolyte, but also conduct ions to form charge-discharge circuit. In this work, an overview is presented for the various IEMs research of the vanadium redox flow battery. Relevant published work is summarized and critically discussed. The limitations and technical challenges in the ion exchange membranes are also discussed and further research opportunities are prospected.%由于全钒氧化还原液流电池(VRB)具有大规模储能和稳定发电的特点,引起了国内外的广泛关注.离子交换膜(IEM)是 VRB 中的重要组件,它不仅要隔开阴阳极电解液,而且还要传输离子以构成闭合回路.对全钒液流电池用离子交换膜做了系统介绍.从离子交换膜的基本功能出发,详细阐述了近年来国内外全钒液流电池用离子交换膜的研究进展及目前面临的问题,并展望了全钒液流电池大规模商业化应用的前景.

  19. Shadow enhancers enable Hunchback bifunctionality in the Drosophila embryo.

    Science.gov (United States)

    Staller, Max V; Vincent, Ben J; Bragdon, Meghan D J; Lydiard-Martin, Tara; Wunderlich, Zeba; Estrada, Javier; DePace, Angela H

    2015-01-20

    Hunchback (Hb) is a bifunctional transcription factor that activates and represses distinct enhancers. Here, we investigate the hypothesis that Hb can activate and repress the same enhancer. Computational models predicted that Hb bifunctionally regulates the even-skipped (eve) stripe 3+7 enhancer (eve3+7) in Drosophila blastoderm embryos. We measured and modeled eve expression at cellular resolution under multiple genetic perturbations and found that the eve3+7 enhancer could not explain endogenous eve stripe 7 behavior. Instead, we found that eve stripe 7 is controlled by two enhancers: the canonical eve3+7 and a sequence encompassing the minimal eve stripe 2 enhancer (eve2+7). Hb bifunctionally regulates eve stripe 7, but it executes these two activities on different pieces of regulatory DNA--it activates the eve2+7 enhancer and represses the eve3+7 enhancer. These two "shadow enhancers" use different regulatory logic to create the same pattern.

  20. Effect of the redox dynamics on microbial-mediated As transformation coupled with Fe and S in flow-through sediment columns.

    Science.gov (United States)

    Moon, Hee Sun; Kim, Bo-A; Hyun, Sung Pil; Lee, Yoon-Ho; Shin, Doyun

    2017-05-05

    Arsenic (As) biogeochemistry coupled with iron (Fe) and sulfur (S) was studied using columns packed with As(V)-contaminated sediments under two phases: a reduction phase followed by an oxidation phase. During the reduction phase, four identical columns inoculated with G. sulfurreducens were stimulated with 3mM acetate for 60days. The As(III) in the effluent rapidly increased then gradually decreased. The Fe(II) and sulfate concentration indicated ferrous sulfide precipitation inside the column after day 14 and X-ray absorption near edge structure spectra showed that As(III) was enriched at the column outlet. The genera Desulfosporosinus and Anaeromyxobacter as well as the Geobacter inoculum played a primary role in As reduction. During the oxidation phase, dissolved oxygen was consumed by heterotrophic aerobes belonging to the phylum Cloroflexi in the column with acetate, resulting in more As in the effluent. When only nitrate was injected, sulfur-oxidizing bacteria such as Thiobacillus thioparus instantly oxidized the sulfide formed during the first phase, resulting in less As(V) in the aqueous phase compared to the column with dissolved oxygen alone. This study showed that redox gradients and dynamics linked to Fe and S biogeochemistry have an important role in controlling As mobility in subsurface environments.

  1. Single flexible nanofiber to simultaneously realize electricity-magnetism bifunctionality

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ming; Sheng, Shujuan; Ma, Qianli; Lv, Nan; Yu, Wensheng; Wang, Jinxian; Dong, Xiangting; Liu, Guixia, E-mail: wenshengyu2009@sina.com, E-mail: dongxiangting888@163.com [Key Laboratory of Applied Chemistry and Nanotechnology at Universities of Jilin Province, Changchun University of Science and Technology, Changchun (China)

    2016-03-15

    In order to develop new-typed multifunctional composite nanofibers, PANI/Fe{sub 3}O{sub 4}/PVP flexible bifunctional composite nanofibers with simultaneous electrical conduction and magnetism have been successfully fabricated via a facile electrospinning technology. Polyvinyl pyrrolidone (PVP) is used as a matrix to construct composite nanofibers containing different amounts of polyaniline (PANI) and Fe{sub 3}O{sub 4} nanoparticles (NPs). The bifunctional composite nanofibers simultaneously possess excellent electrical conductivity and magnetic properties. The electrical conductivity reaches up to the order of 10{sup -3} S·cm{sup -1}. The electrical conductivity and saturation magnetization of the composite nanofibers can be respectively tuned by adding various amounts of PANI and Fe{sub 3}O{sub 4} NPs. The obtained electricity-magnetism bifunctional composite nanofibers are expected to possess many potential applications in areas such as electromagnetic interference shielding, special coating, microwave absorption, molecular electronics and future nanomechanics. More importantly, the design concept and construct technique are of universal significance to fabricate other bifunctional one-dimensional nanostructures. (author)

  2. Environmentally Benign Bifunctional Solid Acid and Base Catalysts

    NARCIS (Netherlands)

    Elmekawy, A.; Shiju, N.R.; Rothenberg, G.; Brown, D.R.

    2014-01-01

    Solid bifunctional acid-​base catalysts were prepd. in two ways on an amorphous silica support: (1) by grafting mercaptopropyl units (followed by oxidn. to propylsulfonic acid) and aminopropyl groups to the silica surface (NH2-​SiO2-​SO3H)​, and (2) by grafting only aminopropyl groups and then parti

  3. Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons

    NARCIS (Netherlands)

    Zecevic, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.

    2015-01-01

    The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts(1-4). Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon source

  4. 暂态边界电压法在线测试全钒液流电池阻抗%On-line resistance measurement for all vanadium redox flow battery by transient-boundary voltage method

    Institute of Scientific and Technical Information of China (English)

    潘建欣; 廖玲芝; 谢晓峰; 王树博; 王金海; 尚玉明; 周涛

    2012-01-01

    国内首次采用暂态边界电压法在线研究了全钒液流电池(VRB)的特性,建立了由电压源、电阻以及一个电阻与电容并联的3部分串联而成的等效电路模型;研究了电流密度和荷电状态(SOC)对等效电路元件的影响。实验结果表明,极化阻抗随电流密度的增加有轻微下降,在充电初期和放电末期达到最大值。与极化阻抗相比,充、放电过程中的欧姆阻抗最大,是导致电压损失的主要因素,分别为1.905Ω.cm2和2.139Ω.cm2,暂态边界电压法是一种简单且有效的表征全钒液流电池性能的新方法。%A single cell of vanadium redox flow battery(VRB) was investigated on-line by the transient-boundary voltage method.An equivalent circuit model was established using the voltage source,resistor,and a resistor in parallel with the capacitance of three-part series.The effects of current density and state of charge(SOC) on equivalent circuit components values were investigated.The experimental results showed that the polarization resistance decreased slightly with increasing current density,and reached its maximum in the beginning of charge and the end of discharge.Compared with polarization resistance,ohm impedance in the charge/discharge process was the highest respectively 1.905 cm2and 2.139 cm2.It was the main factor leading to voltage loss.The transient boundary voltage method is a simple and effective way of characterizing performance of vanadium redox flow battery.

  5. Redox control of teratogenesis.

    Science.gov (United States)

    Hansen, Jason M; Harris, Craig

    2013-01-01

    A number of human teratogens elicit their deleterious effects through mechanisms involving the generation of reactive oxygen species (ROS) and oxidative stress. However, classic definitions of oxidative stress do not fully coincide with basic fundamental principles of teratology. Newer definitions of oxidative stress focus on the targeted redox modification of cysteine/thiol functional groups found in the regulatory domains of critical signaling pathway proteins, suggesting that the targeted disruption of signaling through specific redox couples may account for the specificity of teratogen-induced malformations which previously could not be rationalized. Here, we review examples of teratogens that induce ROS and oxidative injury, describe oxidative stress-related teratogenic mechanisms, and provide rationale for developmental periods of sensitivity and species susceptibility. Understanding how chemicals disrupt redox status, induce oxidative stress leading to dysmorphogenesis becomes important to identify potential teratogens and develop therapeutic interventions for attenuation of harmful chemical effects in utero following exposure.

  6. Comparison of bifunctional chelates for {sup 64}Cu antibody imaging

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Cara L.; Crisp, Sarah; Bensimon, Corinne [MDS Nordion, Vancouver, BC (Canada); Yapp, Donald T.T.; Ng, Sylvia S.W. [British Columbia Cancer Agency Research Centre, Vancouver, BC (Canada); University of British Columba, The Faculty of Pharmaceutical Sciences, Vancouver, BC (Canada); Sutherland, Brent W. [British Columbia Cancer Agency Research Centre, Vancouver, BC (Canada); Gleave, Martin [Prostate Centre at Vancouver General Hospital, Vancouver, BC (Canada); Jurek, Paul; Kiefer, Garry E. [Macrocyclics Inc., Dallas, TX (United States)

    2010-11-15

    Improved bifunctional chelates (BFCs) are needed to facilitate efficient {sup 64}Cu radiolabeling of monoclonal antibodies (mAbs) under mild conditions and to yield stable, target-specific agents. The utility of two novel BFCs, 1-Oxa-4,7,10-triazacyclododecane-5-S-(4-isothiocyanatobenzyl)-4,7,10-triacetic acid (p-SCN-Bn-Oxo-DO3A) and 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-4-S-(4-isothiocyanatobenzyl)-3,6,9-triacetic acid (p-SCN-Bn-PCTA), for mAb imaging with {sup 64}Cu were compared to the commonly used S-2-(4-isothiocyanatobenzyl)-1,4,7,10-tetraazacyclododecane-tetraacetic acid (p-SCN-Bn-DOTA). The BFCs were conjugated to trastuzumab, which targets the HER2/neu receptor. {sup 64}Cu radiolabeling of the conjugates was optimized. Receptor binding was analyzed using flow cytometry and radioassays. Finally, PET imaging and biodistribution studies were done in mice bearing either HER2/neu-positive or HER2/neu-negative tumors. {sup 64}Cu-Oxo-DO3A- and PCTA-trastuzumab were prepared at room temperature in >95% radiochemical yield (RCY) in <30 min, compared to only 88% RCY after 2 h for the preparation of {sup 64}Cu-DOTA-trastuzumab under the same conditions. Cell studies confirmed that the immunoreactivity of the mAb was retained for each of the bioconjugates. In vivo studies showed that {sup 64}Cu-Oxo-DO3A- and PCTA-trastuzumab had higher uptake than the {sup 64}Cu-DOTA-trastuzumab at 24 h in HER2/neu-positive tumors, resulting in higher tumor to background ratios and better tumor images. By 40 h all three of the {sup 64}Cu-BFC-trastuzumab conjugates allowed for clear visualization of the HER2/neu-positive tumors but not the negative control tumor. The antibody conjugates of PCTA and Oxo-DO3A were shown to have superior {sup 64}Cu radiolabeling efficiency and stability compared to the analogous DOTA conjugate. In addition, {sup 64}Cu-PCTA and Oxo-DO3A antibody conjugates may facilitate earlier imaging with greater target to background ratios than

  7. A review of research progress on the synthesis of ion exchange membranes for vanadium redox flow batteries%全钒液流电池离子交换膜合成方法综述

    Institute of Scientific and Technical Information of China (English)

    邱景义; 马骏; 翟茂林

    2011-01-01

    Vanadium redox flow battery (VRFB) was thought to be a promising system for energy storage with excellent features, including high energy efficiency, long cycle life, security and low cost. Ion exchange membrane (IEM) is the key component of VRFB, which should be designed and synthesized with low permeability of vanadium ions, high conductivity as well as satisfying stability. This paper presented the research progress on the design and synthetic approaches of IEM for VRFB use. Current existed problems were pointed out and analyzed. Further research strategies are also proposed.%全钒氧化还原液流电池(VRFB)具有储能效率高、循环寿命长、安全可靠、低成本等优点,在大规模储能中具有良好的应用前景.而作为VRFB的核心部件,离子交换膜应具有钒离子透过率低、电导率高、化学稳定性好等性能.总结了近年来国内外相关的研究进展,对比了不同合成方法的优缺点,并提出了开发适用于VRFB的高性能离子交换膜的建议.

  8. 钒液流电池在不同温度下的充放电特性%Charge-discharge Characteristics of Vanadium Redox Flow Battery at various temperatures

    Institute of Scientific and Technical Information of China (English)

    田戈; 贾明波; 李娟; 张中洋

    2014-01-01

    Influence of the temperature on the polarization curve, cyclic efficiency, charge-discharge capacity and self-discharge performance of vanadium redox flow battery was studied in temperature range 15℃~35℃ by using a 10-cell stack, and the mechanism was analyzed. The results show that, in the process of temperature rising, the current efficiency decreases, and voltage efficiency, charge-discharge capacity and self-discharge rate all gradually increase. In order to ensure stable operation of the vanadium battery, the temperature should be strictly controlled in the actual application.%利用10电池电堆考查了在15~35℃范围内温度对钒电池极化曲线、循环效率、充放电容量以及自放电性能的影响,并进行了机理分析,测试结果表明,在温度逐渐升高的过程中,除电流效率逐渐降低外,电压效率、充放电容量、自放电速率均逐渐升高,在实际应用过程中,应严格对温度进行控制以保证钒电池系统的稳定运行。

  9. Simulation of vanadium redox flow battery in on-grid of micro grid%钒液流电池在微电网并网运行中的仿真研究

    Institute of Scientific and Technical Information of China (English)

    贾华; 安婷; 张飞

    2016-01-01

    随着越来越多大规模光伏、风电等新能源的并网运行,其输出功率随机波动性给电网的安全运行带来的影响也愈发严重,利用储能技术来平滑风电场、光伏电站输出功率的波动是有效手段之一,对储能媒介建模及其控制的深入研究至关重要.介绍了钒液流电池(Vanadium Redox Flow Battery,VRB)的工作原理,在Matlab/Simulink中建立其模型,得到在恒流充放电条件下VRB堆栈电压变化曲线.将该模型应用在微电网并网运行模式中,证明了其可行性.

  10. Modelling and controlling of vanadium redox flow battery to smooth wind power fluctuations%钒液流储能电池建模及其平抑风电波动研究

    Institute of Scientific and Technical Information of China (English)

    李国杰; 唐志伟; 聂宏展; 谭靖

    2010-01-01

    由于风电的随机波动性,大量风电的并网给电网带来了影响,利用储能系统平抑风功率波动的研究变得愈加重要.以钒液流电池(Vanadium Redox Flow Battery,VRFB)为储能元件研究其风电平抑控制策略,建立反映VRFB充放电特性的仿真模型.以钒氧化还原液流电池电化学交流阻抗等效电路为基础,对等效电路重要参数的变化规律做了分析与简化,建立了反映钒液流电池充放电特性的数学模型.以AC/DC变换器的功率解耦控制为基础,建立了基于VRFB储能系统的平抑风电波动控制策略.以某风场的实测风速数据和1.5 MW双馈电机为例,利用PSCAD/EMTDC仿真软件,验证了控制策略的有效性和可行性.

  11. Research on Solution Chemistry of the Electrolyte of Redox Flow Battery, General Technology Report%液流电池电解质的溶液化学研究最终报告

    Institute of Scientific and Technical Information of China (English)

    刘素琴; 越华

    2016-01-01

    针对高稳定性、高活性全钒液流电池电解液以及高能量密度单液流电池沉积型电对及固体电极电化学性能与电解质溶液之间构效关系、高稳定性浓电解质溶液化学理论及作用机制等关键科学问题,以具备较大应用潜力的全钒双液流以及锌/镍、全铅单液流电池体系电解质的溶液化学为研究重点,通过电化学测试与材料物性表征相结合,深入研究了电解质溶液对全钒双液流以及碱性沉积型锌负极和电池性能的影响,阐明了电解液流速、锌沉积面容量和电流密度的关联;考察了不同种类的无机、有机添加剂以及添加剂中的官能团对电解液的热稳定性以及电化学活性的影响,深入研究了电解液溶液及添加剂对固体氧化镍正极活性和稳定性的影响,探讨了电解液添加剂与锌负极和氧化镍正极的相容性;研究了全铅单液流电池电解质溶液的物化性质,探明电解液组成对电极性能的影响规律;研究了电解液添加剂对全铅单液流电池电极性能的影响及其作用机制;考察了支持电解质对电解液的热力学稳定性、电化学活性以及循环稳定性等的影响,优化了电解液的组成,提高了电池充放电的能量效率和循环稳定性。重要的创新点包括以下方面:(1)确定了对于全钒液流电池电解液的热稳定性和电化学性能具有积极作用的添加剂结构和支持电解质组成;(2)阐明全铅单液流电池电解液中铅活性离子对电极性能的影响规律,优化了铅离子浓度;(3)提出电解液中添加电解PbO2,降低沉积型PbO2电极极化,抑制铅累积和枝晶的新方法,获得了高活性、高沉积均匀性Pb负极和PbO2正极。%The all vanadium redox flow battery, Zn/Ni, PbO2/Zn、PbO2/Cu(Cd) and all lead single flow battery systems with great application potential and electrolyte of high concentration are taken

  12. The aminoindanol core as a key scaffold in bifunctional organocatalysts

    Directory of Open Access Journals (Sweden)

    Isaac G. Sonsona

    2016-03-01

    Full Text Available The 1,2-aminoindanol scaffold has been found to be very efficient, enhancing the enantioselectivity when present in organocatalysts. This may be explained by its ability to induce a bifunctional activation of the substrates involved in the reaction. Thus, it is easy to find hydrogen-bonding organocatalysts ((thioureas, squaramides, quinolinium thioamide, etc. in the literature containing this favored structural core. They have been successfully employed in reactions such as Friedel–Crafts alkylation, Michael addition, Diels–Alder and aza-Henry reactions. However, the 1,2-aminoindanol core incorporated into proline derivatives has been scarcely explored. Herein, the most representative and illustrative examples are compiled and this review will be mainly focused on the cases where the aminoindanol moiety confers bifunctionality to the organocatalysts.

  13. 钒电池负极电解液V2(SO4)3溶解性规律%Solubility Rules of Negative Electrolyte V2(SO4)3 of Vanadium Redox Flow Battery

    Institute of Scientific and Technical Information of China (English)

    赵建新; 武增华; 席靖宇; 邱新平

    2012-01-01

    对钒电池负极电解液中活性物质V(Ⅲ)在不同硫酸浓度、不同温度条件下的溶解性规律进行了深入研究,同时对V(Ⅲ)-H2SO4体系电化学性能进行了初步探讨.结果表明:V(Ⅲ)的溶解是一个放热过程,在15~40℃范围内,V(Ⅲ)的溶解度随着温度升高而逐渐降低;并且溶液中V(Ⅲ)会以V-O-V形式形成二聚体,在低硫酸浓度下,V(Ⅲ)可以高浓度长时间稳定存在,随硫酸浓度的增大,V(Ⅲ)溶解度逐渐降低,其中30℃、1 mol/L H2SO4条件下V(Ⅲ)浓度可高达2.730 mol/L;进一步通过电化学测试,发现V(Ⅲ)-H2SO4体系是不可逆体系,H2SO4浓度的增大有益于提高V(Ⅲ)/V(Ⅱ)氧化还原反应的可逆性.%The solubility of Ⅴ(Ⅲ) species in negative electrolyte of all vanadium redox flow battery (VRB) was studied and the solubility parameters of Ⅴ(Ⅲ) species at various concentrations of H2SO4 and different temperatures were preliminarily obtained. The results showed that dissolution of Ⅴ(Ⅲ) was an exothermic process. The solubility of Ⅴ(Ⅲ) decreased with temperature (15-40℃). Also, the presence of Ⅴ(Ⅲ) in the solution was a V-O-V dimmer. The solubility of Ⅴ(Ⅲ) decreased with the increasing of H2SO4 and low concentration of H2SO4 would keep high concentration of Ⅴ(Ⅲ) stable for a long time. Especially, concentration of Ⅴ(Ⅲ) could reach 2.730 mol/L with 1 mol/L H2SO4 at 30 ℃ . Electrochemical properties was further investigated by experiment, the results revealed that Ⅴ(Ⅲ)-H2SO4 solution was an irreversible system for Ⅴ(Ⅲ)/Ⅴ(Ⅱ) redox reaction. Increasing of concentration of H2SO4 had great benefit to improve the reversibility of Ⅴ(Ⅲ)/Ⅴ(Ⅱ) redox reaction.

  14. Rebalancing Redox to Improve Biobutanol Production by Clostridium tyrobutyricum

    Directory of Open Access Journals (Sweden)

    Chao Ma

    2015-12-01

    Full Text Available Biobutanol is a sustainable green biofuel that can substitute for gasoline. Carbon flux has been redistributed in Clostridium tyrobutyricum via metabolic cell engineering to produce biobutanol. However, the lack of reducing power hampered the further improvement of butanol production. The objective of this study was to improve butanol production by rebalancing redox. Firstly, a metabolically-engineered mutant CTC-fdh-adhE2 was constructed by introducing heterologous formate dehydrogenase (fdh and bifunctional aldehyde/alcohol dehydrogenase (adhE2 simultaneously into wild-type C. tyrobutyricum. The mutant evaluation indicated that the fdh-catalyzed NADH-producing pathway improved butanol titer by 2.15-fold in the serum bottle and 2.72-fold in the bioreactor. Secondly, the medium supplements that could shift metabolic flux to improve the production of butyrate or butanol were identified, including vanadate, acetamide, sodium formate, vitamin B12 and methyl viologen hydrate. Finally, the free-cell fermentation produced 12.34 g/L of butanol from glucose using the mutant CTC-fdh-adhE2, which was 3.88-fold higher than that produced by the control mutant CTC-adhE2. This study demonstrated that the redox engineering in C. tyrobutyricum could greatly increase butanol production.

  15. Tuning of redox regulatory mechanisms, reactive oxygen species and redox homeostasis under salinity stress

    Directory of Open Access Journals (Sweden)

    Hossain eSazzad

    2016-05-01

    Full Text Available Soil salinity is a crucial environmental constraint which limits biomass production at many sites on a global scale. Saline growth conditions cause osmotic and ionic imbalances, oxidative stress and perturb metabolism, e.g. the photosynthetic electron flow. The plant ability to tolerate salinity is determined by multiple biochemical and physiological mechanisms protecting cell functions, in particular by regulating proper water relations and maintaining ion homeostasis. Redox homeostasis is a fundamental cell property. Its regulation includes control of reactive oxygen species (ROS generation, sensing deviation from and readjustment of the cellular redox state. All these redox related functions have been recognized as decisive factors in salinity acclimation and adaptation. This review focuses on the core response of plants to overcome the challenges of salinity stress through regulation of ROS generation and detoxification systems and to maintain redox homeostasis. Emphasis is given to the role of NADH oxidase (RBOH, alternative oxidase (AOX, the plastid terminal oxidase (PTOX and the malate valve with the malate dehydrogenase isoforms under salt stress. Overwhelming evidence assigns an essential auxiliary function of ROS and redox homeostasis to salinity acclimation of plants.

  16. Redox-capacitor to connect electrochemistry to redox-biology.

    Science.gov (United States)

    Kim, Eunkyoung; Leverage, W Taylor; Liu, Yi; White, Ian M; Bentley, William E; Payne, Gregory F

    2014-01-07

    It is well-established that redox-reactions are integral to biology for energy harvesting (oxidative phosphorylation), immune defense (oxidative burst) and drug metabolism (phase I reactions), yet there is emerging evidence that redox may play broader roles in biology (e.g., redox signaling). A critical challenge is the need for tools that can probe biologically-relevant redox interactions simply, rapidly and without the need for a comprehensive suite of analytical methods. We propose that electrochemistry may provide such a tool. In this tutorial review, we describe recent studies with a redox-capacitor film that can serve as a bio-electrode interface that can accept, store and donate electrons from mediators commonly used in electrochemistry and also in biology. Specifically, we (i) describe the fabrication of this redox-capacitor from catechols and the polysaccharide chitosan, (ii) discuss the mechanistic basis for electron exchange, (iii) illustrate the properties of this redox-capacitor and its capabilities for promoting redox-communication between biology and electrodes, and (iv) suggest the potential for enlisting signal processing strategies to "extract" redox information. We believe these initial studies indicate broad possibilities for enlisting electrochemistry and signal processing to acquire "systems level" redox information from biology.

  17. Redox theory of aging.

    Science.gov (United States)

    Jones, Dean P

    2015-08-01

    Metazoan genomes encode exposure memory systems to enhance survival and reproductive potential by providing mechanisms for an individual to adjust during lifespan to environmental resources and challenges. These systems are inherently redox networks, arising during evolution of complex systems with O2 as a major determinant of bioenergetics, metabolic and structural organization, defense, and reproduction. The network structure decreases flexibility from conception onward due to differentiation and cumulative responses to environment (exposome). The redox theory of aging is that aging is a decline in plasticity of genome-exposome interaction that occurs as a consequence of execution of differentiation and exposure memory systems. This includes compromised mitochondrial and bioenergetic flexibility, impaired food utilization and metabolic homeostasis, decreased barrier and defense capabilities and loss of reproductive fidelity and fecundity. This theory accounts for hallmarks of aging, including failure to maintain oxidative or xenobiotic defenses, mitochondrial integrity, proteostasis, barrier structures, DNA repair, telomeres, immune function, metabolic regulation and regenerative capacity.

  18. Redox theory of aging

    Directory of Open Access Journals (Sweden)

    Dean P. Jones

    2015-08-01

    Full Text Available Metazoan genomes encode exposure memory systems to enhance survival and reproductive potential by providing mechanisms for an individual to adjust during lifespan to environmental resources and challenges. These systems are inherently redox networks, arising during evolution of complex systems with O2 as a major determinant of bioenergetics, metabolic and structural organization, defense, and reproduction. The network structure decreases flexibility from conception onward due to differentiation and cumulative responses to environment (exposome. The redox theory of aging is that aging is a decline in plasticity of genome–exposome interaction that occurs as a consequence of execution of differentiation and exposure memory systems. This includes compromised mitochondrial and bioenergetic flexibility, impaired food utilization and metabolic homeostasis, decreased barrier and defense capabilities and loss of reproductive fidelity and fecundity. This theory accounts for hallmarks of aging, including failure to maintain oxidative or xenobiotic defenses, mitochondrial integrity, proteostasis, barrier structures, DNA repair, telomeres, immune function, metabolic regulation and regenerative capacity.

  19. Ediacaran Redox Fluctuations

    Science.gov (United States)

    Sahoo, S. K.; Jiang, G.; Planavsky, N. J.; Kendall, B.; Owens, J. D.; Anbar, A. D.; Lyons, T. W.

    2013-12-01

    Evidence for pervasive oxic conditions, and likely even deep ocean oxygenation has been documented at three intervals in the lower (ca. 632 Ma), middle (ca. 580 Ma) and upper (ca. 551 Ma) Ediacaran. The Doushantuo Formation in South China hosts large enrichments of redox-sensitive trace element (e.g., molybdenum, vanadium and uranium) in anoxic shales, which are indicative of a globally oxic ocean-atmosphere system. However, ocean redox conditions between these periods continue to be a topic of debate and remain elusive. We have found evidence for widespread anoxic conditions through much of the Ediacaran in the deep-water Wuhe section in South China. During most of the Ediacaran-early Cambrian in basinal sections is characterized by Fe speciation data and pyrite morphologies that indicate deposition under euxinic conditions with near-crustal enrichments of redox-sensitive element and positive pyrite-sulfur isotope values, which suggest low levels of marine sulfate and widespread euxinia. Our work reinforces an emerging view that the early Earth, including the Ediacaran, underwent numerous rises and falls in surface oxidation state, rather than a unidirectional rise as originally imagined. The Ediacaran ocean thus experienced repetitive expansion and contraction of marine chalcophilic trace-metal levels that may have had fundamental impact on the slow evolution of early animals and ecosystems. Further, this framework forces us to re-examine the relationship between Neoproterozoic oxygenation and metazoan diversification. Varying redox conditions through the Cryogenian and Ediacaran may help explain molecular clock and biomarker evidence for an early appearance and initial diversification of metazoans but with a delay in the appearance of most major metazoan crown groups until close to Ediacaran-Cambrian boundary.

  20. Power Optimization Distribution and Control Strategies of Multistage Vanadium Redox Flow Battery Energy Storage Systems%多级钒电池储能系统的功率优化分配及控制策略

    Institute of Scientific and Technical Information of China (English)

    李辉; 付博; 杨超; 赵斌; 唐显虎

    2013-01-01

    为了更好利用储能系统平抑大容量风电场功率波动,提出采用多级全钒液流电池(vanadium redox flow battery,VRB)储能的功率优化分配控制策略.首先,在建立VRB等效电路基础上,采用交直流变换器级联多重双向直流变换器作为VRB储能系统接口,分别建立了以稳定直流母线电压为目标的DC/AC变换器矢量控制策略,以电池荷电状态为约束的VRB充放电切换的DC/DC变换器双闭环控制策略.其次,以每级电池组的荷电状态值作为吞吐功率的优选目标,以外部端电压作为电池安全充放电的约束条件,提出多级VRB组的功率优化分配策略.最后,以不同荷电状态(state of charge,SOC)值下的2级VRB储能系统为例,对其在风速波动情况下的风电功率平抑效果以及各个储能单元充放电运行性能进行仿真,并与功率平均分配策略进行对比.结果表明,所提出的多级VRB储能系统功率优化分配和控制策略能很好的平滑风电功率波动,又能减少单台VRB组的充放电次数,并确保电池工作于安全运行区域.%In order to make better use of energy storage system to reduce the fluctuation of active power for large-scale wind farm,this paper proposes the optimization power distribution control strategies of the multistage vanadium redox flow battery (VRB) storage.Firstly,based on the equivalent circuit of a VRB and by using the interface of the DC/AC converter cascade multiple bi-directional DC/DC converter,a vector control strategy of DC/AC converter is presented to keep the stable DC bus voltage,and a double closed loop control strategy of DC/DC converter is established to switch charge-discharge style as a constraint of state of charge (SOC) on a single VRB.Secondly,by taking SOC value of each battery as priority target selection of output power,and by using the limit of external terminal voltage as the constraint conditions for battery safety charging and discharging,an optimization

  1. Modification of graphite felt with Ga2O3in vanadium redox flow battery%全钒液流电池石墨毡电极的Ga2O3修饰

    Institute of Scientific and Technical Information of China (English)

    李晨飞; 王树博; 谢晓峰; 张建文

    2015-01-01

    为提高全钒液流电池石墨毡电极的电化学性能,采用热分解法将纳米Ga2O3沉积在全钒液流电池石墨毡电极表面.通过循环伏安测试、动电位极化曲线测试、扫描电镜测试(SEM)、X 射线光电子能谱分析(XPS)和充放电实验考察了 Ga2O3对石墨毡电化学性能和表面形貌的影响.研究结果表明:Ga2O3对电极反应具有显著的催化作用,当用Ga2O3电极修饰石墨毡时,电池正负极反应活性较未处理前分别提高13%和18%,同时也导致全钒液流电池的容量更大,电流效率和能量效率更高.%To improve the electrochemical activities of graphite felt (GF) electrodes of all vanadium flow battery (VRB), nano-Ga2O3 were deposited on the surface of graphite felt (GF) electrode in an VRB using thermal decomposition. Electrochemical performance and morphology of GF were studied by cyclic voltammetry (CV), polarization curves, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and charge-discharge test. The results showed that Ga2O3 has catalytic effects towards redox reaction of the electrode, when modifying the GF with Ga2O3, the anodic and cathodic reactivity of the VRB were increased by 13% and 18% compared with pristine one, while the battery exhibited higher capacity, current efficiency and energy efficiency.

  2. 全钒液流电池支路电流的理论计算及实验分析%Theoretical calculation and experimental analysis of shunt current in all vanadium redox flow battery

    Institute of Scientific and Technical Information of China (English)

    马军; 李爱魁; 杨祥军; 刘飞; 张爱芳

    2012-01-01

    The calculation of shunt current in the all vanadium redox flow battery was described and the calculation process was completed by MATLAB software. The regularity of distribution and effect factors of shunt current was reviewed. In addition, the energy efficiency of 7.5 kW stack was tested. The results show that the center battery has the minimum feed port shunt current and the maximum manifold road shunt current. The modular construction has lower shunt current and higher energy efficiency.%提出了钒电池支路电流计算方法,采用MATLAB软件对不同结构7.5 kW钒电池的支路电流进行了理论计算,分析了支路电流的分布规律及影响因素,并对7.5 kW钒电池进行效率测试,结果表明:支管上的支路电流在电堆中心最小,而总管及主路上的支路电流在电堆中心为最大值,同时单电池个数减少有利于减小支路电流;采用模块化结构的7.5 kW电堆(由2组共30个单电池串联而成,即15个单电池组成一个模块)的支路电流明显降低,其能量效率达到74.4%,高于一体化结构电堆(由1组共30个单电池串联而成,即每组30个单电池)的能量效率(69.4%).

  3. Charge-Discharge Behaviors and Properties of a Lab-Scale All-Vanadium Redox-Flow Single Cell Research Notes%全钒液流单电池充放电行为及特性研究

    Institute of Scientific and Technical Information of China (English)

    赵平; 张华民; 文越华; 衣宝廉

    2007-01-01

    建立具有外置双饱和甘汞参比电极及双液流电池的实验装置系统.使用该装置可在同一时刻同时测定小型液流单电池充放电时的电池电压、电池正负极电位及正负极开路电位,进而计算充放电过程电池的欧姆内阻降(iR)及其正负极过电位.以石墨毡为电极、Nafion 117作隔膜的全钒液流单电池,在60 mA·cm-2电流密度下,每一充放电循环的平均iR降约占总电压损耗的74%,表明该电池的电压效率受制于电池的欧姆内阻.充放电曲线显示,电池放电终点之所以出现主要是由于电池负极电位在放电末期的快速上升而引起的.本文设计的全钒单电池于60 mA·cm-2下工作时,其电压及能量效率分别达89%和85%,表明该电池结构合理,且石墨毡是钒电池合适的电极材料.%An experimental setup with two external saturated calomel reference electrodes(SCE)and two flow cells was established for flow battery research application. By using this setup, the cell voltage, potentials and open circuit potentials of the positive and negative electrodes for a lab-scale flow battery single cell, could be determined simultaneously during charge-discharge (C-D) cycle test. Then, the ohmic internal resistance drop (iR drop), overpotentials at the negative and positive electrodes of the cell during C-D process, were calculated. The average iR drop accounts for about 74% of the total voltage losses during the C-D cycle at current density of 60 mA·cm-2, suggesting the voltage efficiency (VE) of vanadium redox-flow battery (VRB) single cell with graphite felt as electrodes and Nafion 117 as battery separator, was limited by the cell ohmic internal resistance. The C-D curves show that the appearance of the end-point of discharge is mainly due to the zoom of negative electrode over potential. The VRB single cell designed in this work achieves an excellent performance,with voltage and energy efficiency up to ca. 89% and 85

  4. Energy storage: Redox Flow Batteries Go Organic

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Wei; Sprenkle, Vincent L.

    2016-02-19

    Access to sustainable and affordable energy is the foundation for the economic growth of our current society and its future prosperity. Energy harvested from renewable resources, such as solar and wind, although currently at a small fraction, is on a steady trajectory of increasing installation accompanied with falling cost. Driven also by the need to reduce the carbon footprint from electricity generation, they could provide a clean and sustainable energy future. The caveat, however, is the intermittent and fluctuating nature of the renewables, which threatens the stability of the grid when its share surpasses 20% of the overall energy capacity. 1 Besides the on-demand power generation, electrical energy storage is another potentially cost-effective way to provide massive energy storage for not only renewable energy integration, but to balance the mismatch between supply and demand, and the improvement of grid reliability and efficiency also.

  5. Charge transfer to a semi-esterified bifunctional phenol

    Energy Technology Data Exchange (ETDEWEB)

    Brede, O.; Hermann, R.; Orthner, H. [Leipzig Univ. (Germany)

    1996-03-01

    The charge transfer from solvent radical cations of n-butyl chloride and cyclohexane to 2-butyl-6(3`-t-butyl-2`-hydroxy-5`-methylbenzyl)-4-methyl-phenylac rylate (GM) yields in the first step phenoxyl radicals as well as acrylate radical cations of this semi-acrylated bifunctional phenol. Subsequently an intramolecular charge transfer from the acrylate radical cation to the phenol group takes place. Because of the instability of phenol radical cations, under our experimental conditions (nanosecond pulse radiolysis, non-polar solvents, room temperature) phenoxyl radicals are the only observable products of phenol ionization. (author).

  6. A bifunctional perovskite catalyst for oxygen reduction and evolution.

    Science.gov (United States)

    Jung, Jae-Il; Jeong, Hu Young; Lee, Jang-Soo; Kim, Min Gyu; Cho, Jaephil

    2014-04-25

    La0.3(Ba0.5Sr0.5)0.7Co0.8Fe0.2O3d is a promising bifunctional perovskite catalyst for the oxygen reduction reaction and the oxygen evolution reaction. This catalyst has circa 10 nm-scale rhombohedral LaCoO3 cobaltite particles distributed on the surface. The dynamic microstructure phenomena are attributed to the charge imbalance from the replacement of A-site cations with La3+ and local stress on Cosite sub-lattice with the cubic perovskite structure.

  7. Mn2+浓度对钒液流电池正极液的电化学性能影响%Influence of Mn2+ Concentration on the Electrochemical Behavior of the Anolyte for Vanadium Redox Flow Batteries

    Institute of Scientific and Technical Information of China (English)

    黄斐; 王贵欣; 闫康平; 罗冬梅

    2012-01-01

    电解液中金属离子会影响钒液流电池的电化学性能.本文采用循环伏安法和电化学阻抗谱研究了正极液中Mn2+浓度对V(Ⅴ)/V(Ⅳ)电对的氧化还原过程影响规律,发现Mn2+在正极液中没有发生副反应,但严重影响V(Ⅴ)/V(Ⅳ)的反应活性、电极反应可逆性、离子扩散与电荷转移反应等电化学性能.循环伏安测试结果表明Mn2+浓度为0.04~0.13 g·L-1时,V(Ⅴ)/V(Ⅳ)电对电极反应可逆性和反应活性较高,钒离子扩散系数由参照溶液中的8.89×10-7~1.098×10-6增大至1.302×10-6~1.800×10-6 cm2·s-1,提高了~60%;电化学阻抗测试结果表明Mn2+浓度为0~0.04 g·L-1时,V(Ⅴ)/V(Ⅳ)电对电极反应阻抗和界面阻抗均较参照溶液中的增加不明显,但当Mn2+浓度增至0.07 g·L-1时,上述阻抗值较参照溶液增大了25%~28%.基于二者结果,Mn2+对电极反应有不同程度的负面影响,但是适当的Mn2+浓度有利于钒离子的扩散.%Metal ions in the electrolyte will affect the electrochemical performance of vanadium redox flow batteries (VRBs). The influence of Mn2+ concentration in the anolyte on the redox process of V(V)/V(Ⅳ) couple has been investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). It is found that Mn2 + doesn' t cause a side reaction, but greatly affects the electrochemical performance of V (V)/V (Ⅳ) redox reaction, including reaction activity, reversibility of electrode reaction, vanadium ion diffusion, and charge transfer reaction. The results from CV show that the reversibility and the reaction activity of V(V)/V(IV) couple can be improved as the Mn2+ concentration ranges from 0.04 to 0.13 g·L-1. The vanadium ion diffusion coefficient increases from 8.89×10~1.098×10-6 in the reference anolyte to 1.302×l06~1.800×l0-6 cm2·s-1, an increase of ~ 60%. EIS investigation indicates that the electrode reaction resistance and interfacial resistance of V (V

  8. Direct electrochemistry of redox proteins.

    NARCIS (Netherlands)

    Heering, H.A.

    1995-01-01

    The goal of the project was to obtain more detailed insight in interactions between redox proteins and solid electrodes and the mechanisms of electron transfer. In addition to this, the influence of the protein environment on the redox properties of the active site and the possible influence of the

  9. 液流钒电池用TiO_2/Nafion/PP质子交换膜的研究%Study on proton exchange membrane of TiO_2/Nafion/PP for vanadium redox flow battery

    Institute of Scientific and Technical Information of China (English)

    仲晓玲; 黄可龙; 袁国霞; 常晔; 袁伟

    2009-01-01

    以聚丙烯膜(PP)为基体,采用浸渍法制备了新型质子交换膜Nation/PP膜.并通过掺杂的方式制备了复合膜TiO_2/Nafion/PP.采用扫描电镜仪(SEM),红外光谱对复合膜进行了表征,测定了膜的质子交换容量和电导率,并考察了以两种复合膜作为隔膜的液流钒电池的电化学性能.结果表明:TiO_2掺杂改性以后.TiO_2/Nafion/PP的质子交换容量为0.729 8 mmol/g,含水率为17.86%,分别比Nafion/PP膜提高了75%和117%,复合膜电导率比Nafion/PP提高了27%.电化学测试结果表明:以TiO_2Nafion/PP为隔膜的模拟液流钒电池电池效率为67.76%,显示出优良的循环稳定性.%New types of proton exchange membranes Nafion/PP and TiO_2/Nafion/PP based on PP which were prepared by the method of soaking and TiO_2 doping were introduced into the vanadium redox flow battery (VRB). SEM and IR spectra were taken to characterize the membranes. Ion exchange capacity (IEC), electrical conductivity and electrochemical performance of VRB with the composite membranes had also been investigated. The results show that the electrical conductivity of the composite membrane increases about 27% after mixed with TiO_2; the cell efficiency of VRB employing TiO_2/Nafion/PP composite membrane with a IEC value of 0.729 8 mmol/g and a hydrous ratio of 17.86% which are respectively 75% and 117% higher than Nafion/PP membrane is 67.76%; the cycle stability of the VRB with the composite membrane performs well.

  10. Application of novel polymer electrolyte membrane in all vanadium redox flow battery%新型聚合物电解质膜在液流电池中的应用

    Institute of Scientific and Technical Information of China (English)

    王宇翔; 余晴春

    2015-01-01

    选择Nafion117电解质膜作为对比,考察了含咪唑基磺化聚酰亚胺(Im-SPI)电解质膜应用于全钒氧化还原液流电池的可行性,测定了Im-SPI离子交换膜的电导率及在1.5 mol/L VOSO4溶液中VO2+离子的透过率。实验结果表明, Im-SPI膜电导率为0.10 S/cm,高于Nafion117膜;VO2+离子的渗透系数为3.43×10-7 cm2/s,稍大于Nafion117膜。单电池实验充放电电流密度60 mA/cm2时,Im-SPI膜电流效率可达99.67%,电压效率可达82.41%,能量效率相比Nafion117单电池提高了1.65%。%Compared to Nafion117 electrolyte membrane, the feasibility of benzimidazole group-containing sulfonated polyimides (Im-SPI) electrolyte membrane used in al vanadium redox flow battery was investigated. The proton conductivity and VO2+ions penetration rate in 1.5 mol/L VOSO4 solution of Im-SPI membrane were measured. The results show that the proton conductivity of Im-SPI is 0.10 S/cm, much higher than that of Nafion117 membrane, while the permeability of VO2+is 3.43×10-7 cm2/s, a little higher than that of Nafion117 membrane. The single celltest shows that the coulombic efficiency and voltage efficiency of Im-SPI membrane reach 99.67%and 82.41%, and the power efficiency improves by 1.65%than that of Nafion117 membrane under the current density of 60 mA/cm2.

  11. 钒液流电池的建模与充放电控制特性%Researching on vanadium redox flow battery modeling and charge-discharge characteristics

    Institute of Scientific and Technical Information of China (English)

    丁明; 陈中; 林根德

    2011-01-01

    随着风电场、光伏电站并网穿透功率的不断增加,风电场、光伏电站输出功率随机波动性给电网的安全运行带来了一系列影响,储能技术平滑风电场、光伏电站输出功率波动是有效手段之一,因此对储能媒介建模及充放电控制方式的深入研究至关重要.钒液流电池作为一种新型储能电池,具有功率密度和能量密度独立控制、充放电循环寿命长、动态响应快、维护简单等优点,适合于可再生能源发电系统应用.研究钒液流电池(VRB)的充放电模型、电池可用能量预测、荷电状态SOC及充放电输出特性,构建10 kW/h VRB仿真系统模型,详细研究VRB的恒功率、恒电流充放电模式和充放电效率,并讨论应用于独立光伏发电系统的VRB优化充电方式.%With the increasing penetration of grid-connected wind power generation and PV system, the output fluctuation of wind power and PV system brings many effects on the safe operation of power system. Smoothing the output fluctuation with energy storage system is an effective method. Vanadium Redox Flow Battery (VRB) as a new type energy storage system has many advantages, such as the decoupling control of the power and capacity, long life, fast response and low maintenance requirements, which make it suitable for renewable sources generation systems. Base on the study of VRB charge-discharge model, remaining energy prediction,state of charge (SOC) and the output characteristics, a 10 kW/h VRB simulation model is set up in this paper. The constant power mode and the constant current mode are studied in detail as well as the charge-discharge efficiency. At the end, an optimization charging method for VRB system in a stand-alone PV system is proposed, and the simulation results are given.

  12. Modelling and Simulating of Shunt Current in Redox Flow Battery%液流储能电池系统支路电流的建模与仿真分析

    Institute of Scientific and Technical Information of China (English)

    李蓓; 郭剑波; 陈继忠; 惠东

    2011-01-01

    Shunt current loss of vanadium redox flow battery (VRB) was researched and analyzed. The equivalent circuit of shunt current was modelling, and the value and distribution of shunt current were obtained by simulation; and then the shunt current influence on the external characteristics of VRB was analyzed. Based on the classic battery model and controlled unit, the VRB model including shunt current factor was established. From the simulation, the influence on battery system external characteristics became obvious with the large-scale application of VRB. To reduce the loss of shunt current can improve the efficiency of VRB and be useful to keep the consistency of voltage of battery internal modules. Study on shunt current of large scale VRB system has very practical significance, especially for project pre-planning and its operation and maintenance.%对全钒液流电池所特有的支路电流损耗进行理论分析和研究,建立支路电流等效电路模型,通过仿真计算对支路电流进行量化分析,并得出支路电流的分布规律及其对全钒液流电池外特性的影响。同时基于化学电池的经典三阶模型,通过引入受控元件的思想,提出包含支路电流损耗因素的全钒液流电池模型,并通过仿真对比分析发现,大规模全钒液流电池系统的支路电流损耗对电池系统外特性影响显著。尽可能地消减支路电流损耗,对于提高电池储能系统的效率和保障电池系统内部模块的电压一致性至关重要,尤其在电力系统领域大规模应用全钒液流储能电池时,支路电流的研究对于工程前期规划设计和系统运行的操作维护,均具有实际应用价值。

  13. Influence of Cr3+ concentration on the electrochemical behavior of the anolyte for vanadium redox flow batteries%Cr3+浓度对钒液流电池正极液的电化学性能影响

    Institute of Scientific and Technical Information of China (English)

    黄斐; 赵强; 罗春晖; 王贵欣; 闫康平; 罗冬梅

    2012-01-01

    电解液组成对钒液流电池(vanadium redox flow batteries,VRB)的电化学性能影响较大.本文采用循环伏安法(cyclic voltammetry,CV)和电化学阻抗谱(electrochemical impedance spectroscopy,EIS)研究了正极液中Cr3+浓度对V(Ⅴ )/V(Ⅳ)电对的电极过程的影响规律,发现Cr3+没有引发副反应,但影响反应活性、电极反应可逆性、钒离子扩散、界面膜阻抗和电极反应阻抗等电化学性能.实验结果表明,Cr3+在一定浓度范围内可以提高电极反应的可逆性和钒离子扩散,当Cr3+浓度由0增大至0.30 g L-1时,V(Ⅴ )/V(Ⅳ)电极反应可逆性增强,同时扩散阻抗降低,钒离子扩散系数由参照溶液中的(5.48~6.77)×10-7增大至(6.82~8.44)×10-7 cm2 s-1,提高了~24%,但是当浓度大于0.30 g L -1时,扩散阻抗增大,扩散系数降低,而界面、液膜和电荷转移等阻抗持续增大.因此,Cr3+在一定浓度范围内可以强化钒离子的扩散与传质过程,但是会增大液膜、界面和电荷转移等阻抗,并且浓度不超过0.10 g L-1时对电极反应过程影响不大,浓度不超过0.30 g L-1时对钒离子的扩散有利.

  14. 全钒液流电池用PTFE-碳纳米管电极的性能%Characteristics of graphite based composite electrodes containing carbon nanotubes for vanadium redox flow batteries

    Institute of Scientific and Technical Information of China (English)

    李丹丹; 褚有群; 李雯雯; 马淳安

    2013-01-01

      以聚四氟乙烯(PTFE)为黏结剂制备了不同组分的石墨粉(GP)和多壁碳纳米管(MWCNT)复合电极,采用恒电位阶跃、循环伏安、电化学阻抗谱及恒电流充放电等方法系统考察了 GP-MWCNT 复合电极在全钒液流电池(VRFB)体系中的电化学性能。实验结果表明:复合电极中MWCNT含量的增加有利于VRFB正、负极反应的进行,纯MWCNT电极表现出最优的电化学性能;以纯MWCNT电极为正、负极构建的VRFB电池在30 mA/cm2的恒电流充放电条件下表现出了良好的稳定性和电化学性能,电流效率、电压效率和能量效率分别为96%、87%和84%。%Graphite (GP) based composite electrodes containing multi-walled carbon nanotube (MWCNT) were prepared for vanadium redox flow batteries (VRFB) using polytetrafluoroethylene (PTFE) as binding agent. Electrochemical performance of the GP-MWCNT composite electrodes was characterized by chronoamperometry, cyclic voltammetry and electrochemical impedance spectroscopy. The results showed that both positive and negative electrode reactions of VRFB benefited from the use of more MWCNT in the composite electrode, and the best electrochemical performance was obtained with pure MWCNT electrode. A VRFB was therefore constructed using pure MWCNT electrodes as both the positive and negative electrodes. Preliminary charge/discharge tests at a current density of 30 mA/cm2 demonstrated that the VRFB had a good stability and electrochemical performance. The current efficiency, voltage efficiency and energy efficiency were 96%, 87%and 84%, respectively.

  15. Photovoltachromic device with a micropatterned bifunctional counter electrode.

    Science.gov (United States)

    Cannavale, Alessandro; Manca, Michele; De Marco, Luisa; Grisorio, Roberto; Carallo, Sonia; Suranna, Gian Paolo; Gigli, Giuseppe

    2014-02-26

    A photovoltachromic window can potentially act as a smart glass skin which generates electric energy as a common dye-sensitized solar cell and, at the same time, control the incoming energy flux by reacting to even small modifications in the solar radiation intensity. We report here the successful implementation of a novel architecture of a photovoltachromic cell based on an engineered bifunctional counter electrode consisting of two physically separated platinum and tungsten oxide regions, which are arranged to form complementary comb-like patterns. Solar light is partially harvested by a dye-sensitized photoelectrode made on the front glass of the cell which fully overlaps a bifunctional counter electrode made on the back glass. When the cell is illuminated, the photovoltage drives electrons into the electrochromic stripes through the photoelectrochromic circuit and promotes the Li(+) diffusion towards the WO3 film, which thus turns into its colored state: a photocoloration efficiency of 17 cm(2) min(-1) W(-1) at a wavelength of 650 nm under 1.0 sun was reported along with fast response (coloration time photovoltaic functionality was also retained due to the copresence of the independently switchable micropatterned platinum electrode.

  16. Stability and kinetics of a bifunctional amylase/trypsin inhibitor.

    Science.gov (United States)

    Alagiri, S; Singh, T P

    1993-11-10

    The stability of the bifunctional amylase/trypsin inhibitor from ragi (Indian finger millet, Eleusine coracana) has been studied by methods of circular dichroism, UV absorption and intrinsic fluorescence. The inhibitor is stable in 8 M urea and 6 M guanidine-HCl. In 150 mM NaCl, thermal denaturation does not occur up to 90 degrees C. However, it is irreversibly denatured in 5 mM NaCl if heated over 73 degrees C. The acidic denaturation is reversible in both high and low salt conditions, but it shows different behavior below pH 1.65 under similar salt conditions. The helical content is about 2-4% in the pH range of 7-9 at which the inhibitor is active maximally. The NaCl concentration does not have a significant effect on the secondary structure elements. The beta-strand form does not show much variation under various conditions. Arg34-Leu35 is the reactive peptide bond in the trypsin-binding site. Trp and Tyr are involved in the binding with amylase. The bifunctional inhibitor represents the sum of individual inhibitors of trypsin and amylase.

  17. Synthesis and Characterization of a New Bifunctional Dye Containing Spirobenzopyran and Cinnamoyl Moiety

    Institute of Scientific and Technical Information of China (English)

    申凯华; 崔东熏

    2005-01-01

    A novel bifunctional dye containing spirobenzopyran and cinnaznoyl moiety has been prepared and its photochromic behavior following irradiation at different wavelengths of monochrome UV light was investigated.The colourless bifunctional dye in film or solution exhibits unusual photochromism through structural and geometrical transformation from spirobenzopyran to merocyanine accompanying with photocrosslinking reaction in cinnamoyl moieties. Two kinds of photochemical reaction were achieved by irradiation at the different wavelengths of monochrome UV light (275 nm, 365 nm) selectively. The photochromic process of the bifunctional dye was discussed and the dynamic behaviors of the decolorization process were investigated.

  18. Bifunctional chelates of RH-105 and AU199 as potential radiotherapeutic agents

    Energy Technology Data Exchange (ETDEWEB)

    Droege, P.

    1997-03-01

    Research is presented on new bifunctional chelating ligand systems with stability on the macroscopic and radiochemical levels. The synthesis of the following complexes are described: rhodium 105, palladium 109, and gold 198.

  19. Bifunctional chelating agent for the design and development of site specific radiopharmaceuticals and biomolecule conjugation strategy

    Science.gov (United States)

    Katti, Kattesh V.; Prabhu, Kandikere R.; Gali, Hariprasad; Pillarsetty, Nagavara Kishore; Volkert, Wynn A.

    2003-10-21

    There is provided a method of labeling a biomolecule with a transition metal or radiometal in a site specific manner to produce a diagnostic or therapeutic pharmaceutical compound by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radio metal or a transition metal, and covalently linking the resulting metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. Also provided is a method of synthesizing the --PR.sub.2 containing biomolecules by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radiometal or a transition metal, and covalently linking the resulting radio metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. There is provided a therapeutic or diagnostic agent comprising a --PR.sub.2 containing biomolecule.

  20. Redox Properties of Free Radicals.

    Science.gov (United States)

    Neta, P.

    1981-01-01

    Describes pulse radiolysis as a useful means in studing one-electron redox potentials. This method allows the production of radicals and the determination of their concentration and rates of reaction. (CS)

  1. The bi-functional organization of human basement membranes.

    Science.gov (United States)

    Halfter, Willi; Monnier, Christophe; Müller, David; Oertle, Philipp; Uechi, Guy; Balasubramani, Manimalha; Safi, Farhad; Lim, Roderick; Loparic, Marko; Henrich, Paul Bernhard

    2013-01-01

    The current basement membrane (BM) model proposes a single-layered extracellular matrix (ECM) sheet that is predominantly composed of laminins, collagen IVs and proteoglycans. The present data show that BM proteins and their domains are asymmetrically organized providing human BMs with side-specific properties: A) isolated human BMs roll up in a side-specific pattern, with the epithelial side facing outward and the stromal side inward. The rolling is independent of the curvature of the tissue from which the BMs were isolated. B) The epithelial side of BMs is twice as stiff as the stromal side, and C) epithelial cells adhere to the epithelial side of BMs only. Side-selective cell adhesion was also confirmed for BMs from mice and from chick embryos. We propose that the bi-functional organization of BMs is an inherent property of BMs and helps build the basic tissue architecture of metazoans with alternating epithelial and connective tissue layers.

  2. The bi-functional organization of human basement membranes.

    Directory of Open Access Journals (Sweden)

    Willi Halfter

    Full Text Available The current basement membrane (BM model proposes a single-layered extracellular matrix (ECM sheet that is predominantly composed of laminins, collagen IVs and proteoglycans. The present data show that BM proteins and their domains are asymmetrically organized providing human BMs with side-specific properties: A isolated human BMs roll up in a side-specific pattern, with the epithelial side facing outward and the stromal side inward. The rolling is independent of the curvature of the tissue from which the BMs were isolated. B The epithelial side of BMs is twice as stiff as the stromal side, and C epithelial cells adhere to the epithelial side of BMs only. Side-selective cell adhesion was also confirmed for BMs from mice and from chick embryos. We propose that the bi-functional organization of BMs is an inherent property of BMs and helps build the basic tissue architecture of metazoans with alternating epithelial and connective tissue layers.

  3. Chemoselective Reactivity of Bifunctional Cyclooctynes on Si(001)

    CERN Document Server

    Reutzel, Marcel; Lipponer, Marcus A; Länger, Christian; Höfer, Ulrich; Koert, Ulrich; Dürr, Michael

    2016-01-01

    Controlled organic functionalization of silicon surfaces as integral part of semiconductor technology offers new perspectives for a wide range of applications. The high reactivity of the silicon dangling bonds, however, presents a major hindrance for the first basic reaction step of such a functionalization, i.e., the chemoselective attachment of bifunctional organic molecules on the pristine silicon surface. We overcome this problem by employing cyclooctyne as the major building block of our strategy. Functionalized cyclooctynes are shown to react on Si(001) selectively via the strained cyclooctyne triple bond while leaving the side groups intact. The achieved selectivity originates from the distinctly different adsorption dynamics of the separate functionalities: A direct adsorption pathway is demonstrated for cyclooctyne as opposed to the vast majority of other organic functional groups. The latter ones react on Si(001) via a metastable intermediate which makes them effectively unreactive in competition wi...

  4. GSK-3: A Bifunctional Role in Cell Death Pathways

    Directory of Open Access Journals (Sweden)

    Keith M. Jacobs

    2012-01-01

    Full Text Available Although glycogen synthase kinase-3 beta (GSK-3β was originally named for its ability to phosphorylate glycogen synthase and regulate glucose metabolism, this multifunctional kinase is presently known to be a key regulator of a wide range of cellular functions. GSK-3β is involved in modulating a variety of functions including cell signaling, growth metabolism, and various transcription factors that determine the survival or death of the organism. Secondary to the role of GSK-3β in various diseases including Alzheimer’s disease, inflammation, diabetes, and cancer, small molecule inhibitors of GSK-3β are gaining significant attention. This paper is primarily focused on addressing the bifunctional or conflicting roles of GSK-3β in both the promotion of cell survival and of apoptosis. GSK-3β has emerged as an important molecular target for drug development.

  5. GSK-3β: A Bifunctional Role in Cell Death Pathways

    Science.gov (United States)

    Jacobs, Keith M.; Bhave, Sandeep R.; Ferraro, Daniel J.; Jaboin, Jerry J.; Hallahan, Dennis E.; Thotala, Dinesh

    2012-01-01

    Although glycogen synthase kinase-3 beta (GSK-3β) was originally named for its ability to phosphorylate glycogen synthase and regulate glucose metabolism, this multifunctional kinase is presently known to be a key regulator of a wide range of cellular functions. GSK-3β is involved in modulating a variety of functions including cell signaling, growth metabolism, and various transcription factors that determine the survival or death of the organism. Secondary to the role of GSK-3β in various diseases including Alzheimer's disease, inflammation, diabetes, and cancer, small molecule inhibitors of GSK-3β are gaining significant attention. This paper is primarily focused on addressing the bifunctional or conflicting roles of GSK-3β in both the promotion of cell survival and of apoptosis. GSK-3β has emerged as an important molecular target for drug development. PMID:22675363

  6. [Bifunctional inhibitor of alpha-amylase/trypsin from wheat grain].

    Science.gov (United States)

    Islamov, R A; Furusov, O V

    2007-01-01

    A trypsin inhibitor, isolated from whole-wheat grain (Triticum aestivum L.) by the method of bio-specific chromatography on trypsin-Sepharose, was potent in inhibiting human salivary alpha-amylase. The bi-functional alpha-amylase/trypsin inhibitor was characterized by a narrow specificity for other alpha-amylases and proteinases. The high thermostability of the inhibitor was lost in the presence of SH group-reducing agents. The inhibitor-trypsin complex retained its activity against alpha-amylase. The inhibitor-alpha-amylase complex was active against trypsin. Studies of the enzyme kinetics demonstrated that the inhibition of alpha-amylase and trypsin was noncompetitive. Our results suggest the existence of two independent active sites responsible for the interaction with the enzymes.

  7. Opioid bifunctional ligands from morphine and the opioid pharmacophore Dmt-Tic.

    Science.gov (United States)

    Balboni, Gianfranco; Salvadori, Severo; Marczak, Ewa D; Knapp, Brian I; Bidlack, Jean M; Lazarus, Lawrence H; Peng, Xuemei; Si, Yu Gui; Neumeyer, John L

    2011-02-01

    Bifunctional ligands containing an ester linkage between morphine and the δ-selective pharmacophore Dmt-Tic were synthesized, and their binding affinity and functional bioactivity at the μ, δ and κ opioid receptors determined. Bifunctional ligands containing or not a spacer of β-alanine between the two pharmacophores lose the μ agonism deriving from morphine becoming partial μ agonists 4 or μ antagonists 5. Partial κ agonism is evidenced only for compound 4. Finally, both compounds showed potent δ antagonism.

  8. 全钒液流电池用碳纸电极掺氮改性的研究%Nitrogen-doped Carbon Paper as Electrodes for Vanadium Redox Flow Batteries

    Institute of Scientific and Technical Information of China (English)

    何章兴; 刘剑蕾; 何震; 刘素琴

    2015-01-01

    采用在氨气氛下加热(NCP-600:600℃下处理, NCP-900:900℃下处理)对全钒液流电池碳纸电极进行掺氮改性处理。通过此改性处理,含氮官能团成功地引入到碳纸表面。掺氮处理改善了碳纸表面的亲水性, NCP-900的接触角相比于空白碳纸由120.5°降到99.7°,且对表面形貌没有明显影响,不会影响其机械性能。同时,掺氮处理能明显地增强碳纸的电化学活性,循环伏安测试中, NCP-900的V(IV)/V(V)电对氧化峰为92.1 mA,远高于空白碳纸(68.9 mA)。由NCP-900和空白碳纸组装成电池考察了其充放电性能,在20 mA/cm2下进行充放电,由NCP-900组装的电池其能量效率为83.73%,较空白电池高2.59%。掺氮改性处理提高碳纸的电化学性能主要是由于钒电对活性位点的增加和亲水性能的增强。%To improve the electrochemical activity of carbon paper (CP) for vanadium redox flow batteries, CP was modified by heat treatment in atmosphere of NH3 at 600 (NCP-600) and 900℃ (NCP-900), respectively. The FTIR results indicate that the nitrogenous groups have been introduced on the surface of CP by modification successfully. Compared with the pristine sample, the water contact angle of NCP-900 decreases from 120.5° to 99.7°, indicating the improved hydrophilicity of CP by nitrogen doping. The SEM results show that there is no obvious morphology change on the surface of CP after nitrogen doping, which do not affect the mechanical property. The electrochemical activity of CP is enhanced significantly by nitrogen doping. The oxidation current peak of V(Ⅳ)/V(Ⅴ) couple on NCP-900 is 92.1 mA, much higher than that of pristine sample (68.9 mA). The cells with NCP-900 and pristine sample as electrodes were assembled and the charge-discharge performance was evaluated. The energy efficiency of cell with NCP-900 as electrode at a current density of 20 mA/cm2 is 83.73%, 2.59% larger than that with the pristine sample. The improved

  9. Redox regulation of protein damage in plasma

    Directory of Open Access Journals (Sweden)

    Helen R. Griffiths

    2014-01-01

    In this review, we focus on redox regulatory control of those enzymes and processes which control protein maturation during synthesis, produce reactive species, repair and remove damaged plasma proteins. We have highlighted the potential for alterations in the extracellular redox compartment to regulate intracellular redox state and, conversely, for intracellular oxidative stress to alter the cellular secretome and composition of extracellular vesicles. Through secreted, redox-active regulatory molecules, changes in redox state may be transmitted to distant sites.

  10. Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

    KAUST Repository

    Mazoyer, Etienne

    2011-12-02

    1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi-functional catalyst" through 1-butene isomerization on W-hydride and 1-butene/2-butenes cross-metathesis on W-carbene. This active moiety is generated in situ at the initiation steps by insertion of 1-butene on tungsten hydrides precursor W-H/Al2O3, 1 followed by α-H and β-H abstraction. © 2011 American Chemical Society.

  11. WATER TABLE AND REDOX CONDITIONS IN DEEP TROPICAL PEAT

    Institute of Scientific and Technical Information of China (English)

    Hajah Dulima Jali

    2007-01-01

    Redox potential in the well developed tropical peat swamp in Brunei was studied for a year. Generally the redox potential measurements showed a large variation, ranging from -234 mV to 727 mV. The expected rise in redox values did not take place following the drop of water table during the dry months of June to September. The redox value at 100 cm depth indicated that the soil remained reduced throughout the year in spite of the lowering of water table below 150 cm in all sites during dry period. Similarly the redox values did not decrease rapidly following flooding when the water table rose to the surface. This phenomenon could be attributed to the topography of the peat dome which facilitated the fast lateral movement of water and thus promoted oxygen supply down the peat profile, though not great enough to reach the 100 cm depth. The rapid lateral flow of water in the outer Alan batu site facilitated aeration, but in the inner sites remained which was reduced because of the slower water movement. The slower initiation of the reducing condition was likely due to the presence of nitrate which has accumulated as a result of ammonium oxidation during the relatively long aerobic period. Differences in the distribution of redox potential with depth are possibly explained by the different permeability of peat affecting flow patterns and residence time of water. The nature and compactibility of the peat might have slowed the diffusion rates of O2 into the lower layer. Though the bulk density of the peat was low, the composition of the peat might influence the peat permeability and hydraulic conductivity. The tree trunks are not decomposed or large branches must have lowered permeability compared to the other peat material.

  12. Enzyme mediated synthesis of polypyrrole in the presence of chondroitin sulfate and redox mediators of natural origin

    Energy Technology Data Exchange (ETDEWEB)

    Grijalva-Bustamante, G.A. [Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Evans-Villegas, A.G. [Departamento de Ciencias Químico Biológicas, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Castillo-Castro, T. del, E-mail: terecat@polimeros.uson.mx [Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Castillo-Ortega, M.M. [Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Cruz-Silva, R. [Research Center for Exotic Nanocarbons, Shinshu University, 4-17-1 Wakasato, 380-8553, Nagano (Japan); Huerta, F. [Departamento Ingeniería Textil y Papelera, Universitat Politecnica de Valencia, Plaza Ferrandiz y Carbonell, 1, E-03801 Alcoy (Spain); Morallón, E. [Departamento Química Física e Instituto Universitario de Materiales, Universidad de Alicante, Ap. 99, E-03080 Alicante (Spain)

    2016-06-01

    Polypyrrole (PPy) was synthesized by enzyme mediated oxidation of pyrrole using naturally occurring compounds as redox mediators. The catalytic mechanism is an enzymatic cascade reaction in which hydrogen peroxide is the oxidizer and soybean peroxidase, in the presence of acetosyringone, syringaldehyde or vanillin, acts as a natural catalysts. The effect of the initial reaction composition on the polymerization yield and electrical conductivity of PPy was analyzed. Morphology of the PPy particles was studied by scanning electron microscopy and transmission electron microscopy whereas the chemical structure was studied by X-ray photoelectron and Fourier transformed infrared spectroscopic techniques. The redox mediators increased the polymerization yield without a significant modification of the electronic structure of PPy. The highest conductivity of PPy was reached when chondroitin sulfate was used simultaneously as dopant and template during pyrrole polymerization. Electroactive properties of PPy obtained from natural precursors were successfully used in the amperometric quantification of uric acid concentrations. PPy increases the amperometric sensitivity of carbon nanotube screen-printed electrodes toward uric acid detection. - Highlights: • A new method of pyrrole polymerization using naturally occurring redox mediators and doping agents was studied. • The catalytic efficiency of different redox mediators toward pyrrole oxidation was evaluated. • Two different naturally occurring polymers were studied as bifunctional steric stabilizer/doping agents. • Polypyrrole improves the amperometric response of carbon nanotube screen printed electrodes toward uric acid sensing.

  13. Redox Homeostasis in Pancreatic Cells

    Directory of Open Access Journals (Sweden)

    Petr Ježek

    2012-01-01

    Full Text Available We reviewed mechanisms that determine reactive oxygen species (redox homeostasis, redox information signaling and metabolic/regulatory function of autocrine insulin signaling in pancreatic β cells, and consequences of oxidative stress and dysregulation of redox/information signaling for their dysfunction. We emphasize the role of mitochondrion in β cell molecular physiology and pathology, including the antioxidant role of mitochondrial uncoupling protein UCP2. Since in pancreatic β cells pyruvate cannot be easily diverted towards lactate dehydrogenase for lactate formation, the respiration and oxidative phosphorylation intensity are governed by the availability of glucose, leading to a certain ATP/ADP ratio, whereas in other cell types, cell demand dictates respiration/metabolism rates. Moreover, we examine the possibility that type 2 diabetes mellitus might be considered as an inevitable result of progressive self-accelerating oxidative stress and concomitantly dysregulated information signaling in peripheral tissues as well as in pancreatic β cells. It is because the redox signaling is inherent to the insulin receptor signaling mechanism and its impairment leads to the oxidative and nitrosative stress. Also emerging concepts, admiting participation of redox signaling even in glucose sensing and insulin release in pancreatic β cells, fit in this view. For example, NADPH has been firmly established to be a modulator of glucose-stimulated insulin release.

  14. Redox electrode materials for supercapatteries

    Science.gov (United States)

    Yu, Linpo; Chen, George Z.

    2016-09-01

    Redox electrode materials, including transition metal oxides and electronically conducting polymers, are capable of faradaic charge transfer reactions, and play important roles in most electrochemical energy storage devices, such as supercapacitor, battery and supercapattery. Batteries are often based on redox materials with low power capability and safety concerns in some cases. Supercapacitors, particularly those based on redox inactive materials, e.g. activated carbon, can offer high power output, but have relatively low energy capacity. Combining the merits of supercapacitor and battery into a hybrid, the supercapattery can possess energy as much as the battery and output a power almost as high as the supercapacitor. Redox electrode materials are essential in the supercapattery design. However, it is hard to utilise these materials easily because of their intrinsic characteristics, such as the low conductivity of metal oxides and the poor mechanical strength of conducting polymers. This article offers a brief introduction of redox electrode materials, the basics of supercapattery and its relationship with pseudocapacitors, and reviews selectively some recent progresses in the relevant research and development.

  15. Redox regulation of mitochondrial biogenesis.

    Science.gov (United States)

    Piantadosi, Claude A; Suliman, Hagir B

    2012-12-01

    The cell renews, adapts, or expands its mitochondrial population during episodes of cell damage or periods of intensified energy demand by the induction of mitochondrial biogenesis. This bigenomic program is modulated by redox-sensitive signals that respond to physiological nitric oxide (NO), carbon monoxide (CO), and mitochondrial reactive oxygen species production. This review summarizes our current ideas about the pathways involved in the activation of mitochondrial biogenesis by the physiological gases leading to changes in the redox milieu of the cell, with an emphasis on the responses to oxidative stress and inflammation. The cell's energy supply is protected from conditions that damage mitochondria by an inducible transcriptional program of mitochondrial biogenesis that operates in large part through redox signals involving the nitric oxide synthase and the heme oxygenase-1/CO systems. These redox events stimulate the coordinated activities of several multifunctional transcription factors and coactivators also involved in the elimination of defective mitochondria and the expression of counterinflammatory and antioxidant genes, such as IL10 and SOD2, as part of a unified damage-control network. The redox-regulated mechanisms of mitochondrial biogenesis schematically outlined in the graphical abstract link mitochondrial quality control to an enhanced capacity to support the cell's metabolic needs while improving its resistance to metabolic failure and avoidance of cell death during periods of oxidative stress.

  16. Mouse redox histology using genetically encoded probes.

    Science.gov (United States)

    Fujikawa, Yuuta; Roma, Leticia P; Sobotta, Mirko C; Rose, Adam J; Diaz, Mauricio Berriel; Locatelli, Giuseppe; Breckwoldt, Michael O; Misgeld, Thomas; Kerschensteiner, Martin; Herzig, Stephan; Müller-Decker, Karin; Dick, Tobias P

    2016-03-15

    Mapping the in vivo distribution of endogenous oxidants in animal tissues is of substantial biomedical interest. Numerous health-related factors, including diet, physical activity, infection, aging, toxins, or pharmacological intervention, may cause redox changes. Tools are needed to pinpoint redox state changes to particular organs, tissues, cell types, and subcellular organelles. We describe a procedure that preserves the in vivo redox state of genetically encoded redox biosensors within histological tissue sections, thus providing "redox maps" for any tissue and comparison of interest. We demonstrate the utility of the technique by visualizing endogenous redox differences and changes in the context of tumor growth, inflammation, embryonic development, and nutrient starvation.

  17. Redox Couples with Unequal Diffusion Coefficients: Effect on Redox Cycling

    NARCIS (Netherlands)

    Mampallil Augustine, Dileep; Mathwig, Klaus; Kang, Shuo; Lemay, Serge G.

    2013-01-01

    Redox cycling between two electrodes separated by a narrow gap allows dramatic amplification of the faradaic current. Unlike conventional electrochemistry at a single electrode, however, the mass-transport-limited current is controlled by the diffusion coefficient of both the reduced and oxidized fo

  18. Bifunctional avidin with covalently modifiable ligand binding site.

    Directory of Open Access Journals (Sweden)

    Jenni Leppiniemi

    Full Text Available The extensive use of avidin and streptavidin in life sciences originates from the extraordinary tight biotin-binding affinity of these tetrameric proteins. Numerous studies have been performed to modify the biotin-binding affinity of (streptavidin to improve the existing applications. Even so, (streptavidin greatly favours its natural ligand, biotin. Here we engineered the biotin-binding pocket of avidin with a single point mutation S16C and thus introduced a chemically active thiol group, which could be covalently coupled with thiol-reactive molecules. This approach was applied to the previously reported bivalent dual chain avidin by modifying one binding site while preserving the other one intact. Maleimide was then coupled to the modified binding site resulting in a decrease in biotin affinity. Furthermore, we showed that this thiol could be covalently coupled to other maleimide derivatives, for instance fluorescent labels, allowing intratetrameric FRET. The bifunctional avidins described here provide improved and novel tools for applications such as the biofunctionalization of surfaces.

  19. A novel bifunctional transcriptional regulator of riboflavin metabolism in Archaea.

    Science.gov (United States)

    Rodionova, Irina A; Vetting, Matthew W; Li, Xiaoqing; Almo, Steven C; Osterman, Andrei L; Rodionov, Dmitry A

    2017-01-09

    Riboflavin (vitamin B2) is the precursor of flavin mononucleotide (FMN) and flavin adenine dinucleotide, which are essential coenzymes in all free-living organisms. Riboflavin biosynthesis in many Bacteria but not in Archaea is controlled by FMN-responsive riboswitches. We identified a novel bifunctional riboflavin kinase/regulator (RbkR), which controls riboflavin biosynthesis and transport genes in major lineages of Crenarchaeota, Euryarchaeota and Thaumarchaeota. RbkR proteins are composed of the riboflavin kinase domain and a DNA-binding winged helix-turn-helix-like domain. Using comparative genomics, we predicted RbkR operator sites and reconstructed RbkR regulons in 94 archaeal genomes. While the identified RbkR operators showed significant variability between archaeal lineages, the conserved core of RbkR regulons includes riboflavin biosynthesis genes, known/predicted vitamin uptake transporters and the rbkR gene. The DNA motifs and CTP-dependent riboflavin kinase activity of two RbkR proteins were experimentally validated in vitro The DNA binding activity of RbkR was stimulated by CTP and suppressed by FMN, a product of riboflavin kinase. The crystallographic structure of RbkR from Thermoplasma acidophilum was determined in complex with CTP and its DNA operator revealing key residues for operator and ligand recognition. Overall, this study contributes to our understanding of metabolic and regulatory networks for vitamin homeostasis in Archaea.

  20. Bifunctional alkyl nitrates - trace constituents of the atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Kastler, J. [Department of Analytical and Environmental Chemistry, University of Ulm (Germany); Ballschmiter, K. [Center of Technology Assessment in Baden-Wuerttemberg, Stuttgart (Germany)

    1998-04-01

    Mono- and multifunctional esters of nitric acid (alkyl nitrates or organonitrates) form very complex mixtures of organic trace constituents in air. An analytical method was developed which combines selectivity in separation and detection in order to simplify this complexity in analytical terms. Mononitrates, dinitrates, keto nitrates, hydroxy nitrates of alkanes and alkenes, respecitvely, and bifunctional terpene nitrates were synthesized as reference substances. A specially developed new HPLC stationary phase (organonitrate phase) allows a group separation of mono-, di-, and hydroxy nitrates. After the HPLC preseparation the single components were finally separated by capillary HRGC-ECD and HRGC-MSD on polar and non-polar stationary phases. Mass spectrometric detection in the selected-ion-mode using the highly selective NO{sub 2}{sup +} fragment (m/z = 46 amu) led to very good selectivities for the nitric acid ester moiety. The analysis of a 100 m{sup 3} ambient air sample using this new analytical protocol allowed the identification of seven hydroxy nitrates and 24 dinitrates ranging from C2 to C7, 22 of them for the first time ever. (orig.) With 3 figs., 3 tabs., 20 refs.

  1. Bioinspired Bifunctional Membrane for Efficient Clean Water Generation.

    Science.gov (United States)

    Liu, Yang; Lou, Jinwei; Ni, Mengtian; Song, Chengyi; Wu, Jianbo; Dasgupta, Neil P; Tao, Peng; Shang, Wen; Deng, Tao

    2016-01-13

    Solving the problems of water pollution and water shortage is an urgent need for the sustainable development of modern society. Different approaches, including distillation, filtration, and photocatalytic degradation, have been developed for the purification of contaminated water and the generation of clean water. In this study, we explored a new approach that uses solar light for both water purification and clean water generation. A bifunctional membrane consisting of a top layer of TiO2 nanoparticles (NPs), a middle layer of Au NPs, and a bottom layer of anodized aluminum oxide (AAO) was designed and fabricated through multiple filtration processes. Such a design enables both TiO2 NP-based photocatalytic function and Au NP-based solar-driven plasmonic evaporation. With the integration of these two functions into a single membrane, both the purification of contaminated water through photocatalytic degradation and the generation of clean water through evaporation were demonstrated using simulated solar illumination. Such a demonstration should also help open up a new strategy for maximizing solar energy conversion and utilization.

  2. Bifunctional drugs for the treatment of asthma and chronic obstructive pulmonary disease.

    Science.gov (United States)

    Page, Clive; Cazzola, Mario

    2014-08-01

    Over the last decade, there has been a steady increase in the use of fixed-dose combinations of drugs for the treatment of a range of diseases, including hypertension, cancer, AIDS, tuberculosis and other infectious diseases. It is now evident that patients with asthma or chronic obstructive pulmonary disease (COPD) can also benefit from the use of fixed-dose combinations, including combinations of a long-acting β2-agonist and an inhaled corticosteroid, and combinations of long-acting β2-agonists and long-acting muscarinic receptor antagonists. In fact, there are now a number of "triple-inhaler" fixed-dose combinations under development, with the first such triple combination having been approved in India. This use of combinations containing drugs with complementary pharmacological actions in the treatment of patients with asthma or COPD has also led to the discovery and development of drugs having two different primary pharmacological actions in the same molecule, which we have called "bifunctional drugs". In this review, we discuss the state of the art of these new bifunctional drugs as novel treatments for asthma and COPD that can be categorised as bifunctional bronchodilators, bifunctional bronchodilator/anti-inflammatory drugs and bifunctional anti-inflammatory drugs.

  3. Single flexible nanofiber to achieve simultaneous photoluminescence-electrical conductivity bifunctionality.

    Science.gov (United States)

    Sheng, Shujuan; Ma, Qianli; Dong, Xiangting; Lv, Nan; Wang, Jinxian; Yu, Wensheng; Liu, Guixia

    2015-02-01

    In order to develop new-type multifunctional composite nanofibers, Eu(BA)3 phen/PANI/PVP bifunctional composite nanofibers with simultaneous photoluminescence and electrical conductivity have been successfully fabricated via electrospinning technology. Polyvinyl pyrrolidone (PVP) is used as a matrix to construct composite nanofibers containing different amounts of Eu(BA)3 phen and polyaniline (PANI). X-Ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), fluorescence spectroscopy and a Hall effect measurement system are used to characterize the morphology and properties of the composite nanofibers. The results indicate that the bifunctional composite nanofibers simultaneously possess excellent photoluminescence and electrical conductivity. Fluorescence emission peaks of Eu(3+) ions are observed in the Eu(BA)3 phen/PANI/PVP photoluminescence-electrical conductivity bifunctional composite nanofibers. The electrical conductivity reaches up to the order of 10(-3)  S/cm. The luminescent intensity and electrical conductivity of the composite nanofibers can be tuned by adjusting the amounts of Eu(BA)3 phen and PANI. The obtained photoluminescence-electrical conductivity bifunctional composite nanofibers are expected to possess many potential applications in areas such as microwave absorption, molecular electronics, biomedicine and future nanomechanics. More importantly, the design concept and construction technique are of universal significance to fabricate other bifunctional one-dimensional naonomaterials.

  4. Mitochondrially targeted fluorescent redox sensors.

    Science.gov (United States)

    Yang, Kylie; Kolanowski, Jacek L; New, Elizabeth J

    2017-04-06

    The balance of oxidants and antioxidants within the cell is crucial for maintaining health, and regulating physiological processes such as signalling. Consequently, imbalances between oxidants and antioxidants are now understood to lead to oxidative stress, a physiological feature that underlies many diseases. These processes have spurred the field of chemical biology to develop a plethora of sensors, both small-molecule and fluorescent protein-based, for the detection of specific oxidizing species and general redox balances within cells. The mitochondrion, in particular, is the site of many vital redox reactions. There is therefore a need to target redox sensors to this particular organelle. It has been well established that targeting mitochondria can be achieved by the use of a lipophilic cation-targeting group, or by utilizing natural peptidic mitochondrial localization sequences. Here, we review how these two approaches have been used by a number of researchers to develop mitochondrially localized fluorescent redox sensors that are already proving useful in providing insights into the roles of reactive oxygen species in the mitochondria.

  5. CO2 capture performance of bi-functional activated bleaching earth modified with basic-alcoholic solution and functionalization with monoethanolamine: isotherms, kinetics and thermodynamics.

    Science.gov (United States)

    Pongstabodee, Sangobtip; Pornaroontham, Phuwadej; Pintuyothin, Nuthapol; Pootrakulchote, Nuttapol; Thouchprasitchai, Nutthavich

    2016-10-01

    CO2 capture performance of bifunctional activated bleaching earth (ABE) was investigated at atmospheric pressure. The sorbents were characterized by means of X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), Caron-Hydrogen-Nitrogen analysis (CHN), Fourier transform infrared (FT-IR) and thermal gravimetric analysis (TGA). The CO2 capacity was enhanced via basic-modification and monoethanolamine (MEA) loading of the ABE sorbent to obtain a bifunctional surface property. Here, basic-modified calcined ABE with a 30wt.% MEA loading (SAB-30) showed the highest CO2 capture capacity, but this was decreased with excess MEA loading (>30wt.%). At a 10% (V/V) initial CO2 concentration feed, the maximum capacity of SAB-30 increased from 2.71mmol/g at 30°C (without adding moisture to the feed) to 3.3mmol/g at 50°C when adding 10% (V/V) moisture to the feed. Increasing the moisture concentration further reduced the maximum CO2 capacity due to the blocking effect of the excess moisture on the sorbent surface. However, SAB-30 could completely capture CO2 even in a 100% (V/V) initial CO2 concentration feed. A maximum CO2 capacity of 5.7mmol/g for SAB-30 was achieved at 30°C. Varying the ratio of sorbent weight to total flow rate of the gas stream had no discernible effect on the equilibrium CO2 capture capacity. Avrami's equation and Toth's isotherm model provided a good fitting for the data and suggested the presence of more than one reaction pathway in the CO2 capture process and the heterogeneous adsorption surface of SAB-30. Thermodynamics studies revealed that CO2 capture on the bifunctional SAB-30 is feasible, spontaneous and exothermic in nature.

  6. Electrochemical Investigation of Interaction between a Bifunctional Probe and GG Mismatch Duplex.

    Science.gov (United States)

    Li, Jiao; He, Hanping; Peng, Xiaoqian; Huang, Min; Zhang, Xiuhua; Wang, Shengfu

    2015-01-01

    A bifunctional probe (FecNC), containing a recognition part and an electrochemical active center, was applied to electrochemical detection of GG mismatch duplexes. The preparation of gold electrodes modified by mismatch and complementatry duplexes was characterized by electrochemical impedance spectroscopy (EIS) and optimized for better detection in terms of self-assembly time, hybridization time, and incubation time. The interaction between FecNC and DNA duplexes modified on the surface of a gold electrode was explored by square wave voltammetry (SWV) and EIS. The results showed that the DNA duplexes with GG mismatch on the surface of a gold electrode was easily detected by the largest electrochemical signal of the bifunctional probe because of its selective binding to GG mismatches. The bifunctional probe could offer a simple, effective electrochemical detection of GG mismatches, and theoretical bases for development of electrochemical biosensors. Further, the method would be favorable for diagnosis of genetic diseases.

  7. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W.; Meyer, Tricia L.; Zhang, Zhiyong; Lutterman, Daniel A.; Lee, Ho Nyung

    2016-03-02

    Strain is known to greatly influence low temperature oxygen electro catalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and Metal-air batteries. However, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals' such as Pt. We attribute the improved bifunctionality to strain induced splitting of the e(g) Orbitals, which can customize orbital asymmetry at the surface. Analogous to strain induced shifts in the d-band center of noble metals relative to the Fermi level, :such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active Oxides.

  8. Laccase-mediated oxidation of small organics: bifunctional roles for versatile applications.

    Science.gov (United States)

    Jeon, Jong-Rok; Chang, Yoon-Seok

    2013-06-01

    Laccases have been widely used in several biotechnological areas, including organic synthesis, bioremediation, and pulp/textile bleaching. In most applications, the enzymatic actions start with single-electron oxidation of small organics followed by formation of the corresponding radicals. These radicals are subsequently involved in either oxidative coupling (i.e., bond formation) or bond cleavage of target organics. These bifunctional actions--catabolic versus anabolic--are readily identifiable in in vivo metabolic processes involving laccases. Here, we characterize the bifunctionality of laccase-mediated oxidation of small organics and present the view that knowledge of the biological functions of these metabolic processes in vivo can illuminate potential biotechnological applications of this bifunctionality.

  9. [Impulse cytofluorometry of the redox activity of single cells using fluorescent formazan].

    Science.gov (United States)

    Severin, E; Stellmach, J

    1984-01-01

    The first application of a newly developed fluorescent formazan in flow cytometry is described. The cell surface redox activity of isolated mouse hepatocytes after incubation with the tetrazolium salt forming the new fluorescent formazan and the DNA content after Hoechst staining have been measured simultaneously. 2 parametric distribution patterns have been obtained. This new and sensitive fluorometric technique can be used for automatic measurements of single cells correlating redox activity with other cell parameters.

  10. Information processing through a bio-based redox capacitor: signatures for redox-cycling.

    Science.gov (United States)

    Liu, Yi; Kim, Eunkyoung; White, Ian M; Bentley, William E; Payne, Gregory F

    2014-08-01

    Redox-cycling compounds can significantly impact biological systems and can be responsible for activities that range from pathogen virulence and contaminant toxicities, to therapeutic drug mechanisms. Current methods to identify redox-cycling activities rely on the generation of reactive oxygen species (ROS), and employ enzymatic or chemical methods to detect ROS. Here, we couple the speed and sensitivity of electrochemistry with the molecular-electronic properties of a bio-based redox-capacitor to generate signatures of redox-cycling. The redox capacitor film is electrochemically-fabricated at the electrode surface and is composed of a polysaccharide hydrogel with grafted catechol moieties. This capacitor film is redox-active but non-conducting and can engage diffusible compounds in either oxidative or reductive redox-cycling. Using standard electrochemical mediators ferrocene dimethanol (Fc) and Ru(NH3)6Cl3 (Ru(3+)) as model redox-cyclers, we observed signal amplifications and rectifications that serve as signatures of redox-cycling. Three bio-relevant compounds were then probed for these signatures: (i) ascorbate, a redox-active compound that does not redox-cycle; (ii) pyocyanin, a virulence factor well-known for its reductive redox-cycling; and (iii) acetaminophen, an analgesic that oxidatively redox-cycles but also undergoes conjugation reactions. These studies demonstrate that the redox-capacitor can enlist the capabilities of electrochemistry to generate rapid and sensitive signatures of biologically-relevant chemical activities (i.e., redox-cycling).

  11. Redox Active Polymers as Soluble Nanomaterials for Energy Storage.

    Science.gov (United States)

    Burgess, Mark; Moore, Jeffrey S; Rodríguez-López, Joaquín

    2016-11-15

    It is an exciting time for exploring the synergism between the chemical and dimensional properties of redox nanomaterials for addressing the manifold performance demands faced by energy storage technologies. The call for widespread adoption of alternative energy sources requires the combination of emerging chemical concepts with redesigned battery formats. Our groups are interested in the development and implementation of a new strategy for nonaqueous flow batteries (NRFBs) for grid energy storage. Our motivation is to solve major challenges in NRFBs, such as the lack of membranes that simultaneously allow fast ion transport while minimizing redox active species crossover between anolyte (negative electrolyte) and catholyte (positive electrolyte) compartments. This pervasive crossover leads to deleterious capacity fade and materials underutilization. In this Account, we highlight redox active polymers (RAPs) and related polymer colloids as soluble nanoscopic energy storing units that enable the simple but powerful size-exclusion concept for NRFBs. Crossover of the redox component is suppressed by matching high molecular weight RAPs with simple and inexpensive nanoporous commercial separators. In contrast to the vast literature on the redox chemistry of electrode-confined polymer films, studies on the electrochemistry of solubilized RAPs are incipient. This is due in part to challenges in finding suitable solvents that enable systematic studies on high polymers. Here, viologen-, ferrocene- and nitrostyrene-based polymers in various formats exhibit properties that make amenable their electrochemical exploration as solution-phase redox couples. A main finding is that RAP solutions store energy efficiently and reversibly while offering chemical modularity and size versatility. Beyond the practicality toward their use in NRFBs, the fundamental electrochemistry exhibited by RAPs is fascinating, showing clear distinctions in behavior from that of small molecules. Whereas

  12. Energy Storage in Bifunctional TiO2 Composite Materials under UV and Visible Light

    Directory of Open Access Journals (Sweden)

    Jialin Li

    2009-11-01

    Full Text Available This paper provides an overview of recent studies on energy storage in bifunctional TiO2 composite materials under UV and visible light. The working mechanism, property improvements and applications of these bifunctional TiO2 composite systems are introduced, respectively. The latest results obtained in our laboratory, especially a new process for photoelectric conversion and energy storage in TiO2/Cu2O bilayer films under visible light, are also presented. Hopefully this review will stimulate more fundamental and applied research on this subject in the future.

  13. Hydroconversion of n-alkanes on bifunctional zeolites with unusual pore architecture

    Energy Technology Data Exchange (ETDEWEB)

    Doerr, G.; Tontisirin, S.; Ernst, S. [Technische Univ. Kaiserslautern (Germany). Dept. of Chemistry, Chemical Technology

    2010-12-30

    Zeolites MCM-68 and ZSM-18, both possessing unusual pore architectures, were synthesized via hydrothermal synthesis using optimized methods. X-ray powder diffraction and scanning electron microscopy revealed that the obtained zeolites are well crystallized and do not contain visible amounts of amorphous material. The bifunctional forms of MCM- 68 and ZSM-18 (viz. the acid form loaded with small amounts of palladium) were characterized using the hydroconversion of n-decane as catalytic test reaction. In this reaction, both catalysts showed the typical behaviour known from other bifunctional large pore zeolites. (orig.)

  14. Acupuncture mechanism and redox equilibrium.

    Science.gov (United States)

    Zeng, Xiang-Hong; Li, Qian-Qian; Xu, Qian; Li, Fang; Liu, Cun-Zhi

    2014-01-01

    Oxidative stress participates in the pathological process of various diseases. Acupuncture is a component of the health care system in China that can be traced back for at least 3000 years. Recently, increased evidences indicate that acupuncture stimulation could reduce oxidative damage in organisms under pathological state, but the exact mechanism remains unclear. This review focuses on the emerging links between acupuncture and redox modulation in various disorders, such as vascular dementia, Parkinson's disease, and hypertension, ranging from redox system, antioxidant system, anti-inflammatory system, and nervous system to signaling pathway. Although the molecular and cellular pathways studies of acupuncture effect on oxidative stress are preliminary, they represent an important step forward in the research of acupuncture antioxidative effect.

  15. Acupuncture Mechanism and Redox Equilibrium

    OpenAIRE

    Xiang-Hong Zeng; Qian-Qian Li; Qian Xu; Fang Li; Cun-Zhi Liu

    2014-01-01

    Oxidative stress participates in the pathological process of various diseases. Acupuncture is a component of the health care system in China that can be traced back for at least 3000 years. Recently, increased evidences indicate that acupuncture stimulation could reduce oxidative damage in organisms under pathological state, but the exact mechanism remains unclear. This review focuses on the emerging links between acupuncture and redox modulation in various disorders, such as vascular dementi...

  16. Redox signaling in acute pancreatitis

    Directory of Open Access Journals (Sweden)

    Salvador Pérez

    2015-08-01

    Full Text Available Acute pancreatitis is an inflammatory process of the pancreatic gland that eventually may lead to a severe systemic inflammatory response. A key event in pancreatic damage is the intracellular activation of NF-κB and zymogens, involving also calcium, cathepsins, pH disorders, autophagy, and cell death, particularly necrosis. This review focuses on the new role of redox signaling in acute pancreatitis. Oxidative stress and redox status are involved in the onset of acute pancreatitis and also in the development of the systemic inflammatory response, being glutathione depletion, xanthine oxidase activation, and thiol oxidation in proteins critical features of the disease in the pancreas. On the other hand, the release of extracellular hemoglobin into the circulation from the ascitic fluid in severe necrotizing pancreatitis enhances lipid peroxidation in plasma and the inflammatory infiltrate into the lung and up-regulates the HIF–VEGF pathway, contributing to the systemic inflammatory response. Therefore, redox signaling and oxidative stress contribute to the local and systemic inflammatory response during acute pancreatitis.

  17. Redox signaling in acute pancreatitis.

    Science.gov (United States)

    Pérez, Salvador; Pereda, Javier; Sabater, Luis; Sastre, Juan

    2015-08-01

    Acute pancreatitis is an inflammatory process of the pancreatic gland that eventually may lead to a severe systemic inflammatory response. A key event in pancreatic damage is the intracellular activation of NF-κB and zymogens, involving also calcium, cathepsins, pH disorders, autophagy, and cell death, particularly necrosis. This review focuses on the new role of redox signaling in acute pancreatitis. Oxidative stress and redox status are involved in the onset of acute pancreatitis and also in the development of the systemic inflammatory response, being glutathione depletion, xanthine oxidase activation, and thiol oxidation in proteins critical features of the disease in the pancreas. On the other hand, the release of extracellular hemoglobin into the circulation from the ascitic fluid in severe necrotizing pancreatitis enhances lipid peroxidation in plasma and the inflammatory infiltrate into the lung and up-regulates the HIF-VEGF pathway, contributing to the systemic inflammatory response. Therefore, redox signaling and oxidative stress contribute to the local and systemic inflammatory response during acute pancreatitis.

  18. Investigation and simulation on electrolyte distribution for all-vanadium redox flow battery%全钒液流电池电解液分布的数值模拟

    Institute of Scientific and Technical Information of China (English)

    徐波; 齐亮; 姚克俭; 谢晓峰

    2013-01-01

    Based on computational fluid dynamics(CFD), a traditional straight parallel flow channel was equipped with a sloping baffle and a flow weir to improve the uniformity of electrolyte distribution and to investigate the fluid flow behavior for all-vanadium reodx flow battery. The hydrodynamics characteristics of vanadium electrolyte in sectional form multi-channel of serpentine flow channel was discussed. The numerical simulation results showed that the sectional form multi-channel of serpentine flow channel can not only keep the good uniformity of electrolyte distribution, but also be able to reduce flowing resistance and pump consumption. In addition, it can optimize the distribution of electrolyte concentration and improve the battery efficiency by choosing the appropriate flow rate of electrolyte and more uniformity of electrolyte distribution.%为了提高全钒液流电池双极板流道电解液分布均匀性,考察流体流动行为,本文基于计算流体力学,在传统平直并联流道基础上通过增加倾斜挡板和入口流堰,改进流道结构;同时探究钒电池用电解液在分段式多通道蛇形流道内流体水力学特征.数值模拟结果表明:分段式多通道蛇形流道既可以保持传统蛇形流道流体均匀分配的性能,又能有效降低流阻,减少泵耗;合适的电解液流速及其均匀分布可以优化电解液活性物质浓度分布,提高电解液稳定性,增大钒电池能量效率.

  19. Bifunctional catalysts for the direct production of liquid fuels from syngas

    NARCIS (Netherlands)

    Sartipi, S.

    2014-01-01

    Design and development of catalyst formulations that maximize the direct production of liquid fuels by combining Fischer-Tropsch synthesis (FTS), hydrocarbon cracking, and isomerization into one single catalyst particle (bifunctional FTS catalyst) have been investigated in this thesis. To achieve th

  20. Oxidations of amines with molecular oxygen using bifunctional gold–titania catalysts

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; Egeblad, Kresten; Mentzel, Uffe Vie

    2008-01-01

    Over the past decades it has become clear that supported gold nanoparticles are surprisingly active and selective catalysts for several green oxidation reactions of oxygen-containing hydrocarbons using molecular oxygen as the stoichiometric oxidant. We here report that bifunctional gold–titania c...... new and environmentally benign routes to caprolactam and cyclohexanone oxime, both of which are precursors for nylon-6....

  1. Purification, characterization, and cloning of a bifunctional molybdoenzyme with hydratase and alcohol dehydrogenase activity

    NARCIS (Netherlands)

    Jin, J.; Straathof, A.J.J.; Pinkse, M.W.H.; Hanefeld, U.

    2010-01-01

    A bifunctional hydratase/alcohol dehydrogenase was isolated from the cyclohexanol degrading bacterium Alicycliphilus denitrificans DSMZ 14773. The enzyme catalyzes the addition of water to α,β-unsaturated carbonyl compounds and the subsequent alcohol oxidation. The purified enzyme showed three subun

  2. Direct catalytic transformation of carbohydrates into 5-ethoxymethylfurfural with acid–base bifunctional hybrid nanospheres

    DEFF Research Database (Denmark)

    Li, Hu; Khokarale, Santosh Govind; Kotni, Ramakrishna;

    2014-01-01

    carbohydrates. A high EMF yield of 76.6%, 58.5%, 42.4%, and 36.5% could be achieved, when fructose, inulin, sorbose, and sucrose were used as starting materials, respectively. Although, the acid–base bifunctional nanocatalysts were inert for synthesis of EMF from glucose based carbohydrates, ethyl...

  3. Design and Synthesis of Bifunctional Oxime Reactivators of OP- inhibited Cholinesterase

    Science.gov (United States)

    2013-08-01

    military and civilian personnel. Reactivators of OP inhibited cholinesterases can serve as OP agent antidotes but can be limited by their poor...assisted bifunctional catalytic mechanism 46 O N O N OH 11 REPORTABLE OUTCOMES: None CONCLUSION: We have successfully evaluated the synthetic

  4. High surface area carbon for bifunctional air electrodes applied in zinc-air batteries

    Energy Technology Data Exchange (ETDEWEB)

    Arai, H. [on leave from NTT Laboratories (Japan); Mueller, S.; Haas, O. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Bifunctional air electrodes with high surface area carbon substrates showed low reduction overpotential, thus are promising for enhancing the energy efficiency and power capability of zinc-air batteries. The improved performance is attributed to lower overpotential due to diffusion of the reaction intermediate, namely the peroxide ion. (author) 1 fig., 2 refs.

  5. Novel bifunctional double-layer catalysts for application in microreactors for direct DME synthesis

    OpenAIRE

    Lee, Seungcheol

    2016-01-01

    This thesis describes experimental research toward the selective and efficient DME production from syngas in microstructured reactors using bifunctional catalysts. Two catalysts, Cu/ZnO/Al2O3 and ZSM-5, catalyze syngas conversion to methanol and methanol conversion to DME, respectively. The catalysts were prepared and successfully introduced in microchannel reactor for direct DME synthesis.

  6. Enantioselective α-Chlorination of Aldehydes with Recyclable Fluorous (S)-Pyrrolidine-Thiourea Bifunctional Organocatalyst.

    Science.gov (United States)

    Wang, Liang; Cai, Chun; Curran, Dennis P; Zhang, Wei

    2010-01-01

    A novel fluorous (S)-pyrrolidine-thiourea bifunctional organocatalyst is prepared. The catalyst shows good activity and enantioselectivity for direct α-chlorination of aldehydes using N-chlorosuccinimide (NCS) as the chlorine source. It can be recovered from the reaction mixture by fluorous solid-phase extraction with excellent purity for direct reuse.

  7. Redox conditions for mantle plumes

    Science.gov (United States)

    Heister, L. E.; Lesher, C. E.

    2005-12-01

    The vanadium to scandium ratio (V/Sc) for basalts from mid-ocean ridge (MOR) and arc environments has been proposed as a proxy for fO2 conditions during partial melting (e.g. [1] and [2]). Contrary to barometric measurements of the fO2 of primitive lavas, the V/Sc ratio of the upper mantle at mid-ocean ridges and arcs is similar, leading previous authors to propose that the upper mantle has uniform redox potential and is well-buffered. We have attempted to broaden the applicability of the V/Sc parameter to plume-influenced localities (both oceanic and continental), where mantle heterogeneities associated with recycled sediments, mafic crust, and metasomatized mantle, whether of shallow or deep origin, exist. We find that primitive basalts from the North Atlantic Igneous Province (NAIP), Hawaii (both the Loa and Kea trends), Deccan, Columbia River, and Siberian Traps show a range of V/Sc ratios that are generally higher (average ~9) than those for MOR (average ~ 6.7) or arc (average ~7) lavas. Based on forward polybaric decompression modeling, we attribute these differences to polybaric melting and melt segregation within the garnet stability field rather than the presence of a more oxidized mantle in plume-influenced settings. Like MORB, the V/Sc ratios for plume-influenced basalts can be accounted for by an oxidation state approximately one log unit below the Ni-NiO buffer (NNO-1). Our analysis suggests that source heterogeneities have little, if any, resolvable influence on mantle redox conditions, although they have significant influence on the trace element and isotopic composition of mantle-derived melts. We suggest that variations in the redox of erupted lavas is largely a function of shallow lithospheric processes rather than intrinsic to the mantle source, regardless of tectonic setting. [1] Li and Lee (2004) EPSL, [2] Lee et al. (2005) J. of Petrology

  8. A redox-sensitive yellow fluorescent protein sensor for monitoring nuclear glutathione redox dynamics.

    Science.gov (United States)

    Banach-Latapy, Agata; Dardalhon, Michèle; Huang, Meng-Er

    2015-01-01

    Intracellular redox homeostasis is crucial for many cellular functions, but accurate measurements of cellular compartment-specific redox states remain technically challenging. Genetically encoded biosensors, including the glutathione-specific redox-sensitive yellow fluorescent protein (rxYFP), provide an alternative approach to overcome the limitations of conventional glutathione/glutathione disulfide (GSH/GSSG) redox measurements. In this chapter we describe methods to measure the nuclear rxYFP redox state in human cells by a redox Western blot technique. A nucleus-targeted rxYFP sensor can be used to sense nuclear steady-state and dynamic redox changes in response to oxidative stress. Complementary to existing redox sensors and conventional redox measurements, nucleus-targeted rxYFP sensors provide a novel tool for examining nuclear redox homeostasis in mammalian cells, permitting high-resolution readout of steady glutathione state and dynamics of redox changes. The technique described may be used with minimal variations to study the effects of stress conditions which lead to glutathione redox changes.

  9. Redox pioneer: professor Barry Halliwell.

    Science.gov (United States)

    Pervaiz, Shazib

    2011-05-01

    Professor Barry Halliwell is recognized as a Redox Pioneer because he has published eight articles on redox biology that have been each cited more than 1000 times, and 158 articles that have been each cited more than 100 times. His contributions go back as far as 1976, when he was involved in elucidation of the Foyer-Halliwell-Asada cycle, an efficient mechanism for preventing oxidative damage to chloroplasts. His subsequent work established the important role of iron and zinc in free radical reactions and their relevance to human pathologies. Professor Halliwell is also a leader in developing novel methodology for detecting free radical intermediates in vivo, and his contributions to our knowledge of reactive nitrogen species are highly significant. His sustained excellence won him the top-cited scientist award in the United Kingdom in biomedical sciences in 1999, and in 2003 he was recognized as a highly cited scientist by Institute of Scientific Information (ISI) for work on plant antioxidants, and the same year ranked 28 out of 5494 biochemists/biologists for scientific impact. Two pieces of his scholarly work have been listed as Citation Classics by ISI, and in 2007 his laboratory was ranked number 1 worldwide based on highest citation score in research on free radicals.

  10. Energetic methods to study bifunctional biotin operon repressor.

    Science.gov (United States)

    Beckett, D

    1998-01-01

    measurements. The results of quantitative studies of the biotin regulatory system can be interpreted in the context of the biological function of the system. The biotin holoenzyme ligases are a class of enzymes found across the evolutionary spectrum. Only a subset of these enzymes, including BirA, also function as transcriptional repressors. The tight binding of the allosteric effector may be understood in light of the bifunctional nature of the BirA-bio-5'-AMP complex. It is possible that the unusually high thermodynamic and kinetic stability of the complex ensures that the most probable state of the protein in vivo is the adenylate-bound form. This complex, not the unliganded protein, is active in both enzymatic transfer of biotin and site-specific DNA binding. This ensures that on depletion of the intracellular pool of apoBCCP, BirA-bio-5'-AMP accumulates and binds to bioO to repress transcription of the biotin biosynthesis operon. The intracellular demand for and synthesis of biotin are, consequently, tightly coupled in the system. The dimerization that accompanies adenylate binding to BirA appears to be significant for site-specific binding of the protein to bioO. Functionally, the simultaneous binding of the two monomers to the two operator half-sites, regardless of the kinetic mechanism by which it occurs, ensures coordinate regulation of transcription initiation from both biotin operon promoters. The multifaceted approach utilized in studies of the biotin regulatory system can serve as a model for studies of any complex transcriptional regulatory system. It is critical in elucidating the functional energetics of any of these systems that the assembly first be dissected into the constituent interactions and that each of these interactions be studied in isolation. This is not only critical for understanding the physicochemical properties of each individual contributing interaction, but is also a necessary precursor to studies of thermodynamic linkage in the system. (AB

  11. A Metal-Amino Acid Complex-Derived Bifunctional Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries.

    Science.gov (United States)

    Ding, Yanjun; Niu, Yuchen; Yang, Jia; Ma, Liang; Liu, Jianguo; Xiong, Yujie; Xu, Hangxun

    2016-10-01

    Bifunctional oxygen electrocatalyst: A metal-amino acid complex is developed to prepare high-performance mesoporous carbon electrocatalyst for both oxygen reduction and oxygen evolution reactions. Such prepared catalyst can be used to assemble rechargeable zinc-air batteries with excellent durability. This work represents a new route toward low-cost, highly active, and durable bifunctional electrocatalysts for cutting-edge energy conversion devices.

  12. Extraction Kinetics of Lanthanum in Chloride Medium by Bifunctional Ionic Liquid [A336][CA-12] Using a Constant Interfacial Cell with Laminar Flow☆

    Institute of Scientific and Technical Information of China (English)

    Hualing Yang; Ji Chen; Wei Wang; Hongmin Cui; Dongli Zhang; Yu Liu

    2014-01-01

    The extraction kinetics of La(III) from aqueous chloride solutions into n-heptane solutions of bifunctional ionic liquid extractant [A336][CA-12] (tricaprylmethylammonium sec-octylphenoxy acetic acid) was investigated using a constant interfacial cel with laminar flow. The effects of stirring speed, temperature and specific interfa-cial area on the extraction rate were examined. The results indicate that mass transfer kinetics of La(III) is a mixed-controlled process influenced by interfacial reaction. On the basis of mass transfer kinetic results in the ex-traction of La(III) by [A336][CA-12], the extraction rate equation of La(III) is proposed in terms of pseudo-first-order constants, which is supported by the measured thermodynamic equations. The mass-transfer kinetic model deduced from the rate controlling step is adequate to interpret the experimental data qualitatively.

  13. Redox characteristics of the eukaryotic cytosol

    DEFF Research Database (Denmark)

    López-Mirabal, H Reynaldo; Winther, Jakob R

    2007-01-01

    (ROS) and glutathionylated proteins are maintained at very low levels. In the present review, recent progress in the understanding of the cytosolic thiol-disulfide redox metabolism and novel analytical approaches to studying cytosolic redox properties are discussed. We will focus on the yeast model...

  14. Characterization of redox proteins using electrochemical methods.

    NARCIS (Netherlands)

    Verhagen, M.F.J.M.

    1995-01-01

    The use of electrochemical techniques in combination with proteins started approximately a decade ago and has since then developed into a powerfull technique for the study of small redox proteins. In addition to the determination of redox potentials, electrochemistry can be used to obtain informatio

  15. Characterization of redox conditions in pollution plumes

    DEFF Research Database (Denmark)

    Christensen, Thomas Højlund; Bjerg, Poul Løgstrup; Banwart, Steven A.

    2000-01-01

    Evalution of redox conditions in groundwater pollution plumes is often a prerequisite for understanding the behviour of the pollutants in the plume and for selecting remediation approaches. Measuring of redox conditions in pollution plumes is, however, a fairly recent issue and yet relative few...

  16. Palladium on Nitrogen-Doped Mesoporous Carbon: A Bifunctional Catalyst for Formate-Based, Carbon-Neutral Hydrogen Storage.

    Science.gov (United States)

    Wang, Fanan; Xu, Jinming; Shao, Xianzhao; Su, Xiong; Huang, Yanqiang; Zhang, Tao

    2016-02-08

    The lack of safe, efficient, and economical hydrogen storage technologies is a hindrance to the realization of the hydrogen economy. Reported herein is a reversible formate-based carbon-neutral hydrogen storage system that is established over a novel catalyst comprising palladium nanoparticles supported on nitrogen-doped mesoporous carbon. The support was fabricated by a hard template method and nitridated under a flow of ammonia. Detailed analyses demonstrate that this bicarbonate/formate redox equilibrium is promoted by the cooperative role of the doped nitrogen functionalities and the well-dispersed, electron-enriched palladium nanoparticles.

  17. Redox activity of naphthalene secondary organic aerosol

    Directory of Open Access Journals (Sweden)

    R. D. McWhinney

    2013-04-01

    Full Text Available Chamber secondary organic aerosol (SOA from low-NOx photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT assay. Naphthalene SOA was highly redox active, consuming DTT at an average rate of 118 ± 14 pmol per minute per μg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2- and 1,4-naphthoquinone, accounted for only 21 ± 3% of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5% of observations. Similar attempts to predict redox behaviour of oxidised two-stroke engine exhaust particles by measuring 1,2-naphthoquinone, 1,4-naphthoquinone and 9,10-phenanthrenequinone predicted DTT decay rates only 4.9 ± 2.5% of those observed. Together, these results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5 × 10−4 m3 μg−1 for 1,4-naphthoquinone at 25 °C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. As well, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

  18. Redox activity of naphthalene secondary organic aerosol

    Science.gov (United States)

    McWhinney, R. D.; Zhou, S.; Abbatt, J. P. D.

    2013-04-01

    Chamber secondary organic aerosol (SOA) from low-NOx photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT) assay. Naphthalene SOA was highly redox active, consuming DTT at an average rate of 118 ± 14 pmol per minute per μg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2- and 1,4-naphthoquinone, accounted for only 21 ± 3% of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5% of observations. Similar attempts to predict redox behaviour of oxidised two-stroke engine exhaust particles by measuring 1,2-naphthoquinone, 1,4-naphthoquinone and 9,10-phenanthrenequinone predicted DTT decay rates only 4.9 ± 2.5% of those observed. Together, these results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5) × 10-4 m3 μg-1 for 1,4-naphthoquinone at 25 °C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. As well, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

  19. Bifunctional metamaterials with simultaneous and independent manipulation of thermal and electric fields.

    Science.gov (United States)

    Lan, Chuwen; Bi, Ke; Fu, Xiaojian; Li, Bo; Zhou, Ji

    2016-10-03

    Metamaterials offer a powerful way to manipulate a variety of physical fields ranging from wave fields (electromagnetic field, acoustic field, elastic wave, etc.), static fields (static magnetic field, static electric field) to diffusive fields (thermal field, diffusive mass). However, the relevant reports and studies are usually limited to a single physical field or functionality. In this study, we proposed and experimentally demonstrated a bifunctional metamaterial which could manipulate thermal and electric fields simultaneously and independently. Specifically, a composite with independently controllable thermal and electric conductivity was introduced, on the basis of which a bifunctional device capable of shielding thermal flux and concentrating electric current simultaneously was designed, fabricated and characterized. This work provides an encouraging example of metamaterials transcending their natural limitations, which offers a promising future in building a broad platform for the manipulation of multi-physics fields.

  20. Bifunctional Pt-Si Alloys for Small Organic Molecule Electro-oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia Aleksandrovna; Suntivich, Jin; Han, Binghong

    Designing highly active catalysts for electro-oxidation of small organic molecules can help to reduce the anodic overpotential for more efficient utilization of hydrocarbon fuels. The challenge in developing more active electrocatalysts for electro-oxidation reactions is to satisfy the stringent...... bifunctional requirement, which demands both adsorption and water oxidation sites. In this contribution, we explore the possibility of using Pt-Si alloys to fulfill this bifunctional requirement. Silicon, a highly oxophillic element, is alloyed into Pt as a site for water oxidation, while Pt serves as a CO...... adsorption site. We will discuss the enhanced activity of Pt-Si alloys for small organic molecule oxidation, which can be attributed to the improved CO electro-oxidation kinetics on Pt-Si....

  1. Tethering metal ions to photocatalyst particulate surfaces by bifunctional molecular linkers for efficient hydrogen evolution

    KAUST Repository

    Yu, Weili

    2014-08-19

    A simple and versatile method for the preparation of photocatalyst particulates modified with effective cocatalysts is presented; the method involves the sequential soaking of photocatalyst particulates in solutions containing bifunctional organic linkers and metal ions. The modification of the particulate surfaces is a universal and reproducible method because the molecular linkers utilize strong covalent bonds, which in turn result in modified monolayer with a small but controlled quantity of metals. The photocatalysis results indicated that the CdS with likely photochemically reduced Pd and Ni, which were initially immobilized via ethanedithiol (EDT) as a linker, were highly efficient for photocatalytic hydrogen evolution from Na2S-Na2SO3-containing aqueous solutions. The method developed in this study opens a new synthesis route for the preparation of effective photocatalysts with various combinations of bifunctional linkers, metals, and photocatalyst particulate materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Increasing round trip efficiency of hybrid Li-air battery with bifunctional catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Huang, K; Li, YF; Xing, YC

    2013-07-30

    Previously it was shown that Pt as cathode catalyst ha's a large overpotential during charge in rechargeable hybrid Li-air battery with sulfuric acid catholyte. This article demonstrates that a bifunctional catalyst composed of Pt and IrO2 supported on carbon nanotubes can address this problem. The specially designed and synthesized bifunctional catalyst showed significant overpotential reduction and achieved a round trip energy efficiency of 81% after 10 cycles, higher than many achieved in aprotic Li-O-2 batteries. The hybrid Li-air battery was discharged and recharged for 20 cycles at 0.2 mA/cm(2), showing a fairly stable cell performance. A specific capacity of 306 mAh/g and a specific energy of 1110 Wh/kg were obtained for the hybrid Li-air battery in terms of acid weight. (c) 2013 Elsevier Ltd. All rights reserved.

  3. Bifunctional metamaterials with simultaneous and independent manipulation of thermal and electric fields

    Science.gov (United States)

    Lan, Chuwen; Bi, Ke; Fu, Xiaojian; Li, Bo; Zhou, Ji

    2016-10-01

    Metamaterials offer a powerful way to manipulate a variety of physical fields ranging from wave fields (electromagnetic field, acoustic field, elastic wave, etc.), static fields (static magnetic field, static electric field) to diffusive fields (thermal field, diffusive mass). However, the relevant reports and studies are usually conducted on a single physical field or functionality. In this study, we proposed and experimentally demonstrated a bifunctional metamaterial which can manipulate thermal and electric fields simultaneously and independently. Specifically, a composite with independently controllable thermal and electric conductivity was introduced, on the basis of which a bifunctional device capable of shielding thermal flux and concentrating electric current simultaneously was designed, fabricated and characterized. This work provides an encouraging example of metamaterials transcending their natural limitations, which offers a promising future in building a broad platform for manipulation of multi-physics field.

  4. First-Principles Study of Structure Property Relationships of Monolayer (Hydroxy)Oxide-Metal Bifunctional Electrocatalysts

    DEFF Research Database (Denmark)

    Zeng, Zhenhua; Kubal, Joseph; Greeley, Jeffrey Philip

    2015-01-01

    In the present study, on the basis of detailed density functional theory (DFT) calculations, and using Ni hydroxy(oxide) films on Pt(111) and Au(111) electrodes as model systems, we describe a detailed structural and electrocatalytic analysis of hydrogen evolution (HER) at three-phase boundaries...... of information that is inaccessible by purely experimental means, and these structures, in turn, strongly suggest that a bifunctional reaction mechanism for alkaline HER will be operative at the interface between the films, the metal substrates, and the surrounding aqueous medium. This bifunctionality produces...... important changes in the calculated barriers of key elementary reaction steps, including water activation and dissociation, as compared to traditional monofunctional Pt surfaces. The successful identification of the structures of thin metal films and three-phase boundary catalysts is not only an important...

  5. Improving stability and biocompatibility of alginate/chitosan microcapsule by fabricating bi-functional membrane.

    Science.gov (United States)

    Zheng, Guoshuang; Liu, Xiudong; Wang, Xiuli; Chen, Li; Xie, Hongguo; Wang, Feng; Zheng, Huizhen; Yu, Weiting; Ma, Xiaojun

    2014-05-01

    Cell encapsulation technology holds promise for the cell-based therapy. But poor mechanical strength and biocompatibility of microcapsule membrane are still obstacles for the clinical applications. A novel strategy is presented to prepare AC₁ C₂ A microcapsules with bi-functional membrane (that is, both desirable biocompatibility and membrane stability) by sequentially complexing chitosans with higher deacetylation degree (C₁) and lower deacetylation degree (C₂) on alginate (A) gel beads. Both in vitro and in vivo evaluation of AC₁C₂ A microcapsules demonstrate higher membrane stability and less cell adhesion, because the introduction of C₂ increases membrane strength and decreases surface roughness. Moreover, diffusion test of AC₁C₂ A microcapsules displays no inward permeation of IgG protein suggesting good immunoisolation function. The results demonstrate that AC₁C₂ A microcapsules with bi-functional membrane could be a promising candidate for microencapsulated cell implantation with cost effective usage of naturally biocompatible polysaccharides.

  6. Predicting groundwater redox status on a regional scale using linear discriminant analysis

    Science.gov (United States)

    Close, M. E.; Abraham, P.; Humphries, B.; Lilburne, L.; Cuthill, T.; Wilson, S.

    2016-08-01

    Reducing conditions are necessary for denitrification, thus the groundwater redox status can be used to identify subsurface zones where potentially significant nitrate reduction can occur. Groundwater chemistry in two contrasting regions of New Zealand was classified with respect to redox status and related to mappable factors, such as geology, topography and soil characteristics using discriminant analysis. Redox assignment was carried out for water sampled from 568 and 2223 wells in the Waikato and Canterbury regions, respectively. For the Waikato region 64% of wells sampled indicated oxic conditions in the water; 18% indicated reduced conditions and 18% had attributes indicating both reducing and oxic conditions termed "mixed". In Canterbury 84% of wells indicated oxic conditions; 10% were mixed; and only 5% indicated reduced conditions. The analysis was performed over three different well depths, 100 m. For both regions, the percentage of oxidised groundwater decreased with increasing well depth. Linear discriminant analysis was used to develop models to differentiate between the three redox states. Models were derived for each depth and region using 67% of the data, and then subsequently validated on the remaining 33%. The average agreement between predicted and measured redox status was 63% and 70% for the Waikato and Canterbury regions, respectively. The models were incorporated into GIS and the prediction of redox status was extended over the whole region, excluding mountainous land. This knowledge improves spatial prediction of reduced groundwater zones, and therefore, when combined with groundwater flow paths, improves estimates of denitrification.

  7. 3D Ordered Mesoporous Bifunctional Oxygen Catalyst for Electrically Rechargeable Zinc-Air Batteries.

    Science.gov (United States)

    Park, Moon Gyu; Lee, Dong Un; Seo, Min Ho; Cano, Zachary Paul; Chen, Zhongwei

    2016-05-01

    To enhance energy efficiency and durability, a highly active and durable 3D ordered mesoporous cobalt oxide framework has been developed for rechargeable zinc-air batteries. The bifunctional air electrode consisting of 3DOM Co3 O4 having high active surface area and robust structure, results in superior charge and discharge battery voltages, and durable performance for electrically rechargeable zinc-air batteries.

  8. Radiation Induced Crosslinking of Polyethylene in the Presence of Bifunctional Vinyl Monomers

    DEFF Research Database (Denmark)

    Joshi, M. S.; Singer, Klaus Albert Julius; Silverman, J.

    1977-01-01

    Several reports have been published showing that the radiation induced grafting of bifunctional vinyl monomers to low density polyethylene results in a product with an unusually high density of crosslinks. The same grafting reactions are shown to reduce the incipient gel dose by more than a factor...... of fifty. This paper is concerned with the apparent crosslinking produced by the radiation grafting of two monomers to polyethylene: acrylic acid and acrylonitrile....

  9. Preliminary X-ray investigation of a bifunctional inhibitor from Indian finger millet (ragi).

    Science.gov (United States)

    Srinivasan, A; Raman, A; Singh, T P

    1991-11-05

    A bifunctional alpha-amylase/trypsin inhibitor that has two binding sites has been purified from ragi. The inhibitor has been crystallized from its ammonium sulphate solution by the vapour diffusion method. The crystals belong to the orthogonal space group P2(1)2(1)2(1) with unit cell dimensions a = 30.49 A, b = 56.30 A, c = 73.65 A and Z = 4.

  10. Groundwater redox conditions and conductivity in a contaminant plume from geoelectrical investigations

    Directory of Open Access Journals (Sweden)

    V. Naudet

    2004-01-01

    Full Text Available Accurate mapping of the electrical conductivity and of the redox potential of the groundwater is important in delineating the shape of a contaminant plume. A map of redox potential in an aquifer is indicative of biodegradation of organic matter and of concentrations of redox-active components; a map of electrical conductivity provides information on the mineralisation of the groundwater. Both maps can be used to optimise the position of pumping wells for remediation. The self-potential method (SP and electrical resistivity tomography (ERT have been applied to the contaminant plume associated with the Entressen landfill in south-east France. The self-potential depends on groundwater flow (electrokinetic contribution and redox conditions ('electro-redox' contribution. Using the variation of the piezometric head in the aquifer, the electrokinetic contribution is removed from the SP signals. A good linear correlation (R2=0.85 is obtained between the residual SP data and the redox potential values measured in monitoring wells. This relationship is used to draw a redox potential map of the overall contaminated site. The electrical conductivity of the subsoil is obtained from 3D-ERT analysis. A good linear correlation (R2=0.91 is observed between the electrical conductivity of the aquifer determined from the 3D-ERT image and the conductivity of the groundwater measured in boreholes. This indicates that the formation factor is nearly homogeneous in the shallow aquifer at the scale of the ERT. From this correlation, a map of the pore water conductivity of the aquifer is obtained. Keywords: self-potential, redox potential, electrical resistivity tomography, fluid conductivity, contaminant plume

  11. Collagen/chitosan based two-compartment and bi-functional dermal scaffolds for skin regeneration

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Feng [Department of Plastic Surgery and Burns, Shenzhen Second People' s Hospital, Shenzhen 518035 (China); Wang, Mingbo [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); She, Zhending [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shenzhen Lando Biomaterials Co., Ltd., Shenzhen 518057 (China); Fan, Kunwu; Xu, Cheng [Department of Plastic Surgery and Burns, Shenzhen Second People' s Hospital, Shenzhen 518035 (China); Chu, Bin; Chen, Changsheng [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shi, Shengjun, E-mail: shengjunshi@yahoo.com [The Burns Department of Zhujiang Hospital, Southern Medical University, Guangzhou 510280 (China); Tan, Rongwei, E-mail: tanrw@landobiom.com [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shenzhen Lando Biomaterials Co., Ltd., Shenzhen 518057 (China)

    2015-07-01

    Inspired from the sophisticated bilayer structures of natural dermis, here, we reported collagen/chitosan based two-compartment and bi-functional dermal scaffolds. Two functions refer to mediating rapid angiogenesis based on recombinant human vascular endothelial growth factor (rhVEGF) and antibacterial from gentamicin, which were encapsulated in PLGA microspheres. The gentamicin and rhVEGF encapsulated PLGA microspheres were further combined with collagen/chitosan mixtures in low (lower layer) and high (upper layer) concentrations, and molded to generate the two-compartment and bi-functional scaffolds. Based on morphology and pore structure analyses, it was found that the scaffold has a distinct double layered porous and connective structure with PLGA microspheres encapsulated. Statistical analysis indicated that the pores in the upper layer and in the lower layer have great variations in diameter, indicative of a two-compartment structure. The release profiles of gentamicin and rhVEGF exceeded 28 and 49 days, respectively. In vitro culture of mouse fibroblasts showed that the scaffold can facilitate cell adhesion and proliferation. Moreover, the scaffold can obviously inhibit proliferation of Staphylococcus aureus and Serratia marcescens, exhibiting its unique antibacterial effect. The two-compartment and bi-functional dermal scaffolds can be a promising candidate for skin regeneration. - Highlights: • The dermal scaffold is inspired from the bilayer structures of natural dermis. • The dermal scaffold has two-compartment structures. • The dermal scaffold containing VEGF and gentamicin encapsulated PLGA microspheres • The dermal scaffold can facilitate cell adhesion and proliferation.

  12. Bifunctional Catalysts for Upgrading of Biomass-Derived Oxygenates: A Review

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, Allison M.; Hensley, Jesse E.; Medlin, J. Will

    2016-08-05

    Deoxygenation is an important reaction in the conversion of biomass-derived oxygenates to fuels and chemicals. A key route for biomass refining involves the production of pyrolysis oil through rapid heating of the raw biomass feedstock. Pyrolysis oil as produced is highly oxygenated, so the feasibility of this approach depends in large part on the ability to selectively deoxygenate pyrolysis oil components to create a stream of high-value finished products. Identification of catalytic materials that are active and selective for deoxygenation of pyrolysis oil components has therefore represented a major research area. One catalyst is rarely capable of performing the different types of elementary reaction steps required to deoxygenate biomass-derived compounds. For this reason, considerable attention has been placed on bifunctional catalysts, where two different active materials are used to provide catalytic sites for diverse reaction steps. Here, we review recent trends in the development of catalysts, with a focus on catalysts for which a bifunctional effect has been proposed. We summarize recent studies of hydrodeoxygenation (HDO) of pyrolysis oil and model compounds for a range of materials, including supported metal and bimetallic catalysts as well as transition-metal oxides, sulfides, carbides, nitrides, and phosphides. Particular emphasis is placed on how catalyst structure can be related to performance via molecular-level mechanisms. These studies demonstrate the importance of catalyst bifunctionality, with each class of materials requiring hydrogenation and C-O scission sites to perform HDO at reasonable rates.

  13. A New Synthesis of TE2A-a Potential Bifunctional Chelator for {sup 64}Cu

    Energy Technology Data Exchange (ETDEWEB)

    Pandya, Darpan N.; Kwak, Won Jung; Park, Jeong Chan; Gawande, Manoj B.; Yoo, Jeong Soo [Kyungpook National University, Daegu (Korea, Republic of); Kim, Jung Young; An, Gwang Il [Molecular Imaging Research Center, Seoul (Korea, Republic of); Ryu, Eun Kyoung [Korea Basic Science Institute, Chungbuk (Korea, Republic of)

    2010-09-15

    The development of a new bifunctional chelator, which holds radio metals strongly in living systems, is a prerequisite for the successful application of disease-specific biomolecules to medical diagnosis and therapy. Recently, TE2A was reported to make kinetically more stable Cu({Pi}) complexes than TETA. Herein, we report a new synthetic route to TE2A and explore its potential as a bifunctional chelator. TE2A was synthesized using the regioselective alkylation of benzyl bromoacetate and successive de protection of the methylene bridge and benzyl group. Salt-free TE2A was radiolabeled with {sup 64}Cu and micro PET imaging was performed to follow the clearance pattern of the {sup 64}Cu-TE2A complex. TE2A was conjugated with cyclic RGD peptide and the TE2A-c(RGDyK) conjugate was radiolabeled with {sup 64}Cu. TE2A was prepared in salt-free form cyclam in an overall yield of 74%. The micro PET images showed that {sup 64}Cu-TE2A is excreted rapidly from the body by the kidney and liver. TE2A was successfully conjugated with c(RGDyK) peptide through on carboxylate group and the TE2A-c(RGDyK) conjugate was radiolabeled with {sup 64}Cu in 94% yield within 30 min. TE2A can be used by itself as a bifunctional chelator without any further structural modification.

  14. Characterization of a bifunctional xylanase/endoglucanase from yak rumen microorganisms.

    Science.gov (United States)

    Chang, Lei; Ding, Mozhu; Bao, Lei; Chen, Yingzhi; Zhou, Jungang; Lu, Hong

    2011-06-01

    A new gene, RuCelA, encoding a bifunctional xylanase/endoglucanase, was cloned from a metagenomic library of yak rumen microorganisms. RuCelA showed activity against xylan and carboxymethylcellulose (CMC), suggesting bifunctional xylanase/endoglucanase activity. The optimal conditions for xylanase and endoglucanase activities were 65°C, pH 7.0 and 50°C, pH 5.0, respectively. In addition, the presence of Co(+) and Co(2+) can greatly improve RuCelA's endoglucanase activity, while inhibits its xylanase activity. Further examination of substrate preference showed a higher activity against barley glucan and lichenin than against xylan and CMC. Using xylan and barley glucan as substrates, RuCelA displayed obvious synergistic effects with β-1,4-xylosidase and β-1,4-glucosidase. Generation of soluble oligosaccharides from lignocellulose is the key step in bioethanol production, and it is greatly notable that RuCelA can produce xylo-oligosaccharides and cello-oligosaccharides in the continuous saccharification of pretreated rice straw, which can be further degraded into fermentable sugars. Therefore, the bifunctional RuCelA distinguishes itself as an ideal candidate for industrial applications.

  15. Redox subpopulations and the risk of cancer progression: a new method for characterizing redox heterogeneity

    Science.gov (United States)

    Xu, He N.; Li, Lin Z.

    2016-02-01

    It has been shown that a malignant tumor is akin to a complex organ comprising of various cell populations including tumor cells that are genetically, metabolically and functionally different. Our redox imaging data have demonstrated intra-tumor redox heterogeneity in all mouse xenografts derived from human melanomas, breast, prostate, and colon cancers. Based on the signals of NADH and oxidized flavoproteins (Fp, including flavin adenine dinucleotide (FAD)) and their ratio, i.e., the redox ratio, which is an indicator of mitochondrial metabolic status, we have discovered several distinct redox subpopulations in xenografts of breast tumors potentially recapitulating functional/metabolic heterogeneity within the tumor. Furthermore, xenografts of breast tumors with higher metastatic potential tend to have a redox subpopulation whose redox ratio is significantly different from that of tumors with lower metastatic potential and usually have a bi-modal distribution of the redox ratio. The redox subpopulations from human breast cancer samples can also be very complex with multiple subpopulations as determined by fitting the redox ratio histograms with multi- Gaussian functions. In this report, we present a new method for identifying the redox subpopulations within individual breast tumor xenografts and human breast tissues, which may be used to differentiate between breast cancer and normal tissue and among breast cancer with different risks of progression.

  16. Controls on the redox potential of rainwater.

    Science.gov (United States)

    Willey, Joan D; Mullaugh, Katherine M; Kieber, Robert J; Avery, G Brooks; Mead, Ralph N

    2012-12-18

    Hydrogen peroxide acting as a reductant affects the redox potential of rainwater collected at the Bermuda Atlantic Time Series Station, the South Island of New Zealand, the contiguous USA, and the primary study site in Wilmington, NC. Analytical measurements of both halves of redox couples for dissolved iron, mercury, and the nitrate-nitrite-ammonium system can predict the rainwater redox potential measured directly by a platinum electrode. Measurements of these redox couples along with the pH in rain yields pe⁻ between 8 and 11; the half reaction for hydrogen peroxide acting as a reductant using typical rainwater conditions of 15 μM H₂O₂ at pH 4.7 gives pe⁻ = 9.12, where pe⁻ = negative log of the activity of hydrated electrons. Of the six rainwater redox systems investigated, only manganese speciation appeared to be controlled by molecular oxygen (pe⁻ = 15.90). Copper redox speciation was consistent with superoxide acting as a reductant (pe⁻ = 2.7). The concentration of H₂O₂ in precipitation has more than doubled over the preceding decade due to a decrease in SO₂ emissions, which suggests the redox chemistry of rainwater is dynamic and changing, potentially altering the speciation of many organic compounds and trace metals in atmospheric waters.

  17. Redox potential tuning by redox-inactive cations in nature's water oxidizing catalyst and synthetic analogues.

    Science.gov (United States)

    Krewald, Vera; Neese, Frank; Pantazis, Dimitrios A

    2016-04-28

    The redox potential of synthetic oligonuclear transition metal complexes has been shown to correlate with the Lewis acidity of a redox-inactive cation connected to the redox-active transition metals of the cluster via oxo or hydroxo bridges. Such heterometallic clusters are important cofactors in many metalloenzymes, where it is speculated that the redox-inactive constituent ion of the cluster serves to optimize its redox potential for electron transfer or catalysis. A principal example is the oxygen-evolving complex in photosystem II of natural photosynthesis, a Mn4CaO5 cofactor that oxidizes water into dioxygen, protons and electrons. Calcium is critical for catalytic function, but its precise role is not yet established. In analogy to synthetic complexes it has been suggested that Ca(2+) fine-tunes the redox potential of the manganese cluster. Here we evaluate this hypothesis by computing the relative redox potentials of substituted derivatives of the oxygen-evolving complex with the cations Sr(2+), Gd(3+), Cd(2+), Zn(2+), Mg(2+), Sc(3+), Na(+) and Y(3+) for two sequential transitions of its catalytic cycle. The theoretical approach is validated with a series of experimentally well-characterized Mn3AO4 cubane complexes that are structural mimics of the enzymatic cluster. Our results reproduce perfectly the experimentally observed correlation between the redox potential and the Lewis acidities of redox-inactive cations for the synthetic complexes. However, it is conclusively demonstrated that this correlation does not hold for the oxygen evolving complex. In the enzyme the redox potential of the cluster only responds to the charge of the redox-inactive cations and remains otherwise insensitive to their precise identity, precluding redox-tuning of the metal cluster as a primary role for Ca(2+) in biological water oxidation.

  18. Novel Redox Processes for Carbonaceous Fuel Conversion

    Science.gov (United States)

    He, Feng

    The current study investigates oxygen carrier development, process intensification, and oxygen carrier attrition behaviors for a number of novel, redox-based energy conversion schemes. (Abstract shortened by ProQuest.).

  19. Three-dimensional carbon interdigitated electrode arrays for redox-amplification.

    Science.gov (United States)

    Kamath, Rahul R; Madou, Marc J

    2014-03-18

    Three-dimensional (3D) carbon interdigitated electrode arrays (IDEAs) were fabricated using inexpensive, conventional, UV photolithography of SU-8 with modified exposure and post exposure bake settings followed by pyrolysis in an inert environment. The sensor performance was investigated as a function of both the IDEA digit width/gap ratio and digit height under flow and no flow conditions. We demonstrated a gradual increase in redox amplification with an increase in the IDEA digit width/gap ratio. The highest amplification of 37 was obtained for a width/gap ratio of 1.58 and for an electrode height of 1.1 μm. Redox amplification also increases significantly with an increase in the IDEA height, from a factor of 9 at a 0.22 μm digit height to a factor of 37 at a 1.1 μm height. The effect of potential sweep rates on redox amplification was also investigated. As the sweep rate was decreased from 50 mV/s to 5 mV/s, the collection efficiency increased from 0.92 to 0.97, whereas the amplification increased from 7 to 25. Under flow conditions, the amplification decreases substantially as the cycling of the redox species is impeded by convection, resulting in a drop in collection efficiency. The highest amplification of 37 dropped to 4 for the same electrode at a flow rate of 500 nL/s. Under flow, redox amplification increased with an increase in the IDEA height.

  20. Redox Committee: Conference notes and recommendations, meeting of April 11, 1949

    Energy Technology Data Exchange (ETDEWEB)

    Greager, O.H.; MacCready, W.K.; Seckendorff, E.W.

    1949-04-11

    This report discusses recommendations for development work on the Redox Production Plant. It contains an outline for a relationship procedure between the architect engineer and General Electric Design Division; preparation of a material balance and process flow; the preparation of engineering flow diagrams, including lists of standard symbols for these diagrams; a material and equipment list; a project cost estimate; and Procedures covering institution and execution of work involving studies by the Design and Construction Division.

  1. Assessment of redox markers in cattle

    OpenAIRE

    Burke, Nathaniel Caleb

    2007-01-01

    Metabolic redox status may have important implications to cattle health and production. Antioxidants and biomarkers of oxidative stress were evaluated in cattle under three phases of management. Each phase stood alone as a treatment model, and managerial aspects during the phase were evaluated as potential moderators of redox balance. Yearling heifers were used to assess the impact of fescue toxicosis and heat stress on selected markers in study 1. Intravaginal temperatures, ADG, serum prolac...

  2. Poly(3,4-ethylenedioxythiophene)-Modified Electrodes for Microfluidics Pumping with Redox-Magnetohydrodynamics: Improving Compatibility for Broader Applications by Eliminating Addition of Redox Species to Solution.

    Science.gov (United States)

    Nash, Christena K; Fritsch, Ingrid

    2016-02-02

    A new approach using electrodes modified with poly(3,4-ethylenedioxythiophene) (PEDOT) was implemented to perform redox-magnetohydrodynamics (MHD) microfluidics and eliminate the need to add redox species to solution, thus removing interferences with detection, sample, and reagents for lab-on-a-chip applications. This accomplishment not only retains the unique properties of redox-MHD pumping (i.e., programmable fluid speeds and flow patterns without the need for side walls, horizontal flat flow profiles, looping flow, no electrode corrosion, and no bubble formation), but also achieves a wider sustainable voltage range and currents that can be as much as 7+ times higher (and therefore correspondingly higher velocities) than in past studies involving unmodified electrodes and redox species in solution. PEDOT, a conducting polymer that has been shown to exhibit low cytotoxicity, was electropolymerized on microband gold electrodes (25 mm long ×103 μm wide). A cell (325 μL) with distant side walls was formed by placing a 620 μm thick poly(dimethylsiloxane), PDMS, gasket with an opening of 3.2 cm × 1.5 cm on the chip, and a glass slide lid prevented evaporation. A 0.37 T magnet under the chip generated a magnetic field perpendicular to the chip surface. The cell was filled with 0.095 M NaCl electrolyte containing 10 μm polystyrene beads to visualize and quantify fluid flow using optical video microscopy. Fluid speeds of 590 μm s(-1) were observed immediately after applying a potential step. A linear relationship between applied electronic current and fluid velocity was shown. Vertical flow profiles under applied current conditions were curved, with a weak parabolic fit.

  3. 全钒液流电池用新型全氟磺酸离子交换膜制备及性能研究%Preparation and performance study of new perfluorosulfonated acid ion exchange membranes for vanadium redox flow battery

    Institute of Scientific and Technical Information of China (English)

    牛淑娟; 李磊; 张永明

    2012-01-01

    通过溶液流延成膜法制备了具有不同离子交换容量(IEC)的全氟磺酸(PFSA)离子交换膜,并测试了其吸水率、电导率、钒离子(Ⅴ(Ⅳ))透过率和选择性系数。研究发现,具有高IEC值的PFSA离子交换膜具有相对较低的Ⅴ(Ⅳ)离子透过率和较高的质子电导率。其中IEC值为1.10mmol/g的PFSA离子交换膜对Ⅴ(Ⅳ)离子具有最高的选择性,其选择性系数为Nafion 117膜的2.97倍。%Perfluorosulfonated acid (PFSA) ion exchange membranes, with different ion exchange capacities (IECs), were prepared by a solution-casting method for vanadium redox flow battery applications. Water uptake, proton conductivity, vanadium ion permeability and selectivity of the PFSA ion exchange membranes were investigated. It is found that membranes with higher IEC values have relatively lower vanadium ion permeability and higher proton conductivity. The highest selectivity of the membranes being characterized was achieved from the PFSA ion exchange membrane with 1.10 mmol/g, which was 2.97 times higher than that of Nafion 117 membrane.

  4. Energy efficiency of neptunium redox battery in comparison with vanadium battery

    Energy Technology Data Exchange (ETDEWEB)

    Yamamura, T. [Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Sendai, Miyagi 980-8577 (Japan); Watanabe, N. [Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Sendai, Miyagi 980-8577 (Japan); Shiokawa, Y. [Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Sendai, Miyagi 980-8577 (Japan)]. E-mail: shiokawa@imr.tohoku.ac.jp

    2006-02-09

    A neptunium ion possesses two isostructural and reversible redox couples (Np{sup 3+}/Np{sup 4+} and NpO{sub 2} {sup +}/NpO{sub 2} {sup 2+}) and is therefore suitable as an active material for a redox-flow battery. Since the plastic formed carbon (PFC) is known to show the largest k values for Np(IV)/Np(III) and Np(V)/Np(VI) reactions among various carbon electrodes, a cell was constructed by using the PFC, with the circulation induced by bubbling gas through the electrolyte. In discharge experiments with a neptunium and a vanadium battery using the cell, the former showed a lower voltage loss which suggests a smaller reaction overvoltage. Because of the high radioactivity of the neptunium, it was difficult to obtain sufficient circulation required for the redox-flow battery, therefore a model for evaluating the energy efficiency of the redox-flow battery was developed. By using the known k values for neptunium and vanadium electrode reactions at PFC electrodes, the energy efficiency of the neptunium battery was calculated to be 99.1% at 70 mA cm{sup -2}, which exceeds that of the vanadium battery by ca. 16%.

  5. Cobalt and marine redox evolution

    Science.gov (United States)

    Swanner, Elizabeth D.; Planavsky, Noah J.; Lalonde, Stefan V.; Robbins, Leslie J.; Bekker, Andrey; Rouxel, Olivier J.; Saito, Mak A.; Kappler, Andreas; Mojzsis, Stephen J.; Konhauser, Kurt O.

    2014-03-01

    Cobalt (Co) is a bio-essential trace element and limiting nutrient in some regions of the modern oceans. It has been proposed that Co was more abundant in poorly ventilated Precambrian oceans based on the greater utilization of Co by anaerobic microbes relative to plants and animals. However, there are few empirical or theoretical constraints on the history of seawater Co concentrations. Herein, we present a survey of authigenic Co in marine sediments (iron formations, authigenic pyrite and bulk euxinic shales) with the goal of tracking changes in the marine Co reservoir throughout Earth's history. We further provide an overview of the modern marine Co cycle, which we use as a platform to evaluate how changes in the redox state of Earth's surface were likely to have affected marine Co concentrations. Based on sedimentary Co contents and our understanding of marine Co sources and sinks, we propose that from ca. 2.8 to 1.8 Ga the large volume of hydrothermal fluids circulating through abundant submarine ultramafic rocks along with a predominantly anoxic ocean with a low capacity for Co burial resulted in a large dissolved marine Co reservoir. We tentatively propose that there was a decrease in marine Co concentrations after ca. 1.8 Ga resulting from waning hydrothermal Co sources and the expansion of sulfide Co burial flux. Changes in the Co reservoir due to deep-water ventilation in the Neoproterozoic, if they occurred, are not resolvable with the current dataset. Rather, Co enrichments in Phanerozoic euxinic shales deposited during ocean anoxic events (OAE) indicate Co mobilization from expanded anoxic sediments and enhanced hydrothermal sources. A new record of marine Co concentrations provides a platform from which we can reevaluate the role that environmental Co concentrations played in shaping biological Co utilization throughout Earth's history.

  6. Sustainable electrical energy storage through the ferrocene/ferrocenium redox reaction in aprotic electrolyte.

    Science.gov (United States)

    Zhao, Yu; Ding, Yu; Song, Jie; Li, Gang; Dong, Guangbin; Goodenough, John B; Yu, Guihua

    2014-10-06

    The large-scale, cost-effective storage of electrical energy obtained from the growing deployment of wind and solar power is critically needed for the integration into the grid of these renewable energy sources. Rechargeable batteries having a redox-flow cathode represent a viable solution for either a Li-ion or a Na-ion battery provided a suitable low-cost redox molecule soluble in an aprotic electrolyte can be identified that is stable for repeated cycling and does not cross the separator membrane to the anode. Here we demonstrate an environmentally friendly, low-cost ferrocene/ferrocenium molecular redox couple that shows about 95% energy efficiency and about 90% capacity retention after 250 full charge/discharge cycles.

  7. Nanostructured Perovskite LaCo1-xMnxO3 as Bifunctional Catalysts for Rechargeable Metal-Air Batteries

    Science.gov (United States)

    Ge, Xiaoming; Li, Bing; Wuu, Delvin; Sumboja, Afriyanti; An, Tao; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

    2015-09-01

    Bifunctional catalyst that is active for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most important components of rechargeable metal-air batteries. Nanostructured perovskite bifunctional catalysts comprising La, Co and Mn(LaCo1-xMnxO3, LCMO) are synthesized by hydrothermal methods. The morphology, structure and electrochemical activity of the perovskite bifunctional catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and rotating disk electrode (RDE) techniques. Nanorod, nanodisc and nanoparticle are typical morphologies of LCMO. The electrocatalytic activity of LCMO is significantly improved by the addition of conductive materials such as carbon nanotube. To demonstrate the practical utilization, LCMO in the composition of LaCo0.8Mn0.2O3(LCMO82) is used as air cathode catalysts for rechargeable zinc-air batteries. The battery prototype can sustain 470 h or 40 discharge-charge cycles equivalent.

  8. Redox interplay between mitochondria and peroxisomes

    Directory of Open Access Journals (Sweden)

    Celien eLismont

    2015-05-01

    Full Text Available Reduction-oxidation or ‘redox’ reactions are an integral part of a broad range of cellular processes such as gene expression, energy metabolism, protein import and folding, and autophagy. As many of these processes are intimately linked with cell fate decisions, transient or chronic changes in cellular redox equilibrium are likely to contribute to the initiation and progression of a plethora of human diseases. Since a long time, it is known that mitochondria are major players in redox regulation and signaling. More recently, it has become clear that also peroxisomes have the capacity to impact redox-linked physiological processes. To serve this function, peroxisomes cooperate with other organelles, including mitochondria. This review provides a comprehensive picture of what is currently known about the redox interplay between mitochondria and peroxisomes in mammals. We first outline the pro- and antioxidant systems of both organelles and how they may function as redox signaling nodes. Next, we critically review and discuss emerging evidence that peroxisomes and mitochondria share an intricate redox-sensitive relationship and cooperate in cell fate decisions. Key issues include possible physiological roles, messengers, and mechanisms. We also provide examples of how data mining of publicly-available datasets from ‘omics’ technologies can be a powerful means to gain additional insights into potential redox signaling pathways between peroxisomes and mitochondria. Finally, we highlight the need for more studies that seek to clarify the mechanisms of how mitochondria may act as dynamic receivers, integrators, and transmitters of peroxisome-derived mediators of oxidative stress. The outcome of such studies may open up exciting new avenues for the community of researchers working on cellular responses to organelle-derived oxidative stress, a research field in which the role of peroxisomes is currently highly underestimated and an issue of

  9. Transport of gadolinium- and arsenic-based pharmaceuticals in saturated soil under various redox conditions.

    Science.gov (United States)

    Menahem, Adi; Dror, Ishai; Berkowitz, Brian

    2016-02-01

    The release of pharmaceuticals and personal care products (PPCPs) to the soil-water environment necessitates understanding of PPCP transport behavior under conditions that account for dynamic flow and varying redox states. This study investigates the transport of two organometallic PPCPs, Gd-DTPA and roxarsone (arsenic compound) and their metal salts (Gd(NO3)3, AsNaO2); Gd-DTPA is used widely as a contrasting agent for MRI, while roxarsone is applied extensively as a food additive in the broiler poultry industry. Here, we present column experiments using sand and Mediterranean red sandy clay soil, performed under several redox conditions. The metal salts were almost completely immobile. In contrast, transport of Gd-DTPA and roxarsone was affected by the soil type. Roxarsone was also affected by the different redox conditions, showing delayed breakthrough curves as the redox potential became more negative due to biological activity (chemically-strong reducing conditions did not affect the transport). Mechanisms that include adsorptive retardation for aerobic and nitrate-reducing conditions, and non-adsorptive retardation for iron-reducing, sulfate-reducing and biologically-strong reducing conditions, are suggested to explain the roxarsone behavior. Gd-DTPA is found to be a stable complex, with potential for high mobility in groundwater systems, whereas roxarsone transport through groundwater systems is affected by redox environments, demonstrating high mobility under aerobic and nitrate-reducing conditions and delayed transport under iron-reducing, sulfate-reducing and biologically-strong reducing conditions.

  10. MICROSCALE METABOLIC, REDOX AND ABIOTIC REACTIONS IN HANFORD 300 AREA SUBSURFACE SEDIMENTS

    Energy Technology Data Exchange (ETDEWEB)

    Beyenal, Haluk [WSU; McLEan, Jeff [JCVI; Majors, Paul [PNNL; Fredrickson, Jim [PNNL

    2013-11-14

    The Hanford 300 Area is a unique site due to periodic hydrologic influence of river water resulting in changes in groundwater elevation and flow direction. This area is also highly subject to uranium remobilization, the source of which is currently believed to be the region at the base of the vadose zone that is subject to period saturation due to the changes in the water levels in the Columbia River. We found that microbial processes and redox and abiotic reactions which operate at the microscale were critical to understanding factors controlling the macroscopic fate and transport of contaminants in the subsurface. The combined laboratory and field research showed how microscale conditions control uranium mobility and how biotic, abiotic and redox reactions relate to each other. Our findings extended the current knowledge to examine U(VI) reduction and immobilization using natural 300 Area communities as well as selected model organisms on redox-sensitive and redox-insensitive minerals. Using innovative techniques developed specifically to probe biogeochemical processes at the microscale, our research expanded our current understanding of the roles played by mineral surfaces, bacterial competition, and local biotic, abiotic and redox reaction rates on the reduction and immobilization of uranium.

  11. Thiol switches in redox regulation of chloroplasts: balancing redox state, metabolism and oxidative stress.

    Science.gov (United States)

    Dietz, Karl-Josef; Hell, Rüdiger

    2015-05-01

    In photosynthesizing chloroplasts, rapidly changing energy input, intermediate generation of strong reductants as well as oxidants and multiple participating physicochemical processes and pathways, call for efficient regulation. Coupling redox information to protein function via thiol modifications offers a powerful mechanism to activate, down-regulate and coordinate interdependent processes. Efficient thiol switching of target proteins involves the thiol-disulfide redox regulatory network, which is highly elaborated in chloroplasts. This review addresses the features of this network. Its conditional function depends on specificity of reduction and oxidation reactions and pathways, thiol redox buffering, but also formation of heterogeneous milieus by microdomains, metabolite gradients and macromolecular assemblies. One major player is glutathione. Its synthesis and function is under feedback redox control. The number of thiol-controlled processes and involved thiol switched proteins is steadily increasing, e.g., in tetrapyrrole biosynthesis, plastid transcription and plastid translation. Thus chloroplasts utilize an intricate and versatile redox regulatory network for intraorganellar and retrograde communication.

  12. Bifunctional heterogeneous catalysts from oil palm empty fruit bunches ash and alum for biodiesel synthesis simultaneously

    Science.gov (United States)

    Astar, Ismail; Usman, Thamrin; Wahyuni, Nelly; Rudiyansyah, Alimuddin, Andi Hairil

    2017-03-01

    Free fatty acids (FFA) contained in crude palm oil (CPO) and sludge oil has been used as the base material of biodiesel with the aid of a catalyst in the transesterification and esterification reactions. This study aims to synthesize and characterize bifunctional catalysts were synthesized from the ashes of palm empty fruit bunches (EFB) and alum based on the analysis of XRD, XRF and acidity test. Bifunctional catalyst obtained was used as a catalyst to production of biodiesel with different levels of FFA. The optimum ratio alum added was 0.2 mol at 3 hours of reaction time and 3% of catalyst by the FFA samples were used 67,40%. The catalyst with optimum alum mole variations subsequently used on samples with varying levels of FFA, namely 1.29%, 4.98%, 29.21%, 67.40% and 74.47%. Optimum conversion of methyl ester in the esterification reaction occurs in the sample with 67.40% FFA content, which reached 86.17%, while the conversion of methyl ester transesterification process optimum amounted to 45.70% in the samples with 4.98% FFA content. Methyl ester produced has a refractive index of 1.448 (29.8 ° C), density of 0.883 g / mL (25 °C) and a viscosity of 8.933 cSt (25 ° C). The results of GC-MS analysis showed that the main composition of methyl ester result of esterification of sludge oil methyl palmitate (36.84%), while the CPO transesterification shows the main composition of methyl ester is methyl oleic (38.87%). Based on the research results, the catalyst synthesized from alum and EFB ash can be used as a Bifunctional catalysts for biodiesel synthesis.

  13. Vanadium Electrolyte Studies for the Vanadium Redox Battery-A Review.

    Science.gov (United States)

    Skyllas-Kazacos, Maria; Cao, Liuyue; Kazacos, Michael; Kausar, Nadeem; Mousa, Asem

    2016-07-01

    The electrolyte is one of the most important components of the vanadium redox flow battery and its properties will affect cell performance and behavior in addition to the overall battery cost. Vanadium exists in several oxidation states with significantly different half-cell potentials that can produce practical cell voltages. It is thus possible to use the same element in both half-cells and thereby eliminate problems of cross-contamination inherent in all other flow battery chemistries. Electrolyte properties vary with supporting electrolyte composition, state-of-charge, and temperature and this will impact on the characteristics, behavior, and performance of the vanadium battery in practical applications. This Review provides a broad overview of the physical properties and characteristics of the vanadium battery electrolyte under different conditions, together with a description of some of the processing methods that have been developed to produce vanadium electrolytes for vanadium redox flow battery applications.

  14. Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ramasamy, Karthikeyan K.; Gray, Michel J.; Job, Heather M.; Smith, Colin D.; Wang, Yong

    2016-04-10

    tA highly versatile ethanol conversion process to selectively generate high value compounds is pre-sented here. By changing the reaction temperature, ethanol can be selectively converted to >C2alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al2O3cata-lyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensationor the acetone formation is the path taken in changing the product composition. This article containsthe catalytic activity comparison between the mono-functional and physical mixture counterpart to thehydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

  15. Controlled Covalent Functionalization of Thermally Reduced Graphene Oxide To Generate Defined Bifunctional 2D Nanomaterials

    Science.gov (United States)

    Faghani, Abbas; Donskyi, Ievgen S.; Fardin Gholami, Mohammad; Ziem, Benjamin; Lippitz, Andreas; Unger, Wolfgang E. S.; Böttcher, Christoph; Rabe, Jürgen P.

    2017-01-01

    Abstract A controlled, reproducible, gram‐scale method is reported for the covalent functionalization of graphene sheets by a one‐pot nitrene [2+1] cycloaddition reaction under mild conditions. The reaction between commercially available 2,4,6‐trichloro‐1,3,5‐triazine and sodium azide with thermally reduced graphene oxide (TRGO) results in defined dichlorotriazine‐functionalized sheets. The different reactivities of the chlorine substituents on the functionalized graphene allow stepwise post‐modification by manipulating the temperature. This new method provides unique access to defined bifunctional 2D nanomaterials, as exemplified by chiral surfaces and multifunctional hybrid architectures. PMID:28165179

  16. An efficient bifunctional electrocatalyst for water splitting based on cobalt phosphide

    Science.gov (United States)

    Yang, Libin; Qi, Honglan; Zhang, Chengxiao; Sun, Xuping

    2016-06-01

    The development of highly efficient electrocatalysts for water splitting is critical for various renewable-energy technologies. In this letter, we demonstrate a cobalt phosphide nanowire array grown on a Ti mesh (CoP/TM) behaving as a bifunctional electrocatalyst for water splitting. The CoP/TM electrode delivers 10 mA cm-2 at an overpotential of 72 mV for the hydrogen evolution reaction (HER) and 310 mV for the oxygen evolution reaction (OER) in 1.0 M KOH. Furthermore, its corresponding two-electrode alkaline electrolyzer displays 10 mA cm-2 at 1.64 V.

  17. MoO3 nanoparticle anchored graphene as bifunctional agent for water purification

    Science.gov (United States)

    Lahan, Homen; Roy, Raju; Namsa, Nima D.; Das, Shyamal K.

    2016-10-01

    We report here a facile one step hydrothermal method to anchor MoO3 nanoparticles in graphene. The bifunctionality of graphene-MoO3 nanoparticles is demonstrated via dye adsorption and antibacterial activities. The nanocomposite showed excellent adsorption of methylene blue, a cationic dye, from water compared to pristine MoO3 and graphene. However, it showed negligible adsorption of methyl orange, an anionic dye. Again, the graphene-MoO3 nanoparticles exhibited bacteriostatic property against both Gram-negative (E. coli) and Gram-positive (S. aureus) bacteria.

  18. Mutability of bifunctional thigh muscle activity in pedaling due to contralateral leg force generation.

    Science.gov (United States)

    Kautz, S A; Brown, D A; Van der Loos, H F M; Zajac, F E

    2002-09-01

    Locomotion requires uninterrupted transitions between limb extension and flexion. The role of contralateral sensorimotor signals in executing smooth transitions is little understood even though their participation is crucial to bipedal walking. However, elucidating neural interlimb coordinating mechanisms in human walking is difficult because changes to contralateral sensorimotor activity also affect the ipsilateral mechanics. Pedaling, conversely, is ideal for studying bilateral coordination because ipsilateral mechanics can be independently controlled. In pedaling, the anterior and posterior bifunctional thigh muscles develop needed anterior and posterior crank forces, respectively, to dominate the flexion-to-extension and extension-to-flexion transitions. We hypothesized that contralateral sensorimotor activity substantially contributes to the appropriate activation of these bifunctional muscles during the limb transitions. Bilateral pedal forces and surface electromyograms (EMGs) from four thigh muscles were collected from 15 subjects who pedaled with their right leg against a right-crank servomotor, which emulated the mechanical load experienced in conventional two-legged coupled-crank pedaling. In one pedaling session, the contralateral (left) leg pseudo-pedaled (i.e., EMG activity and pedal forces were pedaling-like, but pedal force was not allowed to affect crank rotation). In other sessions, the mechanically decoupled contralateral leg was first relaxed and then produced rhythmic isometric force trajectories during either leg flexion or one of the two limb transitions of the pedaling leg. With contralateral force production in the extension-to-flexion transition (predominantly by the hamstrings), rectus femoris activity and work output increased in the pedaling leg during its flexion-to-extension transition, which occurs simultaneously with contralateral extension-to-flexion in conventional pedaling. Similarly, with contralateral force production in the

  19. Altered Glutathione Redox State in Schizophrenia

    Directory of Open Access Journals (Sweden)

    Jeffrey K. Yao

    2006-01-01

    Full Text Available Altered antioxidant status has been reported in schizophrenia. The glutathione (GSH redox system is important for reducing oxidative stress. GSH, a radical scavenger, is converted to oxidized glutathione (GSSG through glutathione peroxidase (GPx, and converted back to GSH by glutathione reductase (GR. Measurements of GSH, GSSG and its related enzymatic reactions are thus important for evaluating the redox and antioxidant status. In the present study, levels of GSH, GSSG, GPx and GR were assessed in the caudate region of postmortem brains from schizophrenic patients and control subjects (with and without other psychiatric disorders. Significantly lower levels of GSH, GPx, and GR were found in schizophrenic group than in control groups without any psychiatric disorders. Concomitantly, a decreased GSH:GSSG ratio was also found in schizophrenic group. Moreover, both GSSG and GR levels were significantly and inversely correlated to age of schizophrenic patients, but not control subjects. No significant differences were found in any GSH redox measures between control subjects and individuals with other types of psychiatric disorders. There were, however, positive correlations between GSH and GPx, GSH and GR, as well as GPx and GR levels in control subjects without psychiatric disorders. These positive correlations suggest a dynamic state is kept in check during the redox coupling under normal conditions. By contrast, lack of such correlations in schizophrenia point to a disturbance of redox coupling mechanisms in the antioxidant defense system, possibly resulting from a decreased level of GSH as well as age-related decreases of GSSG and GR activities.

  20. Redox regulation of protein damage in plasma.

    Science.gov (United States)

    Griffiths, Helen R; Dias, Irundika H K; Willetts, Rachel S; Devitt, Andrew

    2014-01-01

    The presence and concentrations of modified proteins circulating in plasma depend on rates of protein synthesis, modification and clearance. In early studies, the proteins most frequently analysed for damage were those which were more abundant in plasma (e.g. albumin and immunoglobulins) which exist at up to 10 orders of magnitude higher concentrations than other plasma proteins e.g. cytokines. However, advances in analytical techniques using mass spectrometry and immuno-affinity purification methods, have facilitated analysis of less abundant, modified proteins and the nature of modifications at specific sites is now being characterised. The damaging reactive species that cause protein modifications in plasma principally arise from reactive oxygen species (ROS) produced by NADPH oxidases (NOX), nitric oxide synthases (NOS) and oxygenase activities; reactive nitrogen species (RNS) from myeloperoxidase (MPO) and NOS activities; and hypochlorous acid from MPO. Secondary damage to proteins may be caused by oxidized lipids and glucose autooxidation. In this review, we focus on redox regulatory control of those enzymes and processes which control protein maturation during synthesis, produce reactive species, repair and remove damaged plasma proteins. We have highlighted the potential for alterations in the extracellular redox compartment to regulate intracellular redox state and, conversely, for intracellular oxidative stress to alter the cellular secretome and composition of extracellular vesicles. Through secreted, redox-active regulatory molecules, changes in redox state may be transmitted to distant sites.

  1. Potentiometric Measurements of Semiconductor Nanocrystal Redox Potentials.

    Science.gov (United States)

    Carroll, Gerard M; Brozek, Carl K; Hartstein, Kimberly H; Tsui, Emily Y; Gamelin, Daniel R

    2016-04-06

    A potentiometric method for measuring redox potentials of colloidal semiconductor nanocrystals (NCs) is described. Fermi levels of colloidal ZnO NCs are measured in situ during photodoping, allowing correlation of NC redox potentials and reduction levels. Excellent agreement is found between electrochemical and optical redox-indicator methods. Potentiometry is also reported for colloidal CdSe NCs, which show more negative conduction-band-edge potentials than in ZnO. This difference is highlighted by spontaneous electron transfer from reduced CdSe NCs to ZnO NCs in solution, with potentiometry providing a measure of the inter-NC electron-transfer driving force. Future applications of NC potentiometry are briefly discussed.

  2. Relating hyporheic fluxes, residence times, and redox-sensitive biogeochemical processes upstream of beaver dams

    Science.gov (United States)

    Briggs, Martin A.; Lautz, Laura; Hare, Danielle K.

    2013-01-01

    Abstract. Small dams enhance the development of patchy microenvironments along stream corridors by trapping sediment and creating complex streambed morphologies. This patchiness drives intricate hyporheic flux patterns that govern the exchange of O2 and redox-sensitive solutes between the water column and the stream bed. We used multiple tracer techniques, naturally occurring and injected, to evaluate hyporheic flow dynamics and associated biogeochemical cycling and microbial reactivity around 2 beaver dams in Wyoming (USA). High-resolution fiber-optic distributed temperature sensing was used to collect temperature data over 9 vertical streambed profiles and to generate comprehensive vertical flux maps using 1-dimensional (1-D) heat-transport modeling. Coincident with these locations, vertical profiles of hyporheic water were collected every week and analyzed for dissolved O2, pH, dissolved organic C, and several conservative and redox-sensitive solutes. In addition, hyporheic and net stream aerobic microbial reactivity were analyzed with a constant-rate injection of the biologically sensitive resazurin (Raz) smart tracer. The combined results revealed a heterogeneous system with rates of downwelling hyporheic flow organized by morphologic unit and tightly coupled to the redox conditions of the subsurface. Principal component analysis was used to summarize the variability of all redox-sensitive species, and results indicated that hyporheic water varied from oxic-stream-like to anoxic-reduced in direct response to the hydrodynamic conditions and associated residence times. The anaerobic transition threshold predicted by the mean O2 Damko

  3. Combination of aquifer thermal energy storage and enhanced bioremediation: resilience of reductive dechlorination to redox changes.

    Science.gov (United States)

    Ni, Zhuobiao; van Gaans, Pauline; Smit, Martijn; Rijnaarts, Huub; Grotenhuis, Tim

    2016-04-01

    To meet the demand for sustainable energy, aquifer thermal energy storage (ATES) is widely used in the subsurface in urban areas. However, contamination of groundwater, especially with chlorinated volatile organic compounds (CVOCs), is often being encountered. This is commonly seen as an impediment to ATES implementation, although more recently, combining ATES and enhanced bioremediation of CVOCs has been proposed. Issues to be addressed are the high water flow velocities and potential periodic redox fluctuation that accompany ATES. A column study was performed, at a high water flow velocity of 2 m/h, simulating possible changes in subsurface redox conditions due to ATES operation by serial additions of lactate and nitrate. The impacts of redox changes on reductive dechlorination as well as the microbial response of Dehalococcoides (DHC) were evaluated. The results showed that, upon lactate addition, reductive dechlorination proceeded well and complete dechlorination from cis-DCE to ethene was achieved. Upon subsequent nitrate addition, reductive dechlorination immediately ceased. Disruption of microorganisms' retention was also immediate and possibly detached DHC which preferred attaching to the soil matrix under biostimulation conditions. Initially, recovery of dechlorination was possible but required bioaugmentation and nutrient amendment in addition to lactate dosing. Repeated interruption of dechlorination and DHC activity by nitrate dosing appeared to be less easily reversible requiring more efforts for regenerating dechlorination. Overall, our results indicate that the microbial resilience of DHC in biosimulated ATES conditions is sensitive to redox fluctuations. Hence, combining ATES with bioremediation requires dedicated operation and monitoring on the aquifer geochemical conditions.

  4. Redox potential dynamics in a grassed swale used for storage and treatment

    Science.gov (United States)

    Vorenhout, Michel; Boogaard, Floris Cornelis

    2016-04-01

    Treatment wetlands are used to remove pollutants from water. Most swales are designed to infiltrate stormwater into the subsurface. A combination of both functions can help to enhance water quality and reduce flooding risks in urban areas. The chemical forms and possible removal of pollutants such as nitrate and heavy metals in wetlands are highly dependent on the redox conditions. The redox conditions are expected to be highly dynamic and dependent on water levels and flow. We studied the correlation between these factors in an urban grassed swale system, and show that more factors play a role in these systems than water levels alone. The study system is located in the World Heritage site "Bryggen" in the city of Bergen, Norway. It consists of a series of SUDS, a socalled treatment train. The system is fed by storm water, which is at first stored in a rain garden then led to grassed swales. Water infiltrates into the subsurface in the swales. The reason for implementation of the system at this site is the protection of the highly organic archaeological layers at the site, which requires reduced conditions. Swales 1 and 2 were equipped with pressure loggers and multi-level redox and temperature probes (-2, -5, -10 and -20cm from surface). Redox and temperature probes were connected to a HYPNOS system. Measurements were taken for more than 1 year at 15 minute interval. A weather station supplemented the dataset with precipitation measurements. The redox potential in the swales show a strong correlation with water level. The regularly flooded swale 2 shows frequent anoxic events (Eh < 200mV) where as swale 1 shows oxic conditions (Eh = 650mV) throughout the same measurement period. Swale 1 has fewer flooding events than Swale 2 and a more coarse soil with less organic matter than swale 2. These redox results are as expected given the local conditions, and show that redox conditions are localised phenomena that depend on local soil conditions. Analysis of the redox

  5. A bifunctional spin label reports the structural topology of phospholamban in magnetically-aligned bicelles.

    Science.gov (United States)

    McCaffrey, Jesse E; James, Zachary M; Svensson, Bengt; Binder, Benjamin P; Thomas, David D

    2016-01-01

    We have applied a bifunctional spin label and EPR spectroscopy to determine membrane protein structural topology in magnetically-aligned bicelles, using monomeric phospholamban (PLB) as a model system. Bicelles are a powerful tool for studying membrane proteins by NMR and EPR spectroscopies, where magnetic alignment yields topological constraints by resolving the anisotropic spectral properties of nuclear and electron spins. However, EPR bicelle studies are often hindered by the rotational mobility of monofunctional Cys-linked spin labels, which obscures their orientation relative to the protein backbone. The rigid and stereospecific TOAC label provides high orientational sensitivity but must be introduced via solid-phase peptide synthesis, precluding its use in large proteins. Here we show that a bifunctional methanethiosulfonate spin label attaches rigidly and stereospecifically to Cys residues at i and i+4 positions along PLB's transmembrane helix, thus providing orientational resolution similar to that of TOAC, while being applicable to larger membrane proteins for which synthesis is impractical. Computational modeling and comparison with NMR data shows that these EPR experiments provide accurate information about helix tilt relative to the membrane normal, thus establishing a robust method for determining structural topology in large membrane proteins with a substantial advantage in sensitivity over NMR.

  6. Conversion of cellulose into isosorbide over bifunctional ruthenium nanoparticles supported on niobium phosphate.

    Science.gov (United States)

    Sun, Peng; Long, Xiangdong; He, Hao; Xia, Chungu; Li, Fuwei

    2013-11-01

    Considerable effort has been applied to the development of new processes and catalysts for cellulose conversion to valuable platform chemicals. Isosorbide is among the most interesting products as it can be applied as a monomer and building block for the future replacement of fossil resource-based products. A sustainable method of isosorbide production from cellulose is presented in this work. The strategy relies on a bifunctional Ru catalyst supported on mesoporous niobium phosphate in a H2 atmosphere under pressure without further addition of any soluble acid. Over 50 % yield of isosorbide with almost 100 % cellulose conversion can be obtained in 1 h. The large surface area, pore size, and strong acidity of mesoporous niobium phosphate promote the hydrolysis of cellulose and dehydration of sorbitol; additionally, the appropriate size of the supported Ru nanoparticles avoids unnecessary hydrogenolysis of sorbitol. Under a cellulose/catalyst mass ratio of 43.3, the present bifunctional catalyst could be stably used up to six times, with its mesoporous structure well preserved and without detectable Ru leaching into the reaction solution.

  7. Ternary NiCoP nanosheet arrays: An excellent bifunctional catalyst for alkaline overall water splitting

    Institute of Scientific and Technical Information of China (English)

    Yingjie Li; Haichuan Zhang; Ming Jiang; Yun Kuang; Xiaoming Sun; Xue Duan

    2016-01-01

    Exploring bifunctional catalysts for the hydrogen and oxygen evolution reactions (HER and OER) with high efficiency,low cost,and easy integration is extremely crucial for future renewable energy systems.Herein,ternary NiCoP nanosheet arrays (NSAs) were fabricated on 3D Ni foam by a facile hydrothermal method followed by phosphorization.These arrays serve as bifunctional alkaline catalysts,exhibiting excellent electrocatalytic performance and good working stability for both the HER and OER.The overpotentials of the NiCoP NSA electrode required to drive a current density of 50 mA/cm2 for the HER and OER are as low as 133 and 308 mV,respectively,which is ascribed to excellent intrinsic electrocatalytic activity,fast electron transport,and a unique superaerophobic structure.When NiCoP was integrated as both anodic and cathodic material,the electrolyzer required a potential as low as ~1.77 V to drive a current density of 50 mA/cm2 for overall water splitting,which is much smaller than a reported electrolyzer using the same kind of phosphide-based material and is even better than the combination of Pt/C and Ir/C,the best known noble metal-based electrodes.Combining satisfactory working stability and high activity,this NiCoP electrode paves the way for exploring overall water splitting catalysts.

  8. Bifunctional Ag/C3N4.5 composite nanobelts for photocatalysis and antibacterium

    Science.gov (United States)

    Lei, Renbo; Jian, Jikang; Zhang, Zhihua; Song, Bo; Wu, Rong

    2016-09-01

    Multiple functions can be achieved in carbon nitride-based composite nanomaterials by tuning their components and structures. Here, we report on a large-scale synthesis of novel bifunctional Ag/C3N4.5 composite nanobelts (CNBs) with efficient photocatalytic and antibacterial activity. The Ag/C3N4.5 CNBs were synthesized in high yield by a two-step route including a homogeneous precipitation process and a subsequent calcination treatment. The structural, morphological, compositional, and spectroscopic characterizations revealed that the Ag/C3N4.5 CNBs are composed of N-deficient melem ultrathin nanobelts and crystalline Ag nanoparticles attached to the surface of the nanobelts with good contact. The band gap of the Ag/C3N4.5 CNBs is determined to be about 3.04 eV. The efficient photocatalytic and antibacterial activities of the composite nanomaterials are verified by testing the degradation of Rhodamine B (RhB) and the inhibition zone to bacterium E. coli. The work provides a facile route to bifunctional carbon nitride-based composites with potential applications in the fields of the environment and biology.

  9. Cell Growth on ("Janus") Density Gradients of Bifunctional Zeolite L Crystals.

    Science.gov (United States)

    Kehr, Nermin Seda; Motealleh, Andisheh; Schäfer, Andreas H

    2016-12-28

    Nanoparticle density gradients on surfaces have attracted interest as two-dimensional material surfaces that can mimic the complex nano-/microstructure of the native extracellular matrix, including its chemical and physical gradients, and can therefore be used to systematically study cell-material interactions. In this respect, we report the preparation of density gradients made of bifunctional zeolite L crystals on glass surfaces and the effects of the density gradient and biopolymer functionalization of zeolite L crystals on cell adhesion. We also describe how we created "Janus" density gradient surfaces by gradually depositing two different types of zeolite L crystals that were functionalized and loaded with different chemical groups and guest molecules onto the two distinct sides of the same glass substrate. Our results show that more cells adhered on the density gradient of biopolymer-coated zeolites than on uncoated ones. The number of adhered cells increased up to a certain surface coverage of the glass by the zeolite L crystals, but then it decreased beyond the zeolite density at which a higher surface coverage decreased fibroblast cell adhesion and spreading. Additionally, cell experiments showed that cells gradually internalized the guest-molecule-loaded zeolite L crystals from the underlying density gradient containing bifunctional zeolite L crystals.

  10. Cyclic isoDGR and RGD peptidomimetics containing bifunctional diketopiperazine scaffolds are integrin antagonists.

    Science.gov (United States)

    Panzeri, Silvia; Zanella, Simone; Arosio, Daniela; Vahdati, Leila; Dal Corso, Alberto; Pignataro, Luca; Paolillo, Mayra; Schinelli, Sergio; Belvisi, Laura; Gennari, Cesare; Piarulli, Umberto

    2015-04-13

    The cyclo[DKP-isoDGR] peptidomimetics 2-5, containing bifunctional diketopiperazine (DKP) scaffolds that differ in the configuration of the two DKP stereocenters and in the substitution at the DKP nitrogen atoms, were prepared and examined in vitro in competitive binding assays with purified αv β3 and αv β5 integrin receptors. IC50 values ranged from low nanomolar (ligand 3) to submicromolar with αv β3 integrin. The biological activities of ligands cyclo[DKP3-RGD] 1 and cyclo[DKP3-isoDGR] 3, bearing the same bifunctional DKP scaffold and showing similar αV β3 integrin binding values, were compared in terms of their cellular effects in human U373 glioblastoma cells. Compounds 1 and 3 displayed overlapping inhibitory effects on the FAK/Akt integrin activated transduction pathway and on integrin-mediated cell infiltration processes, and qualify therefore, despite the different RGD and isoDGR sequences, as integrin antagonists. Both compounds induced apoptosis in glioma cells after 72 hour treatment.

  11. Bifunctional composite microspheres of silica/lanthanide-polyoxometalates/Au: Study on luminescence and catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun, E-mail: junwang924@mail.ccnu.edu.cn; Fan, Shaohua; Zhao, Weiqian; Lu, Xuelian; Li, Wuke

    2013-12-02

    In this paper, the synthesis and properties of composite silica microspheres grafted with gold nanoparticles and lanthanide-polyoxometalates are described. This synthesis employs polyethyleneimine as the crosslink polymer to immobilize the Au nanoparticles and lanthanide-polyoxometalates on silica spheres, which results in the formation of bifunctional composite microspheres of silica/lanthanide-polyoxometalates/Au. The composite material was found to be catalytically active in the oxidation of styrene, and benzaldehyde and styrene oxide were the main products. Catalyzed oxidation of styrene demonstrates the size-dependent activity of catalysts and the smaller catalyst shows the higher selectivity. Moreover, the composite particles show bright red luminescence under UV light, which could be seen by naked eyes. The luminescence properties of composite material and the effect of Au nanoparticles on the luminescence of Eu ion were investigated, and energy could be more effectively transferred from ligand to lanthanide ion when Au nanoparticles were grafted on silica spheres. The integration of luminescent components and Au particles makes it possible to label catalyst and monitor the catalyzed reactions. - Highlights: • The bifunctional composite microspheres were fabricated. • Both polyoxometalates and Au nanoparticles could be grafted on silica spheres. • The composite particles exhibit the excellent luminescence and catalytic activity. • The Au nanoparticles affect the luminescence properties of Eu{sup 3+} ions.

  12. Characterization of a bifunctional enzyme with (p)ppGpp-hydrolase/synthase activity in Leptospira interrogans.

    Science.gov (United States)

    He, Ping; Deng, Cong; Liu, Boyu; Zeng, LingBing; Zhao, Wei; Zhang, Yan; Jiang, XuCheng; Guo, XiaoKui; Qin, JinHong

    2013-11-01

    Alarmone Guanosine 5'-diphosphate (or 5'-triphosphate) 3'-diphosphate [(p)ppGpp] is the key component that globally regulates stringent control in bacteria. There are two homologous enzymes, RelA and SpoT in Escherichia coli, which are responsible for fluctuations in (p)ppGpp concentration inside the cell, whereas there exists only a single RelA/SpoT enzyme in Gram-positive bacteria. We have identified a bifunctional enzyme with (p)ppGpp-hydrolase/synthase activity in Leptospira interrogans. We show that the relLin gene (LA_3085) encodes a protein that fully complements the relA/spoT double mutants in E. coli. The protein functions as a (p)ppGpp degradase as well as a (p)ppGpp synthase when the cells encounter amino acid stress and deprivation of carbon sources. N-terminus HD and RSD domains of relLin (relLinN ) were observed to restore growth of double mutants of E. coli. Finally, We demonstrate that purified RelLin and RelLinN show high (p)ppGpp synthesis activity in vitro. Taken together, our results suggest that L. interrogans contain a single Rel-like bifunctional protein, RelLin , which plays an important role in maintaining the basal level of (p)ppGpp in the cell potentially contributing to the regulation of bacterial stress response.

  13. Mechanish of dTTP Inhibition of the Bifunctional dCTP Deaminase:dUTPase Encoded by Mycobacterium tuberculosis

    DEFF Research Database (Denmark)

    Helt, Signe Smedegaard; Thymark, Majbritt; Harris, Pernille;

    2008-01-01

    to be characterised and provides evidence for bifunctionality of dCTP deaminase occurring outside the Archaea kingdom. A steady-state kinetic analysis revealed that the affinity for dCTP and deoxyuridine triphosphate as substrates for the synthesis of deoxyuridine monophosphate were very similar, a result...

  14. Pyrrolidinyl-sulfamide derivatives as a new class of bifunctional organocatalysts for direct asymmetric Michael addition of cyclohexanone to nitroalkenes.

    Science.gov (United States)

    Chen, Jia-Rong; Fu, Liang; Zou, You-Quan; Chang, Ning-Jie; Rong, Jian; Xiao, Wen-Jing

    2011-07-21

    A series of chiral pyrrolidinyl-sulfamide derivatives have been identified as efficient bifunctional organocatalysts for the direct Michael addition of cyclohexanone to a wide range of nitroalkenes. The desired Michael adducts were obtained in high chemical yields and excellent stereoselectivities (up to 99/1 dr and 95% ee).

  15. Electrical Connection of Enzyme Redox Centers to Electrodes

    Science.gov (United States)

    1992-03-20

    complex with a water soluble diepoxide to form a hydrophilic, substrate and product permeable -lItm thick redox epoxy film. In redox-epoxy film based...product permeable -ltm thick redox epoxy film. In redox-epoxy film based glucose sensors interference by electrooxidizable ascorbate, urate and...inhalation (derived of the large lung surface area) and continuous, non-invasive administration, in the case of iontophoresis . The use of these

  16. Fate of Pharmaceuticals and Personal Care Products (PPCPs) in Saturated Soil Under Various Redox Conditions

    Science.gov (United States)

    Dror, I.; Menahem, A.; Berkowitz, B.

    2014-12-01

    The growing use of PPCPs results in their increasing release to the aquatic environment. Consequently, understanding the fate of PPCPs under environmentally relevant conditions that account for dynamic flow and varying redox states is critical. In this study, the transport of two organometallic PPCPs, Gd-DTPA and Roxarsone (As complex) and their metal salts (Gd(NO3)3, AsNaO2), is investigated. The former is used widely as a contrasting agent for MRI, while the latter is applied extensively as a food additive in the broiler poultry industry. Both of these compounds are excreted from the body, almost unchanged chemically. Gadolinium complexes are not fully eliminated in wastewater treatment and can reach groundwater via irrigation with treated wastewater; Roxarsone can enter groundwater via leaching from manure used as fertilizer. Studies have shown that the transport of PPCPs in groundwater is affected by environmental conditions such as redox states, pH, and soil type. For this study, column experiments using sand or Mediterranean red sandy clay soil were performed under several redox conditions: aerobic, nitrate-reducing, iron-reducing, sulfate-reducing, methanogenic, and very strongly chemical reducing. Batch experiments to determine adsorption isotherms were also performed for the complexes and metal salts. We found that Gd-DTPA transport was affected by the soil type and was not affected by the redox conditions. In contrast, Roxarsone transport was affected mainly by the different redox conditions, showing delayed breakthrough curves as the conditions became more biologically reduced (strong chemical reducing conditions did not affect the transport). We also observed that the metal salts show essentially no transport while the organic complexes display much faster breakthrough. The results suggest that transport of these PPCPs through soil and groundwater is determined by the redox conditions, as well as by soil type and the form of the applied metal (as salt

  17. Le reazioni redox: un pasticcio concettuale?

    Directory of Open Access Journals (Sweden)

    Elena Ghibaudi

    2015-10-01

    Full Text Available Le reazioni di ossidoriduzione costituiscono un argomento centrale di qualsiasi corso di base di chimica, sia a livello scolastico che universitario. Il loro apprendimento comporta il superamento di svariati ostacoli concettuali, la cui difficoltà può risultare amplificata da prassi didattiche inadeguate. Gli errori più ricorrenti nel presentare l’argomento sono di due tipi: i fare implicitamente riferimento a modelli esplicativi distinti (es. il numero di ossidazione e il trasferimento elettronico, senza esplicitarli e senza evidenziarne la differente natura e il campo di validità; ii confondere il livello della spiegazione formale con quello della realtà fisica. I fenomeni redox sono normalmente interpretati sulla base di tre distinti modelli empirici, che fanno riferimento al trasferimento di atomi di ossigeno, di atomi di idrogeno, di elettroni; e di un quarto modello, formale, fondato sul cambiamento del numero di ossidazione. La confusione tra questi modelli può generare considerevoli problemi di apprendimento. Il presente lavoro riporta un’analisi critica delle implicazioni concettuali della didattica dei processi redox. L’analisi è articolata in tre sezioni: i disamina della evoluzione storica del concetto di ossidoriduzione; ii analisi dei modelli redox e del loro campo di validità; iii discussione di alcuni aspetti epistemologici inerenti i processi redox che sono rilevanti per la didattica della chimica.

  18. Methods for using redox liposome biosensors

    Science.gov (United States)

    Cheng, Quan; Stevens, Raymond C.

    2002-01-01

    The present invention provides methods and compositions for detecting the presence of biologically-important analytes by using redox liposome biosensors. In particular, the present invention provides liposome/sol-gel electrodes suitable for the detection of a wide variety of organic molecules, including but not limited to bacterial toxins.

  19. Redox regulation in cancer stem cells

    Science.gov (United States)

    Reactive oxygen species (ROS) and ROS-dependent (redox regulation) signaling pathways and transcriptional activities are thought to be critical in stem cell self-renewal and differentiation during growth and organogenesis. Aberrant ROS burst and dysregulation of those ROS-dependent cellular processe...

  20. Metathetical Redox Reaction of (Diacetoxyiodoarenes and Iodoarenes

    Directory of Open Access Journals (Sweden)

    Antoine Jobin-Des Lauriers

    2015-12-01

    Full Text Available The oxidation of iodoarenes is central to the field of hypervalent iodine chemistry. It was found that the metathetical redox reaction between (diacetoxyiodoarenes and iodoarenes is possible in the presence of a catalytic amount of Lewis acid. This discovery opens a new strategy to access (diacetoxyiodoarenes. A computational study is provided to rationalize the results observed.

  1. Redox regulation of transient receptor potential channels.

    OpenAIRE

    2014-01-01

    Abstract Significance: Environmental and endogenous reactive species such as reactive oxygen species (ROS), reactive nitrogen species (RNS), and other electrophiles are not only known to exert toxic effects on organisms, but are also emerging as molecules that mediate cell signaling responses. However, the mechanisms underlying this cellular redox signaling by reactive species remains largely uncharacterized.

  2. Redox Transformations of Mercury in Wetlands

    Science.gov (United States)

    Amyot, M.

    2007-12-01

    Wetlands are valued for their high biodiversity and for their ecosystem services. However, we still have a poor understanding of their role in the redox transformation of contaminants such as mercury. We first propose a brief overview of past studies conducted on wetlands from different latitudes. In most instances, photochemical processes are determinant in the upper portion of the water column. At the sediment/water interface, evidence is currently supporting a significant contribution of bacterial communities, as promoters of Hg(II) reduction, particularly in the presence of anoxia. A multi-year study was recently conducted on Hg redox cycling in a fluvial wetland of the St. Lawrence River, where wetland restoration could have unintended consequences. In addition to photochemistry and bacterial reduction, Hg redox cycling was affected by epiphytes living on macrophytes, through adsorption/absorption processes. Redox studies such as this one have been historically seen as having implication for water/air flux studies, since Hg(0) is volatile. We here also discuss the potential bioavailability of Hg(0) towards bacteria. An emerging axis of our wetland research effort deals with beaver dams, which are in expansion and shown to produce high levels of methylHg

  3. Bimetallic redox synergy in oxidative palladium catalysis.

    Science.gov (United States)

    Powers, David C; Ritter, Tobias

    2012-06-19

    Polynuclear transition metal complexes, which are embedded in the active sites of many metalloenzymes, are responsible for effecting a diverse array of oxidation reactions in nature. The range of chemical transformations remains unparalleled in the laboratory. With few noteworthy exceptions, chemists have primarily focused on mononuclear transition metal complexes in developing homogeneous catalysis. Our group is interested in the development of carbon-heteroatom bond-forming reactions, with a particular focus on identifying reactions that can be applied to the synthesis of complex molecules. In this context, we have hypothesized that bimetallic redox chemistry, in which two metals participate synergistically, may lower the activation barriers to redox transformations relevant to catalysis. In this Account, we discuss redox chemistry of binuclear Pd complexes and examine the role of binuclear intermediates in Pd-catalyzed oxidation reactions. Stoichiometric organometallic studies of the oxidation of binuclear Pd(II) complexes to binuclear Pd(III) complexes and subsequent C-X reductive elimination from the resulting binuclear Pd(III) complexes have confirmed the viability of C-X bond-forming reactions mediated by binuclear Pd(III) complexes. Metal-metal bond formation, which proceeds concurrently with oxidation of binuclear Pd(II) complexes, can lower the activation barrier for oxidation. We also discuss experimental and theoretical work that suggests that C-X reductive elimination is also facilitated by redox cooperation of both metals during reductive elimination. The effect of ligand modification on the structure and reactivity of binuclear Pd(III) complexes will be presented in light of the impact that ligand structure can exert on the structure and reactivity of binuclear Pd(III) complexes. Historically, oxidation reactions similar to those discussed here have been proposed to proceed via mononuclear Pd(IV) intermediates, and the hypothesis of mononuclear Pd

  4. Reciprocal regulation as a source of ultrasensitivity in two-component systems with a bifunctional sensor kinase.

    Directory of Open Access Journals (Sweden)

    Ronny Straube

    2014-05-01

    Full Text Available Two-component signal transduction systems, where the phosphorylation state of a regulator protein is modulated by a sensor kinase, are common in bacteria and other microbes. In many of these systems, the sensor kinase is bifunctional catalyzing both, the phosphorylation and the dephosphorylation of the regulator protein in response to input signals. Previous studies have shown that systems with a bifunctional enzyme can adjust the phosphorylation level of the regulator protein independently of the total protein concentrations--a property known as concentration robustness. Here, I argue that two-component systems with a bifunctional enzyme may also exhibit ultrasensitivity if the input signal reciprocally affects multiple activities of the sensor kinase. To this end, I consider the case where an allosteric effector inhibits autophosphorylation and, concomitantly, activates the enzyme's phosphatase activity, as observed experimentally in the PhoQ/PhoP and NRII/NRI systems. A theoretical analysis reveals two operating regimes under steady state conditions depending on the effector affinity: If the affinity is low the system produces a graded response with respect to input signals and exhibits stimulus-dependent concentration robustness--consistent with previous experiments. In contrast, a high-affinity effector may generate ultrasensitivity by a similar mechanism as phosphorylation-dephosphorylation cycles with distinct converter enzymes. The occurrence of ultrasensitivity requires saturation of the sensor kinase's phosphatase activity, but is restricted to low effector concentrations, which suggests that this mode of operation might be employed for the detection and amplification of low abundant input signals. Interestingly, the same mechanism also applies to covalent modification cycles with a bifunctional converter enzyme, which suggests that reciprocal regulation, as a mechanism to generate ultrasensitivity, is not restricted to two

  5. Redox proteomics for the assessment of redox-related posttranslational regulation in plants.

    Science.gov (United States)

    Mock, Hans-Peter; Dietz, Karl-Josef

    2016-08-01

    The methodological developments of in vivo and in vitro protein labeling and subsequent detection enable sensitive and specific detection of redox modifications. Such methods are presently applied to diverse cells and tissues, subproteomes and developmental as well as environmental conditions. The chloroplast proteome is particularly suitable for such kind of studies, because redox regulation of chloroplast proteins is well established, many plastid proteins are abundant, redox network components have been inventoried in great depth, and functional consequences explored. Thus the repertoire of redox-related posttranslational modifications on the one hand side and their abundance on the other pose a challenge for the near future to understand their contribution to physiological regulation. The various posttranslational redox modifications are introduced, followed by a description of the available proteomics methods. The significance of the redox-related posttranslational modification is exemplarily worked out using established examples from photosynthesis. This article is part of a Special Issue entitled: Plant Proteomics--a bridge between fundamental processes and crop production, edited by Dr. Hans-Peter Mock.

  6. Oxygen electrode bifunctional electrocatalyst NiCo2O4 spinel

    Science.gov (United States)

    Fielder, William L.; Singer, Joseph

    1988-01-01

    A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.

  7. Oxygen electrode bifunctional electrocatalyst NiCo/sub 2/O/sub 4/ spinel

    Energy Technology Data Exchange (ETDEWEB)

    Fielder, W.L.; Singer, J.

    1988-09-01

    A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.

  8. Redox hydrogel based bienzyme electrode for L-glutamate monitoring.

    Science.gov (United States)

    Belay, A; Collins, A; Ruzgas, T; Kissinger, P T; Gorton, L; Csöregi, E

    1999-02-01

    Amperometric bienzyme electrodes based on coupled L-glutamate oxidase (GlOx) and horseradish peroxidase (HRP) were constructed for the direct monitoring of L-glutamate in a flow injection (FI)-system. The bienzyme electrodes were constructed by coating solid graphite rods with a premixed solution containing GlOx and HRP crosslinked with a redox polymer formed of poly(1-vinylimidazole) complexed with (osmium (4-4'-dimethylbpy)2 Cl)II/III. Poly(ethylene glycol) diglycidyl ether (PEGDGE) was used as the crosslinker and the modified electrodes were inserted as the working electrode in a conventional three electrode flow through amperometric cell operated at -0.05 V versus Ag¿AgCl (0.1 M KCl). The bienzyme electrode was optimized with regard to wire composition, Os-loading of the wires, enzyme ratios, coating procedure, flow rate, effect of poly(ethyleneimine) addition, etc. The optimized electrodes were characterized by a sensitivity of 88.36 +/- 0.14 microA mM(-1) cm(-2), a detection limit of 0.3 microM (calculated as three times the signal-to-noise ratio), a response time of less than 10 s and responded linearly between 0.3 and 250 microM (linear regression coefficient = 0.999) with an operational stability of only 3% sensitivity loss during 8 h of continuous FI operation at a sample throughput of 30 injections h(-1).

  9. Engineering artificial redox chains by molecular 'Lego'.

    Science.gov (United States)

    Sadeghi, S J; Meharenna, Y T; Fantuzzi, A; Valetti, F; Gilardi, G

    2000-01-01

    This work reports on a novel approach for building artificial redox chains: the molecular 'Lego' approach. This exploits the scaffold of natural redox proteins by fusing together functional protein modules with the desired properties. The molecular 'Lego' mimics the natural molecular evolution that proceeded by modular assembly of genes/DNA segments. Non-physiological electron transfer partners, flavodoxin (fld) and cytochrome c553 (c553) from Desulfovibrio vulgaris and the haem domain of P450 BM3 (BMP) from Bacillus megaterium have been used as building blocks in different combinations to build artificial redox chains. The kinetic characterization of the electron transfer (ET) between the separate building blocks has been carried out. Under pseudo-first order conditions, a limiting ET rate, klim, of 0.48 +/- 0.05 s-1 and 43.77 +/- 2.18 s-1 and an apparent binding constant, Kapp, of 21 +/- 6 microM and 1.23 +/- 0.32 microM have been found for the fld/c553 and fld/BMP redox pairs, respectively. These results show that fld can be used as a module for transferring electrons to c553 and BMP. A 3D model of the fld/c553 and fld/BMP complexes was used to guide the construction of covalently linked assemblies via engineered disulfide bridges or by fusion of the relevant genes via an engineered loop. The first approach led to the construction, expression and characterization of the S35C and S64C mutants of fld and M23C and G51C mutants of c553. Although the redox potentials of the separate mutants were found to be the same as those of recombinant wild type proteins (-408 mV for the semiquinone/hydroquinone couple of fld and +32 mV for the c553), the c553 homo-dimers M23C-M23C and G51C-G51C were found to have redox potentials of +88 and +105 mV, respectively. These differences have been analysed in terms of exposure of the haem cofactors to the solvent, and these lead to some interesting questions on the redox potentials of the transient redox complexes in physiological

  10. Impact of Sediment-Bound Iron on Redox Buffering in a Landfill Leachate Polluted Aquifer (Vejen, Denmark)

    DEFF Research Database (Denmark)

    Heron, Gorm; Christensen, Thomas Højlund

    1995-01-01

    Sediments sampled along a central flow line of the leachate pollution plume at the Vejen Landfill, Denmark, were characterized in detail with respect to the forms and pools of Fe(ll) and Fe(lll). After 15 yr of leaching, redox reactions had diminished the pool of iron(ll1) oxides and hydroxides...

  11. Redox regulation of Janus kinase: The elephant in the room.

    Science.gov (United States)

    Duhé, Roy J

    2013-10-01

    The redox regulation of Janus kinases (JAKs) is a complex subject. Due to other redox-sensitive kinases in the kinome, redox-sensitive phosphatases, and cellular antioxidant systems and reactive oxygen species (ROS) production systems, the net biological outcomes of oxidative stress on JAK-dependent signal transduction vary according to the specific biological system examined. This review begins with a discussion of the biochemical evidence for a cysteine-based redox switch in the catalytic domain of JAKs, proceeds to consider direct and indirect regulatory mechanisms involved in biological experiments, and ends with a discussion of the role(s) of redox regulation of JAKs in various diseases.

  12. Experimental verifications on chemical carcinogenesis, a bifunctional alkylation between DNA interstrands

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    It is evidenced by the filter elution method that two carcinogenic aromatic hydrocarbons, benzo[a]pyrene and dibenzo[a,h]anthracene, two carcinogenic metal salts, beryllium chloride and cadmium chloride, four carcinogenic aromatic amines, 2-aminofluorene, β-naphthylamine, 4-aminobiphenyl and benzidine, can all induce DNA interstrand and DNA-protein cross-link in L1210 culture. However, under the same condition, the corresponding non-carcinogenic compounds, including benzo[k]fluorancene, anthracene, magnesium chloride, zinc chloride, a -naphthylamine, 2-aminobiphenyl and m-toluidine, cannot produce any cross-link adducts. All these results are consistent with the di-region theory that carcinogens are bio-bifunctional alkylation agents. This method can also be used to discriminate carcinogens and non-carcinogens.

  13. The fabrication of a bifunctional oxygen electrode without carbon components for alkaline secondary batteries

    Science.gov (United States)

    Price, Stephen W. T.; Thompson, Stephen J.; Li, Xiaohong; Gorman, Scott F.; Pletcher, Derek; Russell, Andrea E.; Walsh, Frank C.; Wills, Richard G. A.

    2014-08-01

    The fabrication of a gas diffusion electrode (GDE) without carbon components is described. It is therefore suitable for use as a bifunctional oxygen electrode in alkaline secondary batteries. The electrode is fabricated in two stages (a) the formation of a PTFE-bonded nickel powder layer on a nickel foam substrate and (b) the deposition of a NiCo2O4 spinel electrocatalyst layer by dip coating in a nitrate solution and thermal decomposition. The influence of modifications to the procedure on the performance of the GDEs in 8 M NaOH at 333 K is described. The GDEs can support current densities up to 100 mA cm-2 with state-of-the-art overpotentials for both oxygen evolution and oxygen reduction. Stable performance during >50 successive, 1 h oxygen reduction/evolution cycles at a current density of 50 mA cm-2 has been achieved.

  14. Synthesis of acrylic and allylic bifunctional cross-linking monomers derived from PET waste

    Science.gov (United States)

    Cruz-Aguilar, A.; Herrera-González, A. M.; Vázquez-García, R. A.; Navarro-Rodríguez, D.; Coreño, J.

    2013-06-01

    An acrylic and two novel allylic monomers synthesized from bis (hydroxyethyl) terephthalate, BHET, are reported. This was obtained by glycolysis of post-consumer PET with boiling ethylene glycol. The bifunctional monomer bis(2-(acryloyloxy)ethyl) terephthalate was obtained from acryloyl chloride, while the allylic monomers 2-(((allyloxi)carbonyl)oxy) ethyl (2-hydroxyethyl) terephthalate and bis(2-(((allyloxi)carbonyl)oxy)ethyl) terephthalate, from allyl chloroformate. Cross-linking was studied in bulk polymerization using two different thermal initiators. Monomers were analyzed by means of 1H NMR and the cross-linked polymers by infrared spectroscopy. Gel content higher than 90% was obtained for the acrylic monomer. In the case of the mixture of the allylic monomers, the cross-linked polymer was 80 % using BPO initiator, being this mixture 24 times less reactive than the acrylic monomer.

  15. Mono- and bi-functional arenethiols as surfactants for gold nanoparticles: synthesis and characterization

    Directory of Open Access Journals (Sweden)

    Fratoddi Ilaria

    2011-01-01

    Full Text Available Abstract Stable gold nanoparticles stabilized by different mono and bi-functional arenethiols, namely, benzylthiol and 1,4-benzenedimethanethiol, have been prepared by using a modified Brust's two-phase synthesis. The size, shape, and crystalline structure of the gold nanoparticles have been determined by high-resolution electron microscopy and full-pattern X-ray powder diffraction analyses. Nanocrystals diameters have been tuned in the range 2 ÷ 9 nm by a proper variation of Au/S molar ratio. The chemical composition of gold nanoparticles and their interaction with thiols have been investigated by X-ray photoelectron spectroscopy. In particular, the formation of networks has been observed with interconnected gold nanoparticles containing 1,4-benzenedimethanethiol as ligand.

  16. Bi-functional biobased packing of the cassava starch, glycerol, licuri nanocellulose and red propolis.

    Directory of Open Access Journals (Sweden)

    Samantha Serra Costa

    Full Text Available The aim of this study was to characterize and determine the bi-functional efficacy of active packaging films produced with starch (4% and glycerol (1.0%, reinforced with cellulose nanocrystals (0-1% and activated with alcoholic extracts of red propolis (0.4 to 1.0%. The cellulose nanocrystals used in this study were extracted from licuri leaves. The films were characterized using moisture, water-activity analyses and water vapor-permeability tests and were tested regarding their total phenolic compounds and mechanical properties. The antimicrobial and antioxidant efficacy of the films were evaluated by monitoring the use of the active films for packaging cheese curds and butter, respectively. The cellulose nanocrystals increased the mechanical strength of the films and reduced the water permeability and water activity. The active film had an antimicrobial effect on coagulase-positive staphylococci in cheese curds and reduced the oxidation of butter during storage.

  17. Aldo-X Bifunctional Building Blocks for the Synthesis of Heterocycles.

    Science.gov (United States)

    Ravichandiran, Palanisamy; Lai, Bingbing; Gu, Yanlong

    2017-02-01

    Compounds containing oxygen, nitrogen, or sulfur atoms inside the rings are attracting much attention and interest due to their biological importance. In recent years, several methods for the synthesis of such molecules have been reported by using aldo-X bifunctional building blocks (AXB3 s) as substrates; these are a wide class of organic molecules that contain at least two reactive sites, among them, one aldehyde, acetal, or semiacetal group was involved. Because of the multiple reactivities, AXB3 s are widely used in the one-pot synthesis of biologically important heterocycles. This review summarizes the synthesis of important heterocycles by using AXB3 s as pivotal components in establishing multicomponent reactions, tandem reactions, and so forth. In many cases, the established reaction systems with AXB3 s were characterized by some green properties, such as easy access to the substrate, mild and environmentally benign conditions, and wide scope of the substrate.

  18. Development and computational modeling of novel bifunctional organophosphorus extractants for lanthanoid separation

    Energy Technology Data Exchange (ETDEWEB)

    Goto, Masahiro; Matsumoto, Satoshi; Uezu, Kazuya; Nakashio, Fumiyuki [Kyushu Univ., Hakozaki, Fukuoka (Japan). Dept. of Chemical Science and Technology; Yoshizuka, Kazuharu; Inoue, Katsutoshi [Saga Univ., Honjyo, Saga (Japan). Dept. of Applied Chemistry

    1999-08-01

    Novel organophosphorus extractants, which have two functional groups in the molecular structure, have been developed for the separation of lanthanoids using the liquid-liquid extraction technique. The separation efficiency and extractability of the novel extractants were investigated for nine lanthanoids. These bifunctional extractants have an extremely high extractability to all the lanthanoids compared to those of commercially available organophosphorus extractants. Two isomers having an identical chemical formulation show significantly different behaviors in lanthanoid extraction. This means that the extraction and separation abilities are quite sensitive to the structure of the spacer connecting the two functional groups. The authors also discuss the experimental results with a computational modeling by means of molecular mechanics and semiempirical molecular orbital methods. The novel molecular mechanics (MM) calculation program MOMEC enables them to analyze the stable conformation of a series of lanthanoid complexes. The calculation suggests that the structural effect of the spacer is one of the decisive factors for enhancing selectivity and extractability in lanthanoid extraction.

  19. Bi-functional biobased packing of the cassava starch, glycerol, licuri nanocellulose and red propolis.

    Science.gov (United States)

    Costa, Samantha Serra; Druzian, Janice Izabel; Machado, Bruna Aparecida Souza; de Souza, Carolina Oliveira; Guimarães, Alaíse Gil

    2014-01-01

    The aim of this study was to characterize and determine the bi-functional efficacy of active packaging films produced with starch (4%) and glycerol (1.0%), reinforced with cellulose nanocrystals (0-1%) and activated with alcoholic extracts of red propolis (0.4 to 1.0%). The cellulose nanocrystals used in this study were extracted from licuri leaves. The films were characterized using moisture, water-activity analyses and water vapor-permeability tests and were tested regarding their total phenolic compounds and mechanical properties. The antimicrobial and antioxidant efficacy of the films were evaluated by monitoring the use of the active films for packaging cheese curds and butter, respectively. The cellulose nanocrystals increased the mechanical strength of the films and reduced the water permeability and water activity. The active film had an antimicrobial effect on coagulase-positive staphylococci in cheese curds and reduced the oxidation of butter during storage.

  20. Hydroisomerization of Ethylbenzene on Mordenite-Based Bifunctional Catalysts with Different Platinum Contents

    Directory of Open Access Journals (Sweden)

    Fernandes L.D.

    1998-01-01

    Full Text Available A commercial Na-mordenite sample underwent ion exchange with HCl. The ion-exchanged sample was sequentially submitted to hydrothermal treatments at 823, 873 and 923 K, each followed by acid leaching of the extraframework alumina (EFAL generated. Six mordenite samples, presenting different framework and extraframework compositions, were obtained. These samples were used to prepare bifunctional catalysts by mixing them with Pt/Al2O3 in different proportions. The generated samples presented distinct platinum contents and were tested in the hydroisomerization reaction of ethylbenzene. A maximum xylene selectivity at about 0.45 wt% of platinum was observed. Normally, the total activity increased as the platinum content increased; this effect was more pronounced in the samples which presented lower mesoporosity. The most dealuminated sample, which presented a high mesoporosity, did not show any change in activity with the increase in platinum content.

  1. Bifunctional enzyme FBPase/SBPase is essential for photoautotrophic growth in cyanobacterium Synechocystis sp. PCC 6803

    Institute of Scientific and Technical Information of China (English)

    Chunlan Yan; Xudong Xu

    2008-01-01

    From a random insertion mutant library of Synechocystis sp. PCC 6803, a mutant defective in photoautotrophic growth was obtained. The interrupted gene was identified to be sir2094 (fbpl), which encodes the fructose-l,6-biphosphatase (FBPase)/sedoheptu-lose-1,7-biphosphatase (SBPase) bifunctional enzyme (F-I). Two other independently constructed slr2094 mutants showed an identical phenotype. The FBPase activity was found to be virtually lacking in an sir2094 mutant, which was sensitive to light under mixotrophic growth conditions. These results indicate that sir2094 is the only active FBPase-encoding gene in this cyanobacterium. Inactivation of photosystem 11 by interrupting psbB in sir2094 mutant alleviated the sensitiveness to light. This report provides the direct genetic evi-dence for the essential role of F-I in the photosynthesis of Synechocystis sp. PCC 6803.

  2. New Tailor-Made Alkyl-Aldehyde Bifunctional Supports for Lipase Immobilization

    Directory of Open Access Journals (Sweden)

    Robson Carlos Alnoch

    2016-11-01

    Full Text Available Immobilized and stabilized lipases are important biocatalytic tools. In this paper, different tailor-made bifunctional supports were prepared for the immobilization of a new metagenomic lipase (LipC12. The new supports contained hydrophobic groups (different alkyl groups to promote interfacial adsorption of the lipase and aldehyde groups to react covalently with the amino groups of side chains of the adsorbed lipase. The best catalyst was 3.5-fold more active and 5000-fold more stable than the soluble enzyme. It was successfully used in the regioselective deacetylation of peracetylated d-glucal. The PEGylated immobilized lipase showed high regioselectivity, producing high yields of the C-3 monodeacetylated product at pH 5.0 and 4 °C.

  3. Stable expression of a bifunctional diterpene synthase in the chloroplast of Chlamydomonas reinhardtii

    DEFF Research Database (Denmark)

    Zedler, Julie A Z; Gangl, Doris; Hamberger, Björn Robert;

    2015-01-01

    Chlamydomonas reinhardtii has been shown to hold significant promise as a production platform for recombinant proteins, but transformation of the nuclear genome is still a non-trivial process due to random gene insertion and frequent silencing. Insertion of transgenes into the chloroplasts...... is an alternative strategy, and we report here the stable expression of a large (91 kDa) protein in the chloroplast using a recently developed low-cost transformation protocol. Moreover, selection of transformants is based on restoration of prototrophy using an endogenous gene (psbH) as the marker, thereby allowing...... the generation of transgenic lines without the use of antibiotic-resistance genes. Here, we have expressed a bifunctional diterpene synthase in C. reinhardtii chloroplasts. Homoplasmic transformants were obtained with the expressed enzyme accounting for 3.7 % of total soluble protein. The enzyme was purified...

  4. On the molecular basis of D-bifunctional protein deficiency type III.

    Directory of Open Access Journals (Sweden)

    Maija L Mehtälä

    Full Text Available Molecular basis of D-bifunctional protein (D-BP deficiency was studied with wild type and five disease-causing variants of 3R-hydroxyacyl-CoA dehydrogenase fragment of the human MFE-2 (multifunctional enzyme type 2 protein. Complementation analysis in vivo in yeast and in vitro enzyme kinetic and stability determinants as well as in silico stability and structural fluctuation calculations were correlated with clinical data of known patients. Despite variations not affecting the catalytic residues, enzyme kinetic performance (K(m, V(max and k(cat of the recombinant protein variants were compromised to a varying extent and this can be judged as the direct molecular cause for D-BP deficiency. Protein stability plays an additional role in producing non-functionality of MFE-2 in case structural variations affect cofactor or substrate binding sites. Structure-function considerations of the variant proteins matched well with the available data of the patients.

  5. Cage-like bifunctional chelators, copper-64 radiopharmaceuticals and PET imaging using the same

    Energy Technology Data Exchange (ETDEWEB)

    Conti, Peter S.; Cai, Hancheng; Li, Zibo; Liu, Shuanglong

    2016-08-02

    Disclosed is a class of versatile Sarcophagine based bifunctional chelators (BFCs) containing a hexa-aza cage for labeling with metals having either imaging, therapeutic or contrast applications radiolabeling and one or more linkers (A) and (B). The compounds have the general formula ##STR00001## where A is a functional group selected from group consisting of an amine, a carboxylic acid, an ester, a carbonyl, a thiol, an azide and an alkene, and B is a functional group selected from the group consisting of hydrogen, an amine, a carboxylic acid, and ester, a carbonyl, a thiol, an azide and an alkene. Also disclosed are conjugate of the BFC and a targeting moiety, which may be a peptide or antibody. Also disclosed are metal complexes of the BFC/targeting moiety conjugates that are useful as radiopharmaceuticals, imaging agents or contrast agents.

  6. Hydrogen bonding in transient bifunctional hypervalent radicals by neutralization-reionization mass spectrometry.

    Science.gov (United States)

    Shaffer, S A; Tureček, F

    1995-11-01

    Neutralization-reionization mass spectrometry is used to generate hypervalent 9-N-4 (ammonium) and 9-O-3 (oxonium) radicals derived from protonated α,ω-bis-(dimethylamino)alkanes and α,ω-dimethoxyalkanes, which exist as cyclic hydrogen-bonded structures in the gas phase. Collisional neutralization with dimethyl disulfide, trimethylamine, and xenon of the hydrogen-bonded onium cations followed by reionization with oxygen results in complete dissociation. Bond cleavages at the hypervalent nitrogen atoms are found to follow the order CH2-N>CH3-N>N-H, which differs from that in the monofunctional hydrogen-n-heptyldimethylammonium radical, which gives CH2-N>N-H>CH3-N. No overall stabilization through hydrogen bonding of the bifunctional hypervalent ammonium and oxonium radicals is observed. Subtle effects of ring size are found that tend to stabilize large ring structures and are attributed to intramolecular hydrogen bonding.

  7. Recent Development of Bifunctional Small Molecules to Study Metal-Amyloid-β Species in Alzheimer's Disease.

    Science.gov (United States)

    Braymer, Joseph J; Detoma, Alaina S; Choi, Jung-Suk; Ko, Kristin S; Lim, Mi Hee

    2010-12-08

    Alzheimer's disease (AD) is a multifactorial neurodegenerative disease related to the deposition of aggregated amyloid-β (Aβ) peptides in the brain. It has been proposed that metal ion dyshomeostasis and miscompartmentalization contribute to AD progression, especially as metal ions (e.g., Cu(II) and Zn(II)) found in Aβ plaques of the diseased brain can bind to Aβ and be linked to aggregation and neurotoxicity. The role of metal ions in AD pathogenesis, however, is uncertain. To accelerate understanding in this area and contribute to therapeutic development, recent efforts to devise suitable chemical reagents that can target metal ions associated with Aβ have been made using rational structure-based design that combines two functions (metal chelation and Aβ interaction) in the same molecule. This paper presents bifunctional compounds developed by two different design strategies (linkage or incorporation) and discusses progress in their applications as chemical tools and/or potential therapeutics.

  8. Bifunctional Nanoparticle-SILP Catalysts (NPs@SILP) for the Selective Deoxygenation of Biomass Substrates

    Energy Technology Data Exchange (ETDEWEB)

    Luska, Kylie L. [RWTH Aachen Univ. (Germany); Julis, Jennifer [RWTH Aachen Univ. (Germany); Evonik Industries AG, Marl (Germany); Stavitski, Eli [Brookhaven National Lab. (BNL), Upton, NY (United States); Zakharov, Dmitri N. [Brookhaven National Lab. (BNL), Upton, NY (United States); Adams, Alina [RWTH Aachen Univ. (Germany); Leitner, Walter [RWTH Aachen Univ. (Germany); Max Planck Inst. for Coal Research, Ruhr (Germany)

    2014-08-27

    We immobilized ruthenium nanoparticles onto an acidic supported ionic liquid phase (RuNPs@SILP) in the development of bifunctional catalysts for the selective deoxygenation of biomass substrates. RuNPs@SILPs possessed high catalytic activities, selectivities and recyclabilities in the hydrogenolytic deoxygenation and ring opening of C8- and C9-substrates derived from furfural or 5-hydroxymethylfurfural and acetone. When we tailor the acidity of the SILP through the ionic liquid loading provided a molecular parameter by which the catalytic activity and selectivity of the RuNPs@SILPs were controlled to provide a flexible catalyst system toward the formation of different classes of value-added products: cyclic ethers, primary alcohols or aliphatic ethers.

  9. Peroxiredoxin-2 and STAT3 form a redox relay for H2O2 signaling.

    Science.gov (United States)

    Sobotta, Mirko C; Liou, Willy; Stöcker, Sarah; Talwar, Deepti; Oehler, Michael; Ruppert, Thomas; Scharf, Annette N D; Dick, Tobias P

    2015-01-01

    Hydrogen peroxide (H(2)O(2)) acts as a signaling messenger by oxidatively modifying distinct cysteinyl thiols in distinct target proteins. However, it remains unclear how redox-regulated proteins, which often have low intrinsic reactivity towards H(2)O(2) (k(app) ∼1-10 M(-1) s(-1)), can be specifically and efficiently oxidized by H(2)O(2). Moreover, cellular thiol peroxidases, which are highly abundant and efficient H(2)O(2) scavengers, should effectively eliminate virtually all of the H(2)O(2) produced in the cell. Here, we show that the thiol peroxidase peroxiredoxin-2 (Prx2), one of the most H(2)O(2)-reactive proteins in the cell (k(app) ∼10(7)-10(8) M(-1) s(-1)), acts as a H(2)O(2) signal receptor and transmitter in transcription factor redox regulation. Prx2 forms a redox relay with the transcription factor STAT3 in which oxidative equivalents flow from Prx2 to STAT3. The redox relay generates disulfide-linked STAT3 oligomers with attenuated transcriptional activity. Cytokine-induced STAT3 signaling is accompanied by Prx2 and STAT3 oxidation and is modulated by Prx2 expression levels.

  10. Investigation of the redox chemistry of anthraquinone derivatives using density functional theory.

    Science.gov (United States)

    Bachman, Jonathan E; Curtiss, Larry A; Assary, Rajeev S

    2014-09-25

    Application of density functional calculations to compute electrochemical properties such as redox windows, effect of substitution by electron donating and electron withdrawing groups on redox windows, and solvation free energies for ∼50 anthraquinone (AQ) derivatives are presented because of their potential as anolytes in all-organic redox flow batteries. Computations suggest that lithium ions can increase (by ∼0.4 V) the reduction potential of anthraquinone due to the lithium ion pairing by forming a Lewis base-Lewis acid complex. To design new redox active species, the substitution by electron donating groups is essential to improve the reduction window of AQ with adequate oxidative stability. For instance, a complete methylation of AQ can improve its reduction window by ∼0.4 V. The quantum chemical studies of the ∼50 AQ derivatives are used to derive a relationship that connects the computed LUMO energy and the reduction potential that can be applied as a descriptor for screening thousands of AQ derivatives. Our computations also suggest that incorporating oxy-methyl dioxolane substituents in the AQ framework can increase its interaction with nonaqueous solvent and improve its solubility. Thermochemical calculations for likely bond breaking decomposition reactions of unsubstituted AQ anions suggest that the dianions are relatively stable in the solution. These studies provide an ideal platform to perform further combined experimental and theoretical studies to understand the electrochemical reversibility and solubility of new quinone molecules as energy storage materials.

  11. AmpH, a bifunctional DD-endopeptidase and DD-carboxypeptidase of Escherichia coli.

    Science.gov (United States)

    González-Leiza, Silvia M; de Pedro, Miguel A; Ayala, Juan A

    2011-12-01

    In Escherichia coli, low-molecular-mass penicillin-binding proteins (LMM PBPs) are important for correct cell morphogenesis. These enzymes display DD-carboxypeptidase and/or dd-endopeptidase activities associated with maturation and remodeling of peptidoglycan (PG). AmpH has been classified as an AmpH-type class C LMM PBP, a group closely related to AmpC β-lactamases. AmpH has been associated with PG recycling, although its enzymatic activity remained uncharacterized until now. Construction and purification of His-tagged AmpH from E. coli permitted a detailed study of its enzymatic properties. The N-terminal export signal of AmpH is processed, but the protein remains membrane associated. The PBP nature of AmpH was demonstrated by its ability to bind the β-lactams Bocillin FL (a fluorescent penicillin) and cefmetazole. In vitro assays with AmpH and specific muropeptides demonstrated that AmpH is a bifunctional DD-endopeptidase and DD-carboxypeptidase. Indeed, the enzyme cleaved the cross-linked dimers tetrapentapeptide (D45) and tetratetrapeptide (D44) with efficiencies (k(cat)/K(m)) of 1,200 M(-1) s(-1) and 670 M(-1) s(-1), respectively, and removed the terminal D-alanine from muropeptides with a C-terminal D-Ala-D-Ala dipeptide. Both DD-peptidase activities were inhibited by 40 μM cefmetazole. AmpH also displayed a weak β-lactamase activity for nitrocefin of 1.4 × 10(-3) nmol/μg protein/min, 1/1,000 the rate obtained for AmpC under the same conditions. AmpH was also active on purified sacculi, exhibiting the bifunctional character that was seen with pure muropeptides. The wide substrate spectrum of the DD-peptidase activities associated with AmpH supports a role for this protein in PG remodeling or recycling.

  12. Bifunctional Effect of Human IFN-γ on Cultured Human Fibroblasts from Tenon‘s Capsule

    Institute of Scientific and Technical Information of China (English)

    YanGuo; JianGe; 等

    2002-01-01

    Purpose:To study the effect of human IFN-γ on in ivtro cultured human fibroblasts from Tenon's capsule.Materials and methods:The effect of different concentrations of human IFN-γand mitomycin-C (MMC),5-fluorouracil(5-Fu) on cultured human Tenon's capsule fibroblasts(HTCF) was measured using a MTT[3-(4,5-dimethylthiazo-2-yI)]-2,5-diphenylterazolium bromide;Thiazolyl blue) colorimetric assay.The results were analyzed using ANOVA of the statistical package for social sciences (SPSS) 9.0 version.The difference was considered to be significant if P<0.05.Results:The effects of MMC and 5-Fu on the growth of HTCF were negative,while the effects of IFN-γon the growth of HTCF were both negative(102-104 units/ml in two experiments)and positive(106,105,10 units /ml in two experiments).The inhibition rate of MMC ranged from 5.73% to 46.9% ,which was similar to the inhibition rate of 5-Fu ranged from 12.49% to 38.92%(P=0.351).The inhibition rate of IFN-γ in two experiments was smaller than MMC and 5-Fu (P<0.05).Conclusion: IFN-γ has bifunctional effect (both enhancement and inhibition)on proliferation of cultured HTCF.The antiproliferative effect of IFN-γ was weaker than MMC and 5-Fu.Further study has to be carried out to document theinhibition of scar formation of filtration bleb by IFN-γ and the molecular mechanisms of its bifunctional effect on HTCF proliferation.Eye Science 2000;16:43-47.

  13. Bifunctional Effect of Human IFN-γon Cultured Human Fibroblasts from Tenon's Capsule

    Institute of Scientific and Technical Information of China (English)

    Yan Guo; Jian Ge; Haiquan Liu; Yanyan Li; Jianliang Zheng; Xiangkun Huang; Yuqing Lan

    2000-01-01

    Purpose: To study the effect of human IFN-γ on in vitro cultured human fibroblasts from Tenon's capsuleMaterials and methods: The effect of different concentrations of human IFN-γ and mitomycin-C (MMC), 5-fluorouracil (5-Fu) on cultured human Tenon's capsule fibroblasts (HTCF) was measured using a MIT [3-(4, 5-dimethylthiazo-2-yl)] -2,5-diphenyltetrazolium bromide; Thiazolyl blue) colorimetric assay. The results were analyzed using ANOVA of the statistical package for social sciences (SPSS) 9.0version. The difference was considered to be significant if P < 0. 05.Results: The effects of MMC and 5-Fu on the growth of HTCF were negative, while the effects of IFN-γ on the growth of HTCF were both negative (102 ~ l04 units/ml in two experiments) and positive (106, 105, 10 units/ml in two experiments) . The inhibition rate of MMC ranged from 5.73% to 46. 9%, which was similar to the inhibition rate of 5-Fu ranged from 12.49% to 38.92% ( P= 0. 351) . The inhibition rate of IFN-γ in two experiments was smaller than MMC and 5-Fu ( P < 0.05).Conclusion: IFN-γ has bifunctional effect (both enhancement and inhibition) on proliferation of cultured HTCF. The antiproliferative effect of IFN-γ was weaker than MMC and 5-Fu. Further study has to be carried out to document the inhibition of scar formation of filtration bleb by IFN-γ and the molecular mechanisms of its bifunctional effect on HTCF proliferation. Eye Science 2000; 16: 43~ 47.

  14. Preparation and Characterization of Silica-Coated Magnetic–Fluorescent Bifunctional Microspheres

    Directory of Open Access Journals (Sweden)

    Xiao Qi

    2009-01-01

    Full Text Available Abstract Bifunctional magnetic–fluorescent composite nanoparticles (MPQDs with Fe3O4MPs and Mn:ZnS/ZnS core–shell quantum dots (QDs encapsulated in silica spheres were synthesized through reverse microemulsion method and characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, vibration sample magnetometer, and photoluminescence (PL spectra. Our strategy could offer the following features: (1 the formation of Mn:ZnS/ZnS core/shell QDs resulted in enhancement of the PL intensity with respect to that of bare Mn:ZnS nanocrystals due to the effective elimination of the surface defects; (2 the magnetic nanoparticles were coated with silica, in order to reduce any detrimental effects on the QD PL by the magnetic cores; and (3 both Fe3O4MPs and Mn:ZnS/ZnS core–shell QDs were encapsulated in silica spheres, and the obtained MPQDs became water soluble. The experimental conditions for the silica coating on the surface of Fe3O4nanoparticles, such as the ratio of water to surfactant (R, the amount of ammonia, and the amount of tetraethoxysilane, on the photoluminescence properties of MPQDs were studied. It was found that the silica coating on the surface of Fe3O4could effectively suppress the interaction between the Fe3O4and the QDs under the most optimal parameters, and the emission intensity of MPQDs showed a maximum. The bifunctional MPQDs prepared under the most optimal parameters have a typical diameter of 35 nm and a saturation magnetization of 4.35 emu/g at room temperature and exhibit strong photoluminescence intensity.

  15. Electrochemical formation of transparent nanostructured TiO2 film as an effective bifunctional layer for dye-sensitized solar cells.

    Science.gov (United States)

    Wu, Mao-Sung; Tsai, Chen-Hsiu; Wei, Tzu-Chien

    2011-03-14

    A bifunctional TiO(2) layer having an inner compact layer and an outer anchoring layer coated on fluorine-doped tin oxide (FTO) glass could reduce the charge recombination and interfacial contact resistance between FTO and the main TiO(2) layer; photoelectron conversion efficiency of cell was increased from 7.31 to 8.04% by incorporating the bifunctional layer.

  16. Bacterial biofilm formation versus mammalian cell growth on titanium-based mono- and bi-functional coating

    Directory of Open Access Journals (Sweden)

    G Subbiahdoss

    2010-05-01

    Full Text Available Biomaterials-associated-infections (BAI are serious complications in modern medicine. Although non-adhesive coatings, like polymer-brush coatings, have been shown to prevent bacterial adhesion, they do not support cell growth. Bi-functional coatings are supposed to prevent biofilm formation while supporting tissue integration. Here, bacterial and cellular responses to poly(ethylene glycol (PEG brush-coatings on titanium oxide presenting the integrin-active peptide RGD (arginine-glycine-aspartic acid (bioactive “PEG-RGD” were compared to mono-functional PEG brush-coatings (biopassive “PEG” and bare titanium oxide (TiO2 surfaces under flow. Staphylococcus epidermidis ATCC 35983 was deposited on the surfaces under a shear rate of 11 s-1 for 2 h followed by seeding of U2OS osteoblasts. Subsequently, both S. epidermidis and U2OS cells were grown simultaneously on the surfaces for 48 h under low shear (0.14 s-1. After 2 h, staphylococcal adhesion was reduced to 3.6±1.8 × 103 and 6.0±3.9 × 103 cm-2 on PEG and PEG-RGD coatings respectively, compared to 1.3±0.4 × 105 cm-2 for the TiO2 surface. When allowed to grow for 48 h, biofilms formed on all surfaces. However, biofilms detached from the PEG and PEG-RGD coatings when exposed to an elevated shear (5.6 s-1 U2OS cells neither adhered nor spread on PEG brush-coatings, regardless of the presence of biofilm. In contrast, in the presence of biofilm, U2OS cells adhered and spread on PEG-RGD coatings with a significantly higher surface coverage than on bare TiO2. The detachment of biofilm and the high cell surface coverage revealed the potential significance of PEG-RGD coatings in the context of the “race for the surface” between bacteria and mammalian cells.

  17. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Final technical progress report, September 12, 1991--December 11, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Klier, K.; Herman, R.G.; Deemer, M.; Richards-Babb, M.; Carr, T.

    1995-07-01

    The objective of this research was to investigate sulfur-resistant catalysts for the conversion of synthesis gas having H{sub 2}/CO {le} 1 into C{sub 1}--C{sub 4} alcohols, especially ethanol, by a highly selective and efficient pathway, while also promoting the water gas shift reaction (WGSR). The catalysts chosen are bifunctional, base-hydrogenation, sulfur-tolerant transition metal sulfides with heavy alkali, e.g. Cs{sup +}, promoter dispersed on their surfaces. The modes of activation of H{sub 2} and CO on MoS{sub 2} and alkali-doped MoS{sub 2} were considered, and computational analyses of the thermodynamic stability of transition metal sulfides and of the electronic structure of these sulfide catalysts were carried out. In the preparation of the cesium-promoted MoS{sub 2} catalysts, a variety of preparation methods using CsOOCH were examined. In all cases, doping with CsOOCH led to a lost of surface area. The undoped molybdenum disulfide catalyst only produced hydrocarbons. Cs-doped MoS{sub 2} catalysts all produced linear alcohols, along with smaller amounts of hydrocarbons. With a 20 wt% CsOOCH/MoS{sub 2} catalyst, temperature, pressure, and flow rate dependences of the synthesis reactions were investigated in the presence and absence of H{sub 2}S in the H{sub 2}/CO = 1/1 synthesis gas during short term testing experiments. It was shown that with a carefully prepared 10 wt% CsOOCH/MoS{sub 2} catalyst, reproducible and high alcohol synthesis activity could be obtained. For example, at 295 C with H{sub 2}/CO = 1 synthesis gas at 8.3 MPa and with GHSV = 7,760 l/kg cat/hr, the total alcohol space time yield was ca 300 g/kg cat/hr (accompanied with a hydrocarbon space time yield of ca 60 g/kg cat/hr). Over a testing period of ca 130 hr, no net deactivation of the catalyst was observed. 90 refs., 82 figs., 14 tabs.

  18. Anion permselective membrane. [For redox fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, S.S.; Hodgdon, R.B.

    1978-01-01

    Experimental anion permeselective membranes were improved and characterized for use as separators in a chemical redox, power storage cell being developed at the NASA Lewis Research Center. The goal of minimal Fe/sup +3/ ion transfer was achieved for each candidate membrane system. Minimal membrane resistivity was demonstrated by reduction of film thickness using synthetic backing materials but usefulness of thin membranes was limited by the scarcity of compatible fabrics. The most durable and useful backing fabrics were modacrylics. One membrane, a copolymer of 4 vinylpyridine and vinyl benzylchloride was outstanding in overall electrochemical and physical properties. Long term (1000 hrs) membrane chemical and thermal durability in redox environment was shown by three candidate polymers and two membranes. The remainder had good durability at ambient temperature. Manufacturing capability was demonstrated for large scale production of membrane sheets 5.5 ft/sup 2/ in area for two candidate systems.

  19. Cost projections for Redox Energy storage systems

    Science.gov (United States)

    Michaels, K.; Hall, G.

    1980-01-01

    A preliminary design and system cost analysis was performed for the redox energy storage system. A conceptual design and cost estimate was prepared for each of two energy applications: (1) electric utility 100-MWh requirement (10-MW for ten hours) for energy storage for utility load leveling application, and (2) a 500-kWh requirement (10-kW for 50 hours) for use with a variety of residential or commercial applications, including stand alone solar photovoltaic systems. The conceptual designs were based on cell performance levels, system design parameters, and special material costs. These data were combined with estimated thermodynamic and hydraulic analysis to provide preliminary system designs. Results indicate that the redox cell stack to be amenable to mass production techniques with a relatively low material cost.

  20. Cooperative redox activation for carbon dioxide conversion

    Science.gov (United States)

    Lian, Zhong; Nielsen, Dennis U.; Lindhardt, Anders T.; Daasbjerg, Kim; Skrydstrup, Troels

    2016-12-01

    A longstanding challenge in production chemistry is the development of catalytic methods for the transformation of carbon dioxide into useful chemicals. Silane and borane promoted reductions can be fined-tuned to provide a number of C1-building blocks under mild conditions, but these approaches are limited because of the production of stoichiometric waste compounds. Here we report on the conversion of CO2 with diaryldisilanes, which through cooperative redox activation generate carbon monoxide and a diaryldisiloxane that actively participate in a palladium-catalysed carbonylative Hiyama-Denmark coupling for the synthesis of an array of pharmaceutically relevant diarylketones. Thus the disilane reagent not only serves as the oxygen abstracting agent from CO2, but the silicon-containing `waste', produced through oxygen insertion into the Si-Si bond, participates as a reagent for the transmetalation step in the carbonylative coupling. Hence this concept of cooperative redox activation opens up for new avenues in the conversion of CO2.